CN103304715B - Stereospecific gathers (Beta-hydrocarbyl--alpha-methylene-gamma-butyrolactone) and multipolymer thereof - Google Patents
Stereospecific gathers (Beta-hydrocarbyl--alpha-methylene-gamma-butyrolactone) and multipolymer thereof Download PDFInfo
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- CN103304715B CN103304715B CN201210078471.5A CN201210078471A CN103304715B CN 103304715 B CN103304715 B CN 103304715B CN 201210078471 A CN201210078471 A CN 201210078471A CN 103304715 B CN103304715 B CN 103304715B
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Abstract
The present invention relates to the polymkeric substance and multipolymer with high three-dimensional regularity, high-vitrification invert point and resistance to common organic solvents, particularly relate to the homopolymer of Beta-hydrocarbyl--alpha-methylene-gamma-butyrolactone and the multipolymer with gamma-alkyl-alpha-methylene-gamma-butyrolactone.The invention further relates to the preparation method producing said polymkeric substance, and said polymkeric substance is at materials such as the alternative polymethylmethacrylates of some Application Areas.
Description
Technical field:
The present invention relates to use metallocene and half luxuriant catalysis of rare-earth compound agent catalysis Beta-hydrocarbyl--alpha-methylene-gamma-butyrolactone polymerization obtain homopolymer and with the multipolymer of analog monomer and preparation method.
Background technology:
The polymethylmethacrylate (PMMA) deriving from petroleum products is a kind of important thermoplastics, has the good transparency, chemical stability, weathering resistance, easily processes dyeing and be used widely.But also there are some obvious defects, as surface hardness is low, not scrape resistant, surface hazes, poor toughness, and shock strength is low, and heat resisting temperature is low.For this reason, the scientific research personnel of E.I.Du Pont Company studies the polymerization of the analog alpha-methylene-gamma-butyrolactone (MBL) of methyl methacrylate, to obtaining the better material of performance.Alpha-methylene-gamma-butyrolactone, also known as tulipalin or tulipalin, derives from liliaceous plant turmeric, much all contains this cyclic structural unit in other natural product molecule.Its methyl substituted derivatives (γ-MMBL) also can obtain from biomass product levulinic acid through two step chemical reactions.This kind of monomer, much from plant, is recyclability resource.So far, because cost is higher, the application of alpha-methylene-gamma-butyrolactone base polymer is subject to certain restrictions, in recent years, many companies go out very large interest to polymers exhibit prepared by alpha-methylene-gamma-butyrolactone class monomer, develop the synthetic route with industry attractiveness, for application lays the foundation further.This kind of compound structure can contrast as follows:
The monomers such as MBL, γ-MMBL can carry out radical polymerization, and this is at M.K.Akkapeddi, Polymer, vol.20, and 1979, pp.1215-1216, have open in United States Patent (USP) 99/28234, Japanese Patent 901246.Find these monomers and acrylic or methacrylic acid esters unexpectedly, and its analog performance is different, the second-order transition temperature of the homopolymer of MBL, γ-MMBL is higher than polymethylmethacrylate nearly 100 DEG C, can substitute PMMA in some Application Areas.These two kinds of monomers also can carry out polycoordination, EugeneY.X.Chen (Macromolecules, 2010,43 (11), pp4902-4908; Macromolecules, 2010,43 (22), pp9328-9336) adopt metallocene catalyst to achieve the polymerization of MBL, γ-MMBL, the second-order transition temperature of resulting polymers exceeds PMMA respectively and reaches more than 90 DEG C and 130 DEG C.
Carry out polycoordination and the copolymerization with γ-MMBL with metallocene catalyst or rare earth half cyclopentadienyl catalyst catalysis β-MMBL, yet there are no patent and disclose and bibliographical information.
Summary of the invention:
The present invention relates to and be polymerized the homopolymer obtained and the multipolymer obtained with gamma-alkyl-alpha-methylene-gamma-butyrolactone (MMBL) multipolymer by Beta-hydrocarbyl--alpha-methylene-gamma-butyrolactone through coordinating, be particularly polymerized the polymkeric substance obtained and the multipolymer obtained with γ-methyl-alpha-methylene-gamma-butyrolactone copolymerization by Beta-methyl-alpha-methylene-gamma-butyrolactone.
The invention further relates to the method for producing said polymkeric substance, wherein the method comprises:
Make Beta-hydrocarbyl--alpha-methylene-gamma-butyrolactone or under existing with optional alpha-methylene-gamma-butyrolactone derivative comonomer, contact with metallocene and promotor or single cyclopentadienyl rare-earth metal organic compound, this Beta-hydrocarbyl--alpha-methylene-gamma-butyrolactone:
Wherein R
1r
2independently be selected from C separately
1~ C
6alkyl, aryl or substituted aryl (or R
2=H), wherein R
1, R
2can also be optionally form ring texture.
Monomer for the inventive method includes but are not limited to Beta-methyl-alpha-methylene-gamma-butyrolactone and γ-methyl-alpha-methylene-gamma-butyrolactone.Monomer generally stirs 24 hours at plus hydrogenated sodium, then underpressure distillation under nitrogen protection, in cryopreservation in nitrogen atmosphere.
Optionally in the presence of solvent, the method is carried out temperature is from 0 DEG C to 50 DEG C.
Comonomer under the invention further relates to Beta-hydrocarbyl--alpha-methylene-gamma-butyrolactone and being selected from closes, this comonomer is selected from γ-methyl-alpha-methylene-gamma-butyrolactone, γ-ethyl-alpha-methylene-gamma-butyrolactone, γ-propyl group-alpha-methylene-gamma-butyrolactone, γ-butyl-alpha-methylene-gamma-butyrolactone, γ-amyl group-alpha-methylene-gamma-butyrolactone, γ-cyclohexyl-alpha-methylene-gamma-butyrolactone, γ-phenyl-alpha-methylene-gamma-butyrolactone, γ-cholest--alpha-methylene-gamma-butyrolactone.
Polymkeric substance can be converted into easily under containing trimethylsilyl methyl rare earth metallocene or the 4th subgroup metallocene compound/tri-pentafluorophenyl group boron catalysis at the alpha-methylene-gamma-butyrolactone of β and γ substd.Because the substituent position of monomer is different, can obtain the polymkeric substance of high legislate degree at the alpha-methylene-gamma-butyrolactone of β substd, second-order transition temperature up to 290 DEG C, and can obtain at γ position substituted monomer the polymkeric substance that random structure accounts for more than 50%.
The alpha-methylene-gamma-butyrolactone monomer copolymerization that can be replaced by β and γ position obtains multipolymer, by the ratio of both changes, can obtain second-order transition temperature a series of multipolymers from high to low, adapt to different environments for use.Particular requirement is not had to the molecular weight of obtained polymkeric substance, but preferred molecular weight ranges is 2 × 10
4~ 1 × 10
6between dalton, molecular weight is less than the performance that this scope may affect polymkeric substance, and the fragility of the too low material of such as molecular weight is larger etc.; The too high meeting of molecular weight causes processing difficulties.
In the multipolymer containing β-MMBL and γ-MMBL, the ratio of the amount of substance of two kinds of monomers can be 9: 1 to 1: 9, but preferred ratio is 3: 7,5: 5,7: 3.
In the method for the invention, the second-order transition temperature containing the multipolymer of the alpha-methylene-gamma-butyrolactone of β and γ position replacement can be controlled by both ratios changed in multipolymer.Such as increase the content of β-MMBL, second-order transition temperature can improve, but when needs multipolymer has good flexibility, can use the substituting group that on γ position, alkyl is longer, and suitably reduce the ratio of β alkyl substituted monomer.
In method for producing polymer of the present invention, preferred metallocene catalyst is the title complex of zirconium, titanium, hafnium.
The catalyzer used in the present invention is the metallocene compound of the 4th subgroup and rare earth half cyclopentadinyl compound containing alkylene ligand, the preferably promotor of zirconocene muriate and boracic thereof, part is that bridging is luxuriant or shank type is luxuriant, or single cyclopentadienyl rare-earth metal metallocene catalyst is scandium, yttrium, lutetium, dysprosium etc., part is the derivative of indenes, fluorenes.Alkyl dentate preferably trimethylsilyl methyl in rare earth half cyclopentadinyl compound.Monomer is 400: 1 to 2000: 1 with catalyst levels ratio (amount of substance ratio).
Metallocene compound and the part contained in rare earth half cyclopentadinyl compound of alkylene ligand are mainly following structure:
Wherein, R
3=R
4=CH
3, CH
3cH
2or Me
3siR
5=Me
3siCH
2.
Corresponding main complexes structure is as follows:
Above-mentioned catalyzer is according to document [J.Chem.---Eur.J.2009,15,846-850; J.Organometallics, 2010,29,549-553; B.Wang, D.Cui, K.Lv, Macromolecules2008,41,1983-1988.] method is prepared
In the presence of solvent, the method is carried out temperature is from 0 DEG C to 50 DEG C.
In order to prepare polymkeric substance of the present invention, first need to carry out anhydrous and oxygen-free process to monomer, solvent, after purifying, all polymerizations are all carried out under anhydrous and oxygen-free condition.Schlenk bottle at 120 DEG C dry 2 hours, argon replaces three times, add the solvent of drying then by a certain amount of solvent, add catalyzer again, abundant dissolving after ten minutes after homogeneous phase solution, react between room temperature to 50 DEG C, add polymerization single polymerization monomer, instead with regard to 0.5-1 hour, or according to polymerization situation after the transformation efficiency of monomer reaches 90%, can stopped reaction, stop polymerization with containing 5%HCl solution, gel is poured in a large amount of methyl alcohol, filter, by methanol wash, the polymkeric substance obtained vacuum-drying 12 hours at 50 DEG C, obtains solid polymer.
Copolymerization as above, carries out under the condition that same homopolymerization is same, first β-alkyl-the alpha-methylene-gamma-butyrolactone and γ-alkyl-alpha-methylene-gamma-butyrolactone that determine ratio is mixed, then joins in the solvent containing catalyzer.After polymerization certain hour, the methanol solution added containing 5%HCl stops polymerization.Gained solid polymer methyl alcohol fully washs, then vacuum-drying 12 hours at 50 DEG C, finally copolymerization product.
As mentioned above, polymerization can have any and close and carry out under the medium of polycoordination or solvent exist, and this medium or solvent include but not limited to methylene dichloride, dimethyl formamide, tetrahydrofuran (THF) and ethers.DMF, THF, use front drying, dehydration and deoxidation process.
The homopolymer structure of Beta-hydrocarbyl--alpha-methylene-gamma-butyrolactone described above is as follows:
Or with the copolymer structure of optional γ-alkyl-alpha-methylene-gamma-butyrolactone derivative be:
Polymkeric substance as above, generally has in the homopolymer of high second-order transition temperature, high three-dimensional regularity; The second-order transition temperature of multipolymer is different with the difference of comonomer ratio, adjusts by change ratio, generally can be adjustable the scope of 230 DEG C to 295 DEG C.
For the homopolymer of Beta-hydrocarbyl--alpha-methylene-gamma-butyrolactone monomer, degree of isotacticity is from 80% to 95%, and different with the difference of used catalyst, soluble solvent is trifluoroacetic acid, the vitriol oil etc.For the homopolymer of Gama-monomer, degree of isotacticity is from 55% to 70%, and soluble solvent has DMF, DMSO polar solvent.
The homopolymer of above-mentioned gained has higher than the second-order transition temperature of polymethylmethacrylate more than 100 DEG C, can replace PMMA in a lot of Application Areas, and can life-time service at relatively high temperatures.
Embodiment
Embodiment one
Vacuum-drying 2 hours at 120 DEG C, in the Schlenk bottle that argon replaces is three times, add the methylene dichloride of 6ml drying, add 23.4 μm of ol metallocene catalysts and 23.4 μm of ol promotor triphen carbon four (pentafluorophenyl group) borates, stir after 5 minutes and add Beta-hydrocarbyl--alpha-methylene-gamma-butyrolactone 1.0mL (9.37mmol), after several minutes, reaction soln becomes gel, the methanol solution termination reaction containing 5%HCl is added after 10 minutes, gel reactant is poured in a large amount of methyl alcohol, filter, by methanol wash, the polymkeric substance obtained vacuum-drying 12 hours at 50 DEG C, obtain solid polymer.The second-order transition temperature of resulting polymers is 270 DEG C ~ 295 DEG C, degree of isotacticity 88 ~ 94%.
Embodiment two
In embodiment one, polymer solvent is changed into dry DMF, other operation and condition are with embodiment one.Under these conditions, Beta-hydrocarbyl--alpha-methylene-gamma-butyrolactone polymerization obtains homopolymerization products.The second-order transition temperature of resulting polymers is 270 DEG C ~ 292 DEG C, and degree of isotacticity is between 88 ~ 94%.
Embodiment three
In embodiment one, catalyzer is changed into rare earth list half metallocene, do not need to add promotor boron compound, other operation and condition are with embodiment one.Under these conditions, Beta-hydrocarbyl--alpha-methylene-gamma-butyrolactone polymerization obtains homopolymerization products.The second-order transition temperature of resulting polymers is 270 DEG C ~ 292 DEG C, and degree of isotacticity is between 88 ~ 94%.
Embodiment four
In embodiment one, polymerization single polymerization monomer is changed into the Beta-hydrocarbyl--alpha-methylene-gamma-butyrolactone of 1: 1 and the hybrid monomers of γ-alkyl-alpha-methylene-gamma-butyrolactone, other operation and condition are with embodiment one.Under these conditions, hybrid monomers polymerization obtains copolymerization and gathers product.
The second-order transition temperature of gained multipolymer is 250 DEG C ~ 270 DEG C.
Embodiment five
In embodiment one, polymerization single polymerization monomer is changed into the Beta-hydrocarbyl--alpha-methylene-gamma-butyrolactone of 1: 7 and the hybrid monomers of γ-alkyl-alpha-methylene-gamma-butyrolactone, other operation and condition are with embodiment one.Under these conditions, hybrid monomers polymerization obtains copolymerization and gathers product.
The second-order transition temperature of gained multipolymer is 230 DEG C ~ 250 DEG C.
Claims (4)
1. the alpha-methylene-gamma-butyrolactone polymerization replaced for β position and the alpha-methylene-gamma-butyrolactone copolymerization that replaces with γ position with prepare there is high three-dimensional regularity and high glass transition temperature gather (β-alkyl-alpha-methylene-gamma-butyrolactone) method, wherein the method comprises:
Make Beta-hydrocarbyl--alpha-methylene-gamma-butyrolactone or under existing with optional gamma-alkyl-alpha-methylene-gamma-butyrolactone derivative comonomer, contact with metallocene complex and promotor, described metallocene refers to that IVB race-titanium subgroup comprises titanium, zirconium, hafnium three kinds of metals
This Beta-hydrocarbyl--alpha-methylene-gamma-butyrolactone
This gamma-alkyl-alpha-methylene-gamma-butyrolactone
Wherein R
1r
2independently be selected from C separately
1~ C
6in alkyl, substituted alkyl, aryl or substituted aryl besides methyl;
Optionally in the presence of solvent, the method is carried out temperature is from 0 DEG C to 50 DEG C;
Part in described metallocene complex refers to:
Wherein, R
3=H or CH
3; R
4=CH
3or phenyl;
Described promotor, refers to three (pentafluorophenyl group) boron, triphen carbon four (pentafluorophenyl group) borate, N, N-dimethyl puratized agricultural spray four (pentafluorophenyl group) borate.
2. the product that method according to claim 1 is obtained, homopolymer is poly-(Beta-hydrocarbyl--alpha-methylene-gamma-butyrolactone); Homopolymer structure is as follows:
Wherein R
1independently be selected from C
1~ C
6in alkyl, substituted alkyl, aryl or substituted aryl besides methyl.
3. the product that method according to claim 1 is obtained, multipolymer is β-alkyl-alpha-methylene-gamma-butyrolactone and γ-alkyl-alpha-methylene-gamma-butyrolactone, and the ratio of the two is: 1 ~ 9: 9 ~ 1, and copolymer structure is as follows:
4. the structure of metallocene complex according to claim 1 refers to:
Wherein R is hydrogen or methyl.
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| CN201210078471.5A CN103304715B (en) | 2012-03-13 | 2012-03-13 | Stereospecific gathers (Beta-hydrocarbyl--alpha-methylene-gamma-butyrolactone) and multipolymer thereof |
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| CN201210078471.5A CN103304715B (en) | 2012-03-13 | 2012-03-13 | Stereospecific gathers (Beta-hydrocarbyl--alpha-methylene-gamma-butyrolactone) and multipolymer thereof |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1330666A (en) * | 1998-12-16 | 2002-01-09 | 纳幕尔杜邦公司 | Oligomerization, polymerization and copolymerization of substituted and alpha-methylene-gamma-butyrolactone and products thereof |
| CN101360768A (en) * | 2005-11-30 | 2009-02-04 | 通用电气公司 | Tulipalin copolymers |
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2012
- 2012-03-13 CN CN201210078471.5A patent/CN103304715B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1330666A (en) * | 1998-12-16 | 2002-01-09 | 纳幕尔杜邦公司 | Oligomerization, polymerization and copolymerization of substituted and alpha-methylene-gamma-butyrolactone and products thereof |
| CN101360768A (en) * | 2005-11-30 | 2009-02-04 | 通用电气公司 | Tulipalin copolymers |
Non-Patent Citations (2)
| Title |
|---|
| ansa-Rare-Earth-Metal Catalysts for Rapid and Stereoselective Polymerization of Renewable Methylene Methylbutyrolactones;Yangjian Hu et al;《CHEMISTRY A EUROPEAN JOURNAL》;20120201;第18卷;第3346页第3段、图解1，第3349页，催化剂1催化βMMBL的立体选择性的聚合部分 * |
| Coordination polymerization of renewable butyrolactone-based vinyl;Grret M.Miyake et al;《Dalton Transactions》;20100325;第39卷;第6711页第2段、图表2，第6712页第5段，第6714页表3，第6715页第3段 * |
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