JP3051212B2 - Novel compatibilizer composed of polycaprolactone grafted copolymer - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a compatibilizer comprising a copolymer grafted with a modified polycaprolactone having an epoxy group. More specifically, it effectively prevents delamination that occurs during molding in a polymer blend of a thermoplastic resin compatible with polycaprolactone and an engineering plastic, and is effective in providing a thermoplastic resin with excellent impact resistance. The present invention relates to a novel compatibilizer comprising a copolymer grafted with a novel polycaprolactone.

[0002]

2. Description of the Related Art Polyamide resins, polyphenylene ether resins, aromatic polyester resins, polycarbonate resins, polyoxymethylene resins, ABS resins, polyarylene sulfide resins and polyarylate resins are excellent machines. It is used in many fields because of its excellent properties, chemical resistance, heat resistance and the like.

[0003] In recent years, various researches have been carried out in order to enhance the functions of products and reduce prices, and among others, in order to add more functions, it is necessary to make use of the characteristics of each of a plurality of plastics. Have been tried.

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

On the other hand, polyphenylene ether resins are
Excellent in mechanical properties, electrical properties, heat resistance, and good dimensional stability, so it is useful as a molding resin, but poor in workability, oil resistance and impact resistance That is a disadvantage.

Aromatic polyester resins are excellent in mechanical properties, rigidity and strength, but are inferior in impact resistance and heat resistance. Polycarbonate resins are excellent in mechanical properties, heat resistance and impact resistance. Poor chemical properties, polyoxymethylene resin has excellent dimensional stability and mechanical strength but poor impact resistance, ABS resin has excellent impact resistance, but poor chemical resistance, polyarylene sulfide resin Is heat resistant,
It is excellent in flame retardancy but poor in ductility and brittle, and the polyarylate resin has excellent heat resistance, but has a drawback of poor impact resistance.

Therefore, the polyamide resin is selected from the group consisting of polyphenylene ether resin, aromatic polyester resin, polycarbonate resin, polyoxymethylene resin, ABS resin, polyarylene sulfide resin and polyarylate resin. By blending one or two or more resins, while maintaining the advantages inherent in polyamide resins, the disadvantages are improved,
It is considered that an excellent resin composition having the advantage of another resin can be obtained.

For example, it has been proposed in Japanese Patent Publication No. 45-997 to blend a polyamide resin in order to improve the oil resistance and processability of the polyphenylene ether resin. Is extremely poor in compatibility, the resulting resin composition has poor mechanical properties (especially when the polyamide content is more than 20%), and the molded product obtained by injection molding shows a delamination phenomenon. Goods are not obtained.

As a method for preventing the above-mentioned layered peeling phenomenon, a copolymer comprising a styrene compound and an α, β-unsaturated dicarboxylic anhydride disclosed in JP-A-60-36150 is blended as a compatibilizer. Method, JP-A-60-
No. 260649 and Japanese Unexamined Patent Publication No. Sho 62-27456, in which a copolymer comprising ethylene or a styrene compound and an epoxy group-containing unsaturated compound is blended as a compatibilizer. Epoxy group-containing olefin copolymer described and vinyl (co)
The method of blending a multi-phase thermoplastic resin composed of a polymer as a compatibilizer is relatively excellent, but the first is that foaming that may be caused by decomposition of dicarboxylic acid may occur during heat molding. Unfavorably, the second and third effects are still insufficient in improving the impact resistance.

[0010] Japanese Patent Publication No. 47-19101, Japanese Patent Publication No. 47-24465, and Japanese Patent Publication No. 48-56742.
JP, JP-B-47-114661, JP-A-56
JP-A-34756, JP-A-57-49657 and the like can be used by changing the composition of the polyamide resin and the polyester resin depending on the purpose, or by using a fibrous reinforcing material or an inorganic filler as an additive in combination. Attempts have been made to solve the problems when a polyamide resin and a polyester resin are combined, but the molded product is insufficient in mechanical properties such as delamination.

Further, in order to improve the affinity between the polyamide resin and the polyarylate resin, JP-A-62-2
JP-A-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. These polymers are effective for imparting impact strength, but have the drawback that the rigidity and heat resistance of the composition are liable to decrease.

Although attempts have been made to improve the physical properties of other resins by combining them with polyamide resins, they have little affinity because of their different chemical structures, so that the advantages of each can hardly be exploited. Was.

[0013]

An object of the present invention is to provide a thermoplastic resin excellent in impact resistance which prevents delamination occurring during molding in a polymer blend of a thermoplastic resin compatible with polycaprolactone and an engineering plastic during molding. It is an object of the present invention to provide a novel compatibilizing agent comprising a copolymer grafted with an effective polycaprolactone.

[0014]

Means for Solving the Problems The inventors of the present invention have made intensive studies in view of the above object, and as a result, have found that an alicyclic ring effective as a compatibilizer in a polymer blend of a thermoplastic resin having compatibility with polycaprolactone and an engineering plastic. A novel compatibilizer comprising a copolymer grafted with polycaprolactone having an epoxy group has been found, and the present invention has been achieved.

That is, the present invention relates to a modified polycaprolactone (A) having one vinyl group and one alicyclic epoxy group at one end in one molecule, and at least one or more aromatic vinyl monomers (B And a novel compatibilizing agent comprising a copolymer obtained by grafting polycaprolactone obtained by copolymerizing at least one of these and other copolymerizable vinyl monomers (C).

The present invention will be described in detail below. The modified polycaprolactone having one vinyl group and one alicyclic epoxy group in one molecule at the terminal used in the present invention is represented by the above formula (1), for example, by the method described in Japanese Patent Application No. 2-320255. Can be synthesized. Examples of commercially available products include CYCLOMER M-101 manufactured by Daicel Chemical Industries, Ltd., and these can be used.

As the aromatic vinyl monomer, styrene,
One type or two or more types selected from α-methylstyrene, p-methylstyrene, p-butylstyrene, halogenated styrene, vinyl xylene, and the like are exemplified.

Other copolymerizable vinyl monomers include alkyl esters of acrylic acid or methacrylic acid having 1 to 7 carbon atoms, such as methyl, ethyl, isopropyl, propyl, butyl and glycidyl esters of (meth) acrylic acid. (Meth) acrylic ester monomers such as; (meth) acrylonitrile monomers; vinyl ester monomers such as vinyl acetate and vinyl propionate; (meth) acrylamide monomers; maleic anhydride and maleic acid monomers One or two or more selected from vinyl monomers such as esters and diesters. Among them, (meth) acrylate monomers, (meth) acrylonitrile monomers and vinyl ester monomers are particularly preferably used.

The copolymer as a novel compatibilizer of the present invention comprises a modified polycaprolactone having one vinyl group and one alicyclic epoxy group in a molecule at one end and an aromatic vinyl monomer. The content of the modified polycaprolactone having one vinyl group and one alicyclic epoxy group in one molecule as an essential component is 1 to 70 mol%, preferably 2 to 50 mol%.

A modified polycaprolactone having one vinyl group and one alicyclic epoxy group at one terminal in one molecule is
If it is less than mol%, the effect of improving impact resistance and the effect of preventing delamination are insufficient, which is not preferable. When the content of the modified polycaprolactone having one vinyl group and one alicyclic epoxy group in one molecule exceeds 70 mol%, the effect of improving the impact resistance is sufficiently obtained, but the heat resistance is lowered, which is not preferable. .

A vinyl (co) polymer containing 50% by weight or more of a vinyl aromatic monomer is the most preferred embodiment for improving the hygroscopicity of a polyamide resin.

As a polymerization method for obtaining the copolymer as the compatibilizer of the present invention, a known radical copolymerization is used. A specific method of this radical copolymerization is further appropriately selected from solution polymerization, emulsion polymerization, bulk polymerization, suspension polymerization and the like.

Since the copolymer as the compatibilizer of the present invention has a graft chain, it is difficult to measure its molecular weight accurately, but it is difficult to measure the molecular weight by gel permeation chromatography (GP).
As the molecular weight in terms of standard polystyrene determined by the method C), a number average molecular weight of 5,000 to 200,000 is preferable.

The thus obtained copolymer which is a compatibilizer of the present invention is a polyester resin, an aromatic polycarbonate, a styrene resin, an ABS resin and / or an AS resin or a polycaprolactone such as polyvinyl chloride. It has a good compatibilizing effect between a thermoplastic resin having compatibility and an engineering plastic such as a polyamide resin, and generally has 1 to 30 parts by weight per 100 parts by weight of the total of both resins.
Add in parts by weight.

If this ratio is less than 1 part by weight, the dispersion state between the resins in the polymer blend becomes non-uniform, the mechanical properties of the resulting molded product are not satisfactory, and appearance defects such as surface delamination occur. . On the other hand, if it exceeds 30 parts by weight, excellent heat resistance and mechanical properties inherent to each resin in the polymer blend will be impaired.

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. In the following examples, parts and% indicate parts by weight and% by weight, respectively.

Example 1 A 2 liter flask equipped with a reflux condenser, a stirrer, a thermometer and a nitrogen inlet tube was charged with 1163 parts of ion-exchanged water and 5 parts of polyvinyl alcohol (polymerization degree 500). Was heated and dissolved. After cooling, 563 parts of styrene, 63 parts of CYCLOMER M101 (manufactured by Daicel Chemical Industries) and 5 parts of benzoyl peroxide were added, and a polymerization reaction was performed at 90 ° C. for 5 hours while stirring.
Thereafter, the reaction product was washed with water, dried under reduced pressure, and Mn = 3930.
0, Mw = 99200, and 595 parts of a copolymer having an epoxy equivalent of 3095 were obtained.

(Example-2) In Example 1, 359 parts of styrene, CYCLOMER
M101 (manufactured by Daicel Chemical Industries) except that 267 parts were used, and Mn = 57400, Mw
= 273600, epoxy equivalent 740 copolymer
0 parts were obtained.

Example 3 382 parts of styrene and CYCLOMER in Example 1
Except that 162 parts of M101 (manufactured by Daicel Chemical Industries) and 55 parts of acrylonitrile were used, the same procedure as in Example 1 was carried out to obtain 580 parts of a copolymer having Mn = 54400, Mw = 177,000 and epoxy equivalent of 1160.

(Example-4) In Example 1, 415 parts of styrene, CYCLOMER
M101 (manufactured by Daicel Chemical Industries) 154 parts, methyl methacrylate 25 parts, n-butyl methacrylate 32
Except for changing the part, the same procedure as in Example 1 was carried out, and Mn = 42
000, Mw = 119000, and 600 parts of a copolymer having an epoxy equivalent of 1268 were obtained.

(Example-5) 417 parts of xylene, 359 parts of styrene, and CYCL were blown into a 2 liter flask equipped with a reflux condenser, a stirrer, a thermometer and a nitrogen introducing tube while blowing nitrogen.
The temperature was raised to 110 ° C. while stirring 267 parts of OMER M101 (manufactured by Daicel Chemical Industries, Ltd.), and 40 parts of xylene in which 10 parts of azobisisobutylnitrile were dissolved were successively added dropwise.
The polymerization reaction was performed for 10 hours. After cooling, the precipitate was reprecipitated in methanol, dried under reduced pressure, and Mn = 6800, Mw = 132.
Thus, 610 parts of a copolymer having an epoxy equivalent of 751 was obtained.

[0032]

As described above in detail, the novel compatibilizer of the present invention comprises a modified polycaprolactone having one vinyl group and one alicyclic epoxy group at one terminal in one molecule, and at least one kind of And a copolymer obtained by grafting polycaprolactone obtained by copolymerizing one or more vinyl monomers which can be copolymerized with these aromatic vinyl monomers.

The copolymer obtained by grafting polycaprolactone, which is a novel compatibilizer of the present invention, thus obtained is a polyester resin, an aromatic polycarbonate, a styrene resin, an ABS resin and / or an AS resin or a polystyrene resin. Extremely excellent dispersion can be achieved in a polymer blend of a thermoplastic resin compatible with polycaprolactone such as vinyl chloride and an engineering plastic such as a polyamide resin, and not only does the performance such as mechanical performance decrease It is extremely effective for obtaining a thermoplastic resin having high impact resistance. In addition, it is extremely effective not only as a polymer blend type but also as a modifier for improving the fluidity and imparting flexibility of a thermoplastic resin having compatibility with polycaprolactone.

──────────────────────────────────────────────────の Continuation of the front page (51) Int.Cl. ⁷ identification code FI C08L 63/00 C08L 63/00 (58) Field surveyed (Int.Cl. ⁷ , DB name) C08L 1/00-101/14 C08F 12/00-12/36 C08F 212/00-212/36 C08F 20/00-20/70 C08F 220/00-220/70 C08F 290/00-290/14 C08F 299/00-290/08 C08G 59 / 00-59/72

Claims (3)

(57) [Claims] 1. A modified polycaprolactone (A) having one vinyl group and one alicyclic epoxy group at one end in one molecule, at least one or more aromatic vinyl monomers (B), and A novel compatibilizer comprising a copolymer obtained by grafting a polycaprolactone obtained by copolymerizing at least one vinyl monomer (C) copolymerizable with another vinyl monomer (C). 2. The copolymer according to claim 1, wherein the content of (A) is 1 to 70 mol%, the content of (B) is 99 to 30 mol%, and the content of (C) is 0 to 60 mol%. A novel compatibilizing agent comprising the polycaprolactone-grafted copolymer described above. 3. A modified polycaprolactone having one vinyl group and one alicyclic epoxy group in one molecule is represented by the following general formula: The novel compatibilizing agent comprising the polycaprolactone-grafted copolymer according to claim 1, represented by << R is H or CH ₃ , n = 1 to 20 >>.