JPH0455403A - Epoxy group-containing copolymer - Google Patents

Abstract

PURPOSE:To obtain a new epoxy group-containing ethylene copolymer having a wide use because of excellent reactivity to amine compound, adhesivity to various materials, excellent properties as compatibilizing agent, etc., comprising a specific structure containing an epoxy group at the end of branched chain. CONSTITUTION:The objective copolymer comprising an ethylene unit shown by the formula -(CH2-CH2)- and a unit shown by formula I (R is >=4C straight- chain alkylene; X is CH=CH2 group or group shown by formula II), containing 0.2-20 mol % unit shown by formula I wherein >=1 % group X in the unit shown by formula I is group shown by formula II. The copolymer, for example, is obtained by epoxidizing >=1 % end unsaturated group of side chain of unsaturated copolymer comprising an ethylene unit and 0.2-20 mol % alpha, omega-nonconjugated diene unit shown by formula III by oxidation with peracetic acid. 1,7-Octadiene is used as the alpha,omega-nonconjugated diene to provide the unit shown by formula III.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a novel ethylene copolymer containing an epoxy group at the end of the N chain.

(Prior Art) Olefin homopolymers or copolymers such as ethylene and propylene are used in various fields due to their excellent physical properties and moldability. However, since olefin polymers have a non-polar molecular structure, they have poor affinity with other materials, and their properties such as adhesiveness and printability are significantly affected. Furthermore, it also has the disadvantage of poor miscibility when blended with fats and oils that have a polar structure, including engineering plastics.

In order to compensate for these drawbacks, there is a method of craft-modifying an olefin polymer with a radically polymerizable compound having a polar group, such as maleic anhydride, vinyl acetate, acrylic acid, methyl methacrylate, etc., in the presence of a radical generating agent. Alternatively, a method of copolymerizing an olefin and a polymer containing a polar group has been proposed. Modified polymers produced by these methods are increasingly being put to practical use. However, in recent years, resin materials have been required to have more sophisticated properties and more diversified applications, and new modified polymers with various functions that can be applied to these materials have been required.

% Kaisei 61-854 as one of the modified polymers in this field
No. 05 discloses a modified copolymer in which an unsaturated copolymer resin made from an α-olefin and a 1,4-diene with a specific structure is modified and an epoxy group is introduced into the resin. .

However, because the epoxy group in this modified copolymer is located inside the carbon chain due to its 1,4-diene structure, it is particularly reactive towards clay-based compounds, such as amine compounds and amine group-containing polymers. It has the drawbacks of poor properties, poor performance as a K-based resin, and limited application.

(Problems to be Solved by the Invention) The present invention has been made in view of the above-mentioned current situation. Its task is to provide this information.

(Means for Solving the Problems) The present invention provides an ethylene unit: (-CH, -CH2÷ and (a
Following formula H1 +CHx -CH+ (I)Rχ (wherein, R represents a linear alkylene group having 4 or more carbon atoms, and X is -CH=C)1. The present invention relates to an ethylene copolymer containing units represented by up to groups (2) to 20 molar units (cL) and containing an epoxy group at the end of a certain side chain.

Furthermore, the present invention also provides (5) ethylene unit +C1-], -CH,÷ and (q
A small amount of α-olefin units, preferably α1 to 5 mol: ÷CH, -CH+ R/ (R' represents an alkyl group having 1 to 10 carbon atoms,
) and (B) the following formula tl) ÷CH2-C)1-) (I)x (wherein, R represents a linear alkylene group having 4 or more longitudinal atoms, and A copolymer containing a nest position represented by ?L, containing α2 to 20 moles of ■ units, provided that 1% or more of the group It also relates to an ethylene copolymer containing an epoxy group at the end of the ethylene copolymer.

As mentioned above, the comonomer of the present invention can be polymerized to form the remaining 9
98 to 80 mol% is substantially free ethylene units or (
5) Composed of ethylene units and (qα-olefin units).

In addition, in the copolymer VC of the present invention, the (B) unit group is 10) I=CH2 group, but the synthesis process of the copolymer, for example, the unsaturated copolymer In the epoxidation reaction, there is no problem even if a small amount of other by-resident groups are mixed in depending on the case.

The preferred molecular weight range of the copolymer of the present invention is from 300 to soo, especially 2.0 in terms of number average molecular weight.
0.0 to 2 Q O, ODO.

In addition, the melt index of the copolymer [(190°C, load 116 kl) is α001~s, o o o g71
It is o minutes.

In the copolymer of the present invention, α-olefin units 1,000 H2
The alkyl group R' of -CH) is a linear to branched alkyl group having 1 to 10 carbon atoms, such as a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group,
Ofnal group, inpropyl group, 2-methylpropyl group,
Examples include tertiary butyl group and 2,2-dimethylbutyl group.

Preferred linear alkylenes having 4 or more carbon atoms at the mouth position include butylene, hexylene, octerene, and dicylene.

The copolymer of the present invention has the following formula: (a) x y unit ÷ CH, -CH2+ or (a) ethylene unit; ÷ C12-CH2 ÷ and (α-olefin unit with a small amount of Cl: +CH2-CHR' ( R' represents an alkyl group having 1 to 10 carbon atoms.

) and (bl A linear chain formed by the following formula (Ill 1,000H2-CH ÷ IR-CH=CH2 (wherein, R#-IL represents a linear alkylene group having 4 or more carbon atoms) α,ω non-conjugated diene unit α2~2
It can be produced by epoxylating one or more of the end unsaturated groups of the 'JAJ chain of an unsaturated comonomer containing 0 molar ratio.

The unsaturated copolymer can be produced using methods and equipment similar to those for producing olefin polymers using so-called pre-coordination g'.

An example of such a method is related to the appearance of non-settlement applicants! #
There is a method of No. 218478.

In this method, ethylene or ethylene containing a small amount of α-olefin and linear α, ω carbon atoms of 8 or more are used.
[B] General formula Ti (OR) nX4-, (RF
a hydrocarbon group of iC1 to Ctt, X is a halogen atom, and a beaten insium and titanium-containing catalyst component obtained by reacting a tetravalent titanium compound with 0≦n≦4) as an essential raw material component, and B2] In the presence of a catalyst consisting of an organoaluminum compound, at 50°C or higher, preferably at 130°C
At a temperature of ℃ or higher, without solvent or in the presence of an inert hydrocarbon solvent, at normal pressure to 200 K, preferably 3 to 30 K.
The unsaturated copolymer is developed by copolymerization under a pressure of 9/cIA.

α-olefins include α-olefins having 6 to 12 carbon atoms.
Olefins, such as propylene, butene-1, pentene-111hexene-1, octene-1,3-methyl-
Butene-1,3-methyl-pentene-1,4-methylpentene-1,3,3-'dimethyl-butene-1.44-
dimethylhexene-1, 3-methylhexene-1,
Mention may be made of 4-methyl-hexene-j, 4,4-dimethyl-hexene-1, etc., the amount of which is preferably from 0.1 to 5 molar based on the unsaturated copolymer. Also, carbon! Examples of the linear σ, ω-nonconjugated diene in which 2 is 8 or more include 17-octadiene, t9-decadiene, 1.
Mention may be made of +1 toticacyene, t15-tetradecadiene, etc., the amount of which is from 02 to 20 molar based on the non-jllN copolymer.

No 1! 2! Suitable molecular weight range for the Wakyo-yigo combination is 2000 to 300 to 500,000% with a number average molecular weight of 11 Kl.
The melt index value of the copolymer (190°C, load 2.16KI) is 0.0.
01 to 5,0 OOP/10 minutes.

As a method for introducing an epoxy group into an unsaturated comonomer,
Olefinic non-tI! The most common method is to recognize the sum bond, and specific examples of p1 include t perI1m, peracetic acid,
2. Oxidation with hydrogen peroxide or organic hydroperoxide in the presence or absence of catalysts such as vanadium, molybdenum, tungsten compounds, etc., 5. Oxidation with alkaline hydrogen perester, 4. Examples include oxidation with hypochlorite (IJ) in the presence or absence of transition metal acetyl heptatonate complexes and phorphyrin complexes.

As another method, it is also possible to use a compound containing an epoxy group in 5 molecules, such as a chrycidylthiol compound, to the olefinic unsaturated yFo bond. In this case, the position of formula I +cH, -CH+ K? Te group X 25E -CH=CH, group K y represents a group to which a muricidyl compound is added.

The epoxidation reaction is carried out with the unsaturated copolymer dissolved in a solvent, swollen in a solvent, or molten.

The solvent used is selected from aliphatic, alicyclic, aromatic hydrocarbons, halogenated hydrocarbons, ester ethers, ketones, carbon disulfide, and the like.

The introduction of the epoxy group is carried out at least 1 chain, preferably at least 5 chains, of the olefinic unsaturated bonds in the unsaturated copolymer, t#[20
It is more than 1.

Even if the selectivity is not necessarily 100%, as long as the epoxy group is introduced qualitatively, it is acceptable even if it is due to the introduction of products due to side reactions (Example) Reference Example 1 (1) Preparation of the main reaction product [A-1] In a glass reactor whose interior was thoroughly dried and purged with nitrogen, a di-impropyl ether solution of n-butylmagnesium chloride (80%) was placed in advance.
0m (commercial product 20-butylmagnesium chloride: 1.34cm) was collected, and while stirring, the terminals were capped with trimethylsilyl groups. Methylhydropolysiloxane (viscosity at 25°C is about 30 centistokes) 8α5a
+j (1.34 rere as S+) was added dropwise over 1 hour while maintaining the base. After the dropwise addition, stirring was continued for 1 hour to obtain a brown and transparent main reaction product [A].

After diluting 500- of n-hebutane with an addition D1 to the solution of the main reaction product [A] thus obtained, 1.346+ of 2-ethylhexanol [C] was added dropwise at room temperature over 1 hour.

After completion of the dropwise addition, vacuum distillation was performed at a pressure of 120 to 240 rrmHg to distill out 11. The mixture was diluted with j-hebutane to obtain a colorless and transparent solution of the main reaction product [A-1] in n-hebutane. The concentration of magnesium is I1782 mol/
! It is.

(2) 77.7 aJ of methylcyclohexane, and (
The reaction product port A-1j obtained in 1) was sampled at 10 mm/m using a 95 mm screw. While stirring, 1 g of methylcyclohexane K was dissolved to give 5 mmol of tetra-n-butoishititanium [B] α! was added at room temperature and heated at 70° C. for 1 hour. After completion of the reaction, the mixture was cooled to room temperature to obtain one catalyst component containing magnesium and titanium.

(3) Copolymerization of ethylene and nonconjugated diene 560 ml of methylcyclohexane was placed in a #121 stainless steel autoclave equipped with a stirrer whose interior was dried and replaced with ethylene, and a pressure-resistant container for supplying catalyst and cocatalyst. and U 1.
9-f Kasien (Shell Chemical G) 50m/(37,4
M) was charged and the temperature was raised. When the temperature reached 80°C, α1kv/cM of hydrogen was introduced, and when the temperature reached 148°C, 1.2 mmo! of diethylaluminum chloride [2] was introduced through the attached pressure-resistant container. , yohi above +21
One catalyst component was introduced at an ethylene pressure of I14 in terms of T1.

After raising the temperature to 150° C., ethylene was continuously introduced so that the total pressure became 8 zakigura (cage pressure), and polymerization was carried out under pressure for 1 hour. After polymerization, stabilizer Ircanonx 1076
Polymerization was terminated with methanol containing .

The number average molecular weight of the formed polymer was separated as it was and dried, and the number average molecular weight was determined by infrared absorption spectroscopy (Il'l
・According to the method, the number of terminal Bya groups was 1 + 000 carbon atoms, which was 99.

Reference Example 2 A copolymerization reaction with ethylene was carried out under the same conditions as in Reference Example 1 except that 1,13-tetradecadiene (manufactured by Shell Chemical) 80su was used as the non-conjugated diene. 650 g of ethylene-nonconjugated decadiene copolymer was obtained, and analysis revealed that the number average molecular weight was 35,000 and the number of terminal vinyl groups was 1,000 carbon atoms and 5 atoms.

! l! Example 1 Into a 30 flask equipped with a stirrer, a reflux condenser, and a nitrogen inlet tube, toluene 5 (14), which had been dehydrated and dried after removing the nitrogen atoms, was placed. Next, the ethylene-nonconjugated diene conjugate synthesized in Reference Example 1 Polymer l14II (vinyl group content 0.5 mm
ol white amount), metachloroperbenzoic acid 74■ (α3 mm
o/ ) and raise the temperature while stirring under nitrogen atmosphere.
The reaction was carried out at 90°C for 48 hours. After the reaction, the contents were cooled to room temperature and then poured into 200 m of methanol. The formed precipitate was separated and then dried under reduced pressure. When the structure of the polymer thus obtained was analyzed by IR method, it was found to be 1,260. -1847cya', 837α
A characteristic absorption of the -IK epoxy group appeared, and the conversion rate of the epoxy group was equivalent to 2EL2 mol of the vinyl group before the reaction. The vinyl group content was 1.00 Ell, which was 66 carbon atoms. The infrared set yield spectrum of this copolymer is shown in FIG. Separately, the main base of the jepoxy group was confirmed by nuclear magnetic resonance spectroscopy (13C-NMR method).

Implementation@2 For the same ethylene-nonconjugated diene copolymer α4yK used in Example 1, molybdenum hexacarbonyl 10
my (cLo 4.mmo/), phosphorous enemy hydrogen disodium 15 cape (α1 mmor) 'k Zt Stir well. The temperature of the obtained solution was raised to 90°C and after fc,
t-bunal hydroperoxide α5d (5mmo/ )
was added dropwise, and the reaction was stirred for 5 hours.

After the reaction, the product was treated in the same manner as in Example 1 to obtain a modified copolymer. When this modified copolymer was analyzed by IR method, 317 moles of vinyl groups before reaction were changed to epoxy groups.

Example 5 Raw material copolymer and Example 1 except that an ethylene-decadiene copolymer with a number average molecular weight of 4,700 and a vinyl group content of 9.5 synthesized in the same manner as in Reference Example 1 was used. Epoxidation reaction was carried out in the same manner.

As a result of the analysis, the conversion rate of vinyl groups to epoxy groups in the copolymer was found to be 3α2 molar.

Example 4 Same as Example 1 except that the ethylene-tetradecadiene copolymer synthesized in Reference Example 2 was used as the raw material copolymer.
A 4C epoxidation reaction was performed.

When the obtained modified copolymer was analyzed by IR method, the conversion rate of vinyl groups to epoxy groups was 254 mol.

(Effects of the Invention) The epoxy group-containing copolymer of the present invention has excellent reactivity with other compounds, such as basic compounds such as amine compounds and amine group-containing polymers, compared to polymer epoxy groups. . Therefore, the copolymer of the present invention can be used for various resin materials and resin-modified materials by taking advantage of the various reactivities and properties that are unique to this evocative group in Japan and the United States. It can also be used as a raw material to be modified and modified into functional polymers with high functionality.

For example, the uninvented copolymer has excellent adhesive strength with various materials including metals such as planes and aluminum, so it is used as an adhesive resin with functional groups that are reactive with the epoxy groups of fatty acids, polyamides, and polyesters. It shows excellent properties as a binder or compatibilizer with resins.

■ ■ ■ Forms chemical bonds with various Wm fillers, and some h has good affinity with -2, so when used as an inorganic filler-containing resin composition, it brings about improvements in physical properties such as improved mechanical strength. .

By using a certain crosslinking agent such as holamine or polycarboxylic acid, it can be combined with a three-dimensional 54-shaped structure and has excellent mechanical properties. Once it can be converted into E-fat, it can also be converted into a compound or Ki that has various functional groups such as photosensitivity, ionic coordination or convertibility, antioxidant properties, and can body compatibility by utilizing the reactivity of the epoxy group. ! can be guided.

[Brief explanation of drawings]

Figure 1111 shows Example 1 of the present invention. Infrared absorption spectrum. copolymer of

Claims (2)

[Claims] (1) (A) Ethylene unit: ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ and (B) The following formula ( I ) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ( I ) (In the formula, R is the number of carbon atoms (B) represents a linear alkylene group of 4 or more, and X represents a -CH=CH_2 group or a Ethylene copolymer containing 0.2 to 20 mol% of units and containing an epoxy group at the end of the side chain in which 1% or more of the group X of the unit (B) is a Combined. (2) Claim 1 in which the copolymer contains a smaller amount of (C) α-olefin units: ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (R' represents an alkyl group having 1 to 10 carbon atoms) Ethylene copolymer described.