JPH06145260A - Modified polyolefin - Google Patents

Abstract

PURPOSE:To obtain a modified polyolefin useful as a modifier for various engineering plastics, having high reactivity and reaction efficiency, excellent compatibility with other polymers by grafting a specific monomer mixture onto a polyolefin. CONSTITUTION:(B) 0.01-20 pts.wt. (preferably 0.1-5 pts.wt.) monomer mixture of (i) 5-50(mol)% (preferably 10-30mol%) glycidyl acrylate and/or glycidyl methacrylate and (ii) 95-50(mol)% (preferably 90-70(mol)%) monomer such as acrylamide-based monomer, N-vinyl-N-containing heterocyclic compound, acrylic acid ester and methacrylic acid ester is grafted onto (A) 100 pts.wt. polyolefin composed of a homopolymer of an alpha-olefin (preferably ethylene or propylene) to give the objective modified polyolefin.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a modified polyolefin useful as a modifier for engineering plastics and the like. More specifically, the present invention relates to a modified polyolefin useful as a modifier for engineering plastics such as polyester and polyamide and a material for improving adhesion to fillers mixed in engineering plastics.

[0002]

2. Description of the Related Art Polyolefin is industrially manufactured at low cost and has excellent moldability, insulation properties, chemical resistance, mechanical strength, etc., and is therefore widely used in various applications such as films, fibers, and molded products. Has been. Further, in recent years, research has been actively conducted to obtain a resin composition having the characteristics of each polymer by melt-mixing two or more kinds of polymers having different properties, and a polyolefin is blended in order to utilize the characteristics. Many resin compositions have also been researched and developed. However, in the resin composition containing the polyolefin itself, the compatibility is poor because the polyolefin is non-polar, and it does not disperse uniformly even when simply kneaded, and the rigidity, impact resistance, elasticity, etc. are reduced. , The composition does not have the intended physical properties.

Therefore, in order to improve the compatibility of the polyolefin, the polyolefin or a mixture of the polyolefin and rubber has been modified with maleic anhydride, an unsaturated epoxy compound or the like (Japanese Patent Laid-Open Publication No. Sho.
50-52156, 52-105993, 58-50040, 58-677
43, JP-A 1-236214, etc.). However, in these modified polyolefins or modified olefin-based elastomers, during the production reaction, the decomposition reaction of the main chain of the polyolefin also proceeds at the same time, so only a low molecular weight modified product is obtained, and the maleic anhydride used for modification is also used. As for acid, etc., the monomer is sublimable and has an irritating odor.
Workability during melting reaction is not always good. Further, the modified polyolefin and the modified olefin-based elastomer thus obtained have a problem that they are not necessarily satisfactory as compatibilizers because it is difficult to sufficiently increase the graft ratio of maleic anhydride or the like.

Recently, a modified polyolefin and a modified olefin elastomer using a glycidyl ester of acrylic acid or methacrylic acid as a modifier have been proposed. Since these glycidyl acrylate (GA) and glycidyl methacrylate (GMA) have high reactivity and reaction efficiency, the graft ratio at the time of modification is high, and the modified polyolefin obtained is melt-mixed with the above-mentioned various engineering plastics. Has good dispersion compatibility and excellent physical properties.

[0005]

However, GA and G
Since MA has high homopolymerizability, it does not disperse in monomer units in the polyolefin during the grafting reaction during modification, but is grafted onto the polyolefin as a polymer, and as a result, reactive points are concentrated at specific points on the polymer. Therefore, there is a problem that the reactivity and the reaction efficiency of the modified polyolefin are lowered as a whole. Therefore, it is an object of the present invention to use the GA monomer and GM as a modifier.
Enhance the dispersibility of A monomer in polyolefin,
It is to provide a modified polyolefin having further excellent reactivity and reaction efficiency.

[0006]

Means for Solving the Problems As a result of intensive studies by the present inventors, by modifying the polyolefin by using another monomer having high compatibility with the reactive monomer (GA monomer or GMA monomer) in combination. The inventors have found that a modified polyolefin having excellent reactivity and reaction efficiency can be obtained in which a reactive monomer is well dispersed, and thus the present invention has been achieved.

That is, in the present invention, (B) 5 to 50 mol% of (b-1) GA and / or GMA, and (b-2) acrylamide monomer, N-vinyl, relative to 100 parts by weight of (A) polyolefin. Provided is a modified polyolefin obtained by graft-polymerizing 0.01 to 20 parts by weight of a monomer mixture consisting of 95 to 50 mol% of one or more monomers selected from -N-containing heterocyclic compounds, acrylic acid esters and methacrylic acid esters. It is a thing.

The modified polyolefin of the present invention will be described in detail below. The (A) polyolefin, which is a raw material of the modified polyolefin of the present invention, is a homopolymer of α-olefin (including ethylene), or a copolymer of two or more types of α-olefins such as random, block or graft, and those It is a copolymer of a mixture or a main part of an α-olefin and another unsaturated monomer, such as a random, block or graft copolymer, or an olefin elastomer. Here, as the α-olefin, ethylene, and propylene, butene-1, hexene-1, 3-methylbutene-
1,4-methyl-pentene-1, heptene-1, octene-1, decene-1 and the like. Among these polyolefins, a homopolymer of ethylene or propylene, a copolymer of ethylene and propylene, a copolymer of ethylene or propylene and other α-olefin, and an olefin elastomer are preferable.

As the ethylene polymer, low density polyethylene (LDPE), high density polyethylene (HDPE), linear low density polyethylene (LLDPE) and the like can be used. The polypropylene is not limited to a homopolymer of propylene but includes a block copolymer or a random copolymer of propylene and ethylene. The copolymer is an ethylene-propylene copolymer having an ethylene content of 20% by weight or less, and such polypropylene usually has a melt flow rate (MFR, JISK7210, load 2.16 kg, 230 ° C) of about 0.1 to 200 g / 10 minutes. )
Have. Further, these polyethylene and polypropylene may contain up to about 40% by weight of an olefinic elastomer described later.

The olefin elastomer means a copolymer rubber of ethylene and one or more α-olefins other than ethylene such as propylene, 1-butene, 1-hexene and 4-methyl-pentene. To do. The polymer rubber of ethylene and one or more kinds of α-olefins other than ethylene is typically ethylene-
Examples thereof include propylene copolymer rubber (EPR), ethylene-butene copolymer rubber (EBR), ethylene-propylene-diene copolymer rubber (EPDM) and the like. As the diene in the ethylene-propylene-diene copolymer rubber (EPDM), a non-conjugated diene such as dicyclopentadiene, 1,4-hexadiene, cyclooctadiene, methylenenorbornene or a conjugated diene such as butadiene or isoprene is used. be able to. In addition, these EPR,
The EBR and EPDM may contain other repeating units such as repeating units derived from other α-olefins such as 4-methyl-pentene-1 up to a proportion of 10 mol% or less.

In the present invention, the polyolefin (A) is
(B) As a modifier, (b-1) GA or GMA, and (b-2) the above GA or GMA is graft-copolymerized with another monomer having good compatibility. That is, by using together monomers that are mutually soluble at a relatively low temperature at which GA or GMA having high polymerizability does not initiate polymerization, homopolymerization of GA or GMA is suppressed and graft copolymerization is performed on polyolefin. . In the present invention, GA and GMA may be used together.

(B-2) Other monomers having high compatibility with GA or GMA include acrylamide type monomers,
Examples thereof include N-vinyl-N-containing heterocyclic compounds, acrylic acid ester-based monomers, and methacrylic acid ester-based monomers.

As the acrylamide type monomer, dialkyl acrylamide, dialkyl methacrylamide,
Examples thereof include monoalkyl acrylamide and monoalkyl methacrylamide, and examples of the N-vinyl-N-containing heterocyclic compound include N-vinylpyrrolidone (1-vinyl-2-pyrrolidone) and N-vinylphthalimide.
Examples of acrylic acid-based monomers include acrylic acid alkyl esters such as 2-hydroxyethyl acrylate, and examples of methacrylic acid alkyl esters include 2-hydroxyethyl methacrylate. These monomers are usually used alone, but may be used in combination. Among these monomers, 1-vinyl-2-pyrrolidone, dimethylacrylamide, 2-hydroxyethyl methacrylate and the like are preferably used.

In the present invention, the blending ratio of the component (b-1) reactive monomer and the component (b-2) other monomer is
(B-1) is 5 to 50 mol%, preferably 10 to 30 mol%, and (b-2) is 95 to 50 mol%, preferably 90 to 70 mol%. In the present invention, the component (b-1)
Is less than 5 mol% (component (b-2) is 95 mol%
, The reactivity becomes poor, and the component (b-
When 1) exceeds 50 mol% (the component (b-2) is less than 50 mol%), (b-1) is homopolymerized and the reaction efficiency decreases.

The component (B) modifier mixture consisting of the components (b-1) and (b-2) is graft-copolymerized with the component (A) polyolefin. The proportion of the polyolefin mixture as the component (A) and the modifier mixture as the component (B) is 0.01 to 10 parts by weight with respect to 100 parts by weight of the component (A),
It is preferably 0.1 to 5 parts by weight. If the amount of the component (B) is less than 0.01 parts by weight, it is difficult to achieve the effect of the modifier monomer, and if it exceeds 10 parts by weight, the grafting efficiency is significantly reduced.

The modified polyolefin of the present invention can be obtained by utilizing a known graft polymerization method such as a solution method or a melt kneading method. A specific example of the modification method will be described below.

In the melt-kneading method, a polyolefin (A), a modifier monomer (B) consisting of components (b-1) and (b-2) mixed in advance, and a catalyst, if necessary, are used and these components are used. Is charged into an extruder or a twin-screw kneader,
While heating to a temperature of about 150-250 ° C and melting,
The modified polyolefin can be obtained by kneading for about 0.1 to 20 minutes.

In the case of the solution method, the above-mentioned starting materials are dissolved in an organic solvent such as xylene and a catalyst is added to the solution to give 50 to 50 parts by weight.
The reaction is carried out at a temperature of about 200 ° C. for 0.1 to 100 hours with stirring. In this solution method, it is not necessary to previously mix the components (b-1) and (b-2). After the reaction, the modified polyolefin can be obtained by a conventional method such as pouring the polymer solution into an insoluble solvent.

The graft ratio of the modified polyolefin resin thus obtained is about 0.01 to 10% by weight.

In any of the methods, a conventional radical polymerization catalyst such as benzoyl peroxide, lauroyl peroxide, di-t-butyl peroxide, acetyl peroxide, t-butyl perbenzoate, dicumyl peroxide is used as a catalyst. Peroxides such as perbenzoic acid, peracetic acid, t-butyl perpivalate, and 2,5-dimethyl-2,5-di-t-butylperoxyhexyne, and azo such as azobisisobutyronitrile. Compounds and the like can be used. The amount of the catalyst added is about 0.1 to 50 parts by weight based on 100 parts by weight of all the monomers for modification. It is also possible to add a phenolic antioxidant during the above graft reaction.

[0021]

The modified polyolefin of the present invention is excellent in reactivity and reaction efficiency because the reactive monomer is well dispersed and grafted to the polyolefin. That is, when the polyolefin of the present invention is blended with another polymer to prepare a resin composition, modification sites (reaction points) that affect the compatibility are evenly distributed, and the polyolefin is polymer-alloyed with another polymer. At this time, the reaction points are uniformly dispersed, so that the compatibility is improved, and the physical properties of the obtained resin composition are considered to be excellent properties having the characteristics of each polymer.

[0022]

The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to the following examples. In the examples and comparative examples, the following raw material components and catalysts were used.

Polyolefin (1) Homopolypropylene (homo PP): Tonen Kagaku KK: Y201, MFR (230 ° C., 2.16 kg load) 1.5 g / 10 minutes. (2) High-density polyethylene (HDPE): Tonen Chemical Co., Ltd .: J6170, MI (190 ° C, 1.05 kg load) 7.5 g / 10 minutes. (3) Ethylene-propylene rubber (EPR): manufactured by Nippon Synthetic Rubber Co., Ltd .: EP02P, MFR (230 ° C, 2.
16 kg load) 3.2 g / 10 minutes.

[0024]Radical polymerization catalyst  POX: Perhexin 25B [manufactured by NOF CORPORATION].

Monomer (b-1) Glycidyl methacrylate (GMA).

Monomer (b-2) (1) Dimethylacrylamide (DMAA). (2) 1-vinyl-2-pyrrolidone (2-VP).

Examples 1-6, Comparative Examples 1-9 Monomers (b-1) (GMA) in proportions shown in Table 1 .
And a monomer (b-2) (DMAA, 2-VP) premixed with polyolefin (homo PP, HDP
E, EPR) and the catalyst (POX) were melt-kneaded at a screw rotation speed of 50 rpm and a temperature of 200 ° C. using a single-screw extruder (30 mmφ, L / D ratio of 23), and pelletized. Table 1 shows the melt flow rate of the polyolefin thus obtained and the evaluation of the compatibility with the polyester and the polyamide.

[0028]

[Table 1]

[0029]

[Table 2]

The compatibility evaluation method shown in Table 1 above was performed as follows. (1) Compatibility with Polyester 85 parts by weight of polybutylene terephthalate (Teijin: TRB-H) and the polyolefin resin obtained in Examples or Comparative Examples 15
After dry blending with parts by weight, this was melt-kneaded using a twin-screw extruder (30 mmφ, L / D ratio 42) at a screw rotation speed of 300 rpm and a temperature of 250 ° C., and pelletized. The area average dispersed particle size of the obtained resin composition was measured by a scanning electron microscope (SEM).

(2) Compatibility with Polyamide 80 parts by weight of polyamide (nylon 6) and 20 parts by weight of the polyolefin resin obtained in Examples or Comparative Examples were dry-blended, and then this was mixed with a twin-screw extruder (30 mmφ). , L /
D ratio 42) was used, and the mixture was melt-kneaded at a screw rotation speed of 300 rpm and a temperature of 250 ° C. and pelletized. The area average dispersed particle diameter of the obtained resin composition was measured by the same method as in the above (1).

As is clear from Table 1, the modified polyolefins (Examples 1 to 6) of the present invention comprising polyolefin, GMA and DMAA or 2-VP are small particles in polymer alloying with polyester and polyamide. As dispersed evenly. On the other hand, modified polyolefins (Comparative Examples 1, 4 and 7) radical-grafted with the same amount of GMA (0.2 parts by weight) as the GMA used in Examples, or the reactive monomer (0.7%) used in Examples. In modified polyolefins (Comparative Examples 2, 5 and 8) radical-grafted with more than 1.0 part by weight of GMA (1.0 parts by weight), the dispersion particle size of the polyolefin in the melt-kneaded product with polyester and polyamide is It can be seen that the modified polyolefin of the present invention has better compatibility than the conventional modified GMA alone.

[0033]

INDUSTRIAL APPLICABILITY The modified polyolefin of the present invention has high reactivity and reaction efficiency, has good compatibility with various engineering plastics, and is useful as a modifier for engineering plastics. Also, it is expected that the adhesiveness with various fillers such as glass fiber, carbon fiber, talc, calcium carbonate, and various whiskers, which are added to engineering plastics, will be good. Is also useful.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yuji Fujita 1-3-1 Nishitsurugaoka, Oi-cho, Iruma-gun, Saitama Tonen Research Institute

Claims (1)

[Claims] 1. (A) 5 to 50 mol% of (b) glycidyl acrylate and / or glycidyl methacrylate and (b-2) acrylamide monomer, N-vinyl-based on 100 parts by weight of polyolefin. N
95 or more monomers selected from containing heterocyclic compounds, acrylic acid esters and methacrylic acid esters
.About.50 mol% and a monomer mixture of 0.01 to 20
Modified polyolefin obtained by graft polymerization in parts by weight.