JPH0543653A - Polycaprolactone-grafted epoxy-modified copolymer and its production - Google Patents

Abstract

PURPOSE:To obtain the title copolymer which is an excellent compatibilizer for a polymer blend comprising a thermoplastic resin compatible with polycaprolactone and an engineering plastics by mixing a specified epoxy- modified copolymer with a modified polycaprolactone in a specified ratio. CONSTITUTION:This copolymer comprises 2-98 pts.wt. epoxy modified copolymer comprising an unsaturated epoxy monomer (e.g. glydicyl methacrylate) and at least one copolymerizable vinyl monomer (e.g. styrene) and 98-2 pts.wt. modified polycaprolactone having one carboxyl group or one hydroxyl group in the molecule (e.g. a compound prepared by reacting epsilon-caprolactone with butanol).

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel modified polycaprolactone-grafted copolymer having epoxy groups. Specifically, it is effective in providing a thermal overplastic resin excellent in impact resistance by effectively preventing delamination that occurs during molding in a polymer blend of a thermal overplastic resin compatible with polycaprolactone and an engineering plastic. The present invention relates to a novel copolymer grafted with polycaprolactone effective as a solubilizer.

[0002]

2. Description of the Related Art Polyamide resin, polyphenylene ether
Ter resin, aromatic polyester resin, polycarbonate resin, polyoxymethylene resin, ABS resin, polyarylene sulfide resin and polyarylate resin have excellent mechanical properties and chemical resistance. It is used in many fields because of its high heat resistance.

In recent years, various researches have been conducted in order to improve the function of products and to reduce the price. Among them, in order to add more functions, it is necessary to make use of the characteristics of each of a plurality of plastics. Is being attempted.

Polyamide resins have excellent properties such as moldability, heat stability, abrasion resistance and solvent resistance, and are widely used in various molded products. However, because of high hygroscopicity, there is a problem in dimensional stability and the like, which may limit the use.

On the other hand, polyphenylene ether resin is
It has excellent mechanical properties, electrical properties, heat resistance, and also has good dimensional stability, so it is useful as a molding compound resin, but it has poor processability, oil resistance, and impact resistance. That is a drawback. Further, the aromatic polyester resin is excellent in mechanical properties, rigidity and strength, but is inferior in impact resistance and heat resistance, and the polycarbonate resin is excellent in mechanical properties, heat resistance and impact resistance, Inferior in chemical resistance,
Polyoxymethylene resin has excellent dimensional stability and mechanical strength but poor impact resistance, ABS resin has excellent impact resistance, but poor chemical resistance, and polyarylenene sulfide resin has heat resistance and flame retardancy. It is excellent in ductility but poor in ductility and brittle, and the polyarylate-based resin is excellent in heat resistance but inferior in impact resistance.

Therefore, polyamide-based resin is replaced by polyphenylene ether-based resin, aromatic polyester-based resin, and polycarbonate.
Originally, by blending one or more resins selected from the group consisting of a bonnet resin, a polyoxymethylene resin, an ABS resin, a polyarylene sulfide resin and a polyarylate resin, While maintaining the advantages of polyamide-based resin, improve the drawbacks,
It is considered that an excellent resin composition having the advantages of other resins can be obtained.

For example, Japanese Patent Publication No. 45-997 proposes to blend a polyamide resin in order to improve the oil resistance and processability of the polyphenylene ether resin. The compatibility with polyamide resins is extremely poor, the resulting resin composition is inferior in mechanical properties (especially when the polyamide content exceeds 20%), and the molded product obtained by injection molding exhibits a delamination phenomenon. However, a preferable molded product cannot be obtained.

As a method for preventing the above-mentioned delamination phenomenon, a copolymer of a styrene compound and an α, β-unsaturated dicarboxylic acid anhydride, which is disclosed in JP-A-60-36150, is blended as a compatibilizer. Method, JP-A-60-
JP-A-64-48846, a method of blending ethylene or a copolymer of a styrene compound and an epoxy group-containing unsaturated compound as a compatibilizer described in JP-A-260649 and JP-A-62-27456. Epoxy group-containing olefin copolymer described and vinyl type (co)
The method of blending a multi-phase structural thermoplastic resin made of a polymer as a compatibilizing agent is relatively excellent, but the first is that foaming which may be caused by decomposition of dicarboxylic acid may occur during heat molding. However, the second and third effects are still insufficient in improving the impact resistance.

Further, Japanese Patent Publication No. 47-19101, Japanese Patent Publication No. 47-24465 and Japanese Patent Publication No. 48-56742.
Japanese Patent Publication No. 47-114661, Japanese Patent Laid-Open No. 56-114661.
-34756, JP-A-57-49657 and the like, by changing the compounding composition of the polyamide resin and the polyester resin depending on the purpose, or by using a fibrous reinforcing agent or an inorganic filler together as an additive. Attempts have been made to improve the problems when a polyamide resin and a polyester resin are combined, but the mechanical properties such as the delamination phenomenon of the molded product are insufficient.

Further, polyamide resin and polyaryle
JP-A-62-2 for improving the affinity of resin
77462 and JP-A-62-283146 disclose a method in which an epoxy group-containing ethylene copolymer and an acid anhydride-containing ethylene copolymer are used in combination.

Although these polymers are effective for imparting impact strength, they have the drawback that the rigidity and heat resistance of the composition tend to decrease.

Attempts have been made to improve the physical properties of other resins by combining them with polyamide-based resins, but since they have different chemical structures, they have no affinity and it is almost impossible to take advantage of their respective advantages. It was

[0013]

It is an object of the present invention to provide a thermal superplastic resin excellent in impact resistance, which prevents delamination occurring during molding in a polymer blend of a thermoplastic resin having compatibility with polycaprolactone and an engineering plastic. Another object of the present invention is to provide a novel copolymer grafted with polycaprolactone which is effective as a compatibilizer.

[0014]

Means for Solving the Problems As a result of intensive studies in view of the above-mentioned objects, the present inventors have found that they are effective as a compatibilizing agent in a polymer blend of a thermoplastic resin compatible with polycaprolactone and an engineering plastic. When an epoxy group-modified copolymer grafted with polycaprolactone, or a polycaprolactone-epoxy group-modified copolymer is reacted to produce a graft copolymer, one carboxylic acid per molecule as polycaprolactone or The inventors have found that stable production can be achieved by using a modified polycaprolactone having one hydroxyl group, and have reached the present invention.

That is, the present invention provides "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 a copolymer containing an epoxy group. And an epoxy group-containing copolymer grafted with polycaprolactone, and a method for producing the same. "

The present invention will be described in detail below.

An epoxy group-modified copolymer comprising an unsaturated epoxy group-containing monomer and at least one or more copolymerizable vinyl monomers used in the present invention.

Examples of the unsaturated epoxy group-containing monomer include glycidyl methacrylate, glycidyl acrylate, vinyl monomers having alicyclic epoxy, and the like. The copolymerizable vinyl-based monomer is styrene, α-methylstyrene, p-methylstyrene,
Aromatic vinyl monomers such as p-butyl styrene, halogenated styrene, and vinyl xylene; alkyl esters of acrylic acid or methacrylic acid having 1 to 7 carbon atoms, for example, (meth) acrylic acid methyl, ethyl, isopropyl, propyl. (Meth) acrylic acid ester monomers such as butyl, butyl and glycidyl ester; (meth) acrylonitrile monomers; vinyl ester monomers such as vinyl acetate and vinyl propionate; (meth) acrylamide monomers;
Examples thereof include one or more selected from vinylic monomers such as maleic anhydride, maleic acid monoesters and diesters. Among them, especially aromatic vinyl monomers,
(Meth) acrylic acid ester monomer, (meth) acrylonitrile monomer and vinyl ester monomer are preferably used.

A so-called known radical copolymerization is used as a polymerization method for obtaining the epoxy-modified copolymer of the present invention. A specific method of this radical copolymerization is appropriately selected from solution polymerization, emulsion polymerization, bulk polymerization, suspension polymerization and the like.

The weight average molecular weight of the above epoxy modified copolymer is preferably 5,000 to 150,000, and the amount of epoxy groups in the epoxy modified copolymer is preferably 5 to 50 mol%. The weight average molecular weight is measured by gel permeation chromatography (GPC) method and converted into standard polystyrene.

The epoxy group-containing material is obtained from the analytical value of the oxirane oxygen concentration. Weight average molecular weight is 5
If it is less than 000, the effect of improving the compatibility is insufficient,
If it exceeds 150,000, the melt viscosity becomes high and the molding processability deteriorates, which is not preferable. If the epoxy group content is less than 5 mol%, reactivity with polycaprolactone is low and a graft copolymer is less likely to be produced, which is not preferable. On the other hand, if it exceeds 50 mol%, the reactivity of the epoxy-modified copolymer becomes too high, the melt viscosity of the reaction product increases, and the epoxy-modified copolymer alone tends to form a gel, which is not preferable.

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 200000 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 the modified polycaprolactone having one carboxylic acid in one molecule, the modified polycaprolactone having one hydroxyl group in one molecule can be reacted with the acid anhydride.

Since the epoxy group-modified copolymer grafted with polycaprolactone of the present invention has a graft chain,
It is difficult to measure its molecular weight accurately, but gel
The weight average molecular weight of 6000 to 200,000 is preferable as the molecular weight converted to standard polystyrene, which is determined by the measurement chromatography (GPC) method.

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

In the present invention, in order to graft-polymerize the above polycaprolactone and the epoxy-modified copolymer,
A method such as a melt-kneading method or a melting method can be used. In the case of the melt kneading method, polycaprolactone and the epoxy-modified copolymer are uniaxial extruder, biaxial extruder, Banbury mixer, kneading roll, brabender, kneader.
Using a kneading machine such as the above, kneading is performed at 150 to 300 ° C. in a heated state.

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

In the present invention, the amount of polycaprolactone and the epoxy-modified copolymer compounded is 2 to 98 parts by weight, preferably 20 to 80 parts by weight, whereas the latter is 98 parts by weight.
˜2 parts by weight, preferably 80 to 20 parts by weight.

Less than 2 parts by weight of polycaprolactone or 9
If it is more than 8 parts by weight, the amount of the graft copolymer produced will be small.

The epoxy-modified copolymer obtained by grafting the polycaprolactone thus obtained has a high graft ratio, and is a polyester resin or an aromatic polycarbonate.
, A styrenic resin, an ABS resin and / or an AS resin, or a thermoplastic resin which is compatible with a polycaprolactone such as polyvinyl chloride, and a good blending agent in a polymer blend of an engineering plastic, and generally both of them. 1 to 30 parts by weight is added per 100 parts by weight in total.

If this ratio is less than 1 part by weight, the resin-dispersed state in the polymer-blend becomes non-uniform, the mechanical properties of the resulting molded article are not satisfactory, and the appearance defects such as delamination of the surface occur. Occurs.

On the other hand, if the amount exceeds 30 parts by weight, the excellent heat resistance and mechanical properties inherent in each resin in the polymer blend are impaired.

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

The modified polycaprolactone and the epoxy-modified copolymer used as the raw materials in each example were as follows.

(1) Modified polycaprolactone PCL-1: 98 parts by weight of ε-caprolactone, butano-
0.8 parts by weight and tetrabutyl titanate 0.00
0.57 wt% of unreacted ε-caprolactone obtained by charging 2 parts by weight and reacting at 190 ° C. for 6 hours under a nitrogen atmosphere, 1 in 1 molecule of OH value 5.6 mg KOH / g.
Modified polycaprolactone having one hydroxyl group (number average molecular weight 14,000) PCL-2: 96 parts by weight of ε-caprolactone, butano-
1.5 parts by weight and tetrabutyl titanate 0.00
An acid value of 13.6 mg KOH / g was obtained by charging 2 parts by weight of the reaction mixture at 190 ° C. for 6 hours in a nitrogen atmosphere, further adding 3 parts by weight of phthalic anhydride and reacting at 90 ° C. for 1 hour.
Polycaprolactone having one carboxylic acid in one molecule of (1) (2) Epoxy modified copolymer Copolymer 1: Copolymer of glycidyl methacrylate and styrene (Blemma-CP20S, Japan Yushi Co., Ltd., glycidyl methacrylate content 20.0 mol%, epoxy equivalent 752, number average molecular weight 5300) Copolymer 2: Glycidyl methacrylate, copolymer of styrene and acrylonitrile (Blemma-CP10SA,
Nippon Oil & Fats Co., Ltd., glycidyl methacrylate content 1
0.0 mol%, epoxy equivalent 1500, number average molecular weight 6
900) Copolymer 3: Glycidyl Methacrylate, Styrene, Copolymer of Styrene, Methyl Methacrylate and Butyl Methacrylate (Blemma-CP15, NOF Corporation, Glycidyl Methacrylate Content 15.0 mol) %, Epoxy equivalent 10
00, number average molecular weight 6600) Copolymer 4: Glycidyl methacrylate, a copolymer of acrylonitrile and methyl methacrylate (Blemmer C)
P20MA, manufactured by NOF CORPORATION, glycidyl methacrylate content 20.0 mol%, epoxy equivalent 750, weight average molecular weight 4200) Note that the weight average molecular weight is measured by the GPC method and is in terms of polystyrene. Sought as.

[0035]

Examples-1 to 8 As shown in Table 1, the modified polycaprolactone and the epoxy modified copolymer are in a weight ratio of 30/7.
The ratio is 0, and these are used by a Brabender at 180 ° C. and 60
The graft reaction was allowed to proceed by melt-kneading at rpm for 5 minutes.

The epoxy-modified copolymer grafted with the obtained polycaprolactone was increased from the epoxy equivalent of the corresponding non-grafted epoxy-modified copolymer, which confirmed that the grafting was carried out. ..

Table 1 Example 1 2 3 4 5 6 7 7 8 PCL-1 30 − 30 − 30 − 30 − PCL-2 − 30 − 30 − 30 − 30 Copolymer 1 70 70 − − − − − − Copolymer 2 − − 70 70 − − − − Copolymer 3 − − − − 70 70 − − Copolymer 4 − − − − − − 70 70 Epoxy equivalent 1103 1150 2280 2370 1480 1525 1100 1155 Number average molecular weight 6200 6200 7800 7700 7600 7800 5600 5500 Weight average molecular weight 14300 16400 17400 17200 16100 16000 14700 14900 Note: In Table 1, PCL-1, PCL-2 and copolymers 1-4
The amount of is in parts by weight, PCL-1 and PCL-2 represent modified polycaprolactone, and copolymers 1 to 4 represent modified epoxy copolymers.

[0038]

As described above in detail, in the present invention, an epoxy group-modified copolymer comprising an unsaturated epoxy group-containing monomer and at least one copolymerizable vinyl monomer and one molecule It was possible to obtain an epoxy group-modified copolymer polycaprolactone grafted with polycaprolactone, which is characterized by comprising a modified polycaprolactone having one carboxylic acid or one hydroxyl group therein.

The novel copolymer grafted with the polycaprolactone of the present invention thus obtained is a polyester resin, an aromatic polycarbonate, a styrene resin,
It is possible to enable extremely excellent dispersion in a polymer blend of a thermoplastic resin having compatibility with ABS resin and / or AS resin or polycaprolactone such as polyvinyl chloride, and engineering plastic such as polyamide resin, and mechanically. It is extremely effective as a compatibilizer for obtaining a thermoplastic resin having high impact resistance as well as not deteriorating various performances such as performance. (Below margin)

Claims (3)

[Claims] 1. An epoxy group-modified copolymer comprising 2 to 98 parts by weight of an unsaturated epoxy group-containing monomer and at least one or more copolymerizable vinyl monomers, and 1 per molecule.
An epoxy group-modified copolymer grafted with polycaprolactone, which comprises 98 to 2 parts by weight of modified polycaprolactone having one carboxylic acid or one hydroxyl group. 2. The method for producing an epoxy group-modified copolymer grafted with polycaprolactone according to claim 1, wherein the unsaturated epoxy group-containing monomer and at least one or more copolymerizable vinyl monomers are used. 2 to 98 parts by weight of an epoxy group-modified copolymer consisting of 1 to 98 parts by weight of modified polycaprolactone having one carboxylic acid or one hydroxyl group in one molecule are reacted in a heated state. Method. 3. The content of the unsaturated epoxy group-containing monomer in the epoxy group-modified copolymer is 5 to 50 mol%, and the content of at least one or more copolymerizable vinyl monomer is 95 to.
The epoxy group-modified copolymer grafted with polycaprolactone according to claim 1, which is 5 mol%.