TWI337099B - High activity metal carbene metathesis catalysts generated using a thermally activated n-heterocyclic carbene precursor - Google Patents

Description

1337099 VI. Description of the invention: [Technology of the invention]; field of invention] * This application is the US patent application No. 丨 (Vl〇l, 531 (March 25, 2002) And the name of the invention is "partially suitable for the use of a heat-deprotectable N-heterocyclic carbon-diluted rare earth-substituted ruthenium active Ru-alkylene and ethylene-based derivative,"). (Continued. This U.S. Patent Application (a) requests U.S. Provisional Patent Application No. 60/278,311 (issued on March 23, 2001 and the name of the invention, suitable for use with N-protective N- Highly active rualkylene and 10 vinylidene derivatives produced by heterocyclic carbene-derived olefins") and (b) US Provisional Patent Application No. 60/288,680 (filed on May 3, 2001, and the name of the invention) "Highly active Group 8 alkylene and vinylidene derivatives based on olefin replacement by heat activated Ν·heterocyclic carbene M (NHC) precursors") and (4) US Provisional Patent Application No. Case No. 60/360,775 (applied on March 1, 2002 and the name of the invention is ''the use of a five-coordinate or six-coordinated or hungry replacement 15 catalyst polymerization) Priority is claimed for each of the above-identified applications. C. Prior Art 3 BACKGROUND OF THE INVENTION Displacement catalysts have previously been made, for example, by U.S. Patent No. 5, 312, 940; 20 5, 342, 909; 5, 728, 917; 5, 750, 815; 5, 710, 298 and 5, 831, 108, and PCT Publication No. WO 97/20865 and WO 97/29135, the contents of each of which are incorporated herein by reference. The announcement describes a single component or a hungry catalyst with several advantageous properties. For example, 'this catalyst can tolerate a variety of wood-functional Bean-based cancer systems that are more viable than the previously known replacement catalysts. The patent case reveals that it is hungry and hungry. (4) It has a +2 oxidation state, a metal center with 16 electron numbers and a five-coordinated structure. It is a private structure that has a structure like xV. x<

It is also a starter for ring-opening displacement polymerization (R〇Mp) of strained cyclic olefins such as norbornene, dicyclopentadiene, = cyclopentadiene and functionalized norbornne. The ring-opening displacement polymerization (R〇Mp) of polycyclohexene addition polymerization is generally described by the following reaction scheme: ηφ polymerization inverse

ΘΘ addition polymerization

It is not intended that these compounds may be used as other substitution reactions (including, for example, addition polymerization replacement, ring closure replacement (RCM), acyclic refinement (ADMET), cross-replacement (CM), and degraded dilution. Inlet complex of hydrocarbon replacement (0 Μ)). The synthesis of Ri^XXX^LXL^K^RXR1)) and its associated ring-opening displacement polymerization (ROMP) activity are described, in particular, in U.S. Patent Nos. 5,312,940 and 5,342,909. In these patent cases, both 'L and L1 are Lewis ligands. Further, in each of these patents, Lewisine is preferred as the stupylphosphine. Subsequent to U.S. Patent No. 5,922,863, the disclosure of which is incorporated herein by reference in its entirety in its entire entire entire entire entire entire entire entire entire disclosure active. One of the more active rhodium starter species for olefin replacement is known to contain a saturated or unsaturated N-heterocyclic carbene (NHC) moiety. The increased activity of this portion is reported in, for example, PCT Publication Nos. WO 99/51344, WO 00/15339, WO 00/15339, and WO 00/58322, the contents of each of which are incorporated herein. For reference. To date, the preferred initiator of ROMP of dicyclopentadiene has two tertiary phosphine ligands (PR;) and one having one NHC and one tertiary phosphine (PR3), ie,

A representative starting dance jA can be used, 'single enthalpy method' in the presence of hydrogen and 3-ox-3-methyl-1-butyne from [Ru(C〇D)Cl2]n and tricyclopentyl Phosphine is produced in almost quantitative yield. A representative initial B is based on about 80 t in toluene from RuCl2(PCy3)2 (=CHPh) (from RuCl2(PPh3)3 and stupyldiazocarbazone followed by the addition of tricyclohexylphosphine. And obtained by U-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazolidin-2-yl exchanged as a tricyclohexylphosphine ligand. Under ROMP conditions, initiator a can efficiently polymerize DCPD at about 7500:1 (DCPD: Ru (mole ratio)), and further conversion can be accomplished via additional post-cure of the article. Alternatively, the starter B can be used in an amount up to about 100,000:1 (DCPD: Ru (mole ratio)) and does not require a post cure step. Nowadays, it is more cost effective to prepare the initiator A instead of the mushroom #] B, but the high catalyst efficiency is not achieved 1337099 (i.e., the monomer is converted into a polymer), and the curing after the poly-DCOPD portion is common. One of the disadvantages of using a bright-field alkylene-based catalyst, such as starting A and B, is that it initiates the polymerization (or olefin displacement) immediately upon contact with the replaceable monomer. Another disadvantage of the starter type B species is that the species is more sensitive to the reaction temperature than the starting Maiko A type, and thus the reaction medium of the polycyclic olefin is more rapidly gelled or solidified. The high activity of the starter B is better than the starter A, but the starter a is more treatable than the starting 剤B. The starting Maiko B is also more resistant to atmospheric pressure (oxygen and water), temperature and monomer impurities than the starting Maiko. Literature (for example, in M. A. Sanford, M, Ulman and RH Grubbs, J. Am, 10 Chem. Soc, 2001, 123, 749-750, the contents of which are incorporated herein by reference) The high activity of the olefinic coordination initiator (Starter B), which has been attributed to its ability to promote phosphine dissociation, and conversely appears to be due to (j-bonding π-acid olefin matrix in the presence of free phosphine) The selectivity is improved. Furthermore, because of the competition between olefin and Lewis base, the addition of Lewisine to the starting Maiko A can further slow down the initial treatment of the polymerization reaction. Transition metal derivatives and initiator precursors for the addition polymerization of borneol ("polycyclic olefins") are described in U.S. Patent No. 5,705,503; 5,57I,88i; 5,569,730 and PCT Publication W0 97 WO 00/34344; WO 00/20472; WO 99/14256; W0 20 96/37526; WO 97/20871; WO 97/33198; WO 95/14048; and W0 97/33198 'each of these The contents of this are incorporated herein by reference. The thermal conversion system of 1,3-diphenyltrimethylmethylimidazoline is shown in Scheme 2: 6 1 337099

v

Dehydration (abnormal alpha removal reaction) produces a diphenyl sulphate bite base.

15 In addition, the in-situ deprotection is carried out to carry out the coordination of the ligand at the metal in the reflux of the di-n-bis(triethylphosphine) two-drilling 1,3-di-phenyl _2 _ one gas methyl #ί to protect the effect (four) occurs to produce trans-diqi (1,3-diphenyl sub-scented bite_2_yl) (tri- & phosphine) face (9). Similarly, bis(1,3-diaryl) and bis(1,3-diaryl)-sub. The rice sulphonate compound (bis-NHC·carbene precursor) can be used to produce ruthenium, platinum and palladium compounds containing an imidazolidinium-2-yl moiety. In addition, there have been some use of "instant" or "in situ, the resulting mystery protection of the replaced or unsubstituted 17-meter saliva (ie, the following) in the center of the metal by the taste. Coordination exchange reaction based on trialkylphosphine substitution

Furthermore, Grubbs, Organic Letters (1999), 1 (16), 953-956, describes that alkoxy-protected NHC species do not react with sub-molecular compounds in solvents of ambient temperature; When reacted in situ by heating to 60-8 CTC, 7 5 can easily react with RuC12(PR3)2 (=CHR). However, the isolation of such alkylene groups generally requires no air, anhydrous conditions and most purifications to remove the substituted trialkylphosphine. A method for preparing a compound of the following chemical formula is described by R. H. Grubbs and M. Scholl in PCT Publication No. WO 00/71554, the contents of which are incorporated herein by reference.

The hydrazine or hungry complex used is MCbl^hC^RKR1), wherein L is a Lewis base. The ether-based imidazolium is prepared as shown in the following scheme:

In the case of these systems, the ether is not isolated, but is used in situ. The deprotection step occurs most efficiently when the ether derivative is heated, and the free imidazolium NHC is produced and the ligand at the metal complex is replaced in about 10 minutes. Representative examples of suitable bases include t-BuOK/THF, t-BuONa/THF and

NaOCH3/CH3OH. Highly active N-heterocyclic carbene coordinated olefin displacement catalysts for in situ preparation have been described by Morgan and Grubbs in Org. Letters. (2000), 2(20), 3153 (the content of which is here Incorporate for reference) cross-linking and closed-loop displacement reactions. This document discloses that the active quinonealkyl starter can be produced without prior isolation of the catalyst. However, activation of this in situ catalyst with HC1 or other phosphine scavengers can be used to improve the reaction time required for high conversion and overcome phosphine inhibition. Furthermore, the NHC precursors in this system are not isolated, but are produced in a solvent, for example,

(a)!COBU', THF, less than 25 points in the art; OORuC^PCy^CHPlO, 80. (:, a mixture of PCy3 30 points "'Generates RuCWs-lmesXPC^XXHPh) and 丨 equivalent diagram 4 Therefore, the desired system can make a less active (ie, slower start) system (such as initiator A) Converted to a higher active paper (ie, starting thorn B), so at the end of the polymerization, the most effective species are present in the heart of the system. These reactions are expected to be effective at the beginning of the reaction, at the end of the reaction. When it is excellent, it can be converted into a silk compound. Furthermore, the 'starting of heat stability' _ species can survive longer than the high temperature of RQMP« of polycyclic hydrocarbons. Further advantageously, there are - (1) components which can be easily obtained, (H) reduced synthesis (four) number '(iv) removal of the necessity of substitution, (iv) removal of by-product separation, and (iv) production of appropriate ligands at high yield The starting agent produces a synthetic method such as the species of the initiator b. It is not praised by the use of protected NHC to slow down the polymerization of cyclosporin while achieving excellent conversion of monomers into polymers to overcome conventional techniques. An exothermic polymerization reaction using (10) a clear starter or addition initiator as an initiator for the X337099 source that deprotects the Nhcx2_y reagent and which thereby promotes the initial polymerization (eg, r〇mp or addition polymerization) The activity is done to complete the matter. The reagents described herein are air-stable and isolated and deprotectable NHC reagents, i.e., NHC-X2-Y. In addition, the present invention provides novel NHC decyl alkyl starters, and novel synthetic routes for ruthenium starters. In particular, the present invention relates to in situ preparation of NHC metal carbene displacement reaction catalyst species for polycyclic olefin compositions which exhibit activity comparable to those previously described. However, the process of the present invention does not require extensive purification in the absence of air and moisture, nor does it require removal of the free phosphine ligand, and is prepared from an isolated and cleavable starting complex. L 曰月3 3 SUMMARY OF THE INVENTION The present invention provides a method of converting a less active or slower starting system into a more active system such that at the end of the polymerization, the most active 15 species are present in the system. The present invention generally relates to a process for converting a less active or slower starting catalyst system to a higher activity catalyst system, wherein the process comprises protecting the protected N-heterocyclic carbene and the displacement catalyst in the presence of energy and Olefin contact. One of the benefits of the present invention is that the desired amount of the catalyst is 4 compared to the lack of the protected n-heterocyclic carbon dilute, and the desired amount of silk #丨 is less or less in the presence of the protected n-heterocyclic carbon 2 reduce. The protected _ ring carbon dilution can be unsaturated or saturated. Furthermore, the present invention describes novel indole initiators and methods for their preparation. I: Embodiments; 3 DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention provides a method for converting a less active or slower starting system into a higher activity system, such that at the end of the polymerization, the most active Species are present in this system. The present invention generally relates to a process for converting a less active or slower starting catalyst system to a higher activity catalyst system, wherein the process comprises protecting the protected N-heterocyclic carbene with a replacement 5 in the presence of energy. Catalyst and olefin contact. One of the benefits of the present invention is that the desired catalyst content is less or reduced in the presence of the protected N-heterocyclic carbene than is required for the lack of protected N-heterocyclic carbene. "Catalyst", "starter" and "complex" are used interchangeably herein. The unmodified ruthenium and the carbene complex of the moth have been described in U.S. Patent Nos. 10, 312, 940, 5, 342, 909, 5, 342, 909, 5, 728, 917, 5, 750, 815 and 5, 710, 298, all of which are incorporated herein by reference. . The ruthenium and hungry carbene complexes disclosed in these patents all have a metal center with a +2 oxidation state and a 16-electron number and a five-coordinated position. These catalysts have the following general formula:

15

Where: Μ is 钌 or hungry; X and X1 are the same or different, and each is an anionic ligand; L and L1 are the same or different, and each is individually neutral Electron ligand; 20 R and R1 are the same or different, and each is hydrogen or selected from CrCw alkyl, C2-C20, C2-C20 fast radical, square, Ci-C2 Sour vinegar, C!-C2 nonyloxy, C2-C2G alkenoxy, C2-C2G alkynyloxy, aryloxy, C2-C2Q alkoxy-........------ -------------------- Several tables, C1-C20 alkylthio group, C1-C20 alkyl group, C1-C2G alkylsulfite base 11 JL337099 And a substituent of a group consisting of a decyl group. Alternatively, each of the R or R1 substituents may be one or more selected from the group consisting of CrC1() alkyl, CrC1G alkoxy, and aryl groups (each of which may further be one or A plurality of substituents selected from the group consisting of halogen, Q-C5 alkyl, CrCs alkoxy, and phenyl are substituted. Further, any of the catalyzed ligands may further comprise one or more functional groups. Examples of suitable functional groups include, without limitation, hydroxyl groups, thiols, alcohols, sulfonic acids, phosphines, thioethers, ketones, aldehydes, esters, ethers, amines, imines, guanamines, quinones, imino groups, nitrates. Base, carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide, carbamoyloxy, carbamate, acetal, ketal, borate, cyano, II alcohol, hydrazine, hydrazine, hydrazine Anthracene, alkene 10 amine, hindrance, sulfide, sub-basic and halogen. The catalyst having higher activity is as described above, but L1 may be an unsubstituted or substituted azole beta.

a complex of the following formula

Wherein: each of R6, R7, R8, R9, R10 and R11 is hydrogen or substituted or unsubstituted, selected from the group consisting of C1-C20, C2-C20, C2-C20, and aryl. 12 1337099 1 20 夂 8th CVC20 oxy, c2-C20 diloxy, C2_c2 decynyloxy, aryloxy, Crc-oxygenate, Ci_c-based thio-c core pit continuation, Substituents of the group consisting of Kea Sulfur. Selectively 'R6, R7, R8, R9, R, R" each of the substituents may be one or more of the 1 1Q Hyun*-based Ci-C1 () (The parent may be substituted with - or a plurality of substituents selected from the group consisting of _, Ci C, oxime, Ci_C5 alkoxy, and stupid). Furthermore, R6, R7, R8, R9, Rio and Rii are taken

If you are a substitute, you can include - or more functional groups. Examples of suitable functional groups include, without limitation, hydroxyl, thiol, alcohol, sulfonate 'phosphine, thioether, ketone, alicyclic H, amine, imine, decylamine, SS imine, imino, schlossyl, carboxylic acid , disulfide, carbonate, isocyanate, carbodiimide, carbalide, carbamate, acetal, ketal, borate, cyano, cyanohydrin, hydrazine, hydrazine, hydrazine , maple, sulfide, secondary sputum and dentate. Further, the unsubstituted or substituted imidazolium may be unsaturated, resulting in the following formula 15 complex:

Wherein R6, R7, R10 and R11 are as defined above. In some preferred embodiments of such catalysts, the R substituent is hydrogen and the RI substituent is selected from the group consisting of Ci-C2 fluorenyl, C2-C2 fluorene, and aryl. In a more preferred embodiment, the 'R1 substituent phenyl or ethylene group' is optionally one or more selected from the group consisting of a C1-C5 pit group, a C!-C5 alkoxy group, a stupid group, and a functional group. A group of people. In a specific example of private phase, R1 is a phenyl group or a vinyl group, and 13 1337099 is one or more selected from the group consisting of a gasification 'grain, telluride, fluoride, -no2-, NMe2, methyl' Part of the group consisting of an oxy group and a stupid group is substituted. In the preferred embodiment of the preferred embodiment, R1 is substituted for the base group or ((3) preferred embodiment of the catalyst, the L is selected from the group consisting of phosphine, sulfonate 5 scale, sulfite, phosphinic acid. Salt, fat, victory, mystery, amine, amine, imine, sulfur oxide, carboxyl, nitrosonyl, pyridine and thioether. In a more specific example, L is a phosphine of the formula PR R R5 'where r3, Each of r4ar5 is individually an aryl group or a CrC1Q alkyl group, particularly an alkyl group, a secondary alkyl group or a cycloalkyl group. In the best example, each L is selected from the group consisting of Ρ (cyclohexyl) 3 , _p (cyclopentyl) 3 'isopropyl) 3 10 and -P (stupid) 3 group of ethnic groups. In a preferred embodiment of such catalysts, each of X and X1 is independently hydrogen, a halide, or the following: -Ci_C2Q alkyl, aryl, CrC2 decane oxide, aryl oxide, C3-C2 decyl diketonate, aryl diketonate, Ci_c2 oxime carboxylate, aryl sulfonate, Cl_C2Q alkyl sulfonate, Ci_C2 () alkylthio, 15 Cl-C2G alkane Alkyl sulfo group or a Cl-C 2 decyl sulfinyl group. Alternatively, X and X1 may be one or more selected from the group consisting of CrCw alkyl, CrCioalkoxy and aryl (each of which may be selected from one or more selected from the group consisting of halogen, Ci_C5 alkyl, and oxygen. The base and the base of the stupid base are replaced by a part of the group consisting of. In a more preferred embodiment, X and X1 are halides, benzoate, Ci_c5 carboxylate, Ci_c5 alkyl 'stupoxy 20', Cl-C5 alkoxy, C1-C5 alkylthio, aryl And crc5 alkyl sulfonate. In a more preferred embodiment, each of X and X1 is a halide, C:F3C〇2, CH3C〇2, CFH2C02, (CH3)3CO, (CF3)2(CH3)CO, (CF3)(CH3) 2CO, PhO,

MeO, EtO, a benzoic acid ester, a methanesulfonate or a trifluorosulfonate. In the most preferred embodiment, each of X and X1 is a vapor. 14 1337099 ' In a preferred embodiment of such a catalyst, each of R7 and RIQ is hydrogen, phenyl, or together form a cycloalkyl or aryl group, which is optionally selected from one or more. CrC1Q alkyl, CVCw alkoxy, aryl and selected from the group consisting of hydroxyl, thiol, thioether, ketone, aldehyde, ester, ether, amine, imine, decylamine, nitro, carboxylic acid, disulfide 5, carbonic acid Partially substituted by a group consisting of a functional group of a group consisting of an ester, an isocyanate, a carbodiimide, a carbamoyloxy group, a carbamate, and a halogen; and each of R6 and R11 is a system of CrC1 ( An alkyl or aryl group optionally having an alkyl group, a CrC5 alkoxy group, an aryl group and selected from the group consisting of a hydroxyl group, a thiol, a thioether, a ketone, an aldehyde, an ester, an ether, an amine, an imine, a guanamine, a nitro group Substituted by a functional group of a group consisting of a carboxylic acid, a disulfide, a carbonate, a 10 isocyanate, a carbodiimide, a carbamoyloxy group, a carbamate, and a halogen. In a more preferred embodiment, R7 and R1Q are both hydrogen or phenyl, or R7 and R1G together form a cycloalkyl group; if present, each of R8 and R9 is hydrogen; and each of R6 and R11 is substituted Or unsubstituted aryl. Without being bound by theory, it is believed that the larger R6 15 and R11 groups result in catalysts with improved properties such as thermal stability. In a particularly preferred embodiment, R6 and R11 are the same, and each is individually a chemical formula as follows:

Wherein: R12, R13 and R14 are each independently hydrogen, CVCh) alkyl, CrC1 () alkoxy 20 base, aryl or selected from the group consisting of hydroxyl, thiol, thioether, ketone, aldehyde, ester, ether, amine a functional group of a group consisting of an imine, a guanamine, a nitro group, a carboxylic acid, a disulfide, a carbonate, an isocyanate, a carbon 2 15 4337099 quinone imine, a carbon alkoxy group, a carbamate, and a dentate. In a particularly preferred embodiment, each of R12, R13 and R14 is independently hydrogen, methyl, ethyl, propyl, isopropyl, hydroxy and dentate. In a preferred embodiment, R12, R13 and R14 are the same and each is a methyl group. 5 Examples of preferred specific examples of such catalysts include:

Ή3 W3

Mes

(also known as "Lecky"); i-Pr is isopropyl; and PCy3 is -P(cyclohexyl)3. The inclusion of imidazolium in the foregoing rhodium or iridium catalysts has been found to dramatically improve the properties of such complexes. The catalyst maintains the functional group tolerance of the aforementioned ruthenium complex while having a promoting displacement activity which is advantageously comparable to the conventional tungsten and molybdenum system 16 1337099. In addition, Grubbs and Trnka are hereby incorporated by reference in PCT Publication No. WO 00/58322 (the title of the invention to a novel ruthenium metal alkylene complex coordinated by a triazolyl ligand with a high olefin displacement activity). For reference purposes, the phenylene alkylene group of (PCy3)(L)Cl2Ru(=CHPh) type (L=triazolyl ligand) is disclosed. As shown in Scheme 5, the triazolium-based ligand is produced in situ by removal of the alcohol from the corresponding 5-methoxytriazole:

Ph

Unintentional loops 1 1 〇 These catalysts are more active at elevated temperatures for olefin displacement than the parent catalyst Ru(PCy3)2Cl2(=CHPh)(2) or type A initiator. For example, 1 (L = 1,4,4-triphenyl-4,5-dihydro-1H-triazol-5-yl) catalyzes the substituted diene

A closed loop displacement of 15 produces a tetrasubstituted cyclic olefin in good yield. In addition, this complex demonstrates the similar stability to moisture and moisture exhibited by a catalyst of the general formula:

J. Louie and RH Grubbs have been reported in Angew. Chem. Int. Ed., 2001, 40, 247 (the contents of which are incorporated herein by reference) for The active displacement catalyst is synthesized in situ. This catalytic 17 1337099 agent precursor was prepared by the [(p-cymene) (Imes)RuCl2]2 species, which is deprotected by imidazolium salts to form 1,3-didecyl The imidazole-2 group is produced by substituting p-cymene. The p-cymene complex is then formed and exchanged with the third butyl acetylene to form a vinylidene complex. This can then be displaced with the essential carbene to produce the active species, RuCl2(Imes) (=CH2;). The following structure, NHC-X2-Y, generally indicates the protected form of N-heterocyclic carbon dilute (NHC).

10 Also considered to be insured, the NHC-X2-Y may have an unsaturated portion, such as

Wherein R6, R7, R8, R9, R丨. And R" is as defined above. As shown in Figures 6a and 6b, the mode employed in the present invention relates to the thermal production of NHC from a stabilized (protected) NHC derivative and the release of a χ2_γ.

Schematic circle 6a 18 1337099

One of the best methods for generating reactive NHC without 6b is to use a stable carbene precursor, wherein the Χ2-Υ compound also repairs the reactive NHC, as shown in the schematic and 邛:

Δ

R7

Schematic 7a and

Δ

R〆 N

R1〆? 10 indicates «7b where...^, ~. And the subtle system is as defined above. R K and R2 ° are each group, and the individual is selected from the group consisting of its state, r7, r8, r9 and Rn. The first derivative studied was 丨,3-di-system 15 (s-ImesCHC13)(1), ie, dimethyl di-methyl taste ° sitting on 19 1337099

s-ImesHCCl3 wherein R6 and Ru=2,4,6-tridecylphenyl, and R7, R8, R9 and Ri〇=HaX2=H and Y=CCly from carbene produced by (I) only monomer species There is a tendency to have no polymerization under general condition 5. The monomeric nature of this carbene makes it suitable for in situ generation and reaction with transition metal containing species. The starting material of 1,3-dimercaptotriylmethylidene can be tested by using (ie, potassium hydride (KH), lithium diisopropylamide (LiN(CHMe2)2 or LDA), double ( Deprotection of trimethylsulfonylamino)potassium (KN(SiMe3)2), sodium methoxide (NaOMe) and third potassium pentoxide (KOBu1) to produce i,3-dimercaptodihydroimidazoline The formed NHC was reacted with a gas-like reaction in a room temperature hexane to synthesize. In addition, and as disclosed in U.S. Patent No. 4,161,528, the disclosure of which is incorporated herein by reference in its entirety in its entirety in its entirety, in the s s s s In addition, the ether s-Imes (H) (OCMe3) (formed by the action of KOCMe3 on the imidazolium hydride salt) 15 reacts with an excess of the gas (CHCI3) in a reflux mixture of gas and hexane to produce 1,3 - Two of the three bases of a breathable 〇 〇 〇 〇 〇 〇 〇 〇 〇.

Schematic circle 8 20 1337099 · Similarly, the imidazoline dimethylamine protection version can be equal to the molar fraction of the appropriate diamine and tris(didecylamino)methane (CH(NMe2)3) or third Oxy (bis-dimethylamino) decane ((: Η ΝΜ ε 2) 2 ΟΒ ι ^ reaction produces:

5

10

15 Scheme 9 Such a compound for use in the present invention has the formula NHC-X2-Y which, upon heating to a suitable temperature or providing sufficient energy, produces a free N-heterocyclic carbon and releases the Χ2·γ moiety. In the above structure, X2 is preferably a ruthenium, but may also be Si, Sn, Li'Na, MgX3 (wherein X3 is any halogen) and a brewing group, and γ may be selected from cci3; CHAC^Ph; QF5; OR21: And a group consisting of N(R22)(R23), wherein R2! is selected from the group consisting of Me, C2H5 'i-C3H7, CH2CMe3 'CMe3, C6Hn (cyclohexyl), CHzPh, CHZ norbornyl, CH2 norbornene, a group consisting of C6H5, 2.4.6-(CH3)3C6H2 (Lickey), 2,6-iso-Pr2C6H2, 4-Me-C6H4 (tolyl), 4-Cl-C6H4; and wherein r22 and R23 are individual Selected from Me, C2H5, i-C3H7, CH2CMe3, CMe3, C6H" (cyclohexyl), CH2Ph, CH2 norbornyl, CH2 norbornene, c6H5, 2,4,6-((^3)3(: 6 groups of 2 (mercapto), 2.6-iso-Pr2C6H2, 4-Me-C6H4 (nonylphenyl), 4-Cl-C6H4. In a preferred embodiment of NHC-X2-Y, R7, Each of R8, R9 and R1〇 is selected from the group consisting of hydrogen, methyl, aralkyl and aryl groups, and each of R6 and RI1 is individually selected from a substituted or unsubstituted CrCiQ alkyl group. , Ci_Cig naphthenic 21 20 1337099 base, c2-c1Q alkenyl, aralkyl and aryl group. In the system, 'R7, R8, R9 and R10 are each hydrogen, and the R6 and R11 substituents are selected from the group consisting of phenyl, decyl, isopropyl, tert-butyl, neopentyl or benzyl. The population, each of which is optionally substituted with one or more moieties selected from the group consisting of CrC5 alkyl, CrC5 alkoxy, 5 phenyl and functional groups. In a particularly preferred embodiment, R6 and R11 a phenyl group optionally selected from the group consisting of one or more selected from the group consisting of a vapor, a bromide, an iodide, a fluoride, a -N〇2, a -NMe2, a methyl group, a decyloxy group, and a stupid group. Partially substituted. In a more specific example, R6 and R11 are substituted or unsubstituted aryl groups. Not limited by theory, it is believed that the larger R6 and R11 groups cause improved properties (such as heat And the initiator of oxidation stability. In a particularly preferred embodiment, R6 and R" are the same, and each of them is a chemical formula as follows:

Wherein each of R12, R13 and R14 is independently hydrogen, CrC10 alkyl, CrCw alkoxy-15, aryl or selected from the group consisting of hydroxyl, thiol, thioether, ketone, aldehyde, ester, ether, amine, imine, A functional group of a group consisting of a guanamine, a nitro group, a carboxylic acid 'disulfide, a carbonate, an isocyanate, a carbodiimide, a carbamoyl group, a carbamate, and a halogen. In a particularly preferred embodiment, each of R12, R13 and R14 is selected from the group consisting of hydrogen, methyl, ethyl, propyl, isopropyl, hydroxy and dentate. In the most preferred embodiment, R12, R13 and R14 are the same and each is a thiol group. In another embodiment, any or all of R7, R8, R9 and R1Q, if present, may be combined to form a substituted or unsubstituted, saturated or unsaturated ring structure. This 22 1337099 outer 'R6 and R11 can be combined. The unsaturated ring structure can be aromatic or formed from individual carbon-carbon single bonds and double bonds. Examples of such ring species include:

Examples of the best specific examples for use in the present invention include:

23 5 1337099 Examples of such di-carbene species of Χ2-lanthanide NHC are:

In the case of a tetraaminoethylene complex, the strength of the carbon-carbon double bond (or the diene stability to the two-shot reaction) is used to estimate its use as a source of NHC 5 . A specific example of the NHC-X2-Y species is 1,3-diyl-2-(methoxy-imidazolidinium, 1,3-diyl-2-ethoxy-isoxazole, 1,3-di Leki-2-tert-butoxy_mi-pyridinium, 1,3-diyl-2-benzyloxy-isoxazole, 1,3-diphenyl-2-(tris) Imidazolium, 1,3-bis(3-phenylphenyl)-2-(trimethylmethyl)imidazolidinium, 1,3-bis(4-10 decyl)-2-(tris) Imidazopyridine, 1,3-bis(4-fluorophenyl)-2-(trimethylsulfonyl) imidazolium, i,3-bis(3-methylphenyl)-2-(trimethylmethyl) Imidazolium, 1,3-bis(4-phenylphenyl)-2-(trimethylmethyl)imidazolium, 1,3-bis(4-bromophenyl)-2-(trimethylmethyl)imidazolidinium , 1,3-bis(4-iodophenyl)-2-(trimethylsulfonyl)imidazolium, 1,3-bis(4-decyloxyphenyl)-2-(trimethylmethyl)imidazolidinium ,丨,3_bis(4-ethoxyphenyl)·2·(trimethylmethyl) 15 imidazolium, U-bis(4-ethylphenyl)-2-(trimethylmethyl)imidazolidinium ' l,3-bis(4-nitrophenyl)-2-(trimethylmethyl)imidazolidinium, iota,3-bis(3,4-dimethylphenyl)_2-(trimethylsulfonyl) Imidazolium, 1,3-bis(3,5-diphenyl)-2-(trimethylsulfonyl)imidazolium, anthracene, 3_ 24 1337099 bis (3,5- Nonylphenyl)-2-(trimethylmethyl)imidazolidinium, i-('phenylphenyl)-3-phenyl-2-(trimethylmethyl)imidazolidinium, iota,3-bis(4-fluoro Phenyl)-2-(trimethylsulfonyl)imidazolidinium, 1-(4-mercaptophenyl)-3-phenyl-2-(trimethylmethyl)imidazolidinium, 2-(trimethylsulfonyl) -1,3·bis(2,6-dimercapto-4-t-butylphenyl)imidazolidinium, 2·(trimethylmethyl)-1,3_bis 5 (2,6-diisopropyl Imidazolyl, iota, dimethyl-2-didecylamino-imidazolium, 1-(1,3-dimethyl-2-imidazolidinyl)-decalidine, ι, 3_Didiyl·2·(trimethylsulfonyl) imidazolium ' and 4-(1,3-didecyl-2-imidazolidinyl)-morpholine. The temperature range for deprotection of the NHC-X2-Y compound is from about _50 to about 250 C; preferred ranges are from about 0 to about 200. (:; more preferably from about 50 to about 50. (: 10 range; and the optimum range is from about 75 to about 125 ° C. Both polar and non-polar solvents can be used as NHC-X2-Y The heat is used to protect the proper medium of the reaction, even in the absence of solvent polymerization. The use of special solvents depends on the stability of the NHC_X2_Y and the solubility of the starting metal derivative and the final metal initiator. Containing hexane, heptane, octane, decane, decane, decalin, stupid, toluene, 15 ethyl stupid, o-bi-indene, m-dimethyl stupid and anti-two stupid, sputum, stupid , benzene, bromobenzene, dibromo, ethanol, propanol, butanol, pentanol and hexanol. Suitable polycyclic monomers include borneol thin, sulfhydryl ice (4), butyl norbornene, hexyl Thin ice tablets, sulphur-based borneol thin, bicyclic bismuth dihalide, tricyclic bismuth dilute, methyl tetracyclic twelve carbon roast and four ring twelve carbon dilute, and its cyclopentane roasting same species. NHC can be 20 The solution is produced in the presence of a ruthenium or a hungry complex. A preferred method of deprotecting the NHC precursor is by providing energy in the form of heat (ie, 'heat' However, laser, electron beam radiation, tau radiation, electropolymerization, sound, ultraviolet (UV) or microwave radiation can also be used. Schematic 10 describes the thermal activation of unsaturated NHC precursors and the coordination of the ligand 25 4337099 To form a more active replacement initiator:

Schematic 10

This interchange can be carried out in a solvent or monomer. Generally, the selected NHC needs to be more basic than the leaving group (i.e., L or L1). Thus, for example, a saturated or unsaturated NHC is expected to be capable of replacing one of the following exemplified starter species, phosphine (in a solvent or reactive monomer), ether or imidazolium (wherein R5Qa, R5Gb, 115() £ and 115() £1 may be selected from any of the groups selected as R6 and R11. Preferably, in these examples, R5Qa, R5t)b, R5Qe&R5()d are each an alkane. Or aralkyl (eg, phenyl fluorenyl)): 10

Preferably, the initiator is selected from the group 8 alkylene species or cumulative species. Furthermore, the initiator can be tetracoordinate, pentacoordinate or hexacoordination. An example of a hexacoordination initiator can be found in U.S. Patent Application Serial No. 10/017,489, filed on Jan. 14, 2001, the title of the invention, the six-coordinated ruthenium or ruthenium metal carbene replacement catalyst, the contents of which are hereby incorporated by reference. Incorporated for reference). 26 15 1337099 For example, a pentacoordination complex can lose an L or L1 ligand to form a permutation-activated tetracoordinate species as described in Scheme 11 below: R1

R

Άι

R Schematic Circle 11 As shown in Scheme 11, the L or L1 ligand can also be attached to a tetracoordinate species to form a pentacoordinate complex.

Then, when in the presence of an olefin, the tetracoordinate species can initiate the polymerization (as shown in Scheme 12) or, in the presence of deprotected protected NHC, form a five-coordinated complex dominated by NHC. Substance, or loss of X3 and Y, to form free NHC-coordination 10 or carbon thin (Scheme 13):

L R1

=C=C

R

X

R1 R

Schematic 12 + R* R9 R7-4 I R10

Re-N, -R11

V RJ X, 丄-r·〆x, a c-c, r R9 R7- 4-r10 R8-Nv 'n-R11 Schematic circle 13 27 1337099 Then the five-coordinate NHC complex can lose the L-coordination To form a displacement-activated tetracoordinate NHC species (Scheme 14):

Scheme 14 5 Then, when in the presence of an olefin, the tetracoordinate NHC species can initiate a polymerization reaction, as shown in Scheme 15:

Schematic 15 In addition, the four-coordinate species in the presence of protected NHC can be exchanged for NHC tetracoordinate species by the ligand 10, and then the polymerization is initiated in the presence of olefins and energy without intermediate A five-coordinated complex of the product. More preferably, the initiator has the general formula wherein the leaving group (i.e., L or L1) is capable of being substituted with NHC. 28 1337099 The general formula of the above-mentioned replacement catalyst: M is preferably sputum or hungry; - each of X and oxime is an anionic ligand, preferably a, Br, I, , ch3co2^cf3co2; [And each of B1 is an arbitrary neutral electron donating ligand, for example, Lewis base' in which L or L1 can be substituted by an NHC ligand; and R and R1 are preferably each Individually hydrogen or selected from Ci_C2q alkyl, C2_C2 〇, c2-c20 fast radical, aryl, Ci C vinegar, C| C2 〇 methoxy, C2-c2 〇 • diloxy, C2'C2° Alkynyl, aryloxy, c2-c20 alkoxy group, Crc20^10-ylthio, CrC2D; base group, Ci.c-carbosulfide group and substituents of the group consisting of . Alternatively, each of the r&r1 substituents may be selected from one or more selected from the group consisting of CVCs. a part of the group consisting of the base of the Cl_Ci broth and the aryl group (the parent may be further - or more selected from the group consisting of halogen, c]-c5 alkyl, c丨-(:5 alkane The oxy group and the phenyl group are substituted). Further, any of the catalyst ligands may further comprise one or more functional groups. Examples of suitable functional groups include, without limitation,: leaven, shout, phosphine, Alcohol, sulphur, sulphur, sulphur, vinegar, domain, amine imine, ruthenium, imine, imino, arginine, acid, disulfide, carbonate, acetonic acid, carbitol , carbon hospital oxygen, carbamate vinegar, shrinkage, shrinkage steel, acid salt, alcohol, alcohol, fight, defense, brewing, amine, sister, sulfide, secondary 20 fluorenyl and halogen. In a preferred embodiment of the isotactic thorn, the R substituent is hydrogen, and the R1 substituent is selected from the group consisting of CrC2 fluorene, (^2·~ gynecyl and aryl groups. In a more preferred embodiment) The R1 substituent is a phenyl group, a methyl group, an ethyl group, an isopropyl group or a tributyl group, each of which is optionally selected from one or more selected from the group consisting of Cl. Base and functional group Partially replaced by a partial group. RX is a tributyl or stupyl or vinyl group, which is optionally selected from the group consisting of vapors, deserts, moths, and fluorides. And Ν〇2_, -NMe2 'substituted by a group consisting of a methyl group, a methoxy group and a phenyl group. In a preferred embodiment of the catalysts, each of the oxime and the oxime is hydrogen, Halide or one of the following groups: Ci_c2 decyl, aryl, CrC2 decane, aryl oxide, CrCu alkyl di-acid salt, aryl diketo acid salt, Cr (: 2 hydrazine carboxylate , aryl sulfonate, alkyl sulfonate, Ci_C 2 () alkylthio, Ci_C 2 decyl sulfo or alkyl sulfinylene. Alternatively, hydrazine and 1 may be one or more Selected from ci-ci 〇 alkyl, crc10 alkoxy and aryl (each of which may be selected from one or more selected from halogen, Crc5 alkyl, (:: 5 alkoxy and stupid) The base group is further substituted by a part of the group consisting of. In a more specific example, X and X1 are a halide, a benzoate, a Ci_c5 carboxylate, a Ci_c5 alkyl, a phenoxy group, a CrC5 alkane. Base, CVCs alkylthio, aryl and Ci_C5 alkyl sulfonate. In a further preferred embodiment, each of X and χ1 is a halide, cf3co2, CH3C02, CFH2CO2 '(CH3)3CO ' (CF3 2(CH3)CO ' (CF3)(CH3)2CO ' PhO ' MeO, EtO, tosylate, sulfonate or trifluoromethanesulfonate. In the best specific example 'X and X1 each Preferably, the catalysts are preferably selected from the group consisting of 20 phosphine, sulfonated phosphines, phosphites, phosphinates, hydrazines, hydrazines, ethers. , amines, guanamines, imines, sulfur oxides, carboxyl groups, nitrosonides, pyridines, thioethers and heterocyclic carbene. In a more preferred embodiment, L and L1 are phosphines of the formula PRW, wherein each of R3, R4 and R5 is individually aryl or CVCw alkyl, especially a primary alkyl, a secondary alkyl or a cycloalkyl. 30 1337099 In the most preferred embodiment, each of L and L1 is selected from the group consisting of -P(cyclohexyl)3, -P(cyclopentyl)3, -p(isopropyl)3, P (second a group consisting of butyl) and -P (stupid). Preferred starters for use with the thermally activated NHC precursor may be selected from the following compounds (designated by their appropriate molecular weight):

31 -T337099

Ru731

Ru751

Ru779 v

Ru799

Ru801

Ru 815

Ru823

32 1337099 yr=c

Ro 801(B) —CHj'

Ru 801(C)

Rn 815 (B): win PCy9

Cl, 2CH, , CHj,

Ru843

Cl,

Ru 831

rOft '〇«$ Preferred examples of Ru or 〇s initiators to be mixed with NHC-X2-Y species are as follows: X, x2

R7 R® 33士337099 wherein M=Ru or Os ; 乂1 and 2 indicate that each is selected from the group consisting of chloride (C丨), bromide (Br), iodide (I), thiocyanate (SCN), Cyanide (CN), carboxylate (〇C(〇)R), triseoacetate (OC(O)CF3), trifluoromethanesulfonate (ojcj; 3), trifluoromethane a group consisting of amine 5 (N(S〇2CF3)2), acetoacetate vinegar (acac), alkoxide (R〇), aryl oxide (ArO) and tosylate (〇3SC6H4CH3) Any anionic ligand; the X system can be bonded to the functional group of the metal center and also attached to the alkylene moiety of the initiator (the "starting position" and the subsequent strain ring via the carbon skeleton, , catalyzed, open 10 ring); and wherein X is selected from the group consisting of alkoxy (-OR), thiooxy (-SR), phosphine (-PR2), scale (-P(0)R2), guanamine (-NR2), hydrazine (-AsR2), acetamidine (-SbR2), dilute (-CR=CR2), block (-CCR), carboxylic acid vinegar (-OC(O)R), acetic acid vinegar (- C(O)OR), sulfinyl (-S(O)R), sulfonyl (-S(O)R), sulfonate (〇S(0)2R), _ (-C(O) Group 15 consisting of R), aldehyde (-C(O)H) and imino group (-C=NR or CN=R) And an L-type electron donor, wherein the electron donor can be anionic, neutral, free radical or cationic. Typical electron supply systems are neutral, for example, imidazolium, pyridine, ethers, amines, phosphines, phosphinates, phosphonates, and phosphites. Phosphine is a preferred ligand for the present invention. The trialkylphosphine system is superior to the triarylphosphine. More preferably, the phosphine contains 20 at least a secondary alkyl or cycloalkyl group, and is preferably exemplified by an alkyl group such as isopropyl, isobutyl, t-butyl, neopentyl, cyclopentyl or a ring. Hexyl or the like, that is, triisopropylphosphine or tricyclohexylphosphine. L is selected to be weaker than the NHC produced from NHC-X2-Y. R ' R7, R8, R9 and R10 are as defined above. Preferably, R, R7, R8, 34 1337099 R and are each selected from hydrogen or selected from cvc2. Burning base, c2-c2. The group consisting of the smoke group or Weiji of the group consisting of (9) groups. More preferably, R, R7, R8, R9 and Rl. Each is selected from the group consisting of hydrogen, a thiol group, a polycyclic ring, a stimulating polycyclic ring or a secret group. When r7, R8, R and R are attached to a carbon atom to form an ethylene group or an aromatic bond, only two such groups are required. Representative polycyclic and polycyclic ring structures such as cyclodecyl, cyclohexyl, stupid or naphthalene. The following structures are examples of RU or Os starter agents to be mixed with NHC-X2-Y species.

10 At room temperature, the complex RuX2(PPh3)3 (X=cl, Br) reacts with CCMe3 for 24 hours to generate the vinylidene group of the chemical formula RuX2(PPh3)2(=C=CHCMe3). Compound. In related chemistry and catalysts, chemical formula has been proved

RuX2(PR3)2(=C=CHCMe3) (R=Ph, i-pr, Cy(cyclohexyl) and Cp(cyclodecyl)) vinylidene oxime complex ROMP or norbornene precursor A good catalyst for the 15 agent. These species have previously been explored to have lower catalyst efficiencies than the prevailing Grubb starter system. A vinylidene complex having R = Ph is prepared by reacting RuClJPPh3)3 with a third butylacetylene; a ligand interchange is used to obtain i-Pr, Cy, and Cp complexes. In addition, 'various RuX2(PR3)2(=c=C(H)R) 35 1337099 species can be obtained by [RuCl2(p-cymene)]2, phosphine (2 equivalents/Ru) and alkyne (1 equivalent/ The toluene solution of Ru) is obtained by heating at 80 ° C to selectively form a corresponding vinylidene species and producing it in high yield. Conversely, the present invention also proposes a method for in situ generation and thermal deprotection of NHC 5 as a method for producing an alkylene-containing alkylene derivative containing NHC under conditions similar to those described above, that is,

Not intended for the above reaction. The neutral electron donor (L) may be selected from PMe3, PPhMe2, iO ΡΕί3 ' Ρ(〇ϊνίε)3 ' PPh2Me ' PPh2Et ' PBz3 ' PCyPh2 ' Pi-Bu3 ' P(4-CH3OC6H4 3' P(4-CH3OC6H4)3' P(4-FC6H4)3' P(4-C1C6H4)3^P(4-CF3C6H4)3, PCy3, PCy2Ph, P(〇Ph)3, pi-prAPPh3. Preferably, the L group is selected from the group consisting of trisylphosphine, triisopropylphosphine, tricyclohexylphosphine, and tricyclopentylphosphine (pCp3). Aromatic hydrocarbon = hydrocarbon-containing benzene, i.e., benzene, p-cymene, diterpenoid, and hydrazine 15 benzene. Preferred aromatic hydrocarbons are para-cymene. The synthesis of several RuX2(PR3)2(=OC(H)R) species and how these species are in cyclic olefins is described in U.S. Patent No. 6,107,420, the disclosure of which is incorporated herein in There is a hot start. In this same patent, a vinylidene derivative (i.e., RuCl2(ImeS)(PCy3) (=C=C(H)-CMe3)) similar to that described above is disclosed. The following Scheme 17 additionally uses a thermally deprotectable NHC to prepare the NHC in situ with an appropriate amount of Lewis base and an α,α-dihalo-substituted terpene, i.e.,

The schematic circle 17 is used for the above reaction. The neutral electron donor (L) may be selected from the group consisting of PMe3, PPhMe2, 10 pEt3, P(OMe)3, PPl^Me, PPh2Et, PBz3, PCyPh2, Pi-Bu3, P(4- CH3OC6H4)3, P(4-CH3OC6H4)3, P(4-FC6H4)3, P(4-C1C6H4)3, P(4-CF3C6H4)3, PCy3, PCy2Ph, P(OPh)3, pi-PrAPPh3. Preferably, the L is selected from the group consisting of triphenylphosphine (PPhO, tricyclohexylphosphine (PCy3), triisopropylphosphine (Pi-Pr3), and tricyclopentylphosphine (PCp3). X' and X" may be selected from X and 15 X1 are the same as defined above. In addition, Scheme 18 is another route for mixing NHC/PR3, suitable for protecting NHC and solvent. NHC can be any previously discussed NHC. Restrictedly containing hospital and ring-burning solvents 'such as pentane, hexane and cyclohexane; halogenated alkane solvents, such as dioxane, gas, four gasified carbon, ethane, 1, 1-37 1337099 10 Di-ethane, 1,2' di-ethane, 1-propane, 2-propane, 1-butane, 2_gas, sinter, 1 gas, 2' methylpropanol and 1-gas ;_, such as, THF and diammine; aromatic solvents, such as benzene, dimethyl, toluene, lyon, gas benzene and o-gas, grade one and three alcohols, and southern carbon solvents, such as, ΡΓ6〇η®112; and its 'thinking compound. Preferred solvents include stupid, fluorobenzene, o-difluoro stupid, p-one gas, five gas stupid, hexafluoro stupid, o-di-benzene, gas benzene, Toluene, o-, m-, and p-one , vegetable, cyclohexane, thf, dioxane liquid rubber and liquid helium oxidizing agent. The preferred solvent comprises secondary and tertiary alcohols, which can be chemical formula HC (r4°) (r41) 〇hU4〇c<,) a compound of oh, wherein each of r4, and R42 is _^κ: 20 alkyl or c4 - c12 cycloalkyl (which is unsubstituted or C! (: base, Cr (: 6_ silk, · or ci-substituted with Ci C), or C6_Cl6 aryl (which is unsubstituted or substituted with crc6, Ci-C6 dentate, -N〇2 or Ci (: substituted) 'or ^·~arylalkyl (which is unsubstituted or substituted with 15 20 'initial 2 or in the form of anoxin); or the heart and R radicals are tetra- or penta-methyl (they are not Substituted or substituted with a base, c! c6-fossil-no2 or substituted with Ci C6 alkoxy), or a tetra- or penta-methyl group (which is unsubstituted or "(:!_(: 成基,统基) , _Nq2 or with C "C6 he published ancestors #八八兴μ« - or two 丨, 2_ phenyl condensation", and Re is as defined above RR and R are better each one is c] _C2 calcined or C4_Ci2 ring pit (the wire is taken from HXCVC6 filament, Ci_C6 (tetra), if or replaced by CVC6 alkoxy). r41 and r42 More preferably, each is individually CA cyclyl or Qh cycloalkyl...., R4 丨 and π optimal methyl, ethyl, propyl, isopropyl 'butyl, isobutyl and second butyl Base. 38 1337099

(External _

The catalytic activity of the phosphine-containing hydrazine-substituted olefin initiator can be significantly improved by the addition of such heat to protect the NHC. The open-loop displacement polymerization of DCPD is useful, wherein the polymerization exotherm exceeds about 2 ° C, because the protected form becomes deprotected during the reaction, and at the end of the polymerization. NHC is more effective than phosphine in stabilizing the ROMP catalyst at higher temperatures. For example, the addition of compound (1) to RuCl2(PCy3)2 (=CH-CH=CMe2) can reduce the content of 7,500:1 (DCPD:Ru (mole ratio)) from a general use to a better value of 10 ( 4〇, 〇〇〇: 1), while still maintaining excellent conversion rate (see example). Thus, the enhanced ROMP activity can be obtained without isolating the individual NHC-containing initiator and in the presence of the free phosphine ligand. The reactivity of the Type A initiator system can also be further improved by the addition of a neutral electron donor ligand such as triphenylphosphine or trisylphosphite, whereby the gelation and heat release time can be 15 It is delayed for a longer time at lower temperatures. However, once an exothermic reaction occurs, complete conversion can be achieved by in situ generating a more active NHC metal carbene displacement catalyst. 39 1337099 Any base (proton acceptor) and any acid (proton donor) are suitable in the following schemes 19-22. A better test system has a greater tester than water. Examples are tertiary amines, metal hydroxides, metal alkoxides and metal phenates. Preferred base is triethylamine, 1,8-diarhebicyclo[5.4.0]undec-7-ene, KOH, NaOH, KO- 5th tributyl and NaO-fluorenyl, especially three Ethylamine and diazabicyclo[5.4.0]undec-7-ene. Preferred is an acid hydrohalic acid. Examples are selected from the group consisting of HF, HC1, HBr and HI, particularly preferably HC1 and HBr.

L

Schematic circle 19 40 1337099

Schematic 20 [RuClt(COD))n ♦ L ♦

Dissolved steel "ΊϋΓ" ·Χ2·Υ

Illustration 21 41 1337099

Scheme 22 In Schemes 19-22, suitable solvents include, without limitation, alkane and naphthenic solvents such as 'pentane, hexane, heptane and cyclohexane; halogenated alkane solvents such as dioxane, gas imitation , four gasified carbon, gasified ethane, 1,1-diethane, 1,2-diethylene, 1-propane, 2-propane, 1-butane, 2-butane , 1-gas·2-methylpropane and 1-cyclopentane; ethers, such as THF and diethyl hydrazine; aromatic solvents, such as, stupid, diphenyl, stupid, anthracene, gas and stupid Dioxane; primary, secondary and tertiary alcohols, and halocarbonate solvents such as Freon® 112; and mixtures thereof. 〇 Preferred solvents include stupid, fluorobenzene, o-difluorobenzene, p-difluorobenzene, pentafluorobenzene, hexafluoro, stannoid, benzene, benzene, o-, m- and p-dimethyl Stupid, anthracene, cyclohexane, THF, dinitromethane, liquid rubber and liquid antioxidants. More preferred solvents include secondary and tertiary alcohols which may be compounds of the formula HC(R4〇)(R4i)〇H or RC(R41)(R42)〇H, wherein R4〇, R41&R42 each are each other Individual 15 is CrC2() alkyl or C4_Cl2 cycloalkyl (which is unsubstituted or Q-C6 alkyl, 42 1337099

10 15

CrC6 haloalkyl, -N02 or substituted with CVC6 alkoxy), or c6-c16 aryl (which is unsubstituted or crc6 alkyl, (: 丨-<:6 haloalkyl, -N02 or C丨-c6 alkoxy substituted)' or (:7-(:16 arylalkyl (which is unsubstituted or as CrCe alkyl, CrC6 haloalkyl, -N02 or C)-C6 alkoxy Substituted): or the R40 and R41 groups are together a tetra- or penta-methyl group (which is unsubstituted or substituted with QG alkyl, CrC6 haloalkyl, -no2 or CrC6 alkoxy) or four- or Five-extension methyl group (which is not substituted or

Ci-C6 炫, C丨-C6 halogen-based, -N〇2 or substituted with C]-C6 alkoxy, and with one or two 1,2-phenylene), and R42 is as defined above . R4〇, p41 and R42 are preferably each of which is individually CVC2. An alkyl group or a c4_cl2 cycloalkyl group (which is unsubstituted or substituted with a pit group, a CrC6 alkyl group, a _N〇2 group or a fluorenyl group). Preferably, each of R 4 , R 41 and R 42 is each a G alkane. Base or C4_Ci2 cycloalkyl. R 0 , R41 and R42 are preferably methyl, ethyl, propyl, isopropyl, butyl, isobutyl and t-butyl groups. In the intentions 19-22, L, L1, R, and R are as defined above. R, may be selected from any of the groups optionally selected as R or R. Further, the protected mash (: χ2 γ can be protected as described above for the protected NHC-X2-Y. Similarly, the present invention provides the addition of the following triazole

Ph

As for the phosphine-based mesogenic base mixture in the DCPD to reduce the concentration of the Ru initiator added to the system, since the more active catalyst can remove the sterol from the methoxide in situ. form. In addition, any suitable carbon dilution can be mixed with the initiator to achieve a catalytic reduction efficiency of 43 20 , ie

Reaction Thermodynamics The successful part of the deprotection of NHC_X2_Y is determined by the amount of energy released during the cyclic olefin polymerization. The faster the energy is released and the more energy is released, the critical concentration of NHC can be formed. For example, the release of ring strain during ring-opening displacement polymerization (ROMP) of dicyclopentadiene (DCPD) results in an exothermic reaction with polymerization of about 180 °C. The internal temperature of the polymer produced in situ rises above the glass transition temperature of polyDCPD (Tg = 15 (TC). Therefore, in some polymerizations, this polymerization exotherm and temperature deviation provide excellent monomer conversion. In the present invention, if the internal temperature of the polymer formulation is raised to about the deprotection temperature of the NHC-X2-Y species, it is preferred to utilize the polymerization energy as much as possible to thereby complete the deprotection reaction. And at the same time, the monomer is converted into a polymer, and the polymerization enthalpy per unit mass of the monomer is preferably high. The desired one is to release all the polymerization energy in the ROMP or addition polymerization reaction. The internal temperature reaches about its glass transition temperature or 44 J/U99

exceed. In other words, the higher the concentration of the double bond in the unit mass per unit, the higher the exothermic energy of the polymerization reaction. Therefore, the desired one has a monomer exhibiting a low ratio of carbon to norbornene double bonds. For example, the ratio of carbon atoms to double bonds in norbornene is 7^ in heptyl norbornene, which is a ratio of 14. Therefore, a large amount of polymerized norbornene is expected to be about twice the internal temperature of the heptane norbornene. For the polymerization of polycycloolefins, the polymerization time is preferably short to ensure that the internal temperature of the polymer to be formed reaches a high temperature. Single system norbornene (proportion system 7), dimethanol hexahydronaphthalene (TDD) (proportion system 6) and norbornadiene dimer (proportion system 7) with low carbon to norbornene bond ratio It is advantageous in the present invention. In addition, the glass transition temperature of the final polymer is important for selecting the starting single system. The NHC-X2-Y derived initiator system of the present invention is suitable for the preparation of a wide range of polymers comprising polymerized cyclic and linear repeating units. The polymer mainly composed of the annular fumed tobacco is prepared by the ring-opening displacement polymerization or the addition reaction of the catalyst for the polymerization of the hydrocarbon monomer in the presence of a catalyst amount <starting agent and a greasy precursor mixture. The monomer can be concentrated in the presence or absence of a solvent. ^, such as cyclopropene, cyclobutene, cyclopentazone octene, 5-acetoxycyclooctene, 5 ·, "polycyclic" and "norbornene type," monomer, etc. at least one of the following The secret of the fall: Shi, "· Art, into. Cyclic olefins are such simple olefins, olefins, methylcyclopentenes, cycloheptenes, ring-based 1 octyl, cyclooctane di-rings" Field, as stated herein, 'polycycloolefin,' is used interchangeably and means that the monomer contains a house ring terpene and cyclododecene. The norbornene moiety shown below:

45 1337099 The simplest polycyclic single-system bicyclic monomer of the present invention, bicyclo [2.2.1] heptane->, generally referred to as norbornene. The norbornene-type monomer includes a norbornene, substituted norbornene, and any substituted or unsubstituted higher cyclic derivative as long as the monomer contains at least one norbornene or is substituted Please take part in the ice tablets. The substituted norbornene and its higher cyclic derivative contain a pendant hydrocarbyl substituent or a pendant functional substituent. The single system of the norbornene type is represented by the following structure: R22 - R23 10 wherein "a" represents a single bond or a double bond, and R22 to R25 each independently represents a hydrocarbon group or a functional substituent, and m is an integer of 0 to 5, and when" When a" is a double bond, one of R22, R23 and one of R24 and R25 does not exist. 15

When a substituent is a hydrocarbon group, a halohydrocarbyl group or a wholly South carbon group, R22 to R25 are each a single meter hydrocarbyl group, a halogenated hydrocarbon group and a fully toned hydrocarbon group selected from the group consisting of hydrogen, linear and branched CrC1G alkyl groups, linear and branched. C2-C1() alkenyl, linear and branched (: 2-(: 1 decynyl, C4-C12 cycloalkyl, (: 4-(:12cycloalkenyl, C6-Cl2 aryl, and C7-) C24 aralkyl, R22 and R23 or R24 and R25 may together represent a CrC1Q alkylene group. Representative alkyl groups include, without limitation, methyl, ethyl, propyl, isopropyl, butyl, isobutyl. a second butyl group, a tert-butyl group, a pentyl group, a neopentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group and a fluorenyl group. Representative alkenyl groups include, without limitation, a vinyl group, an allyl group, Butenyl and cyclohexenyl. Representative alkynyl groups include, without limitation, ethynyl, indolyl, 2-propynyl, 1-butynyl and 2-butynyl. The cycloalkyl group includes, without limitation, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group. The representative aryl group includes, without limitation, a phenyl group, a naphthyl group, and an onion group. Representative aralkyl groups are not Restricted to contain 46 1337099

10 15 Stupid methyl and stupid ethyl. Representative alkylene groups include methylene and ethylene. Preferably, the fully toothed hydrocarbon group comprises a fully toothed stupid base and a pit base. The halogenated alkyl group used in the present invention is linear or branched and has the chemical formula czx"'2z+1, wherein X," may be selected from the same groups as indicated above for X and X1, and the Z series is selected from 1 to 10 Integer, preferably, X"' is a fluorine. Preferred perfluorinated substituents include perfluorophenyl, perfluoromethyl, perfluoroethyl'perfluoropropyl, perfluorobutyl and perfluorohexyl. In addition to the halogen substituent, the cycloalkyl, aryl and aralkyl groups of the present invention may be further substituted with linear and branched indole-alkyl and dentate alkyl, aryl and cycloalkyl groups. When R22 to R25 are individually selected from -(CH2)nC(0)0R26, -(CH2)nC(0)0R26, -(CH2)nOR26, _(CH2)n-0C(0)0R26, -(CH2 a group of nC(0)R26, -(CH2)n-0C(0)0R26, -(CH2)nSiR26, -(CH2)nSi(0R26)3A-(CH2)nC(0)0R27, Wherein n each represents an integer from 0 to 10, and R26 individually represents hydrogen, linear and branched CrCio alkyl, linear and branched C2-C|decenyl, linear and branched C2-C10 fluorenyl, Cs-Ci2 cyclized a base, a Ce-C) 4 aryl group and a C7-C24 aromatic pit group. Representative hydrocarbon groups shown by the definition of R26 are as above R22 to R25 are the same as defined above. As indicated above for R22 to R25, the hydrocarbon group defined for R26 may be halogenated and perhalogenated. The r27 group is selected from -C(CH3)3, -Si(CH3)2'-CH ( R28) OCH2CH3, -CH(R28)OC(CH3)3 or part of the following cyclic group:

47 20 1337099 wherein R28 represents hydrogen or a linear or branched (CrC5) alkyl group. The alkyl group includes a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, a third pentyl group, and a neodecyl group. In the above structure, a single bond line protruding from the cyclic group indicates the position at which the cyclic group is bonded to the acid substituent. Examples of the R27 group include 1-mercapto-1-cyclohexyl, isobornyl, 2-methyl-2-isobornyl, 2-methyl-2-adamantyl, tetrazole, tetrahydropyridyl A decyl group, a 3-oxocyclohexanone group, a hydroxy valerolactone group, a 1-ethoxyethyl group, and a 1-tert-butoxyethyl group. The R27 group may also represent a dicyclopropyl fluorenyl group (Dcpm) and a dimethylcyclopropylmethyl group (Dmcp), which are represented by the following structures: 10

In the above structure, R22 to R25 together with the bicyclic carbon atom to which they are attached may represent a substituted or unsubstituted cycloaliphatic group having 4 to 30 ring carbon atoms, or 6 to 18 rings. An aryl group substituted or unsubstituted with a carbon atom, or a mixture thereof. The cycloaliphatic group can be monocyclic or polycyclic. When unsaturated, the cyclic group may contain monounsaturated or polyunsaturated, and the monounsaturated cyclic radical is preferred. When substituted, the rings contain a mono- or poly-substituent wherein the substituents are each selected from hydrogen, linear and branched CrC5 alkyl, linear and branched CrC5-dentate alkyl, linear and branched alkoxy, halogen or Its mixture. R22 to R25 may together form a divalent bridging group, -C(0)-Q-(0)C-, when combined with the two ring carbon atoms to which they are attached, form a five-ring ring, wherein Q represents An oxygen atom or an N(R29) group, and R29 is selected from the group consisting of hydrogen, dentate, linear and branched iQ-Cm alkyl, and C6-C18 aryl. Representative 48 1337099 structure is as follows:

Wherein m is an integer from 0 to 5. The crosslinked polymer can be produced by copolymerizing a norbornene-type monomer as shown in Structure VII with a polyfunctional norbornene-type crosslinking monomer. The polyfunctional norbornene type crosslinked single system means that the crosslinking monomer contains at least two norbornene-type moieties, each of which can be subjected to addition polymerization, ROMP, CM, in the presence of the catalyst system of the present invention. ADMET, RCM and OM polymerization. In the case of CM, ADMET and RCM reactions, the functionality comprises one or more acyclic olefins. The crosslinkable single body comprises a fused multi-ring ring system and a linked multi-ring ring system. Examples of the fused cross-linking agent are exemplified by the following structures. Briefly, norbornadiene is included as a fused polycyclic crosslinker. Q) OXi) (ϊ〇3)

Wherein m is an integer from 0 to 5. 15 The multi-ring cyclic crosslinking agent is exemplified by the following structure. 49 1337099

Wherein m is an integer of 0 to 5, and R3Q is selected from the group consisting of a divalent hydrocarbon group and a divalent group of a decyl group and a divalent ether group. Bivalent means that the free price at each terminal of the base is attached to the norbornene-type moiety. 5 Preferred divalent hydrocarbon groups are an alkylene group and a divalent aromatic group. The stretching system is represented by the chemical formula -(CdH2d)-, wherein d represents the number of carbon atoms in the alkyl chain and is an integer from 1 to 10. The alkylene group is preferably selected from the group consisting of linear and branched (CrC1D) alkylene groups, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, hexyl Base, stretch base and stretch base. When a branched alkyl group is considered, it is necessary to understand that the hydrogen atom on the alkyl octyl group is linear or branched ((: 丨 to (: 5) alkyl substituted. Preferably 矽 alkyl is selected from CH2OSi(R)2OCH2, wherein R = methyl, ethyl, butyl, dipropyl, propyl, methyl or phenyl. The divalent aromatic group is selected from the group consisting of divalent phenyl and divalent naphthyl. The divalent ether group is represented by a -R31-0-R31- group, wherein R31 is the same as R3G. The specific linking polycyclic 15 crosslinking agent is represented by the following structures Villa to VIIIc:

Examples of preferred and polyfunctional crosslinkable monomers include: 50 1337099

An economical route for the preparation of hydrocarbyl-substituted and functionally substituted norbornene monomers is carried out using a Diels-Aderder addition reaction in which CPD or substituted CPD is at elevated temperature and The appropriate diene affinity is reacted to form a substituted norbornene-type adduct, which is generally represented by the following Scheme 23: + R^R^CsCR^R25 Δ

♦ Schematic 23 wherein R to R25 individually represent the milk, the ketone group and/or the functional groups as described above. Other norbornene-type adducts can be prepared by pyrolysis of dicyclopentadiene (DCPD) in the presence of a suitable diene affinity. This reaction produces an adduct by pyrolysis of DCPD to CPD as shown in Scheme 24 followed by a Diels Alder addition reaction of CDP and diene affinity. 51 10 4337099

Illustrated circle 24 wherein n represents the number of cyclic units in the monomer, and R22 to R25 individually represent argon, a hydrocarbyl group and/or a functional group as defined above. The norbornadiene and its higher Diels Adel adduct are similarly prepared by the CPD and DCPD thermal reactions in the presence of the acetylene reactant as shown in Scheme 25 below. 〇 ♦ ft22—~CSC~ Δ

R22

+ R22—C=C~R24- Schematic circle 25 where n, R22 and R24 are as defined above. 10 Norbornadiene can be used as the crosslinking agent of the present invention, but a higher homologous system is preferred. The norbornadiene can be converted to a higher homolog or Diels Alder product using a variety of different dipolymerization catalysts or heating it with cyclopentadiene. In the case of crosslinking a monomeric norbornadiene dipolymer, an additional synthesis reaction is employed in which the norbornadiene is catalytically coupled to produce a 15 isomer mixture of norbornadiene dipolymer, which is as follows Illustrated: Fig. 26 52 1337099 The dimerization reaction of norbornadiene is readily achieved by a number of catalysts to produce a mixed composition of up to six isomers, for example, as described in U.S. Patent No. 5,545,790, the disclosure of which is incorporated herein by reference. It is hereby incorporated by reference. Preferred hetero-structures-external-anti-reverse, intra-inverse-inner and outer-inverse-inner-l,4,4a,4b,5,8,8a,8b-At 5 -1,4:5, 8-dimethylhydrazine-biphenylene ("norbornadiene dimer, or" [NBD] 2,,). The outer-reverse-norbornne diene dimer is the best crosslinking agent. Higher oligomers of norborn dilute dimer can be prepared by heating the norbornadiene dimer with dicyclopentadiene or cyclopentadiene. Other crosslinkers are made up of cyclopentadiene with two or more reactive olefins (eg, cyclooctadiene, 1,5-hexadiene, 1,7-octadiene, and tricycloheptene 10). The reaction of alkene) is obtained. More preferably, the crosslinkable single system contains a second reactive norbornene type moiety. - a preferred monosystem of 5,5'-(1,2-ethanediyl)bibicyclo[2 2丨]heptane 2 (NBCHsCHaNB) by 5-(3-butenyl) bicyclo [2.2.1] Hept-2-ene is obtained by dilute with cyclopentan and is reacted via Diels Alder. The higher homologue of 5-(3-butenyl)bicyclo 15 [2.2.1]hept-2-ene is also the selected co-monomer, ie, 2 (3 butenyl)-l, 2, 3, 4,4a,5,8,8a-octane-1,4:5,8-dimethyl-bromonaphthalene. Similarly, _ 1,4,43,5,6,63,7,10,1〇3,11,12,123-dodecahydrol,4:7,1〇_dimethyl aryl [ae]Cyclooctene is a 1,4,4a,5,6,9,1 〇-octahydro-1,4-fluorenylcyclooctene and cyclopentadiene Made by ear reaction. 14 4a,5,6,9,1〇,1〇a_ 20 The higher homologue between octahydro-1,4-carbamimidocyclooctene is also the selected comonomer, ie ' 1,4 , 43, 5, 53, 6, 7, 10, 11, 113, 12123_dodecyl _14: 5,12-dimethylhydrazine ring VIII [b] naphthalene. Symmetrical and asymmetric terpolymers of cyclopentadiene are also useful parenting agents, ie, 4,4a, 4b, 5,8,8a,9,9a-octahydrogen, 4:5,8- Dimethyl hydrazin-1 hydrazine - hydrazine and 3a, 4, 4a, 5, 8, 8a, 9, 9a-octa argon-4, 9:5,8-dimethylhydrazine-1 fluorene-benzene [f]. Another 53 preferred single system is obtained from the reaction of cyclopentadiene with norbornene and borneol, ie, Ma, 5, 8, 8a_hexahydro·M: 5,8_:匕 稀 稀 苯 苯 苯 苯 苯 苯 苯 苯 苯 苯 苯 苯 苯 苯 苯 苯 苯 苯 苯 苯 苯 苯 苯 苯10 15 20 The preferred polymerizable norbornene thin type Zhao Zhao's example includes unrestricted inclusion of norbornene (double ring [2.2.im-2 price 5-methylm water thinner, ethyl norbornene diluted propyl ice tablets #,isopropyl borneol, butyl norbornene, isobutyl norbornene, pentyl norbornic thin, hexyl norbornene, heptyl norbornic thin, octyl norbornic thin, sulfhydryl ice thin , 12-carbon-based borneol thin, 18-carbon-based borneol thin, p-f stupyl norbornene, methylene norbornene, stupid norbornene thin ethylidene ice-baked, Ethyl-based norbornene Diluted, exo. dicyclopentadiene, inner dicyclopentadiene, tetracyclododecene, methyltetracyclododecene, tetracyclododecadiene dimethylenetetradecyl Symmetrical and asymmetrical terpolymers and tetramers of olefins, ethyltetracyclododecene, ethylene tetracyclododecene, phenyltetracyclononene'cyclopentadiene, 5,6- Dimethyl norbornene, propenyl norbornene, 5 mustard methyl 5a, 8a-dihydroindole, cyclohexenyl norbornene, dimethyl hexahydronaphthalene, internal and external _5, 6 Dimethoxy borneol thin, inner, inner-5,6-two Oxynorbornene, 2,3-dimethoxynorbornadiene, 5,6-bis(gas fluorenyl)bicyclo[2·2·1]hept-2-ene, 5-tris(ethoxy)矽alkyl norbornene, 2-dimethyldecylbicyclo[2_2.1]heptane-2,5-diene, 23-bistrifluoromethylbicyclo[2·2·1]hept-2,5- Diene, 5-fluoro-5-pentafluoroethyl-6-,6-bis(trifluoromethyl)bicyclo[2.2.1]hept-2-ene, 5,6-difluoro-5-heptafluoroiso Propyl-6-trifluoromethyl)bicyclo[2.2.1]hept-2-ene, 2,3,3,4,4,5,5,6-octafluorotricyclo[5.2.1.〇]癸-8-ene and 5-trifluoromethylbicyclo[2.2.1]hept-2-ene, 5,6-dimethyl-2-norbornene, 5-a-naphthyl-2-norbornene, 5 ,5-dimethyl-2-norbornene, 1,4,4a,9,9a,10-hexahydro-9,10[1,2,]benzoquinone-1,4-carbenyl onion Indanyl norbornene (ie, 1,4,4,9-tetrahydro-1,4-mercapto 54 1337099

10

Exo-trans-trans (2+2 dimer) 芴, the reaction product of CPD and hydrazine), 6,7,10,10-tetrahydro-7,10-methyl fluorenyl onion (ie, 0卩0 with The reaction product of hydrazine) '1,4,4,9,9,10-hexahydro-9,10[1',2']-benzoinyl-1,4-methylmercapto onion, inner, inner-5 ,6-dimethyl-2-norbornene, internal and external-5,6-dimethyl-2-norbornene, external, external-5,6-dimethyl-2-norbornene, l , 4,4,5,6,9,10,13,14,14-decahydro-l,4-mercaptobenzocyclododecene (ie, CPD with 1,5,9-ring twelve a reaction product of a carbene triene, 2,3,3,4,7,7-hexahydro-4,7-methylindolyl-1H-indole (ie, a reaction product of CPD and cyclopentene), 1,4 , 4,5,6,7,8,8-octahydro-1,4-carboxynaphthalene (ie, the reaction product of 0卩0 and cyclohexene) '1,4,4,5,6,7 , 8,9,10,10-decahydro-1,4-carbenyl benzocyclooctene (ie, the reaction product of CPD and cyclooctene), and 1, 2, 3, 3, 3, 4, 7,7,8,8-Decahydro-4,7-methionylcyclopenta[a]pyrene. It is particularly useful for single systems to contain more than one polymerizable double bond because it releases more energy, but also because it binds to the polymer chain. The smallest polycyclic structure is norbornadiene, which has a carbon-to-polymerizable double bond ratio of 3.5, i.e., 2 double bonds per 7 carbon systems. Polycyclic structures which can be used in the polymerization can be derived from norbornadiene and its products. Crosslinkers of such single system dimers and trimers, and isomerization products of norbornadiene, ie, _ ΟιΦΘ

Norborn diene dimer external-trans (4+2 dimer norbornadiene terpolymer)

Norbornadiene dimer exo-indole (4+2 dimer) 55 1337099 The cyclic olefins contemplated herein also include U.S. Patent Nos. 4,301,306 and 4,324,717 (the contents of each of which are incorporated herein by reference. For reference, the monomers disclosed. These two references disclose a monomer containing a norbornene structure as described above. 5 The invention is also used to polymerize a "norbornene type monomer" comprising norbornene 'dicyclopentadiene, tricyclodecadiene (symmetric and asymmetric cyclopentadiene terpolymer), four Cyclododecene and other cyclic olefin monomers containing norbornene functional groups. Dicyclopentadiene is a general cyclic olefin monomer used to prepare a ring-opening displaced polymer, since it can be easily obtained as a by-product in the preparation of ethylene. For these polymerization reactions, liquid reagents are preferred because they are easier to handle than solids, as long as they are not too viscous. The problem arises from the use of dicyclopentadiene because it is solid at ambient temperatures when pure enough. The melting point of high purity dicyclopentadiene is generally above about 31 ° C to 32 ° C. Although dicyclopentadiene can be slightly heated to form a liquid, this high melting temperature presents a major commercial disadvantage. In addition, when transporting this monomer, considerable annoyance and expense can be used to melt the monomers as they arrive at their destination. However, the impurities will generally provide a liquid dicyclopentadiene mixture, but will also hinder the polymerization. The addition of an inert solvent or diluent adversely affects the product obtained because the unreacted component reduces impurities and/or leaches from the final polymer, rendering it useless. Similarly, it is noted that the use of the norbornene monomer (bicyclo[2.2.1]hept-2-ene) in some applications is reduced because it is also a solid at room temperature. In addition, norbornene is characterized by its relatively low boiling point and flash point. A preferred mixture of endo- and exo-stereoisomers of the norbornene type, as such materials are generally liquid. The use of two or more different monomers is preferred. The mixed component inhibits the freezing point of the monomer mixture relative to the use of a single monomer component. In this way, the monomer mixture 56 1337099 system can be used in a wider range of processing conditions. When the solid norbornene thin monomer is used, the I body can be dissolved or expanded in a solvent or co-mixed with other monomers. Further, the solid-state norbornene-thin monomer can be efficiently polymerized by heating the monomer to its point of scent or exceeding and inducing dissolution of the components of the catalyst system. 5 The isomers of the norbornene-single-single system prepared by the Ales-Alder reaction are known to have their composition changed according to the starting dilute affinity. The inner and outer norbornee thinner single vessels are substantially equally incorporated into the polymer. However, "for special reasons, the composition of the isomer is superior to the other (for example, the monomer and the liquid is liquid at the temperature), the reaction may be different in the presence of a suitable Lewis acid or a solid acid. The internal type of aromatic-containing norbornene-thin monomer can be converted into its external form by contacting the solid catalyst with the internal isomer to produce an aromatic-containing norbornene-thin monomer. The mixture of structures is obtained to obtain a mixture of extraneous isomers. Single "purity commercial polycyclic olefins can be obtained in various purities, the range of which is about '··' 9·9 Λ, the upper purity range is steaming, Cracking and regeneration and the effect of further processing to remove contaminants and dilute hydrocarbons under polymerization conditions. The degree of progress reflects the overall composition of the single Zhao. It excludes any ternary polymer. Or a tetradecene polymer or any higher oligomer. The polycyclic monomer of the present invention may contain a nominal amount of phase, but if = in 'they should not adversely affect the type of the reaction If the norbornene-type TM used is a non-slave hydrocarbon, then this is not desired.蛵 can be removed by known means. 'The removal will interfere with the impurities in this polymerization. Even if these steps have been broken, the monomer will still contain some impurities. The purity of the monomer should be greater than About 57 i^J/099 90% 'more than about 95%' and more than %, and the best system is greater than about 99.5% to ensure that the monomer is converted to the polymer as completely as possible. Unintentionally added during preparation The water and oxidation products of the composition component will not be conducive to the storage stability of the initiator component. The water will be a cycloaliphatic monomer and an inert compound S technology (mainly an impact modifier 'plastic (four), resistance _ 'Blowing agent filler and strengthening agent' impurities into the composition. _HC_x2_Y or starter is added to the composition, the water content of the mixture of the ring thinner monomer and the inert combination is preferably low The water content in (4) ppm' and better system 丨 _ pm 韵 缚 烟 单 赵 赵 赵 于 NH NH NH NH NH NH NH NH NH NH NH NH NH NH NH NH NH NH NH NH NH NH NH NH NH NH NH NH ppm ppm ppm ppm ppm ppm ppm ppm Most of the hydrocarbons are heterogeneous to form heterogeneous symmetry, and a small portion of the sulphuric acid monomer will remove most of the distillation. Contamination. Traditionally, residual water can be removed by the addition of molecular sieves to cyclic dilute hydrocarbons. Polymerization In general, the process of the invention comprises forming a reactive monomer composition such that 15 proliferating species are formed in situ. Can occur in the presence or absence of a solvent as a metal carbon-dioxide replacement catalyst or an NHC precursor or a norbornene-thin monomer to be polymerized. < In the L丨 of the present invention, the sub-system and the dirty The composition component and the ice-reducing (four) type monomer are mixed. In the other, the Zhaozhong Zhongya-burning system is mixed with the NHC pre- Zhao and the mitigating component and the norborne field type monomer. In another specific example, The heat-treated solution of the NHC precursor and the initiator is mixed with at least one norbornene-type monomer. In this specific example, the appropriate solvent of the catalyst component includes, without limitation, a calcined and cyclized solvent, such as pentane. Alkane, hexane, heptane and cyclohexane; toothing solvent, such as 'di-methane, gas, four-gas carbon, gasified ethane, bismuth-hexane, 1,2-two gas Alkane, 1-aeropropane, 2-propane, helium, butane, 2_58 1337099, butane, 1- 2-methylpropane and 1-cyclopentane; ethers such as THF and diethyl ether; aromatic solvents such as benzene, dimethyl, toluene, lysine, gas and o-dichlorobenzene; A hydrocarbon solvent such as Freon® 112; and mixtures thereof. Preferred solvents include benzene, fluorobenzene, o-diphenyl, p-difluorobenzene, pentafluorobenzene, hexafluoro 5 stupid, ortho-dibenzene, gas, toluene, o-, m-, and p-.曱 stupid, lyon, cyclohexane, THF, dioxane, liquid rubber and liquid antioxidants. Preferably, the ratio of monomer to initiator reactant is from about 100:1 to about 1,000,000:1, more preferably about 100, of the monomer to initiator (based on Ru or Os). : 1 to about 500,000:1. More preferably, the molar ratio of 10 monomer to starter is from about 1000:1 to about 100,000:1, and most preferably from about 5,000:1 to about 60,000:1. Preferably, the proportion of NHC-X2-Y to the initiator reactant is preferably from about 25:1 to about 0.1:1 for the molar ratio of NHC-X2-Y to the initiator (based on Ru or Os). (Based on Mohr), more preferably from about 5:1 to about 0.5:1, 15 and the optimum is from about 2:1 to about 1:1. The monomer temperature polymerization rate is determined by the initial temperature, and therefore, the gelation and curing time can be controlled by adjusting the polymerization temperature. Generally, as the temperature at which the reaction proceeds increases, the reaction rate also increases. The rate of temperature rise for every 8 ° C is approximately doubled. Therefore, in order to control the reaction rate to a higher reaction temperature, a less active polymerization composition can be used. As the temperature at which the reaction proceeds increases, the time for gelation and solidification decreases. After completion of the polymerization, the polymer is subjected to an additional post-cure treatment at a temperature in the range of about 10 ° C to 300 t for about 15 minutes to 24 hours, preferably 1 to 2 hours 59 hours. This post-cure treatment promotes polymer properties including glass transition temperature and heat distortion temperature. In addition, post-cure is desirable, but not necessary, to enable the sample to reach its final stable size state, minimize residual odor, and improve the final physical properties. The process of the invention can be used to prepare norbornene-type thermoplastic homopolymers or copolymers or thermally curable norbornene-type homopolymers or copolymers. Polymerization Time Once the polymerization is initiated, the polymerization needs to occur relatively quickly, typically in about one minute, and preferably in about 10 seconds, and is accomplished by rapid rise in temperature. However, the time required to complete the polymerization is a function of the reactivity of the monomer and the initiator, and the rate of deprotection of NHC-X-Y. Substantially complete reactions can be obtained in as little as one second and as long as several hours. One of the advantages of the reactive heat curing formulation is that it does not gel as quickly as the previous R〇Mp composition. Modification of Catalytic Maid Production Rate, Control of Catalyst Reactivity, and Polymerization Activity The present invention can be carried out under relatively wide range of different reaction times, temperatures, pressures, reactant phases, and mixtures. The choice of conditions is the activity and selectivity of the initiator, the rate of deprotection of NHC-X2-Y, and the type of polymer desired. Control of the gelation and curing time is particularly important in the polymerization system. The control of knee coagulation and solidification in the present invention is derived from several sources. ', inherently, (meaning natural by component) or "exogenous, (meaning external additives or other reactants that can be added to the system). To date, the easiest way to control the reactivity of the catalyst system The characteristics of the ligand attached to the hydrazine or hydrazine derivative are adjusted. The correct ligand selection is important for the intrinsic anti-1337099 control reagent. For example, RuCl2(PPh3)2(=CHPh) ratio RuCWPCyAhCHPh) reacts more slowly. The catalyst substituents can also be varied to control the gelation and cure time of the resulting catalyst system. Similarly, the nature of the leaving group (X2-Y) of NHC-X2-Y can affect the reaction rate, That is, the CHC13 system is removed from the NHC-x2-Y more than HOCMe3 5. Similarly, the desired gelation and solidification of the system can be achieved by appropriately selecting the rate mitigation ligand (exogenous reactivity control). The use of a Lewis base rate slowing agent in this system is selective, i.e., an external or "exogenous" modification that causes further gelation and cure time control. Suitable exogenous rate mitigating agents include, for example, water, Tetrahydrofuran (T HF), 2-methyltetrahydrofuran (2-Me-THF), diethyl ether ((C2h5)2〇), decyl-t-butyl ether (CH3OC(CH3)3), two Methoxyethane (ch3OCH2CH2OCH3), diethylene glycol dimethyl mystery (CH30CH20CH20CH3), trimethylphosphine (PMe3), triethylphosphine (PEt3)' tributylphosphine (PB113), tris(o-tolyl) Phosphine (P_0_methylidene 3), tri-tert-butyl scale (P·Terd-Bu3), tricyclopentylphosphine (pcP3), tricyclohexylphosphine (PCy3), triiso 15 propylphosphine ( Pi-pr3), trioctylphosphine (POct3), triphenylphosphine (PPh3), tris(pentafluorophenyl)phosphine (P(C6F5)3) 'methyldiphenylphosphine (pMePh2), dimercapto Styrene phosphine (PMe2Ph), trimethyl phosphite (p(〇Me)3) 'Triethyl sulphate (P(OEt)3), triisopropyl phosphite (p(〇-i_pr) 3), ethyl diphenylphosphinate (P(0Et)Ph2), tributyl phosphite (p(〇Bu)3), triphenylphosphite 2〇(P(〇Ph) 3) diethyl diethylphosphonate (p(〇Et)2Ph) and tris-methylphosphine (P(CH2Ph)3), 2-cyclohexenone and triphenylphosphine, etc. The rate slowing agent is triphenylphosphine and triphenylphosphine oxide. Exogenous source control of reactivity can be achieved by attaching a Lewis base species to the polymerizable monomer. In this manner, the slowing agent can be polymerized into a polymer structure that produces the system with an important functionality of 61 1337099. Examples of suitable functional groups are ethers, trialkoxydecanes, esters, carboxylic acids and alcohols. Specific examples are triethoxynonylnorbornene, norbornene methanol and butoxynorbornene. Other Components 5 Various additives may be included to improve the properties of the polycyclic olefin polymer. The polymerization reaction can be used for non-interfering additives (such as solvents, blowing agent fillers, fibers, pigments, dyes, lubricants, antioxidants, antiozonants, UV absorbers, crosslinkers, odor absorbers or masking agents). , flame retardant, light stabilizer, plasticizer, foaming agent, single crystal fiber smoothing surface, toughening agent' enhancer, organic liquid, 10 inorganic liquid, ultraviolet stabilizer, electromagnetic wheel absorbing material, electromagnetic Jurisdiction reflective materials, electromagnetic light-emitting materials, electromagnetic radiation-conducting materials, physical bonding agents 'mechanical bonding agents, chemical bonding agents, materials or reagents that conduct or conduct electricity, materials that are insulated or electrically insulated, radioactive materials, radioactive Emissive materials, radioactive reflective materials, radioactive absorption materials, radioactive conductive materials, corrosive applications or sacrificial materials or additives in 15 environments, nano-sized fillers or reinforcements, impact and polymerization modifiers and thickeners) In progress. Preferably, such additives do not affect the catalytic activity. Anti-deuteration agents and anti-ozonants include any antioxidant or anti-ozonant used in the rubber or plastics industry. "Commercial Antioxidants and Antiozonants Index, 4th Edition" 20 available from Goodyear Chemical, The Goodyear Tire and Rubber Company, Akron, OH, 44316. The antioxidant may be a compound mainly composed of phenol, phosphorus, sulfur or an amine. The antioxidants may be used singly or in combination. The composition ratio is more than 〇. 5 parts (preferably 0.5) to 100 parts by weight of norbornene polymer. The antioxidant can be combined with the monomers of 62 1337099 such as 5-(3,5-di-t-butyl-4-hydroxybenzyl-2-norbornene (which is a norbornylphenol-based compound) Copolymerization 'see Japanese Patent Publication No. 57-83522. 'The polymerization reaction may further contain a stabilizer for oxidative degradation. For this purpose, the selected compound preferably does not significantly interfere with the polymerization reaction. The appropriate stabilizer may be selected from 5 The following groups: 2,6-di-t-butyl-4-methylphenol (BHT); styrenated phenols, such as, for example, Wingstay S (Goodyear); 2- and 3-tert-butyl-4-methyl Oxygen; an alkylated hindered phenol such as 'Wingstay C (Goodyear); 4-hydroxymethyl-2,6-di-t-butylphenol; 2,6·di-t-butyl-4 - a second butyl phenol; 2.2, -methyl bis(4-φ methyl-6-tert-butylphenol); 2,2'-methyl bis(4-ethyl-6-tributyl) 10 4,4,-extended methyl bis(2,6-di-t-butylphenol); heterobiphenols such as cyanox 55 and Permanax WSO; 2,2'-ethylene bis ( 4,6-di-t-butylidene); 2,2'-extended methyl bis(4-methyl-6-(1-methylcyclohexyl)phenol); 4,4'-butylene (6 - Tributyl-3-methylphenol); polybutylated bisphenol A; 4,4'-thiobis(6-tert-butyl-3-methylphenol); 4,4'-extension Bis(2,6-dimercaptophenol); 1,1'-thiobis(2-naphthol); 1,1,-15 thiobis(2-naphthol); Phenol, such as ethyl antioxidant 738; 2,2'-thiobis(4-methyl-6-tert-butylphenol); 2,2,-isobutylene double • (4,6-di Methylphenol); 2,2'-extended methyl bis(4-mercapto-6-cyclohexylphenol); p-cresol and dicyclopentadiene such as Wingstay L; tetra (methyl-3-) , 5-di-t-butyl-4-transhydrocinnamate)methane, ie, Irganox 1010; 1,3,5-trimethyl-2,4,6-2〇2 (3,5- —-Secondyl-4-carbylmethyl)benzene', for example, Ethanox 330; 1,3,5·bis(3,5-di-t-butyl-4-carbylbenzyl) Uric acid vinegar, ie, Good-rite 3114 ' 2,5-di-third amyl hydroquinone, tert-butylhydroquinone, tris(nonylphenyl phosphite), bis (2,4-di- Tertiary butyl) pentaerythritol) diphosphite, distearyl pentaerythritol diphosphite, phosphite phenol and bisphenol, such as , Naugard 63 1337099 492, phosphite/pan aldehyde antioxidant blends > such as, (10) B215; di-n-octadecyl (3,5-di-t-butyl-4-hydroxymethyl)phosphoric acid Salts such as, for example, Irganox 1093 M, 6-hexamethylene bis(3-(3,5-di-t-butylhydroxyphenylpropionate), such as 'Irganox 259, and octadecyl_3 5 Di-tert-butyl·4_ 5 trans-hydrogen cinnamate, ie, Irganox 1076, tetrakis(2 4 · di-butyl butyl) 4,4'-exophenyl diphosphonate, diphenyl Alkylamine and 44,-dimethoxy-phenylamine. These materials are generally employed in amounts of from about 0.05% to about 5% by weight of the polymer, but preferably from 0.1% to 1% by weight based on the polymer. The method of the present invention is also suitable for use by making a filler or a nano-sized filler or reinforcing component (which may be particles, filaments, powders, fibers, tubes, particles, strands, beads) Or other uniform- or non-uniform-geometric shapes to prepare the reinforced polymer. Examples of reinforcing components and/or fillers include pieces of glass fiber or short glass transfer temperature, fiberglass cloth or woven roving, fiberglass mat, carbon or graphite bismuth, organic fibers, aromatic (four) lyvi, inorganic fibers, Wood pulp, wood flour, milled or crushed green shell, metal, women or flakes 'carbonate, thermoplastic or elastomer-reinforced material or filler, ground or pulverized thermosetting polymer, Shi Xishi, Oxidation, carbon Black, ashes, sulphate, such as mica, talc, clay, sand, π, work, mountain ash or ash, Nan〇structuredTM 匚 丨 (3) 丨 such as, multi-faceted oligolith P0SSTM is the main material, insect to stone, asbestos and ashes 20, such as 'Shishi limestone. These compounds increase the flexural modulus of the polymer and sacrifice impact resistance only in small amounts. Surprisingly, even with the high polarity of the surface, these fillers can be added without significantly affecting the rate of polymerization. Preferably, such fillers can be surface treated with Shixia Hyun coupling agent. About 5% by weight to about 75% by weight can be combined. These and subsequent percentages are based on the weight of the final polymer. The addition of a filler having a nature of 64 1337099 is particularly advantageous. The correct amount of the particular filler to be used in a particular situation can be readily determined and is chosen by the implementer. After curing at 150-200 C for a short time, the unfilled polymer will shrink from about 3.0 to about 3.5%, while adding 2〇·25% by weight will reduce the shrinkage to 1.5-2%, and add 33 A filler weighing 5 % by weight will shrink further to about 1%. In some embodiments of the invention, a preformed elastomer can be added to the initiator system to increase the impact strength or other mechanical properties of the polymer. An important factor in the selection of elastomers is their ability to dissolve in the monomer. The short dissociation time is better. It means that the elastic system is quite soluble in this green body. The addition of elastomer can increase the impact strength of the polymer by 5-10 times and only slightly reduce the flexural modulus. The elastomeric system is dissolved in the monomer in an amount of from about 1 to about 5% by weight based on the weight of the monomer. A preferred concentration range for the elastomer is between about 3 and about 1% by weight. The elastomer can be dissolved in the monomer in an amount of from 5 to 10% by weight without causing an excessive increase in the viscosity of the solution. The target viscosity range at room temperature is from about 1 Torr to about 10 〇〇 cp, and more preferably from about 2 Torr to about 15 cp. Preferably, the elastomer is miscible with the polycyclic olefin monomer between about TC and about TC. Suitable elastomers include, for example, natural rubber, butyl rubber, polyisoprene. , polybutadiene, polyisobutylene, ethylene-propylene copolymer, stupid ethylene-butadiene-stupid ethylene triblock rubber 'random styrene-butadiene rubber, stupid ethylene-isoprene-styrene Triblock rubber, ethylene-propylene-diene terpolymer 20, ethylene-vinyl acetate and nitrile rubber. Preferred elastomeric polybutadiene. Diene

55AC10 (Firestone), Polyethylene Diene 55AM5 (Firestone), EPDM

Royalene 30IT, EPDM Buna T9650 (Bayer), Polysar Butyl 301 (Bayer), Polybutan Taktene 710 (Bayer), B-Shen-Engage 8150 (DuPont-Dow), Stupid Ethylene-Butadid Kraton D1184 (Shell ), EPDM 65 1337099

Nordel 1070 (DuPont-Dow) and polyisobutylene Vistanex MML-140 (EXX〇n). Various polar elastomers can also be used. The amount of elastomer used is determined by its molecular weight. Brooklyn (Br〇〇kfield), a polycyclic hydrocarbon, has a viscosity of between about 5 and about 10 cp at 35 C. It is preferred to increase the viscosity to between about 1 〇〇 cp and about 5 Torr in the polymerization reaction. The increase in viscosity simplifies the use of the filler by reducing the rate of solids settling. In addition, pre-formed elastomers or polymers which are substantially insoluble in the monomers are also used to improve the impact resistance of ROMP and addition-polymerized norbornene monomers. Core-shell polymer particles can be defined as cores and shells of polymer particles having different physical and/or chemical properties. By elastomeric core shell particles is meant that at least the core of the particles consists of an elastomeric material. Elastomeric core-shell polymer particles have been found to stabilize the impact properties of certain cyclic olefin thermoset polymers, such as ROMP DCPD polymers, such as disclosed in PCT Publication No. WO 94/19385, the disclosure of which is here It is used for reference. Elastomeric core-shell particles having a size of no more than about 2 #m are dispersed in the starting monomer in an amount of from about 5 to about 20% by weight based on the weight of the monomer. The elastomeric core shell particles have a size in the range of from about 0.01 to about 2/z in, and more preferably in the range of from about 0.1 to about 1 μm. Examples of elastomeric core shell particles suitable for use in the present invention are sold under the tradename PARALOID EXL, in particular PARALOID EXL 2300/3300 Elastomeric Core Shell Polymer Series and/or PARALOID 20 EXL 2600/3600 Elastomeric Core Shell Polymer Series And/or PARALOID KM elastomer core shell polymer series and / or PARALOID BTA elastomer core shell polymer series. Since the sensitivity to the added compound is different for each system, it is experimentally determined whether the compound to be added interferes with the reaction. 66 1337099 EXAMPLES The following examples are for illustrative purposes only and the invention should not be considered as limited to the particular materials or conditions used in these examples. The polycyclic monomers which are commercially available or obtained are preferably of the highest purity. The typical 5' monomers need to be purified so that the polycyclic monomers are free of impurities that would reduce the activity of the catalyst. This can be accomplished by distillation alone or by passing the monomer through the BTS and 3 Λ molecular tube branches to remove residual oxygen and water prior to use. It is generally desirable to purify the starting material with a vermiculite gel or an equivalent (including, for example, alumina) to remove the monomeric oxidation product. However, when a suitable NHC precursor and initiator are used at an appropriate concentration, the catalyst of the present invention can polymerize a polycyclic monomer of a lower purity grade. The polymerization is carried out by argon or nitrogen to test the tube' rubber tube shape. The bottle and the glass bottle are reacted in the reaction tank 4. Generally, the polymerization is accomplished by the addition of an initiator (not in solution or monomer) to the corresponding NHC in the monomer. The mixing of the components is accomplished by vortexing, magnetic stir bar 'static, mechanical or impact mixing. 15 The reaction conditions are maintained at ambient temperature or heated at a fixed temperature on a hot bath or hot surface. Gel time (U«) is provided by observing the change in initial viscosity (where the mixture changes from flowable to non-flowable material) or when the rod is inserted into the mixture and slowly removed, the polyether olefin is provided, Estimated by time. This is generally confirmed by observing that the magnetic stir bar stops stirring due to the increased viscosity of the polymerized material. The polymerization time (Ttl»*) of the gel point is also recorded. The special exothermic temperature (ie, T100-c or t2 QQ · (: The time is when the temperature of the polymerization reaction rises to the temperature and the maximum temperature of the polymerization reaction (Τ * Λ) is recorded. The maximum temperature (Tu) of the polymerization reaction is also recorded. The residual monomer content in the polymer sample is extracted and quantified by thermogravimetric analysis (TGA) or using capillary gas chromatography. 67 1337099 Starting 剤 name

Ru575

Ru595

Ru 716

Rn731

Re 751

Ru779

Ru799

68 1337099 c c

Ra 801

C

C

Rti 815

Ru 823,

C C

Cu

Cl^ such as 891(9) PCn CM,

Ra β〇1 (〇 :f u=C=0H, CH, ^Cy,

Ra 815(B) cu a〆 Ρ<?Λ 69 1337099

Rd 843

Ra 831 Example 1

50 g of mass of DCPD (containing 8 wt% of tri-polymerized DCPD) using Ru 716 = 0,0361 g and in the presence of s-Imes HCCl3 = 0.015 g (5500:1:1) 5 DCPD:Ru:s- The ImesHCCl3 reactant ratio was polymerized by heating the mixture to a starting temperature of 49 °C. Result: Time to maximum temperature (Tu) = 81 seconds. Ta large = 227 ° (:. The conversion measured by thermogravimetric analysis (D) was 97.35%. The glass transition temperature measured by thermomechanical analysis (TMA) = 154 ° C. Residual monomer % (Phenylbenzene extraction at room temperature) = 0.51%. 10 Example 2 50 g mass of DCPD system using Ru 716 = 0.00677 g and in the presence of s-ImesHCCl3 = 0.0041 g (40,000:1:1) DCPD:Ru :s-ImesHCCl3 reactant ratio and polymerized by heating the mixture to a starting temperature of 49 ° C. Result: time to maximum temperature (T**) = 510 seconds. Th = 192 15 t. for 400 ° The conversion rate measured by thermogravimetric analysis (TGA) at pH C was 87.53%. The glass transition temperature measured by thermomechanical analysis (TMA) = 105 ° C. Residual monomer % (at room temperature) Example 7 70 1337099 5 gram mass of DCPD (containing 8 wt% of tri-polymerized DCPD) using Ru 716 = 0.0090 g and in the presence of S-lmes HCCl3 = 0.0054 g (30,000: 1:1) DCPD: Ru:s-ImesHCCl3 reactant ratio and polymerized by heating the mixture to a starting temperature of 5 ° C. Result: Time to maximum temperature (Tsa) = 312 〇 seconds. 5 Tu = 205 ° C. The conversion measured by TGA at 4 ° C under nitrogen = 90.95%. The glass transition temperature measured by thermomechanical analysis (tma) = ι 17 ° C. Residual monomer % (at room temperature) Benzene extraction) = 6 94 〇 / 〇. Example 4 5 gram mass of DCPD (containing 8 wt% of tri-polymerized DCPD) using Ru 10 7^6-0.0361 g and in the absence of s_imesHCCl3 (7,500:1) DCPD:Ru:S-ImesHCCl3 reactant ratio and polymerized by heating the mixture to a starting temperature of 48 〇C. Result: time to maximum temperature (Tu) = 42 5 seconds. T**= 192 C. Conversion measured by thermogravimetric analysis (TGA) at 400 ° C under nitrogen = 82.42%. Glass transfer measured by thermomechanical analysis (TMA) 15 temperature = 68 ° C. Residue Monomer % (toluene extraction at room temperature) = 15.51%. Example 5 50 g mass of DCPD (containing 8 wt% of tri-polymeric dcpd) using Ru 716 = 0.00677 g and s-ImeSHCCl3 = 〇.〇〇41 The gram was present in a ratio of DCPD:RU:S-ImeSHCCl3 reactant in (30,000:1:2) and polymerized by heating the mixture to a starting temperature of 49 20 c. Result: Time to maximum temperature = 121 seconds. T* big - 229C. The conversion was determined by thermogravimetric analysis (TGA) at 400 C under nitrogen = 95.65%. The glass transition temperature measured by thermomechanical analysis (TMA) = 145 °C. % residual monomer (abstract extraction at room temperature) = 1 57%. Example 6 71 1337099 50 g mass of DCPD (containing 8 wt% of tripolymerized DCPD) using Ru 716 = 0.0088 g and in the presence of s-Imes HCCl3 = 0.0209 g with (30,000: 1: 4) DCPD: Ru: s -Imes HCCl3 reactant ratio and polymerized by heating the mixture to an initial temperature of 49 °C. Result: Maximum temperature (Ta> time = 120 sec. 5 Tu = 222 ° C. Conversion at TGA measured at 400 ° C under nitrogen = 96.98%. Thermomechanical analysis (TMA) The measured glass transition temperature = 146 ° C. Residual monomer % (toluene extraction at room temperature) = 1.10%. Example 7 50 g mass of DCPD (containing 8 wt% of tri-polymerized DCPD) using Ru 10 716 = 0.00677 grams and polymerized in the presence of s-ImesHCCl3 = 0.0041 grams in a ratio of (30,000:1:2) DCPD:Ru:s-ImesHCCl3 reactant and polymerized by heating the mixture to a temperature of 29,5 °C Results: Time to maximum temperature (Tu) = 715 sec. Tu = 203 ° C. Conversion at TGA measured at 400 ° C under nitrogen = 97.40%. Thermomechanical analysis (TMA) The measured glass transition temperature = 155 15 ° C. Residual monomer % (abstract extraction at room temperature) = 0.61%. Example 8 50 g mass of DCPD (containing 8 weights of tri-polymerized DCPD) was used Ru 716 = 0.00677 g and in the presence of s-ImesHCCl3 = 0.0164 g in a ratio of (40,000:1:4) DCPD:Ru:s-ImesHCCl3 reactant and by heating the mixture to 50 20 . And gathering Result: Time to maximum temperature (Tu) = 151 seconds. T*x = 220 ° C ^ Conversion at TGA measured at 400 ° C under nitrogen = 95.51%. Example 9 50 g mass DCPD (containing 24% by weight of tri-polymerized DCPD) was polymerized using Ru 72 801 -0.0372 g and at a DCPD:Ru reactant ratio of (7500: i) and by heating the mixture to a starting temperature of 30_2 t. The body was sprayed with argon for about 30 minutes, but filtered before the polymerization. Result: time to maximum temperature (Τβλ) = 280 sec. Τ " = 200.1 °c. % residual monomer (toluene extraction at room temperature) = 3,03%. Measured by thermogravimetric analysis (TGA) at 3 〇 (rc and 4 〇 (% of weight loss of rc = 2.85% and 4.51%. Measured by thermomechanical analysis (tma)) Glass transition temperature = 153 ° C. Example 10 50 g mass of DCPD (containing 24 wt% of tri-polymeric DCPD) using Ru 801 = 0.0372 g and in the presence of s-Imes HCCl 3 = 0.0396 g (7500: 1: 2) The DCPD:Ru:s-ImesHCCl3 reactant ratio was polymerized by heating the mixture to a starting temperature of 30.0 °C. The DCPD monomer was sprayed with argon for about 30 minutes, but filtered before polymerization. Result: Time to maximum temperature (Tu) = 273 seconds. Tu = 207.6 °C. % residual monomer (toluene extraction at room temperature) = 0.06%. The weight loss % at 300 ° C and 400 ° C was measured by pyrolysis weight analysis (TGΑ) = 1.05% and 2.17%. The glass transition temperature measured by thermomechanical analysis (TMA) = 192 °C. Example 11 50 grams of mass of DCPD (containing 24% by weight of tri-polymerized DCPD) using RU 801 = 0.0093 grams and at a ratio of (30,000:1) DCPD:Ru reactant and by heating the mixture to 30.4 °C Aggregate at the initial temperature. The DCPD monomer was sprayed with argon for about 30 minutes, but filtered with activated Al2〇3 before the polymerization. Result: Time to maximum temperature (Ta*) = 593 seconds. T* large = 164.2 °C. % residual monomer (A solution at room temperature) = 0.06%. The weight loss % at 300 ° C and 400 ° C was determined by thermogravimetric analysis (TGA) = 17.9% and 21.6%. The glass transition temperature of 1337099 was measured by thermomechanical analysis (TMA) = 86. (:. Example 12 5 gram mass of DCPD (containing 24% by weight of tri-polymerized DCPD) using ru 801 = 0.0093 grams and in the presence of s_imesHCCl3 = 0.0099 grams and with (300:1:2> 5 of DCPD:Ru :s-ImesHCCl3 reactant ratio and polymerized by heating the mixture to an initial temperature of 30.3 ° C. The DCPD monomer was sprayed with argon for about 30 minutes, but was filtered with activated barley 2 〇 3 before polymerization. : time to maximum temperature (Tu) = 588 seconds. T * large = 199.9 t. % residual monomer (abstract extraction at room temperature) = 0.78% by thermogravimetric analysis (D (3) It is obtained at 3〇〇. (: and 4〇〇. (: 10% weight loss = 1.35% and 2.56%. Glass transition temperature measured by thermomechanical analysis (TMA) = 178 ° C. Example 13 50 g of mass of DCPD (containing 24% by weight of tri-polymerized DCPD) using RU 835 = 0.0388 g and in the presence of S-Imes HCCl3 = 0.0396 g and (7500: 1: 2) 15 DCPD: Ru: s-Imes HCCl3 The ratio of reactants was polymerized by heating the mixture to an initial temperature of 53 ° C. The DCPD monomer was sprayed with argon for about 30 minutes, but filtered with activated hydrazine 3 before the polymerization. Time for large temperature (T**) = 239 seconds. Ta large = 219.6 ° C. Residual monomer % (extracted at room temperature) = 1.64%. Measured by thermogravimetric analysis (TGA) 3 001 and 4001 20% weight loss = 2.41% and 3.99%. Glass transition temperature measured by thermomechanical analysis (TMA) = 168 ° C. Example 14 50 g mass DCPD (containing 24% by weight) The third polymerized DCPD) uses Ru 835 = 0.0097 g and is present in the presence of s-Imes HCCl 3 = 0.009 g and is in the ratio of (3 〇, 〇〇〇: 1:2) 74·DcpD:Ru:s-ImesHCCl3 reactant and The mixture was polymerized by heating the mixture to an initial temperature of 52 ° C. The DCPD monomer was sprayed with argon for about 30 minutes, but filtered with activated ai 2o 3 before the polymerization. Results: time to maximum temperature (Tu) = 484 T. Large = 202.6. (: Residual monomer 0 / 〇 (toluene extraction at room temperature > 5.24%. Measured by thermogravimetric analysis (TGA) at 300. (: and 400 ° C % weight loss = 4.64% and 7.30%. The glass transition temperature measured by thermomechanical analysis (TMA) = 149 ° C. Example 15

5 gram mass of DCPD (containing 24% by weight of tri-polymerized DCPD) using RU 1 〇〇 /% * 0048 g and in the presence of s-ImesHCCl3 = 0.0049 g and (60,000:1:2) DCPD:Ru :s-ImesHCCl3 reactant ratio and polymerized by heating the mixture to an initial temperature of 33,8 °C. The DCPD monomer was sprayed with argon for about 30 minutes, but filtered with activated ai2o3 prior to polymerization. Result: Time to maximum temperature (T**) = 134 seconds. τ *large = 204.6. (: % residual monomer (toluene extraction at room temperature 15) = =1. 84%. Weight loss at 300 t and 400 ° C measured by thermogravimetric analysis (TGA) = 1.99 and 3.56%. The glass transition temperature measured by thermomechanical analysis (TMA) = 165t. Example 16 5 gram mass of DCPD (containing 24 weight / 〇 tri-polymerized DCPD) using Ru 20 823 = 〇 · 48 grams and polymerized at a ratio of DCPD:Ru reactant of (6〇,〇〇〇:1) and by heating the mixture to a starting temperature of 33.2 ° C. The DCPD monomer was sprayed with argon for about 30 minutes. However, it was filtered with activated gossip 2〇3 before the polymerization. Result: the maximum temperature (T* large) time = 182 seconds. Th = 158.rc. Residual monomer % (at the room temperature) = 20.35%. Weight loss at 300 ° C and 75 1337099 400 ° C by thermogravimetric analysis (TGA) = 20.70% and 24.71%. Glass measured by thermomechanical analysis (TMA) Transfer temperature = 72 ° C. Example 17 50 g mass of DCPD (containing 24 wt% of tri-polymeric DCPD) was used in the presence of RU 5 823 = 0.0048 g and in the presence of s-Imes HCCl 3 = 0.1 99 g and (60,000 :1:4) DCPD:Ru:s-lmesHCCl3 reaction The ratio was raised and polymerized by heating the mixture to a starting temperature of 32.2 C. The DCPD monomer was sprayed with argon for about 30 minutes, but filtered with activated ai2o3 before the polymerization. Result: maximum temperature (T* large) Time = 162 seconds. τ 4 large = 188.8 t. Residual monomer % (toluene extraction at room temperature 10 夂) = 6.45%. Determined by thermogravimetric analysis (TGA) at 300 ° C and 400 % weight loss at °C = 5.20% and 7.82%. Glass transition temperature measured by thermomechanical analysis (D1/4 8) = 130 ° C. Example 18 5 gram mass DCPD (containing 24% by weight) The third polymerized DCPD) uses Ru 15 8l5 = 379.0379 g and in the presence of s-ImesHCCl3 = 0.0396 g and in the ratio of DCPD:Ru:s-ImesHCCl3 reactant of (7,500:1:2) and by making the mixture The polymer was polymerized by heating to an initial temperature of 47.9 ° C. The DCPD monomer was sprayed with argon gas for about 30 minutes, but was activated by activating AI 2 O 3 before the polymerization. Result: time to maximum temperature (Τ*Λ·) = 228 seconds Tn = 219.3 ° C. Glass transition temperature measured by thermomechanical analysis (ΤΜΑ) = 191. (: Example 19 50 g mass of DCPD (containing 24 wt% of tri-polymerized DCPD) is used Ru 0095 g and in the presence of s-ImesHCCl3 = 0.0099 g and in the ratio of DCPD:Ru:s-ImesHCCl3 reactant of (30,000:1:2) and by heating the mixture to a starting temperature of 76 1337099 50.2 °C polymerization. The DCPD monomer was sprayed with argon for about 30 minutes, but filtered with activated Al2〇3 before the polymerization. Result: The time to reach the maximum temperature (Tu) J = 239 seconds. T* is large = 217.2 °C. Residual monomer % (solvent extraction) = 0.98%. The glass transition temperature measured by thermomechanical analysis (TMA) = 175 °C. 5 Example 20 50 g of mass DCPD (containing 24 wt% of tri-polymeric DCPD) using Ru 716 = 0.0333 g and in the presence of s-ImesHCCl3 = 0.009 g and (00,0:1111 of (7,500:1:0.5) :3-111^81^(:13 reactant ratio and polymerized by heating the mixture to a starting temperature of 31.6 ° C. The DCPD monomer was sprayed with argon for about 10 30 minutes, but before the polymerization Filtration with activated Al2〇3. Results: time to maximum temperature (T* large) = 193 seconds. T* large = 210.1 ° C. Residual DCPD monomer % (solvent extraction) was 0.17%. The glass transition temperature measured by the analytical analysis (TMA) = 189 ' ° C. Example 21 15 50 g of DCPD (containing 24 wt% of tripolymerized DCPD) using Ru 779 = 0.0362 g and s-Imes HCCl3 = 0.0396 g Polymerization 1 in the presence and at a ratio of DCPD:Ru:s-ImesHCCl3 reactant of (7,500:1:2) • and heating the mixture to an initial temperature of 75 ° C. DCPD monomer is sprayed with argon gas for about 30 Minutes, but filtered with activated ai2o3 before polymerization. Result: time to maximum temperature (T**) 20 = 421 seconds. T* large = 205 ° C. Example 22 75 g mass of DCPD (containing 24% by weight Triple polymerization DC PD) using Ru 731 = 0.0191 g and in the presence of s-Imes HCCl3 = 0.0223 g and in a ratio of DCPD:Ru:s-ImesHCCl3 reactant of (20,000:1:2) and by heating the mixture to 77 1337099 50.3 C Polymerization at the initial temperature. DCPD single-warp was sprayed with argon for about 30 minutes, but filtered with activated ai2o3 before polymerization. Result: time to maximum temperature (d) was 442 seconds. T**=227.9 °C Residual DCPD% (solvent extraction) = 0.68%. Average Tg (via TMA) = 180.07. (: 5 Example 23 75 g of mass of DCPD (containing 24% by weight of tri-polymerized DCPD) using Ru 751 = 0.0393 g and Polymerization was carried out in the presence of s-ImesHCCl3 = 0.0445 g and at a ratio of (10,000:1:2) DCPD:Ru:s-ImesHCCl3 reactant and by heating the mixture to a starting temperature of 50.1 °C. Argon was sprayed for about 30 minutes, but ίο was filtered with activated ai2o3 before polymerization. Result: Maximum temperature (Tu) time = 1791 sec. 1^=218.1° (: Residual 00?0% (solvent extraction) = 1.82%. Average Tg (via TMA) = 167.71 °C. Example 24 75 g of mass of DCPD (containing 24 wt% of tri-polymerized DCPD) using Ru 15 801 (C) = 0.0209 g and in the presence of S-Imes HCCl 3 = 0.0111 g and with (20,000: 1:1) DCPD: Ru: s-Imes HCCl3 reactant ratio and polymerized by heating the mixture to a starting temperature of 50.2 °C. The DCPD monomer was sprayed with argon for about 30 minutes' but was filtered with activated Al2〇3 prior to polymerization. Result: Time to maximum temperature (Tu) = 328 seconds. T* is large = 217.1 °C. Residual DCPD% (solvent extraction) = 4.17%. 20 Average Tg (via TMA) = 142.62 °C.

Example 2S 75 g mass of DCPD (containing 24 wt% of tripolymerized DCPD) using Ru 801 (C) = 0.0209 g and in the presence of s-Imes HCCl3 = 0.023 g and 0 ( (20,000:1:2)? 0:1111:3-111^1^(:13 reactant ratio and polymerized by heating the mixture 78 to an initial temperature of 49.5 t. The DcpD monomer is sprayed with an argon nozzle for about minutes, but before the polymerization. The decrease in the activation of Al2〇3. Result: Time to maximum temperature (maximum D) = 310 seconds. Th = 2I8.9t. Residual DCPD% (solvent extraction) = 3 83%. Average Tg (via TMA) = 147.46° C. 5 Example 26 75 g of mass of DCPD (containing 24 wt% of tri-polymeric DCPD) using Ru 831 0.0434 g and in the presence of S-imes HCCl3 = 〇.0223 g and (1〇000:1:1) DCPD: Ru:s-ImesHCC丨3 reactant ratio and polymerized by heating the mixture to a starting temperature of 50.3 C. The DCPD monomer was sprayed with argon for about 3 minutes, but 10 before activation to activate Al2〇. 3 Filtration. Results: Time to maximum temperature (Ta*) = 645 sec. T*p218.1 ° C. Residual DCPD% (solvent extraction) = 2.34%. Average Tg (via TMA) = 159.87 ° C. Example 27 75 g of mass of DCPD (containing 24% by weight of tri-polymerized DCPD) using Ru 15 831 = 0.0434 g and in the presence of s-Imes HCCl 3 = 0.0223 g and (2 〇, 〇〇〇: 1: 2) DCPD: Ru: s-ImdsHCCl3 reactant ratio and borrow The mixture was heated by heating to a starting temperature of 50.1 ° C. The DCPD monomer was sprayed with argon for about 30 minutes, but filtered with activated barley 2 〇 3 before the polymerization. Result: time to maximum temperature (Ts λ) = 869 seconds. Ding * dog = 213.2 ° (:. Residual 0 € 0 0 (solvent extraction) = 2.87%. Average 20 Tg (via TMA) = 156.12 ° C. Example 28 75 g mass of DCPD (containing 24% by weight The third polymerized DCPD) uses Ru 801 (Β) = 0.1 〇 209 g and is present in the presence of s-Imes HCCl 3 = 0.023 g and is in the ratio of DCPD:Ru:s-ImesHCCl3 reactant of (20,000:1:2) Polymerization was carried out by heating the mixture 79 1337099 to a starting temperature of 50.1 C. The DCPD was sprayed with argon for about 30 minutes, but was filtered with activated ΑΙΑ3 before the polymerization. Result: time to maximum temperature (Tu) = 249 Seconds. D * Large = 226.6 ° (:. Residual 00? 0% (solvent extraction) = 1.13%. Average Tg (via TMA) = 164.28 ° C. 5 Example 29 75 g of mass DCPD (containing 24% by weight of three Polymerized DCPD) using Ru 815(Β)=0·0213 g and in the presence of s-ImesHCCl3=0.0223 g and in a ratio of (20,000:1:2) DCPD:Ru:s-ImesHCCl3 reactant and by making the mixture plus To a starting temperature of 49.6 ° C and polymerized. The DCPD monomer was sprayed with argon for about 30 minutes and 10 minutes, but was filtered with activated helium 3 prior to polymerization. Result: Time to maximum temperature (Tu) = 303 seconds. D * * large = 220.1 ° C. Residual DCPD% (solvent extraction) = 3 62% a Average Tg (via TMA) = 145.41 °C. Example 30 75 g of mass of DCPD (containing 24% by weight of tri-polymerized DCPD) using Ru 15 843 = 0.0220 g and in the presence of s-Imes HCCl 3 = 0.0223 g and (200.). 2) DCPD: Ru: s -Imes HCCl3 reactant ratio and by heating the mixture to 49 4 . (: The polymerization was started at the initial temperature. The DCPD monomer was sprayed with argon for about 30 minutes, but filtered with activated gossip 2〇3 before the polymerization. Result: Time to reach maximum temperature (Tu) = 282 seconds^Th= 220.8 ° C. Residual DCPD% (solvent extraction) = 2.90%. Average Tg (by TMA from TMA) = 140.10 DC. Example 31 75 g of mass of DCPD (containing 24 wt% of tri-polymeric DCPD) using Ru 815 = 0.0213 And in the presence of s-ImesHCCl3=0.0223 g and in the ratio of DCPD:Ru:s-ImesHCCl3 reactant of (2〇,(9)〇:丨.2) and by heating the mixture to 80 1337099 50, 4 °C Polymerization was carried out at the initial temperature. The DCPD monomer was sprayed with argon for about 30 minutes 'but filtered with activated Al 2 〇 3 before the polymerization. Results: Time to maximum temperature (Tu) = 245 sec. D = ** = 230.9. : Residual DCPD% (solvent extraction) = 0.72%. Average • Tg (via TMA) = 183.6 ° C. 5 Example 32 75 g of mass DCPD (containing 24 weights of tri-polymerized DCPD) using ru 815 = 0.0213 grams and polymerized at a DCPD:Ru reactant ratio of (20,〇〇〇:1) and polymerized by heating the mixture to a starting temperature of 49.7 ° C. The DCPD monomer was sprayed with argon gas for about 30 minutes, but Filtration with activated Al2〇3 before polymerization. Results: Time to maximum temperature 10 ° (Τη) = 200 sec. T* large = 192.4 ° C. Residual DCPD% (solvent extraction) = 13.71%. Via D. 14) = 84.47° (:. Example 33 75 g of DCPD (containing 24 wt% of tri-polymerized DCPD) using ru 815 (B) = 0.0213 g and reacted with (20,000:1) DCPD.Ru The ratio was and polymerized by heating the mixture to an initial temperature of 49.9 ° C. The DCPD monomer was sprayed with argon for about 30 minutes 'but the solution was activated by activation of the gossip 2 〇 3 before the polymerization. Temperature time = 264 seconds. τ * large = i65.rc. Residual DCPD% (solvent extraction) = 26.16%. Average Ding Dan (via D = 1 VIII) = 44.56. (: Example 34 20 75 g mass DCPD (containing 24% by weight of tri-polymerized DCPD) was polymerized using Ru 801 (C) = 0.0209 g and at a DCPD:Ru reactant ratio of (20,000:1) and by heating the mixture to a starting temperature of 49.5 °C. The DCPD monomer was sprayed with argon for about 30 minutes, but filtered with activated A12〇3 before the polymerization. Results: Time to maximum temperature (T* large) = 334 seconds. Τ"=165.Γ(:.Residual DCPD% (solvent extraction 81 1337099) = 26·12%. Average Tg (via TMA) = 42.30 ° C. Example 35 75 g mass of DCPD (containing 24% by weight of three) Polymerization DCPD) was carried out using Ru 801 (Β) = 0. 0209 g and at a ratio of (20,00 〇:1) of 0匚?0:1111 and heating the mixture to 51.1 by 5 (start of: Polymerization at temperature. DCPD monomer was sprayed with argon for about 30 minutes, but filtered with activated a1203 before polymerization. Result: time to maximum temperature (Tu) = 170 seconds. Tu = 183.6 ° C. Residual DCPD% (solvent) Extraction) = 18.36%. Average Ding Lu (via Ding 1 ^ 8) = 66.06. (: Example 36 10 ng mass of DCPD (containing 24% by weight of tri-polymeric DCPD) using Ru 843 = 0.020 g and DCPD: Ru reactant ratio of 20,000:1) and by heating the mixture to 49.7. (: The initial temperature is polymerized. The DCPD monomer is sprayed with argon for about 30 minutes' but before the polymerization to activate eight 12〇 3 Filtration.Results: The maximum temperature (Tu) time = 267 seconds. Τη = 169·8Ϊ. Residual DCPD% (solvent extraction 15) = 24.58%. The average Ding § (via Ding 1^8) = 42.01. :. Example 37 75 The mass of hexyl norbornene is used in the presence of RU 815 = 0.0171 g and in the presence of s-Imes HCCl3 = 0.0179 g and in a ratio of (20,000:1:2) HXN:Ru:s-ImesHCCl3 reactant and by heating the mixture to 50.11 20 Polymerization at initial temperature. Result: Time to maximum temperature (T**) = 198 seconds. T* large = 172.2 ° C. Example 38 50.0 g of 1,3-double-(2,4,6- The dimethyl sulphate beta sulphide gasification was added to a 1 〇〇〇 ml single-necked round bottom 82 1337099 bottle containing a Teflon-coated spar. 15.2 g of the third oxidized Lithium (1.3 mole equivalent of the third lithium pentoxide ruthenium, 3·bis-(2,4,6-dimethylphenyl)imidazole iron oxylate) was added to the ι 〇〇〇 烧J bottle. 90 ml of anhydrous hexane was added to a 1000 ml flask and the flask was capped with a septum, and the headspace was purged with argon for 15 minutes and stirred. The mixture was stirred at room temperature for 2 hours. After 2 hours, The septum on the 丨000 ml flask was replaced with a 25 cc addition funnel. 250 ml CHC1S was added to the addition funnel and blocked with septa and purged with argon for 5 minutes. 250 ml CHC After dropping I3 into the reaction mixture in a 1 mL flask, an additional 130 mL of CHCI3 was added to the addition funnel, and the funnel was capped with 10 sheets and purged with argon for 5 minutes. An additional 130 ml of CHC13 was dropped into the reaction mixture of the 1000 ml flask and was dispensed. A total of 380 ml of CHC丨3 was dropped into a 1000 ml flask under an argon atmosphere at room temperature and mixed. Once 380 ml of CHCh was added to the 1000 ml flask, the addition funnel was removed from the flask and the flask was capped with a septum. The headspace of the flask was purged with argon for 15 minutes. The ? reaction mixture was stirred under an argon atmosphere for 24 hours to give an off-white solution.

This off-white solution was cooled to 〇 ° C and then at 22-25. (: The separation bucket is cleaned with saturated NH4C丨X 200 ml). The organic layer was then washed with a saturated solution of NaCI^ yp X (200 mL) in a sep. 22-25 C. The 'organic layer was then placed in a one-necked round bottom flask and excess gas was vacuum removed to produce a crude product which was a powdery off-white 20 color solid. This off-white solid was washed with a minimum of cold methanol (0. EtOAc and filtered to yield &lt;RTI ID=0.0&gt;&gt; Crystalline powder, 85% yield. Example 39 Preparation of bis-bis-trimethylphenylamine 83 1337099 125 ml clear glass bottle with iron velon substrate cover and coated stir bar Note 2-propanol (25% w/w aqueous solution, 32 4 g), 2,4,6 trimethylaniline (10.0 g, 74.0 mmol) and glyoxal (4〇% w/w water) Solution, 5 3 g, 37 mmol.) Glyoxal was added last, and in the minute, the reaction began to precipitate yellow in 5 mother liquor with precipitation with a yellow solid. The mixture was stirred at ambient temperature for 24 hours, then The reaction mixture was thickened with a precipitate. The product was isolated by filtration and washed with EtOAc (2 <RTI ID=0.0></RTI> <RTIgt;忮 忮 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 Methylphenyl) imine (square ι〇 · g, 34.2 mmol). The flask was divided by μ to remove air and backfilled with argon. Toluene (Aldrich anhydrous grade, 20 ml) was added and the reaction vessel was placed in an ice water bath. Sodium di(2-carbamimidyloxy)aluminate dihydrogenate (7〇0/.w/w, in a stupid, d 15 i.036 '12'5 ml '44.8 mmol) was injected dry It was purged with argon and added to the stirred yellow diimine slurry over a period of about 15-20 minutes. The reaction is fast and exothermic. During the addition of sodium dihydro(2-methoxyethoxy)dicarboxylate, the mass is gradually homogenized until all solids are dissolved, and the yellow starting diimine has flowed out to produce a transparent to slightly opaque Poe color solution. . The reaction flask was removed from this bath and allowed to warm to room temperature and stirred overnight. Prior to inspection, it was observed that the initial clear reaction mixture had become opaque. Aqueous sodium hydroxide (25% w/w, 5 g) was added to the resulting off-white slurry until all solids had dissolved. This clear, biphasic mixture was transferred to a separatory funnel and the (upper) organic layer was removed &quot; then the aqueous portion was washed with a 3 x 25 ml solution. Mixing the organic extract of 84 1337099 by rotary evaporation to give 1 2 g of N,N'-bis-(2,4,6-dimethylphenylamino)ethane as a gas chromatography % pure*, brown oil, which is crystallized over time. - N,N'-bis-(2,4:6-?-ylphenylamine ruthenium dinitride) 5 A 250 ml Erlenmeyer flask containing a stir bar coated with iron gas was injected with N, N-bis(2,4,6-dimethyl basic amino) ethyl bromide (26.6 g, 89,7 mmol), methyl stupid (7 g), 2-propanol (64 ml) and deionized water (64 ml). The vessel was cooled in an ice water bath and HC1 (12 M, 21 ml, 252 mmol) was added dropwise over a period of about 5 hours. When the acid was added, the reaction mixture was quickly precipitated in white. 10 The material thickens and precipitates heat. After the addition, the reaction is warmed to ambient temperature and the liquid is stirred. The product is isolated by filtration from the light pink mother liquor and is in continuous methanol fraction (3 X 50 ml) and The alkane (1 X 100 ml) was washed and then vacuum dried to give 31.3 g (94%) of hydrazine, Ν1-bis-(2,4,6-trimethylphenylamino)ethane dihydrogenated hydrogen, white to Grayish white microcrystalline powder. 15 1^1-bis (2,4.6-trimethylammonium) imidazoline mishydride 500 ml three-necked round bottom flask (containing Teflon coated stir bar and equipped with ® Internal thermometer and short path distillation ) is injected with bis(2,4,6-trimethylphenylamino)ethane dihydrogenated hydrogen (2 〇.18 g, 54.63 mmol) and triethyl orthodecanoate (200 ml) Acetic acid (98%, about 4 drops from a Pasteur pipette) was added, and the reaction vessel was placed in an oil bath of 13 CTC. The ash color slurry was heated and stirred, and the water white liquid began to be pink. The reaction mixture was distilled off. Heating was continued until the distillation was stopped for about 4 hours. The final temperature of the reaction mixture was 120 ° C. After the reaction mixture had cooled to ambient temperature, the pink color was removed. The solid product was isolated by filtration and Alkane (3 X 1 〇〇 ml) was washed. Vacuum drying provided 18.21 g of 85 1337099 (97%) 1,3-bis-(2,4,6-trimethylphenyl)imidazoline drill gas, white crystalline powder Example 40 75 g of a mass of a monomer mixture (prepared by mixing 67.5 g of DCPD (containing 24 wt% of a tri-polymerized DCPD) and 7.5 g of hexylnorbornene) using Ru 815 = 0.0209 g and s-ImesHCCl3=〇.0218g in the presence of (20,000:1:2) DCPD:Ru:s-ImesHCCl3 reactant ratio and (2〇,〇〇〇: 1:2) HxN: Ru:s-ImesHCCl3 reactant ratio and polymerized by heating the mixture to an initial temperature of 50 ° C. 1〇Result··Maximum temperature (T*large) Time = 218 Seconds. Tmax = 219.2. (:. Example 41 75 g mass of monomer mixture (by making 67.5 g of DCPD (containing 24 wt. /. Three of the polymerized DCPD) and 7.5 grams of hexyl norbornene were prepared by mixing together. Using R 815 = 0.0209 g and (20,000:1) DCPD:Ru reactant ratio of 15 and (20,000:1) of HxN:Ru reaction The ratio was raised and polymerized by heating the mixture to an initial temperature of 51.3 °C. Result: Time to maximum temperature (D) = 194 seconds. Ding" big = 190.9. (:. Example 42 75 g mass of monomer mixture (prepared by mixing 56.25 g of DCPD (containing 24 wt% of tri-polymerized DCPD) and 18.75 g of hexyl norbornene) using Ru 823=0.0136 And in the presence of s-ImesHCCl3=〇.〇141g DCPD: (30,000:1:2) DCPD:Ru:s-ImesHCCl3 reactant ratio and (3〇,〇〇〇: 1.2) HxN:Ru.s -Imes HCCl3 reactant ratio and polymerized by heating the mixture to a starting temperature of 27.6 ° C. 86 1337099 Result: Time to maximum temperature (T* large) = 192 seconds. Tmax = 199.3 ° C. Example 43 75 a gram mass of monomer mixture (prepared by mixing 56.25 grams of DCPD (containing 24% by weight of tri-polymerized DCPD) and 18.75 grams of hexyl norbornene) (5) using Ru 823 = 0.0136 g and (30,000: 1) The DCPD:Ru reactant ratio and the (30,000:1) HxN:Ru reactant ratio were polymerized by heating the mixture to a starting temperature of 27.7 ° C. Result: Time to maximum temperature (Tu) = 155 Seconds. Tu = 171.4 ° C. Example 44 10 75 g of mass of hexyl norbornene using Ru 823 = 0.0115 g and s-ImesHCCl3 = 0.119 The ratio of HxN:Ru:s-ImesHCCl3 reactant in (30,000:1:2) was present and polymerized by heating the mixture to a starting temperature of 28.3 ° C. Result: Time to maximum temperature (Tu) = 175 Seconds. T*大=155.7°C. 15 [Simple description] (None) [Main component symbol description] (None) 87

Claims (2)

1337099 Patent No. 98104062 Applicant for Qin Xiang Patent Fan JL Amendment. Yongzheng Date: June 1999~~^ y — ^'― ------ VII. Application for Patent A: I - ; '; A method of converting a less active or slower starting catalyst system to a higher activity catalyst system comprising the step of reforming the protected rhodium-heterocyclic carbene with a tetra-position in the presence of energy And olefin contact; wherein the 5-protected fluorene-heterocyclic carbene has the chemical formula: 'R, R, r8, r9, r1Q and Rl1 are each independently hydrogen or substituted or unsubstituted from c丨-Cm alkyl, &lt;:2_(:2〇 alkenyl, ( :2-(: 2 decynyl, aryl 10, CrC2 (acid cool, CI-C2 (T oxooxy, (: 2-(:20 dioxyoxyl, C2_C20 alkynyloxy, aryloxy, C2- a C2 nonyloxycarbonyl group, a C丨-C20 alkylthio group, a ci Cm-based thiol group, and a group consisting of (^-(^)-based sulphur-based aryl group; X2 is selected from 1^ a group consisting of 311, 1^, he, 1^:^ and sulfhydryl, wherein X is any halogen; and Y is selected from CC13; CH2S02Ph; c6f5; 0R21; and N(R22)(r23) a group of which is selected from the group consisting of Me, C2H5, i c3H7, CH2CMe3, CMe3, c6h&quot; (cyclohexyl), CH2ph, CH2 norbornyl, cH2 norbornic, QH5, 2, 4, 6-(called)3 (: 6 (Lecky), a group consisting of a small sigh, Me QH4 (A stupid) and 4_ci-C6H&lt;t; and wherein r22 and R23 are individually selected from Me, C2H5, i_C3H7, CH2CMe3, CMe3 , 88 C6H11 (cyclohexyl), CH2Ph, CH2 norbornyl, CH2 norbornene c6h5, 2,4,6-(CH3)3c6H2 ($ ) 'And 26 it coffee a group consisting of 4-Me-C6H4 (曱 基 基), 4-c丨-QH4, wherein the energy is selected from the group consisting of thermal energy, laser, electron beam (four), #射电浆, sound, ultraviolet light and microwave radiation. Ethnic group. 2. If the method of applying for a full-time item is made, the rare (four) is replaced or not replaced. 3. The method of claim 1, wherein the hydrocarbon is a substituted or unsubstituted dicyclopentadiene. 4. A method for converting a less active or slower starting catalyst system into a higher activity catalyst. The method is included in the presence of energy to make the N-heterox and the replacement of the insured It is intended to be in contact with smoke; wherein the protected N-heterocyclic carbon is chemically: Each of R, R, R, r9, ri, and R11 is independently hydrogen or substituted or unsubstituted from C|-c2 alkyl, C2-C2. Alkenyl, C2-C2. Alkynyl, aryl, CrC20 carboxylate, ci-c20 alkoxy, (: 2-(:20 alkenyloxy, c2-c20 fastoxy, aryloxy, C2-C2 nonyloxycarbonyl, C a substituent of a group consisting of 丨-C2 decylthio group, CrCw pit base group, and c]_c carboxyalkyl group; 89 1337099 · X is selected from the group consisting of ruthenium, Si, Sn, Li, Na, MgX3 and sulfhydryl, wherein X3 is any halogen; and Y is selected from CC13; CH2S02Ph; C6F5; OR21; and n(R22) a group consisting of (R23), wherein R2 is selected from the group consisting of 5 CMe3, C6Hii (cyclohexyl), CHJh, CH2 norbornyl, CH2 norbornyl, C6H5, 2,4,6-(CH3)3C6H2 (dish a group consisting of 2,6-i-Pr2C6H2, ^Me-CeH4 (methyl phenyl) and 4_Ci_C6H4; and wherein R22 and R23 are each selected from the group consisting of Me, C2H5, i-C3H7, CH2CMe3, CMe3, C6Hn ( Cyclohexyl), CH2Ph, CH2 norbornyl, cH2 norbornene, 1〇C6H5, 2,4,6-(CH3)3C6H2(莱基), 2,6-i-Pr2C6H2 and 4_Me-C6H4 a group consisting of 4-Cl-C6H4, wherein the displacement initiator is any Ru or 0s metal carbene displacement catalyst, and wherein the energy is selected from the group consisting of thermal energy, laser, electron beam radiation, τ radiation, electricity A group of poly, sound, ultraviolet and microwave radiation. 15 5. A process for the preparation of a protected rhodium-heterocyclic carbene, which comprises contacting a fluorene heterocyclic carbene salt with a base to form a fluorene heterocyclic carbene; and subjecting the hydrazine heterocyclolene to gas imitation reaction. 6. If you apply for a patent The method of item 5, wherein the test is selected from the group consisting of: a third butyl sulfonate, a third oxidized clock, a third sodium hydride, a sodium hydride, a hydrogenation, a hydrogenation, Bis(trimethylweiyl) amide amine, bis(trimethylphenyl)-sodium amide, bis(trimethyl sulphate) amide clock, sodium oxynitride, hydrazine hydroxide and hydroxide. 7. The method of claim 5, wherein the method occurs in a solvent that is absent. 90 ' 闭环 more closed-loop displacement method of acyclic flue gas is included in the presence of energy to contact the protected rhodium-heterocyclic carbonaceous woman with the displacement initiator and the one or more non-cyclic olefins, wherein 4 It is difficult to start any Ru or 0s metal carbon dilute replacement catalyst, and the energy is selected from the group consisting of thermal energy, laser, electron beam ray, r-ray, electric combustion, sound, ultraviolet light and microwave radiation. 9. The method of claim 8, wherein the protected N-heterocyclic ring has a chemical formula: Rn Wherein R R , R ' R and R11 are each independently hydrogen or substituted or unsubstituted selected from crc2. Burning base, c2_C2. Dilute base. 2 (: 2. Block group, aryl φ group, CrC20 carboxylate, ci-c2 decyloxy' (: 2 &lt; 20 alkenyloxy group, C2_C20 alkynyloxy ' aryloxy group, c2_c2. Oxygen base, a substituent of a group consisting of C|_C2G alkylthio, C1 C2 alkylsulfonyl and alkylsulfinylene; X is selected from the group consisting of day, 81, 311, 1^, &gt;^, 1^\ 3 and a group consisting of sulfhydryl groups, wherein X is any dentate; and Y is selected from the group consisting of CC13; CH2S02Ph; C6F5; OR21; and N(R22)(R23), wherein R21 is selected from Me, C2H5 , i-C3H7, CH 2CMe3, 91, C6Hn (cyclohexyl), CH2Ph, CH2 norbornyl, cH2 norbornic, c6h5, 2,4,6-(CH3)3C6H2 (Like, 4) a group consisting of a stupid base and a 4_CI-C6H4; and its Yin r22 and R23 are individually selected from the group consisting of Me, C2H5, %Η7, CH2CMe], CW, C6Hn (cyclohexyl), CH2Ph, ^norbornyl, cH2 descending a group of borneol, C6H5, 2,4,6_(CH3)3c6H2($base)' 2 6aca and 4 Me C6H4 (tolyl), 4-Cl-C6H4. The method of claim 9, wherein the at least one substituent is substituted with one or more The unsubstituted one is selected from the group consisting of C|C|, and C|C, which is a group consisting of a methoxy group and an aryl group. The method of claim 9, wherein the r7, rS, R9^, __ are selected from the group consisting of hydrogen 'W, New Zealand and aryl, and r6 and R&quot; are each selected from C|_Ci which is substituted or unsubstituted. a group consisting of an indole cycloalkyl group, a C2_C|G dilute group, an aralkyl group, and an aryl group. α is as in the method of claim _, wherein the r7, r8r^ri&gt; is 虱' and R6 and R11 are substituted Each group is individually or unsubstituted and is selected from the group consisting of phenyl, ethylene, methyl, isopropyl, tert-butyl neopentyl or methyl. The method of claim 9, wherein the r6, r7 r8 r9 r|〇 and R to y are joined to form a substituted or unsubstituted, fluorene or unsaturated ring structure. The method of item 8, wherein the protected ν·heterocyclic carbon is selected from the group consisting of 1,3-t-based-2-methoxy-flavored beta bites, 92 1337099 1, 3- Benzyl-2-(trimethylmethyl)imidazolium, 1,3-dimercapto-2-ethoxy-imidazole, 1,3-diyl-2-t-butoxy-imidazolium, 1,3-diyl-2-ethyloxy-imidazolium, 1,3-dipyridyl-2-(trimethylmethyl)imidazolium, 1,3-bis(3-indolyl) -2-(trimethylmethyl)imidazolium, 1,3-bis(4-methylphenyl)-2-(trimethylmethyl)-5 imidazolium, 1,3-bis(4-fluorophenyl) -2-(trimethylmethyl)imidazolium, 1,3-bis(3-methylphenyl)-2-(trimethylmethyl)imidazolidinium, l,3-bis(4-indolyl)- 2-(trimethylmethyl)imidazolidine, 1,3-bis(4-bromophenyl)-2-(trimethylmethyl)imidazolidinium, l,3-bis(4-iodophenyl)-2- (trimethylsulfonyl) imidazolium, iota, 3-bis(4-methoxyphenyl)-2-(trimethylmethyl)imidazolium, 1,3-bis(4-ethoxyphenyl)_2 -(trimethylmethyl)imidazolium, 10 bis(4-ethylphenyl)-2-(trimethylsulfonyl)imidazole, 1,3-bis(4-mercapto)-2-(three Gas methyl)imidazolium, iota, 3_bis(3,4-dimethylphenyl)-2-(trimethylmethyl)imidazolium, 1,3-bis(3,5-diphenyl) _2_(trimethylmethyl)imidazolium, n bis(3,5-dimethylphenyl)-2-(trimethylmethyl)imidazolidinium, ι·(4_ Styyl) 3-phenyl-2-(trimethylmethyl)imidazolium, 1,3_bis(4.fluorophenyl)2 (trimethylmethyl)imidazole 15 pyridine, 1-(4-methoxy) Styrene)-3-phenyl-2-(trimethylmethyl)methane bite, 2-(trimethylmethyl)-U-bis(2,6-dimethyl-4-4-tert-butylphenyl) )mum. Sitting 々, 2_(trimethylmethyl)-1,3-bis(2,6-diisopropylphenyl)imidazolium, anthracene, 3·dilyl 2 dimethylamino carbazole bite, 1 -(1,3·二莱基_2_咪 坐 sit bite base biting and 4_(1,3_diyl-2-imidazolidinyl)-morpholine. 15. As claimed in item 8 The method of the present invention, wherein the dilute hydrocarbon contains more than one polymerizable double bond. The method of claim 8, wherein the replacement catalyst is tetracoordinate, pentacoordinate or hexacoordinate. The method, wherein the starting (4) has a +2 oxidized 93 state, has a metal number of 16 and is a five-coordinate metal center. The method of claim 17 (7), wherein the initiator has the following formula: 5 wherein M is 钌 or 锇; X and X are the same or different, and each is an anionic ligand; each of the L and L stalks are the same or different, and each is individually neutral Electron-coordination; 〇R and R are the same or different, and each is hydrogen or is selected from the group consisting of crc2, alkyl, c2-c20, C2-C20 alkynyl, aryl, c rC2 Carboxylic acid ester, ci _c2 oxime alkoxy group, Ch: 2 deceneoxy group, c2_c20 alkynyloxy group, aryloxy 'C2_C20 alkoxy group, CrC2G alkylthio group, Ci_C2G alkyl sulfo group, C|_C2 . a substituent of the group consisting of an alkylsulfinyl group and a decyl group, and wherein R and R1 5 are each independently substituted or unsubstituted. 19. The method of claim 17, wherein the initiator is selected from the group consisting of: Ru575 94 1337099 Ru 595 Ru716 Ru731 Ru751 Ru779 Ru799 Ru801 Ru815 Ru823 95 1337099 Ru835 Ra 801(B) Rh 801(C) PC», R»S1S(B) PCy* CHj, ^Cy, RuS43 20. The method of claim 8, wherein the reaction occurs in the absence of a solvent. 21. A method of forming a metal carbene displacement catalyst comprising an N-heterocyclic carbene ligand comprising the step of replacing a protected N-heterocyclic carbene with a Ru or Os source in the presence of energy Or unsubstituted acetylene and olefin contact. 22. The method of claim 21, wherein the method further comprises contacting the metal carbene displacement catalyst with a substituted or unsubstituted acyclic olefin. 96 1337099 23. A method of forming a metal carbene displacement catalyst comprising an N-heterocyclic carbene ligand, the method comprising: protecting a protected N-heterocyclic carbene with a source of Ru or Os in the presence of energy Substituted or unsubstituted aryl and olefin contacts. 24. A method of replacing a non-cyclic diene of one or more non-cyclic diolefins, the method comprising: in the presence of energy, a protected N-heterocyclic carbene and a replacement initiator and the Or more non-cyclic diene contacts, wherein the displacement initiator is any Ru or Os metal carbene displacement catalyst, and t is energy selected from the group consisting of thermal energy, laser, electron beam radiation, 7 radiation, plasma The group of sound, ultraviolet light and microwave radiation. 97