JPH0423813A - Alpha-olefin copolymer and its production - Google Patents

Abstract

PURPOSE:To obtain a copolymer useful as a compatibilizing agent having excellent miscibility and adhesion to polyolefin, etc., by copolymerizing alpha-olefin, an alicyclic epoxy group-containing unsaturated monomer and an ethylenic unsaturated monomer using a radical polymerization catalyst. CONSTITUTION:(A) An alpha-olefin is copolymerized with (B) an unsaturated monomer having at least a species of alicyclic epoxy group [preferably a compound expressed by the formula (R1 is H or methyl; R2 is 1-6C bifunctional aliphatic saturated hydrocarbon)] and (C) at least a species of ethylenic unsaturated monomer using a radical polymerization catalyst [preferably peroxide or azo compound expressed by the formula X-O-O-Y type (X is aryl, alkyl or H, etc.; Y is X, etc.)] to afford the objective copolymer.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a novel α-olefin copolymer having an alicyclic epoxy group and a method for producing the same.

(Prior art) As an α-olefin copolymer having an epoxy group,
A monomer having a glycidyl group, such as a copolymer of glycidyl methacrylate, ethylene, and vinyl acetate, is well known (Japanese Unexamined Patent Publication No. 11388-1971).

These copolymers retain the excellent properties of polyethylene, such as processability, chemical resistance, and low-temperature embrittlement resistance, and have good compatibility with other resins, so they can be used with other polyolefins, polyamide resins, polyester resin, vinyl chloride resin,
Polycarbonate resin, AS resin, ABS resin, polystyrene resin, polyarylene ester resin, polyarylene sulfide resin, polyphenylene oxide resin, polyetherketone resin, polyetherimide resin,
It is blended with polyoxymethylene resins and used as a modifier for them.

Furthermore, when blending incompatible resins, adding it as a compatibilizer increases the compatibility, making it possible to blend resins that are otherwise difficult to blend.

As a result, various polymer alloys have been developed.

It is also widely practiced to utilize the reactivity of epoxy groups in copolymers to introduce various functional groups by reacting resins and compounds with various active hydrogens.

(Problems to be Solved by the Invention) However, despite such usefulness, conventional ethylene copolymers having glycidyl groups have various problems because their epoxy groups are unstable at high temperatures. was there.

First, when producing this copolymer, when an α-olefin compound and glycidyl methacrylate are radically polymerized at high temperature, the glycidyl group is cleaved at the reaction temperature, and the resulting copolymer contains epoxy groups. There was a problem in that the amount decreased significantly, and in some cases, crosslinking reactions occurred due to decomposition, resulting in an increase in the melt viscosity of the copolymer.

Therefore, in order to avoid such problems, it has been impossible to increase the content of the glycidyl group-containing monomer in the copolymer, and copolymerization has been possible only below a limited proportion.

Moreover, if the polymerization temperature in copolymerization is also high, decomposition or cleavage of the epoxy group will occur, so copolymerization is also carried out while keeping the polymerization temperature below a certain temperature.

However, in such cases, the molecular weight of the copolymer increases and the melt viscosity of the copolymer itself increases, which not only makes the polymerization operation difficult but also causes problems such as poor blending characteristics with other resins. there were.

In addition, when blending with other resins using an extruder, etc., if the cross-mixing temperature is increased or the cross-mixing time is increased in order to achieve sufficient blending, the epoxy groups in the copolymer themselves may decompose or become self-contained. There were problems such as cleavage, resulting in significant coloring of the blended resin and failure to obtain the original blending effect.

As a result of intensive studies to solve the above-mentioned problems, the present inventors discovered that an unsaturated monomer having an alicyclic epoxy group and an α-
It was discovered that a copolymer with an olefin compound has excellent thermal stability, leading to the present invention.

(Structure of the Invention) That is, the present invention provides: "(a) an α-olefin; (b) an unsaturated monomer having one or more alicyclic epoxy groups; and (c) one or more ethylenically unsaturated monomers." ``A copolymer obtained by copolymerizing ``(a) α-olefin and (b) one or more types of alicyclic epoxy groups (c ) A method for producing an α-olefin copolymer, which comprises copolymerizing one or more ethylenically unsaturated monomers using a radical polymerization catalyst.

Examples of the α-olefin compound used in the present invention include ethylene and propylene, but α-olefins with larger molecular weights can also be used, and one type or a mixture of two or more types may be used.

The unsaturated monomer having an alicyclic epoxy group used in the present invention has one unsaturated bond copolymerizable with an α-olefin monomer in one molecule, and one or more alicyclic epoxy groups. It is a monomer with

For example, such monomers include those shown below.

R3 R+0 mouth CH2 -C-C-O- cave ■ (II) R.

Hz=CC -R2 (V,) CH.

CH.

■ -C-C-0-R2 R.

■ -C-C-O- (Vll+) R.

Punishment CH2 -C-C-O- R,0 Xi CH2 Sanction CCOR20CN□ - Seki CH2-C-COR2 -O-C-N- [In each general formula, R1 is a hydrogen atom or a methyl group, and R2 has a carbon number of 1 -6 divalent aliphatic saturated hydrocarbon group, R3 represents a divalent hydrocarbon having 1 to 10 carbon atoms].

However, an unsaturated monomer having a glycidyl group, such as glycidyl methacrylate, can also be used in combination with an unsaturated monomer having an alicyclic epoxy group within a range that does not impair the characteristics of the present invention. Among (1) to (Xm), (I I +) is particularly preferred because it can be easily produced manually.

For example, ■ and ■ are METHB or AE by Daicel Chemical Industries, Ltd.
It is commercialized as THB.

Further, specific examples of ethylenically unsaturated monomers to be ternary copolymerized with an α-olefin compound and an unsaturated monomer having an alicyclic epoxy group include the following.

Vinyl esters such as vinyl acetate and vinyl propionate, vinyl compounds such as styrene and acrylonitrile,
Further examples include acrylic esters and methacrylic esters, but vinyl acetate is particularly preferred.

The radical polymerization catalyst used in the present invention generates radicals under polymerization conditions to cause a radical polymerization reaction of unsaturated monomers. It includes compounds that have.

Oxygen, hydrogen peroxide, organic peroxides, azo compounds, and the like are effective as such catalysts.

Among them, the general formula (blank below) x-o-o-y type x-c-o-o-y type ■ x-c-o-o-c-y type 1l1 x-o-c-o-o- y type and x-o-c-o-oc-y type +1 1 (wherein X is an aryl group, a derivative group thereof, an alkyl group,
Particularly effective are peroxides and azo compounds such as hydrogen, where X and Y may be the same or different.

In producing the polymer of the present invention, the reaction temperature is 40
~250°C.

At temperatures above 250°C, some cleavage of the epoxy groups occurs and the content of epoxy groups in the copolymer decreases.

If the polymerization temperature is below 40° C., the polymerization reaction rate becomes extremely slow and a large amount of catalyst is required, which is industrially disadvantageous.

The copolymerization reaction can be carried out without using a solvent, but it can also be carried out in the coexistence of an inert solvent such as ethane, propane, butane, heptane, hexane, etc. Copolymerization can also be carried out to make small amounts of propylene, butene-1, isobutyne, and other α-olefins present.

The reaction may be carried out either batchwise or continuously, but it goes without saying that a reaction vessel capable of withstanding high pressure is required.

(Effects of the Invention) The α-olefin copolymer having an alicyclic epoxy group obtained by the present invention has good compatibility with polyolefins, etc., and can be blended with other polyolefins to produce useful polyolefin compositions. Can you provide?

In addition, it has high adhesion to metals such as iron and aluminum, cellophane, paper, etc., so it can be used for laminates, bonded products, laminates, etc.

Furthermore, the α-olefin copolymer can be used to produce reinforced polyolefin compositions with improved mechanical strength, dimensional stability, heat resistance, cold resistance, etc. by adding fillers such as polyolefin and glass fiber or glass powder. Can be used.

Furthermore, it can be used as a solubilizing agent (by adding it to many thermoplastic molding resins such as polyester resins, polycarbonate resins, polyphenylene oxide resins, polystyrene resins, polyamide resins, and polymer alloys that are a blend of two or more of them). You can also do it.

Furthermore, it can be added to various composites made by mixing these polymer alloys with glass fibers, carbon fibers, glass powder, glass hollow particles, etc.

In particular, the epoxy group of the α-olefin copolymer having an alicyclic epoxy group of the present invention has excellent thermal stability, so the epoxy group will not be damaged even under high temperature and long-term cross-wire conditions. , polymer blends and fillers can be mixed sufficiently, resulting in excellent polymer compositions.

The α-olefin copolymer of the present invention is an antioxidant, a stabilizer, an antistatic agent, an ultraviolet absorber, an antiblocking agent,
Conventional additives and modifiers useful in conventional resin and plastics technology, such as lubricants, pigments, colorants, etc., can be included.

The present invention will be explained in detail below using examples.

However, the present invention is not limited to these in any way.

EXAMPLE In a 300 ml stainless steel autoclave equipped with a stirrer, 15 mg of cabrylyl peroxide and M
ETHB [Methacrylic acid ester having an alicyclic epoxy group, a part of Daicel Chemical Industries, Ltd. Structural formula % Formula % 6g1 7g of vinyl acetate and 24g of propane as a solvent were charged.

After that, ethylene was introduced to the appropriate pressure.
Start the internal stirrer and place the container in an oil bath for 19 minutes.
The reaction was started at 0° C. and a pressure of 1300 kg/cm 2 by starting the internal stirrer.

After 120 minutes, when the pressure dropped to 800 kg/cm2, the container was cooled, the pressure was released, and the ethylene-
12 g of METHB-vinyl acetate copolymer was obtained.

The infrared absorption spectrum of this copolymer shows an absorption at 1150 cm-1 characteristic of alicyclic epoxy groups and an absorption at 2900 cm"-1 characteristic of polyethylene, and acetic acid was detected due to hydrolysis of the copolymer. In addition, the results obtained from an infrared absorption spectrum calibration curve created based on elemental analysis and characteristic absorption of epoxy groups revealed that it contained 30% by weight of METHB and 5% by weight of vinyl acetate. Furthermore, when the oxirane oxygen content was measured by chemical analysis, it showed almost the theoretical value, and no cleavage of the epoxy group occurred during the polymerization reaction.

Comparative Example A terpolymer containing an epoxy group was obtained by carrying out the same reaction as in the example, replacing METHB with glycidyl methacrylate.

When the epoxy group concentration of the copolymer was measured, 5% of the epoxy groups had disappeared.

Claims (2)

[Claims] (1) (a) an α-olefin and (b) an unsaturated monomer having one or more alicyclic epoxy groups, and (c) one or more ethylenically unsaturated monomers using a radical polymerization catalyst. A copolymer obtained by copolymerization. (2) (a) an α-olefin and (b) an unsaturated monomer having one or more alicyclic epoxy groups, and (c) one or more ethylenically unsaturated monomers using a radical polymerization catalyst. A method for producing an α-olefin copolymer, characterized by copolymerization.