JPH06287222A - Method for producing modified polyolefin - Google Patents

Abstract

(57) [Summary] [Structure] A polyolefin is represented by the formula (I) (wherein R ₁ and R ₂ represent a hydrogen atom, an alkyl group or an acyl group, or together with an adjacent nitrogen atom) in the presence of a radical initiator. To form a heterocycle, and R ₃ and R ₄ represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms) and are modified with an oxazoline compound represented by the following:
A method for producing a modified polyolefin having improved compatibility with a polymer selected from polycarbonate, polysulfone, polyphenylene sulfide, and polyphenylene oxide. [Chemical 1] [Effects] Excellent compatibility with various engineering plastics and adhesion with inorganic fillers, contributing to the improvement of physical properties of polymer alloys, exterior parts for automobiles, home appliances parts, industrial material parts, packaging materials, etc. It is useful as a raw material for producing a polymer alloy suitable for producing a molded product used as.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a modified polyolefin having excellent compatibility with different polymers.
The modified polyolefin obtained by the present invention is particularly useful for the production of polymer alloys, the production of composite materials in combination with various inorganic fillers such as glass fibers or metals, and the use as tyresin (binder resin).

[0002]

2. Description of the Related Art Polyolefin has the characteristics that it is lightweight, has excellent impact resistance, and has good environmental characteristics such as moldability, water resistance, and chemical resistance. Therefore, conventionally, an attempt has been made to form a material having superior characteristics by copolymerizing or blending with a different kind of polymer to form an alloy, combining with various inorganic materials to form a composite material, or laminating on a metal. Has been. However, polyolefin, which is a high molecular hydrocarbon, has poor compatibility with different types of polymers having characteristic groups, in particular, so-called engineering plastics such as polyamide, polyester, polyphenylene sulfide, and polyphenylene oxide. However, the impact resistance and mechanical strength are low, and there is a problem that surface peeling occurs in the molded product. Further, polyolefin alone has almost no adhesiveness to inorganic materials and metals.

Therefore, recently, a polyolefin is modified with a compound having a specific structure to be used as a polyolefin component, or a polyolefin thus modified is blended in a polymer alloy as a compatibilizer to improve the compatibility between the component polymers. Improvements are being made. As such modifier compounds, unsaturated carboxylic acids or their derivatives, particularly unsaturated dicarboxylic acid anhydrides such as maleic anhydride (MAH) are well known. However, the blending of the above modified polyolefin still fails to improve the mechanical properties and surface properties of the polymer alloy. Therefore, compounds that replace MAH are being investigated.

For example, JP-A-4-36345 and JP-A-4-59857.
No., No. 4-59858, etc.

[Chemical 2]

[In the formula, R ₅ represents a hydrogen atom or an alkyl group. ] A thermoplastic resin composition comprising a polyolefin-based elastomer or polypropylene modified with an unsaturated glycidyl compound represented by the following and polypropylene, polycarbonate, polyamide or polyester is described. Further, JP-A-4-159269 discloses the following formula

[0006]

[Chemical 3]

[Wherein R ₁ and R ₂ each represent a hydrogen atom, an alkyl group or an acyl group, or
₁ and R ₂ may combine with an adjacent nitrogen atom to form a heterocycle containing a nitrogen atom bonded to a benzene ring, R
₃ and R ₄ each represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. ] A reference example in which a polyolefin modified with a compound represented by the formula [1] is used as a compatibilizer for a polyolefin-polyamide polymer alloy is described.

[0008]

Means for Solving the Problems As a result of intensive investigations by the present inventors, it has been found that the modified polyolefin modified with the oxazoline compound has excellent compatibility with various engineering plastics other than polyamide, particularly polyester. The heading has arrived at the present invention.

[0009]

That is, according to the present invention, a polyolefin is represented by the following general formula (I) in the presence of a radical initiator.

[0010]

[Chemical 4]

[Wherein R ₁ and R ₂ each represent a hydrogen atom, an alkyl group or an acyl group, or
₁ and R ₂ may combine with an adjacent nitrogen atom to form a heterocycle containing a nitrogen atom bonded to a benzene ring, R
₃ and R ₄ each represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. ] A modified polyolefin having improved compatibility with a polymer selected from polyester, polycarbonate, polysulfone, polyphenylene sulfide and polyphenylene oxide, characterized by being modified with an oxazoline compound represented by

The polyolefins used for producing the modified polyolefin of the present invention include ethylene, propylene, 1
-Butene, 1-hexene, 3-methyl-1-butene, 4
-Homopolymers of α-olefins having 3 or more carbon atoms such as methyl-1-pentene, 1-heptene, 1-octene, 1-decene, styrene, etc., random, block, graft etc. of two or more kinds of these monomers Copolymers of ethylene, α-olefins having 3 or more carbon atoms and other unsaturated monomers, random copolymers, block copolymers and graft copolymers, or a mixture thereof.

Examples of ethylene polymers include high-pressure low-density polyethylene (LDPE), low-pressure high-density polyethylene (HDPE) and linear low-density polyethylene (LLDPE). Examples of propylene polymers include homo, block or random polypropylene.

Further, examples of the copolymer of two or more kinds of α-olefins include rubber (EPDM) made of a terpolymer of ethylene, propylene and diene, and ethylene-propylene copolymer rubber ( Examples thereof include EPR) and ethylene-butene copolymer rubber (EBR). Further, a propylene random copolymer (PPDM) containing a non-conjugated diene comonomer represented by the following general formula (III) can also be used as a polyolefin component.

[0015]

[Chemical 5]

[Wherein, R _{6 to} R ₉ are hydrogen atoms or alkyl groups having 1 to 6 carbon atoms, and m represents an integer of 1 to 20]. ]

Examples of styrene copolymers include styrene-butadiene-styrene block copolymer (SBS).
Hydrogenated product of styrene-ethylene-butylene-styrene block copolymer (SEBS), hydrogenated product of styrene-butadiene copolymer (SB), styrene-ethylene-butylene block copolymer (SEB), styrene- Hydrogenated product of isoprene copolymer (SI), styrene-ethylene-
A propylene block copolymer (SEP), a styrene-isoprene-styrene block copolymer (SIS) hydrogenated product, such as styrene-ethylene-propylene-styrene block copolymer (SEPS), has a polyolefin structure in the polymer. Examples include polymers. As the polyolefin containing an unsaturated monomer other than α-olefin,
For example, the above PPDM can be mentioned.

In the method for producing a modified polyolefin of the present invention, the above-mentioned various polyolefins are radical-grafted with a 2- (4-aminophenyl) -2-oxazoline compound represented by the general formula (I) to modify the polyolefin. . Here, examples of the alkyl group represented by R ₁ and R ₂ in the above formula (I) include methyl, ethyl, propyl, isopropyl, butyl, and isomers thereof, and examples of the acyl group include acryloyl, methacryloyl, Examples thereof include crotonyl group, and examples of the heterocycle containing a nitrogen atom include maleimide, itaconiimide, and 2,3-dimethylmaleimide group. In addition, R in the formula (I)
Examples of the alkyl group having 1 to 5 carbon atoms represented by ₃ and R ₄ include methyl, ethyl, propyl, isobutyl, butyl and isomers thereof, amyl and isomer groups thereof. Preferred oxazoline compounds include those represented by the following formulas (IV) to (VI).

2- (4-N-acryloylaminophenyl) -2-oxazoline:

[Chemical 6]

2- (4-N-methacrylaminophenyl) -4,4-dimethyl-2-oxazoline:

[Chemical 7]

2- (4-N-maleylaminophenyl)
-4,4-Dimethyl-2-oxazoline:

[Chemical 8]

Such an oxazoline compound can be produced, for example, by the method described in JP-A-4-159269, and these oxazoline compounds can be used alone or in combination of two or more kinds.

In the present invention, a usual radical initiator can be used as a catalyst for the modification reaction. Examples of such catalysts include benzoyl peroxide, lauroyl peroxide, di-t-butyl peroxide, acetyl peroxide, t-
Peroxides such as butylperoxybenzoic acid, dicumyl peroxide, peroxybenzoic acid, peroxyacetic acid, t-peroxypivalate, 2,5-dimethyl-2,5-di-t-butylperoxyhexyne, and azobis Diazo compounds such as isobutyronitrile are used. It is also possible to add a phenolic antioxidant.

The radical grafting can be carried out according to a known method except that the above oxazoline compound is used. A solution method or a melt-kneading method is known as such a radical grafting method, and any method can be used.

That is, in the case of the solution method, 100 to 1000 parts by weight of an organic solvent such as xylene is added to 100 parts by weight of a polyolefin, and the oxazoline compound 1 to 100 is added.
Parts by weight, preferably 10 to 50 parts by weight, catalyst 0.1 to 20
Parts by weight, preferably 1 to 10 parts by weight and polyolefin are dissolved, 50 to 200 ° C., preferably 80 to 150
10 minutes to 30 hours at a temperature of about ℃, preferably 30 minutes
Denaturation is carried out with stirring for 10 hours. After the reaction, the solvent is distilled off, or the polymer is isolated by a usual method of pouring the reaction solution into a solvent in which the polymer is insoluble.

In the melt-kneading method, polyolefin, the above-mentioned oxazoline compound, and a catalyst are used, and these components are charged into a melt-kneading device such as a single-screw extruder or a twin-screw extruder, preferably at 150 to 300 ° C. 180-2
While heating to a temperature in the range of 50 ° C and melting, 0.1-2
The modified polyolefin is obtained by kneading for about 0 minutes. The amount of the oxazoline compound is 0.1 to 20 parts by weight, preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the polyolefin, and the amount of the catalyst is 0.001 to 5 parts by weight, preferably
It is 0.01 to 1 part by weight.

The conditions such as the reaction temperature, the reaction time, the solvent in the solution method, the kneading method in the melt kneading method and the like can be appropriately changed depending on the polyolefin used and the amount thereof.

The modified polyolefin obtained by the method of the present invention has a melt flow rate (MFR, JISK7210, load 2.16 kg, 230 ° C.) of about 1 to 1000 g / 10 minutes, and various polymers and sub-micron fine dispersion. Compatibilize with. Therefore, it can be mixed with various polymers and used for producing a polymer alloy.

Examples of such polymers include polyester and various other engineering plastics such as polycarbonate, polysulfone, polyphenylene oxide, polyphenylene sulfide, etc. The compatibility improving effect is particularly remarkable in polyester.

Specifically, for example, by blending the modified polyolefin of the present invention and polyester, a molded article material excellent in impact resistance, heat resistance, mechanical strength, insulation and surface peeling resistance is produced. be able to. The modified polyolefin and the polyester can be compounded in the production according to a known method.

Polyester as the alloy component is a thermoplastic resin generally obtained by polycondensation of saturated dicarboxylic acid and saturated dihydric alcohol, such as polyethylene terephthalate, polypropylene terephthalate, polytetramethylene terephthalate (polybutylene terephthalate), Examples thereof include polyhexamethylene terephthalate, polycyclohexane-1,4-dimethylol terephthalate, and polyneopentyl terephthalate. Of these, polyethylene terephthalate and polybutylene terephthalate are preferred.

The terephthalic acid component in these polyesters may be substituted with an alkyl group, a halogen group or the like, and the glycol component may be up to about 50% by weight of other glycol such as 1%. , 4-butylene glycol, propylene glycol,
Hexamethylene glycol and the like may be contained.

Further, since the modified polyolefin obtained by the method of the present invention has excellent adhesiveness with various inorganic materials used as a reinforcing material for polymer alloys, it improves the addition effect of the reinforcing material and also improves the effect of adding a metal. It can also be used as an adhesive layer with a polyolefin. Specifically, for example, kneading glass fiber, talc, calcium carbonate, carbon fiber, mica, etc., iron, aluminum,
Copper, zinc, nickel, tin, stainless steel, brass, tinplate,
It can be laminated on a metal such as galvanized iron to form a composite material.

[0034]

EXAMPLES The present invention will be described in more detail with reference to Examples and Comparative Examples. In each of the examples and comparative examples, the following materials were used as raw materials and additives.

Polyolefin (1) Ethylene-propylene copolymer rubber (EPR): P0180 manufactured by Mitsui Petrochemical Co., Ltd., melt flow rate (M
FR, 230 ° C, 2.16 kg load) 8.1 g / 10 minutes, (2) Polyethylene homopolymer (HDPE): Tonen Chemical Co., Ltd. J6170, melt flow rate (MFR, 23
(0 ° C, 2.16 kg load) 11 g / 10 minutes, (3) Polypropylene homopolymer (PP): Y201 manufactured by Tonen Kagaku KK, melt flow rate (MFR, 230)
℃, 2.16kg load) 1.0 g / 10 minutes.

Polyester (1) Polybutylene terephthalate (PBT): TRB-H manufactured by Teijin Limited.

Oxazoline compound

(1) 2- (4-N-acryloylaminophenyl) -2-oxazoline (OZ-1)

[Chemical 9]

(2) 2- (4-N-methacrylaminophenyl) -4,4-dimethyl-2-oxazoline (OZ-
2)

[Chemical 10]

(3) 2- (4-N-maleylaminophenyl) -4,4-dimethyl-2-oxazoline (OZ-
3)

[Chemical 11]

Examples 1-5, Comparative Examples 1-3 Polyolefins, oxazolines and organic peroxides (D
CP: dicumyl peroxide) was dry-blended in the proportions shown in Table 1, and this was melt-kneaded using a twin-screw extruder having a diameter of 30 mm at a cylinder set temperature of 200 ° C. and a screw rotation speed of 200 rpm to obtain a polyolefin. Denaturation was performed. Table 1 shows the melt flow rate (MFR, 230 ° C., 2.16 kg load) of the obtained modified polyolefin.

[0042]

[Table 1]

Reference Examples 1 to 8 The compatibility between the modified polyolefin and the polyester was evaluated by the following method. The modified polyolefin obtained in the above example and polybutylene terephthalate were mixed at a weight ratio of 1: 4 using a Labo Plastomill at a temperature of 250 ° C. for 3 minutes. The average dispersed particle size of the polyolefin in the obtained polymer alloy was determined by image analysis of a scanning electron micrograph. For comparison, the modified polyolefin component is the unmodified polyolefin (EPR, HDPE, P
The same evaluation was performed in place of P) (Reference Examples 4, 6 and 8). The results are shown in Table 2.

[0044]

[Table 2]

[0045]

The modified polyolefin produced according to the method of the present invention has good compatibility with engineering plastics such as polyester and adhesion with inorganic fillers added as modifiers of these engineering plastics. It has excellent impact resistance, heat resistance, mechanical strength, insulation, and good surface properties such as resistance to surface peeling, making it ideal for exterior parts of automobiles, household electrical appliances, industrial material parts, packaging materials, etc. It is useful as a raw material for producing a polymer alloy suitable for producing a molded product to be used.

 ─────────────────────────────────────────────────── ─── 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 polyolefin represented by the following general formula (I) in the presence of a radical initiator: [Wherein R ₁ and R ₂ represent a hydrogen atom, an alkyl group or an acyl group, respectively, or R ₁ and R ₂ together with an adjacent nitrogen atom represent a nitrogen atom bonded to a benzene ring. To form a heterocycle containing R ₃ and R ₄ ,
Each represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. ] It is modified with the oxazoline compound shown by these, The manufacturing method of the modified polyolefin which improved the compatibility with the polymer selected from polyester, polycarbonate, polysulfone, polyphenylene sulfide, and polyphenylene oxide.