JPH059298A - Polyolefin copolymer grafted with polycaprolactone and preparation thereof - Google Patents

Abstract

PURPOSE:To prepare stably a graft copolymer with a high grafting ratio from a modified polycaprolactone and a modified polyolefin. CONSTITUTION:A modified polycaprolactone having a carboxylic acid and a hydroxyl group in the molecule is grafted with a modified polyolefin copolymer containing an epoxy or carboxyl group in the proportion of 2-98 to 98-2 parts by weight.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition of an engineering plastic such as polycarbonate and a polyolefin, and a copolymer obtained by grafting polycaprolactone effective as a compatibilizing agent for both, and a resin composition thereof. More particularly, it relates to a method for stably producing a graft copolymer having a high graft ratio from a modified polycaprolactone and a modified polyolefin.

[0002]

Aromatic polycarbonates have excellent impact resistance, heat resistance, rigidity and dimensional stability, but have the disadvantages of poor solvent resistance and moldability.

In order to obtain a composition having well-balanced mechanical properties while covering these drawbacks, various studies have been conducted on blending with polyolefin.

However, polyolefins and polycarbonates
Since the compatibility with the bone is not so good, it has been attempted to add various third components in order to improve the compatibility. For example, JP-A-57-108151 discloses butyl rubber as various third components to be added to a composition of a polycarbonate resin and a polyolefin resin. Further, JP-A-57-108152 discloses an ethylene / propylene copolymer and / or an ethylene / propylene / diene copolymer, and JP-A-57-1113.
No. 51 discloses isobutylene rubber and / or methylpentene polymer.

However, none of these third components is sufficient as a compatibilizing agent for the polycarbonate resin and the polyolefin, and the impact resistance of the molded article is not only sharply lowered when the amount of the polyolefin is increased. The problem of surface peeling also occurs.

Further, various compositions in which polyester and / or modified polyolefin and the like are added to aromatic polycarbonate have been disclosed (Japanese Patent Laid-Open No. 22425/1986).
No. 5, No. 61-225246, No. 61-238847.
issue).

However, since neither of these compositions contains polyolefin, there is a problem that the solvent resistance is poor.

Japanese Unexamined Patent Publication No. 64-75547 discloses that 95 to 5% by weight of aromatic polycarbonate and 5 to 9 of polyolefin.
5% by weight, 2 to 100 parts by weight of the modified polyolefin, based on 100 parts by weight of the aromatic polycarbonate and the polyolefin, and 100 parts by weight of the aromatic polycarbonate and the polyolefin. 2 to
Disclosed is a thermoplastic resin composition containing 100 parts by weight of polybutylene terephthalate.

In this composition, the modified polyolefin and the polybutylene terephthalate form a graft copolymer, and this graft copolymer is an aromatic polycarbonate.
It provides a good compatibilization between the polyolefin and the polyolefin.

Further, 2 to 98 parts by weight of polyester and 98 to 2 parts by weight of a modified polyolefin containing a carboxyl group or an epoxy group are melt-kneaded and 40 to 150 ° C. from the melting point of the polyester in an inert atmosphere.
Disclosed is a method for producing a polyolefin-polyester graft copolymer which can be used as a good compatibilizing agent for a polycarbonate resin and a polyolefin by subjecting it to a heat treatment at a low temperature for 1 to 100 hours. (JP-A-3-81333).

Further, 2 to 98 parts by weight of polyester,
When reacting with 98 to 2 parts by weight of a modified polyolefin containing a carboxyl group or an epoxy group, 0.01 to 5 parts by weight of an acid catalyst is added to 100 parts by weight of the polyester and the modified polyolefin. , A method for producing a polyolefin-polyester graft copolymer which can be used as a good compatibilizing agent for a polycarbonate resin and a polyolefin (JP-A-3-81334).

However, the above-mentioned Japanese Laid-Open Patent Publication No. 3-81333.
In the method for producing a polyolefin-polyester graft copolymer described in JP-A No. 3-81334 and JP-A No. 3-81334, a reaction for increasing the graft ratio due to gelation due to the presence of functional groups at both ends of the polyester. Is difficult to control.

The present invention provides a polycaprolactone-grafted copolymer as a compatibilizing agent.
It has been found that the polycarbonate resin can be blended with the thermoplastic resin with significantly improved compatibility.

[0014]

OBJECT OF THE INVENTION The object of the present invention is to provide a process for producing a polycaprolactone-polyolefin copolymer from a modified polyolefin and a modified polycaprolactone, which is characterized in that the graft ratio thereof can be improved and the product can be stably produced. To do.

[0015]

Means for Solving the Problems As a result of intensive studies in view of the above-mentioned objects, the present inventor has found that when a graft copolymer is produced by reacting polycaprolactone with a modified polyolefin, the amount of polycaprolactone is 1 The present inventors have found that the use of a modified polycaprolactone having one carboxylic acid or one hydroxyl group improves the grafting ratio and enables stable production, and has reached the present invention.

That is, according to the present invention, "2-98 parts by weight of modified polycaprolactone having one carboxylic acid or one hydroxyl group in one molecule and a modified polyolefin copolymer 98 containing an epoxy group or a carboxyl group are used. ~ 2
And a polycaprolactone-grafted polyolefin copolymer and a method for producing the same ”.

The present invention is described in detail below.

The polycaprolactone used in the present invention is a modified polycaprolactone having one carboxylic acid or one hydroxyl group in one molecule and has a number average molecular weight of 50.
In the case of modified polycaprolactone having a hydroxyl group of 0 to 200,000 and having one hydroxyl group in one molecule, monovalent alcohol and caprolactone can be reacted in the presence of a polymerization catalyst. Further, in the case of modified polycaprolactone having one carboxylic acid in one molecule, modified polycaprolactone having one hydroxyl group in one molecule can be reacted with an acid anhydride.

The modified olefin used in the present invention is a polyolefin obtained by copolymerizing an unsaturated monomer having a carboxyl group or an epoxy group.

Examples of unsaturated monomers having a carboxyl group include unsaturated carboxylic acids or their anhydrides, such as monocarboxylic acids such as acrylic acid and methacrylic acid, dicarboxylic acids such as maleic acid, fumaric acid and itaconic acid. Examples thereof include dicarboxylic acid anhydrides such as maleic anhydride and itaconic anhydride, and dicarboxylic acid and its anhydride are particularly preferable.

Further, unsaturated monomers having an epoxy group
Examples thereof include methacrylic acid glycidyl ester and acrylic acid glycidyl ester.

The olefin copolymerizable with the unsaturated monomer having a carboxyl group or an epoxy group is ethylene, propylene, butene-1, pentene-1.
And olefins such as.

These olefins can be used alone or in admixture of two or more. In addition, if necessary, 10% by weight or less of vinyl acetate,
Monomers such as isoprene, chloroprene and butadiene may be added.

Among these modified polyolefins, copolymers of ethylene with acrylic acid, maleic anhydride, glycidyl methacrylate, etc. are particularly preferable.

The carboxyl group- or epoxy group-containing modified polyolefin may be a block copolymer, a graft copolymer, a random copolymer or an alternating copolymer. In the case of the graft copolymer, the polyolefin serving as the main chain. It is preferable to carry out graft copolymerization by melt-kneading the above unsaturated monomer.

The modified olefin has a weight average molecular weight of 8
000 to 300,000 is preferable, and the amount of the carboxyl group or epoxy group in the modified polyolefin is 0.1 to 2
It is preferably 0 mol%.

The weight average molecular weight is measured by gel permeation chromatography (GPC) method and converted into unmodified polyolefin.

The carboxy group content is determined from elemental analysis values, and the epoxy group content is determined from oxygen elemental analysis values. Weight average molecular weight is 8000
If it is less than 300, the effect of improving the compatibility is insufficient, and 300
If it exceeds 000, the melt viscosity becomes high and the molding processability deteriorates, which is not preferable.

If the carboxyl group or the epoxy group is less than 0.1 mol%, the reactivity with polycaprolactone is low and the graft copolymer is hardly formed, which is not preferable.

In the present invention, an acid catalyst may be added to the polycaprolactone and the modified polyolefin. Examples of the acid catalyst include sulfuric acid, phosphoric acid, hydrogen fluoride, organic sulfonic acid and the like. Among these, organic sulfonic acids are preferable, and p-toluenesulfonic acid is particularly preferable.

In the present invention, a method such as a melt kneading method or a melting method can be used for graft-polymerizing the above polycaprolactone and the modified polyolefin.

In the case of the melt kneading method, polycaprolactone,
And modified olefins with a single-screw extruder, a twin-screw extruder,
Banbury mixer, kneading roll, brabender, knee
Knead in a heated state using a kneader such as a dough.

In the case of the solution method, the above starting materials are dissolved in an organic solvent such as xylene, and the solution is stirred at a temperature of 80 to 140 ° C.

In the present invention, the compounding amounts of polycaprolactone and modified polyolefin are 2 to 98 parts by weight for the former, preferably 20 to 80 parts by weight, and 98 for the latter.
˜2 parts by weight, preferably 80 to 20 parts by weight.

When the amount of polycaprolactone is less than 2 parts by weight or more than 98 parts by weight, the amount of graft copolymer produced is small.

The polycaprolactone-grafted polyolefin copolymer thus obtained has a high graft ratio and is good as a compatibilizing agent for engineering plastics such as polycarbonate resin and polyolefin and is generally used. 1 to 30 per 100 parts by weight of both
Add in parts by weight.

The present invention will be described in more detail by the following examples.

The modified polycaprolactone and modified polyolefin used as raw materials in each example were as follows.

(1) Production of modified polycaprolactone PCL-1: 96 parts by weight of ε-caprolactone, butano-
1.5 parts by weight, and tetrabutyl titanate 0.0
Unreacted ε-caprolactone obtained by reacting 02 parts by weight in a nitrogen atmosphere at 190 ° C. for 6 hours has 0.45% by weight, and has one hydroxyl group in one molecule having an OH value of 10.7 mgKOH / g. Modified polycaprolactone (weight average molecular weight 17300) PCL-2: 98 parts by weight of ε-caprolactone, butano-
0.8 parts by weight and tetrabutyl titanate 0.0
0.5 parts by weight of unreacted ε-caprolactone obtained by reacting 02 parts by weight of the mixture with each other at 190 ° C. for 6 hours in a nitrogen atmosphere was added in an amount of 0.57% by weight, and OH value was 5.7 mgKOH / g per 1 molecule.
Modified polycaprolactone having one hydroxyl group (weight average molecular weight 30600) PCL-3: 96 parts by weight of ε-caprolactone, butano-
1.5 parts by weight, and tetrabutyl titanate 0.0
02 parts by weight were charged and reacted at 190 ° C. for 6 hours in a nitrogen atmosphere.
Acid value obtained by reacting for 13.6 mgKOH /
Modified polycaprolactone having one carboxylic acid in one molecule of g (weight average molecular weight 16700) (2) Modified polyolefin PO-1: a copolymer of glycidyl methacrylate and ethylene [Bondfast E, Sumitomo Chemical Co., Ltd. Co., Ltd., glycidyl methacrylate content 4.0 mol%, weight average molecular weight 263000] PO-2: copolymer of glycidyl methacrylate and ethylene [LEXPAR RA3150, Nippon Oil Co., Ltd.] PO- 3: Copolymer of maleic anhydride and ethylene [Bondaine FX8000, manufactured by Sumitomo Chemical Co., Ltd.]
The weight average molecular weight was measured by the GPC method, and was calculated as a polyethylene conversion value for the modified polyolefin and as a polystyrene conversion value for the modified polycaprolactone.

[0040]

Examples-1 to 8 As shown in Table 1, the modified polycaprolactone and the modified polyolefin are contained in a weight ratio of 30/7.
The ratio was 0, 50/50, and 70/30, and these were melt-kneaded with a Brabender at 150 ° C. and 60 rpm to proceed the graft reaction.

The graft ratio of the obtained polycaprolactone-grafted polyolefin copolymer was measured.

The graft ratio is a value obtained by isolating unreacted polycaprolactone in the reaction product as a xylene-soluble component and obtaining the amount of the remaining xylene-insoluble component by the following formula.

Graft ratio = (insoluble matter of xylene-amount of modified polyolefin used) / insoluble matter of xylene × 100
(Wt%) Table 1 Example 1 2 3 4 5 6 7 7 8 Modified polycaprolactone (parts by weight) PCL-1 30 − − − − − − − PCL-2 − − 30 50 70 30 PCL-3 − 30 − − − 30 30 − Modified polyolefin (parts by weight) PO-1 70 70 − − − − − − PO-2 − − 70 50 30 70 70 − PO-3 − − − − − − − 70 Melt time (min) 5 5 5 5 5 5 30 5 5 Graft ratio (wt%) 9.5 12.5 9.3 18.6 29.6 14.5 15.6 14.4

[0044]

As described above in detail, in the present invention,
When a modified polycaprolactone is used in obtaining a polyolefin copolymer grafted with polycaprolactone, the graft ratio is high and stable production is possible.

The polyolefin copolymer grafted with the polycaprolactone of the present invention thus obtained is extremely effective as a compatibilizer for engineering plastics such as polycarbonate resin and polyolefin. (Below margin)

Claims (4)

[Claims] 1. 2 to 98 parts by weight of modified polycaprolactone having one carboxylic acid or one hydroxyl group in one molecule and 98 to 2 parts by weight of modified polyolefin copolymer containing an epoxy group or a carboxyl group. A polyolefin copolymer grafted with polycaprolactone, comprising: 2. The polyolefin copolymer grafted with the polycaprolactone according to claim 1, wherein the modified polyolefin copolymer is 0.1 to 20 mol% of an unsaturated carboxylic acid, an anhydride thereof or an epoxy group. A polyolefin copolymer grafted with polycaprolactone, which is a polyolefin modified with an unsaturated compound. 3. A method for producing a polyolefin copolymer grafted with polycaprolactone, comprising 2 to 98 parts by weight of modified polycaprolactone having one carboxylic acid or one hydroxyl group in one molecule, an epoxy group or a carboxyl group. Group-containing modified polyolefin copolymer 9
A method comprising reacting 8 to 2 parts by weight. 4. The method for producing a polyolefin copolymer grafted with polycaprolactone according to claim 3, wherein the modified polyolefin copolymer is 0.1 to 2
A process characterized in that it is a polyolefin modified with 0 mol% of an unsaturated carboxylic acid, its anhydride or an epoxy group-containing unsaturated compound.