JPH0420556A - Polyphenylene sulfide resin composition - Google Patents

Abstract

PURPOSE:To prepare the title compsn. excellent in resistance to impact, heat, and solvent by mixing a polyphenylene sulfide resin having specified properties with an N-arylmaleimide-vinyl monomer copolymer. CONSTITUTION:The title compsn. is prepd. by mixing 90-10 pts.wt. polyphenylene sulfide resin having a ratio of the wt.-average mol. wt. (Mw) to the number- average mol.wt. (Mn) satisfying formula I, a melt flow rate (MF5) according to ASTM D1238-86 (at 315.5 deg.C, 5kg load) of 2000g/10 min or lower, and a retention of melt flow rate satisfying formula II; with 10-90 pts.wt. maleimide copolymer comprising 90-10wt.% N-arylmaleimide units and 10-90wt.% vinyl monomer units (e.g. an N-phenylmaleimide-styrene copolymer).

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Field of Application> The present invention relates to a polyphenylene sulfide resin composition having excellent impact resistance, heat resistance, and resistance to toughening agents.

<Prior art> Polyphenylene sulfide resin (hereinafter abbreviated as PPS resin) has properties suitable as a crystalline engineering plastic, such as excellent heat resistance, impact resistance and rigidity, in a reinforced system reinforced with glass fiber etc. It is used for various purposes, mainly injection molding. However, unreinforced PPS resin that is not reinforced with glass fiber or the like lacks toughness and is extremely brittle. Furthermore, the glass transition temperature is 90℃
Due to its low heat resistance, it is currently difficult to use it for various molding applications.

In recent years, various polymer combinations have shown that combining crystalline thermoplastic resins with non-grade thermoplastic resins with high glass transition points to form polymer alloys is an effective means of improving the lack of heat resistance of crystalline thermoplastic resins. ing. One of the non-grade thermoplastic resins suitable for such purposes is styrene/N-phenylmaleimide copolymer, and it is known that particularly useful resin compositions can be obtained by blending with polyamide resin. (e.g. Plastic Swage 1990
(January issue). Modification of PPS resin with maleimide resin is proposed in JP-A No. 61-9452, but here mainly a crosslinked type PPS resin is used, and maleimide resin improves the fluidity of PPS resin. It is only added as an agent, and the resulting resin composition has insufficient practical properties such as strength and impact resistance.

Problems to be Solved by the Present Invention> Therefore, the present inventors have developed a solution for ppsv! As a result of intensive study to obtain a resin material with excellent practical properties such as heat resistance, strength, impact resistance, and solvent resistance in the combination of J resin and maleimide resin, we decided to use PP5I! Molecular weight distribution of l-fat, melt flow rate value, retention rate of melt flow rate value, composition ratio of ppsm fat and maleimide copolymer, and N-arylmaleimide structural unit and vinyl system constituting the maleimide copolymer. We have discovered that by optimizing the composition ratio of the constituent units, it is possible to create a ppsm fat composition glue composition that has excellent impact resistance, heat resistance, and solvent resistance and can be used for molding applications, and has arrived at the present invention. .

Means for Solving the Problems〉 That is, the present invention solves the following problems: has a molecular weight distribution that satisfies the following formula (1), and ASTM
D1238-86 (315,5°C15,000g
The melt flow rate value (MF5) specified for the load) or 2. PP that is OOOg/101in or less and whose melt flow rate retention rate satisfies the following formula (2)
S resin 90-10% by weight and Mw/Mn<20
(1) 50<(MF5/MF+5)X100<150
(2) (Here, MF5 and MF+5 represent melt flow rate values at residence times of 5 minutes and 15 minutes, respectively.) (B) 90 to 10% by weight of N-arylmaleimide structural units and 10 to 90% of vinyl structural units. The present invention provides a PPS resin composition comprising 10 to 90% by weight of a maleimide copolymer.

The PPS resin (A) used in the present invention has a number average molecular weight (1 ml) and a weight average molecular weight (WW
), and has a molecular weight distribution that satisfies the following formula (1), and meets ASTM D1238-86 (315,5°C25
In order to achieve the object of the present invention, it is necessary that the melt flow rate value determined by extremely important.

Mw/Mn<20
(1) 50< (MF5/MF+5) X100・
150 (2) (here M
P 5 and M P Is represent melt flow rate values at residence times of 5 minutes and 15 minutes, respectively. ) A PPS resin composition made of a PPS resin and a maleimide copolymer that does not satisfy these conditions can hardly improve impact resistance, although improvements in heat resistance and solvent resistance can be observed.

Typical examples of PPS resins (^) that satisfy the above conditions include M2588 and M2888 manufactured and sold by Toshi Phillips Vetroleum Co., Ltd.
Next, the maleimide copolymer fB) used in the present invention is represented by the following formula (3).
-A copolymer consisting of an arylmaleimide structural unit and a vinyl structural unit represented by the following formula (4). These may be random copolymers or block copolymers.

-CH-CH- (X+ and , a methyl group, an ethyl group, a phenyl group, or a substituted phenyl group are generally used.) (Y represents an aryl group, a carboxyl group and its ester, a cyan group, etc.) R represents hydrogen or a methyl group. ) The maleimide copolymer (B) can be synthesized by, for example, copolymerizing an N-arylmaleimide monomer and a vinyl monomer, or by copolymerizing a vinyl copolymer containing maleic anhydride. A method of synthesis by reacting with aniline followed by dehydration and ring closure may be considered, but the method is not limited to these methods.

The N-arylmaleimide monomer used in the method of copolymerizing an N-arylmaleimide monomer and a vinyl monomer is expressed by the following formula (5) % Formula % Here, Xl and X2 are the above 5-membered Substituents having any chemical structure can be applied to the present invention as long as they have a ring imide structure, but usually hydrogen, bromine,
Chlorine, methyl group, ethyl group, phenyl group, and f-substituted phenyl group are generally used.

Vinyl monomers include styrene, P-methylstyrene,
Aromatic vinyl monomers represented by vinyltoluene, t-butylstyrene, α-methylstyrene, monobromostyrene, dipromostyrene, tribromostyrene, monochlorostyrene, dichlorostyrene, trichlorostyrene, dimethylstyrene, etc., methacryl Examples include (meth)acrylic acid ester monomers represented by methyl acid and methyl acrylate, and vinyl cyanide monomers represented by acrylonitrile and methacrylonitrile. Two or more of these monomers are mixed. It can also be used as Among these vinyl monomers, preferable single X monomers are:
Examples include styrene, α-methylstyrene, methyl methacrylate, and acrylonitrile, and a particularly preferred monomer is styrene from the viewpoint of heat resistance.

'X! Maleimide copolymer (B) from N-arylmaleimide monomer and vinyl monomer. There are no particular limitations on the method of a), and the preparation can be carried out by conventional emulsion polymerization, cloud polymerization, bath liquid polymerization, situational polymerization, and bulk-backside polymerization.

The maleic anhydride-containing vinyl copolymer used in the synthesis method by reacting the maleic anhydride-containing vinyl copolymer with anilines and then dehydrating and ring-closing the maleic anhydride-containing vinyl copolymer is a maleic anhydride-containing vinyl copolymer. It is a copolymer obtained by copolymerizing other polymerizable vinyl monomers, and contains maleic anhydride of the following formula (6).

Here, other vinyl monomers that can be copolymerized with maleic anhydride include styrene, p-methylstyrene, vinyltoluene, t-butylstyrene, α-methylstyrene, monobromostyrene, dipromostyrene, and tribromostyrene. Aromatic vinyl monomers represented by bromostyrene, monochlorostyrene, dichlorostyrene, trichlorostyrene, dimethylstyrene, etc.; (meth)acrylic acid ester monomers represented by methyl methacrylate, methyl acrylate, etc. and vinyl cyanide monomers represented by acrylonitrile, methacrylonitrile, etc., and two or more of these can also be used as a mixture.

Among these vinyl monomers, preferred monomers are styrene, α-methylstyrene, methyl methacrylate, and acrylonitrile, and a particularly preferred monomer is styrene from the viewpoint of heat resistance.

These maleic anhydride-containing vinyl copolymers are produced by conventional solution polymerization or bulk polymerization.

The anilines used for imidizing the maleic anhydride-containing vinyl copolymer are compounds represented by the following formula (7).

(X represents hydrogen, chlorine, methyl group, or methoxy group.

) Examples of these compounds include aniline, P-chloroaniline, P-toluidine, and P-methoxyaniline, and two or more of these can also be used in combination. Among these, aniline is particularly preferred.

The reaction for forming a maleimide copolymer by this method consists of the following two steps: a first reaction and a second reaction.

First reaction The second reaction, that is, the first reaction, is a ring-opening reaction in which aniline is added to the maleic anhydride unit of the maleic anhydride-containing vinyl copolymer, and a copolymer with adjacent carboxyl groups and amide groups is formed. be done.

The second reaction is a ring-closing reaction in which the carboxyl group and the amide group of the copolymer in which the carboxyl group and the amide group are adjacent are imidized by dehydration, thereby forming the maleimide copolymer (B). Dehydration means in the second reaction include physical dehydration by heating and chemical dehydration using a dehydrating agent.

Note that by adjusting the reaction conditions of the first reaction and the second reaction and the amount of aniline added, it is also possible to leave maleic anhydride in the maleimide copolymer (B).

The N-arylmaleimide structural unit in the maleimide copolymer (B) is preferably 10 to 90% by weight, particularly 30 to 70% by weight. If it is less than 10% by weight, the heat resistance of the resulting maleimide copolymer fB) will decrease, and if it exceeds 90% by weight, the impact resistance and chemical resistance of the PPS resin composition will decrease. unfavorable because it reduces

The resin composition of the present invention is obtained by blending a specific PPS resin (^) and a maleimide copolymer (B), but the blending ratio of these is 90 to 10 % by weight, especially 90 to 20% by weight, maleimide copolymer (B) 10 to 90% by weight, especially 10 to 80% by weight.
% by weight. If the amount of the PPS resin (^) is less than 10% by weight, a composition with very poor solvent resistance will be obtained, and if it is more than 90% by weight, the heat resistance will decrease, which is not preferable.

As described above, the PPS resin composition of the present invention is composed of each component (A) and (6), but if necessary, the PPS@fat composition paste composition of the present invention may be Fibrous reinforcing agents such as glass fiber, glass fiber, alumina fiber, silicon carbide fiber, ceramic fiber, asbestos fiber, gypsum fiber, metal fiber, carbon fiber, wollastenite,
Silicates such as sericite, kaolin, mica, clay, bentonite, asbestos, talc, alumina silicate, metal compounds such as alumina, silicon chloride, magnesium oxide, zirconium oxide, titanium oxide, calcium carbonate, magnesium carbonate, dolomite, etc. carbonate,
Sulfates such as KM calcium and barium sulfate, glass peas, boron nitride, silicon carbide, non-fibrous reinforcing agents such as Saroyan and silica, various flame retardants, crystallization accelerators (nucleating agents), mercaptosilane, vinylsilane, aminosilane ,
Silane coupling agents such as epoxy silane, antioxidants, heat stabilizers, ultraviolet absorbers, colorants, etc. can also be added.

The means for preparing the ppsl fat composition of the present invention is not particularly limited.
For example, a heating melt kneading method using a single screw extruder, twin screw extruder, kneader, Brabender, etc. is used. Among these, a melt-kneading method using a single-screw or twin-screw extruder is preferred. The melt-kneading temperature is preferably 280° C. or higher in order to sufficiently melt the PPS, and 340° C. or lower in order to prevent thermal decomposition.

The ppsm fat composition of the present invention obtained in this way is
Various conventionally known processing methods such as injection molding, extrusion molding, and foam molding are possible. In addition, it can be widely used as a molding material with excellent heat resistance, impact resistance, flammability, and moldability in industrial materials fields such as automobiles, electricity, electronics, and machinery.

<Examples> Hereinafter, the present invention will be further described in detail using examples. Unless otherwise specified, percentages, parts and ratios used in the examples represent percentages by weight, parts by weight and ratios by weight, respectively.

In addition, the Izot impact strength, heat distortion temperature,
Melt flow rate, molecular weight, molecular weight distribution, and solvent resistance were each measured by the following measuring methods.

Izot impact strength: ASTM D256 Heat distortion temperature: ASTM D648 Melt flow rate: ASTM D1238-86 (
(315.5°C, 5.000g load) Measurement of molecular weight and molecular weight distribution: Water
Solvent resistance was tested using a gel permeation chromatography device manufactured by S Company, using the method disclosed in Kobunshi Ronsen Vol. 44 <1987), February issue, pages 139-141.

Test: ASTM No. 1 dumbbell test Place the specimen in heptane at 25°C. After soaking in the water for 60 minutes, Observe whether or not rack occurs. did.

Reference Example 1 The PPS resin bulk powder not used in the present examples and comparative examples is shown below. Further, these characteristic values are shown in Table 1.

PP5-1: Manufactured by Toshi Phillips Petroleum Company M2588PPS-2: Manufactured by Toshi Phillips Vetroleum Company M2888PPS-3: Manufactured by Phillips Vetroleum Company P-4PPS-4: Manufactured by Phillips Vetroleum Company ■-1 Table 1 Reference Example 2 The method for preparing maleimide copolymers (B-1 to B-11) synthesized from the N-arylmaleimide monomer and vinyl monomer used in the present examples and comparative examples is shown below.

Among the raw material monomers shown in Table 2, 100 parts of a vinyl monomer mixture was dissolved in 100 parts of methyl ethyl ketone along with 0.3 parts of an initiator benzoyl peroxide, and the mixture was charged into a reaction tank and the temperature inside the tank was raised to 75%. Sufficient stirring was performed while maintaining the temperature at °C. Polymerization was carried out while a predetermined amount of N-arylmaleimide dissolved in 100 parts of methyl ethyl ketone was added dropwise at a predetermined rate to obtain maleimide copolymers (B-1 to B-11) having various compositions. .

Reference Example 3 A method for preparing a maleimide copolymer (B-12>), which is synthesized by reacting a maleic anhydride-containing vinyl copolymer with aniline and then subjecting it to dehydration ring closure, is shown below.

A polymerization tank equipped with a reflux condenser, a stirrer, and a dropping funnel was charged with 60 parts of styrene and 50 parts of methyl ethyl ketone, and after purging the inside of the system with nitrogen gas, the temperature was raised to 85°C.

On the other hand, separately 40 parts of maleic anhydride and 0 parts of benzoyl peroxide
．． A solution of 15 parts dissolved in 180 parts of methyl ethyl ketone was prepared and charged into a dropping funnel. While maintaining the tank internal temperature at 85° C. and stirring, a maleic anhydride-benzoyl peroxide-methyl ethyl ketone solution was continuously added from the dropping funnel over a period of 8 hours. After the addition, the temperature was kept at 85°C for an additional hour. A colorless and transparent viscous liquid was obtained.

When a portion of the polymer was sampled and the polymerization rate was measured by gas chromatography, it was found that styrene was 98% and maleic anhydride was 99%. The copolymer solution obtained here was added with 1.02 times equivalent amount of aniline 4 to maleic anhydride.
0.4 parts of triethylamine and 03 parts of triethylamine were added thereto and reacted at 160°C for 5 hours to obtain a maleimide copolymer (B-12). According to 13 C-NMR analysis, the conversion rate of acid anhydride groups to imide groups was 99.5%.

Examples 1 to 4 PPS-1 and the maleimide copolymers B-1, B-2, B-5, and B-8 prepared in Reference Example 2 were triblended with the compositions shown in Table 3, and 290 to 310 Using a co-rotating twin-screw extruder set at ℃, the screw rotation speed was 100 r.
Test pieces were molded by injection molding using an in-line screw molding machine using melt-kneaded and pelletized crab pellets under pn conditions (temperature condition setting: 290-31
0°C1 mold temperature: 140-150°C). Izot impact strength, heat distortion temperature, and
The solvent resistance test results are shown in Table 3.

Examples 5 to 8 Examples except that PPS-2 and the maleimide copolymers B-3, B-4, B-6, and B-7 prepared in Reference Example 2 were triblended with the composition shown in Table 3. Kneading, molding and measurement were carried out in exactly the same manner as in 1. The results are shown in Table 3.

Example 9 Kneading, molding, and measurement were performed in exactly the same manner as in Example 1, except that PPS-1 and the maleimide copolymer B-12 prepared in Reference Example 3 were triblended with the composition shown in Table 3. . The results are shown in Table 3.

As is clear from Table 3, the composition of the present invention (Example 1
Items 9) to 9) are excellent in Izot impact strength, heat deformation temperature, and solvent resistance in a balanced manner.

Comparative Example 1.2 Kneading was carried out in the same manner as in Example 1, except that PPS-3 and the maleimide copolymers B-1 and B-5 prepared in Reference Example 2 were triblended with the composition shown in Table 4. , molded and measured. The results are shown in Table 4.

Since the molecular weight distribution and the retention rate of the melt flow rate value deviate from the present invention, the Izot impact strength is lower than that of Example 1.
It has decreased significantly compared to .

Comparative Example 3 Kneading, molding, and measurement were carried out in the same manner as in Example 1, except that PPS-4 and the maleimide copolymer B-1 prepared in Reference Example 2 were triblended with the composition shown in Table 4. Ta. The results are shown in Table 4. Melt flow rate value (M
Since F5) exceeds 2°000 t/1011 in, the Izot impact strength is significantly lower than that of Example 1.

Comparative Example 4.5.6 Except that PPS-1 and PP5-2 and maleimide copolymers B-9, B-10, and B-11 prepared in Reference Example 2 were triblended with the composition shown in Table 4. Crosstalk, molding, and measurement were carried out in exactly the same manner as in Example 1. The results are shown in Table 4.

Comparative Example 4.5 has a lower heat distortion temperature than Example 1 because the N-arylmaleimide base unit in the maleimide copolymer is less than 10% by weight. Further, in Comparative Example 6, since the N-arylmaleimide structural unit in the maleimide copolymer exceeds 90% by weight, the Izot impact value is low, and cracks are observed in the solvent resistance test.

Comparative Example 7.8 Kneading, molding, and measurement were carried out in exactly the same manner as in Example 1, except that PPS-1 and maleimide copolymer B-1 prepared in Reference Example 2 were triblended with the composition shown in Table 4. Ta.

The results are shown in Table 4.

In Comparative Example 7, the PPS resin exceeds 90% by weight, so the heat distortion temperature is lower than that in Example 1. In Comparative Example 8, since the PPS resin content was less than 10% by weight, cracks were observed in the solvent resistance test.

<Effects of the Invention> The polyphenylene sulfide resin composition of the present invention has excellent impact resistance, heat resistance, and solvent resistance in balance.

Claims (1)

[Claims] (A) Number average molecular weight (@Mn@) determined by gel permeation chromatography using 1-chloronaphthalene as a solvent
and has a molecular weight distribution in which the ratio of weight average molecular weight (@Mw@) satisfies the following formula (1), and ASTM D1238-8
6 (315.5℃, 5,000g load), the melt flow rate value (MF_5) is 2,000g/10
90 to 10% by weight of polyphenylene sulfide resin whose retention rate of melt flow rate satisfies the following formula (2) and @Mw@/@Mn@<20(1) 50<(MF_5/MF_1_5) ×100<150(
2) (Here, MF_5 and MF_1_5 represent melt flow rate values at residence times of 5 minutes and 15 minutes, respectively.) (B) 90 to 10% by weight of N-arylmaleimide structural units and 0 to 90% of vinyl-based structural monopositions. A polyphenylene sulfide resin composition comprising 10 to 90% by weight of a maleimide copolymer.