JPS63205357A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To enable molded products having high mechanical strengths to be formed by stabilizing melt viscosity during molding, by blending a polyphenylene sulfide and/or a block copolymer composed of a polyphenylene sulfide moiety and a polyphenylene sulfide sulfone moiety with a maleimide compd. CONSTITUTION:100pts.wt. polyphenylene sulfide (a) and/or block copolymer (a) composed of a polyphenylene sulfide moiety and a polyphenylene sulfide sulfone moiety are/is blended with 0.1-20pts.wt. maleimide compd. (b) formula I (wherein R i s an arom. alicyclic or aliph. org. group; X1 and X2 are each H, halogen or an alkyl group; n is 1-10).

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention provides polyphenylene sulfide (hereinafter abbreviated as PPS) that stably increases melt viscosity and has excellent moldability.
and/or a block copolymer consisting of a polyphenylene sulfide moiety and a polyphenylene sulfide sulfone (hereinafter abbreviated as ppss) moiety, and a maleimide compound. It relates to resin compositions used for electronic parts, mechanical parts, automobile parts, miscellaneous parts, etc.

[Conventional technology and problems]

PPS is known as a high-performance engineering plastic that has excellent chemical resistance, heat resistance, electrical insulation, and the like.

In addition, the block copolymer of PPS and PP5S is PPS
It is an excellent engineering plastic that has a low molding shrinkage rate and a low coefficient of thermal expansion while maintaining almost the same performance as that of 100%, and has a high elastic modulus retention at high temperatures.

PPS and block copolymers of pps and ppss are
Special Publication No. 45-3 '368 and Special Patent Application No. 60-252
However, it is known that the resulting polymer has a low molecular weight, sufficient strength, and low viscosity, making it difficult to even produce pellets. Therefore, a method has been used to increase the molecular weight of synthesized low-molecular-weight polymers by subjecting them to oxidative thermal crosslinking in air at a temperature below their melting point, thereby increasing the strength of molded products and improving their moldability. Currently, polymers with high molecular weight obtained by this method are used industrially. However, the high molecular weight polymer obtained by this oxidative crosslinking does not have sufficient stability of melt viscosity, making it difficult to obtain good strands during pellet production, resulting in a stable supply of pellets to the feeder during injection molding. It can cause problems in terms of sexuality, etc.

Also known is a method of directly increasing the molecular weight using only a polymerization reaction, such as in JP-A-53-136100. However, a large amount of polymerization catalyst is required, and the polymer purification process is complicated and costly, which is a problem.

[Means for solving problems]

In view of the above-mentioned circumstances, the present inventors have conducted intensive research and found that the viscosity of a block copolymer of 'pps and/or PPS and ppss can be stably thickened, and that it can be easily adjusted and has improved mechanical properties. The present invention was achieved by discovering a maleimide compound as a compound that can be used.

That is, the present invention provides (a) PPS and/or PP
100 parts by weight of a block copolymer of S and ppss and (
b) A maleimide compound represented by the following general formula (1) 0.
A thermoplastic resin composition comprising 1 to 20 parts by weight is provided.

The pps used in the present invention can be obtained by various known methods. For example, its production methods include polymerizing p-dichlorobenzene in the presence of sulfur and sodium carbonate, sodium sulfide, sodium bisulfide and sodium hydroxide, hydrogen sulfide and sodium hydroxide, or sodium amino acid in a polar solvent. Examples include polymerization in the presence of an alkanoate, and self-condensation of p-chlorothiophenol. A common method involves reacting p-dichlorobenzene with p-dichlorobenzene. At this time, in order to adjust the degree of polymerization, an alkali metal salt of carboxylic acid or sulfonic acid or an alkali hydroxide may be added. As long as the copolymerization component is less than 30 moles, meta-bonds may also be present within a range that does not significantly affect the crystallinity of the polymer. When a trifunctional or more functional phenyl, biphenyl, naphthyl sulfide bond, etc. is selected for copolymerization, the amount is preferably 3 molar or less, more preferably 1 molar or less.

As a specific method for producing such pps, for example, (1)
Reaction of a halodane-substituted aromatic compound with an alkali sulfide (see U.S. Patent No. 2,513,188, Japanese Patent Publication No. 44-27671 and Japanese Patent Publication No. 45-3368), (2) in the coexistence of an alkali catalyst or copper salt of thiophenols, etc. (3) condensation reaction of an aromatic compound with sulfur chloride in the presence of a Lewis acid catalyst (see Japanese Patent Publication No. 46-27255 and Belgian Patent No. 46-27255 and Belgian patent). No. 29437
(see No.), (4) Furthermore, Special Publication No. 12240/1983,
Methods for producing high molecular weight type pps known from Japanese Patent Publication No. 54-8719 and Japanese Patent Publication No. 53-25588 can also be applied.

The block copolymer of PPS and ppss in the present invention can be obtained by, for example, reacting the terminal group of ppss with the terminal group of pps, as disclosed in Japanese Patent Application No. 60-252857. , it is necessary to make the terminal group of PPS a reactive group such as a sodium sulfide group (structural formula: NaS -). As a method for obtaining such PPS, there is a method in which the monomer is sulfurized in advance during the polymerization reaction in such a manner that the amount of the IJium component is 1 to 20 molar excess relative to the p-dichlorobenzene component.

Defined as a rimmer. The molecular weight of this polymer is the logarithmic viscosity ηinh (where ηinh is 0.5/1007
phenol/1.1 at a polymer concentration of solution d
．． The value was measured at 30° C. in a mixed solvent of 2.2-tetrachloroethane (3:2 weight ratio) and calculated according to the following formula: ηinh = Ln (relative viscosity)/polymer concentration. ) is preferably in the range of 0.05 to 1.0. The polymerization method for this polymer includes, for example, a method in which a dihaloaromatic sulfone and an alkali metal sulfide are reacted in an organic amide solvent (US Pat. No. 410,287).
(See No. 5).

PP5 used when synthesizing the block copolymer of the present invention
S has, for example, a 1+Ct group at the end of the polymer, and the method for obtaining it is to use a condition in which the amount of dihaloaromatic sulfone is in excess of, for example, 5 moles relative to the amount of alkali metal sulfide during the polymer synthesis reaction. (see US Pat. No. 4,301,274).

When carrying out the copolymerization reaction of ppss and PP5O in the method of the present invention, it is also permissible to use a method of adding a binder such as dihaloaromatic sulfone or sulfurized IJium as a third component. In addition, PPS and ppss, which are block copolymers, may be used without departing from the purpose of the present invention.
It is also possible to use a method in which the other heptamer component is polymerized in the presence of one of the polymers to finally obtain a copolymer.

Furthermore, when carrying out the copolymerization reaction, it is most preferable to make the number of terminal reactive groups of PPS and ppss the same, since a block copolymer can be obtained with good yield. On the other hand, when the number of terminal groups of either component is excessive, only the block copolymer can be recovered by fractionating or extracting only the unreacted homopolymer component after the reaction is completed.

The maleimide compound used in the present invention has the following general formula (
This is a compound represented by 1).

The maleimide compound represented by the above formula can be produced by a known method of preparing maleamic acid by reacting maleic anhydride with a monoamine or polyamine, and then cyclodehydrating the maleamic acid. As for the amines to be used, aromatic amines are preferred from the viewpoint of heat resistance of the final composition, but alicyclic or aliphatic amines may be used if flexibility is desired. Examples of preferred maleimide compounds include phenylmaleimide, N,N'-(methylenedi-p-7enylene) simaleimide, N,N'-(oxydyl-phenylene)simalimide, N,N'-m-7enylene dimaleimide, NJJ '-p-7 e=enzimaleimide, N+N'
-m-quizylene dimaleimide, N,N'-p-quizylene dimaleimide, N,N'-hexamethylene dimaleimide, and a compound represented by the following general formula (2).

(n=0.1-10) The amount of the maleimide compound added is suitably 0.1-20 parts by weight per 100 parts by weight of PPS and/or block copolymer of PPS and ppss.

If the amount of the maleimide compound added is less than 0.1 parts by weight, the thickening effect will not be sufficient, and if it is more than 20 parts by weight, it will have a significant adverse effect on moldability, which is not preferred.

In order to improve the performance as an engineering plastic such as strength, heat resistance, and dimensional stability, the composition of the present invention may contain an arbitrary filler of up to 70% by weight. Specifically, fillers include glass fibers, carbon fibers, potassium titanate, asbestos, silicon carbide, ceramic fibers, metal fibers, fibrous reinforcements such as silicon nitride, barium sulfate, calcium sulfate, kaolin, clay, and pyrophyllite. , bentonite, sericite,
Zeolite, mica, mica, nephelinsinite, talc, atalpulgite, wollastonite, PMF,
Inorganic fillings such as ferrite, calcium silicate, calcium carbonate, magnesium carbonate, dolomite, antimony trioxide, titanium oxide, magnesium oxide, iron oxide, molybdenum dioxide, graphite, lithium carbonate, gypsum, glass beads, glass balloons, quartz powder, etc. Examples include organic reinforcing agents such as aramid fibers. When adding these reinforcing agents or fillers, known silane coupling agents can be used. In addition, additives having an effect on thermal stability such as a compound having a benzotriazole group or an imidazole group, or a carposiimide compound can be used.

The composition of the present invention may also include a small amount of epoxy resin, a mold release agent, a coloring agent, a heat stabilizer,
It can contain ultraviolet stabilizers, foaming agents, flame retardants, flame retardant aids, rust preventives, and the like.

The composition of the invention can be prepared in various known ways. For example, the raw materials may be uniformly mixed in advance using a mixer such as a tumbler or Henschel mixer, fed to a single or twin screw extruder, melted and kneaded at 0 to 400°C, and then pelletized. You can take it.

〔Effect of the invention〕

Since the composition of the present invention has a stable melt viscosity during molding, it has excellent moldability and can provide molded products with high mechanical strength.

〔Example〕

Next, the present invention will be specifically explained using Examples, but the present invention is not limited only to these Examples.

(Reference Example-1) (Manufacture of PP8) IJum (60% purity) 984F, sodium hydroxide 4711 were added to N-methylpyrrolidone 308 (l), and the temperature was raised while dehydrating to 205°C. Chlorbenzene 11131.N-Methylpyrrolidone 510
After adding y, the mixture was heated at 262° C. for 5 hours under pressure, and after cooling, it was washed with water and dried. The obtained PPS had a melt viscosity of 150 poise. This is called Polymer A.

Polymer A was thermally crosslinked in air at 270°C for 5 hours, and the melt viscosity was 440. O Poise (Polymer B
)Met.

(Reference Example-2) (Manufacture of PPS) Sodium sulfide (60% purity) 984#, sodium hydroxide 47g, and lithium acetate dihydrate 765y were added to N-methylpyrrolidone 3080.9 and dehydrated to 205°C. After raising the temperature, p-dichlorobenzene 1113.
! i', 510 g of N-methylpyrrolidone was added, heated under pressure at 230°C for 2 hours and at 267°C for 3 hours, and after cooling,
Washed with water and dried. The obtained PPS has a melt viscosity of 3800
It was Poise.

This will be referred to as Polymer C.

(Reference Example-3) (Production of PPS-PPSS block copolymer) (A) Synthesis of terminal chlorphenyl group type PP5S 10A?N-methylpyrrolidone 198 in autoclave
0, li', sodium sulfide 2.7 hydrate 65i (5,0
mol), sodium hydroxide 2.011, and bis(p
-chlorophenyl) sulfone 1431 (5.0 mol) was charged, the temperature was raised to 200° C. under a nitrogen atmosphere, and the reaction was carried out at that temperature for 6 hours with stirring. Then, 72.9 (0.25 mol) of this system nibis(P-chlorophenyl)sulfone was added to N
-Methylpyrrolidone20. , a solution dissolved in OM was added, and the reaction was further continued for 1 hour.

After the reaction vessel was cooled, the contents were taken out, washed several times with hot water and acetone, and the polymer cake was sent door to door.

This cake was dried under reduced pressure at 80 to 150°C to obtain light brown polymer 1190.9 (yield 96%). The logarithmic viscosity of this polymer ηinh (here, ηinh is 0.5.
Phenol/1,1.2.2-tetrachloroethane (3
:2 weight ratio) was measured at 30°C in a mixed solvent, and the following formula η1nh
It is a value calculated according to =tn (relative viscosity)/polymer concentration. ) was 0.22.

(B) Synthesis of PPS with terminal sodium sulfide group 10
7 N-methylpyrrolidone in autoclave 3100.9
and sodium sulfide 2.7 hydrate 1009g (7.7 mol)
and sodium hydroxide 3.5. ! 1009 mol) was charged, and the temperature was raised to 200° C. over about 2 hours with stirring under a nitrogen atmosphere, and 220 TLl of water was distilled out. After cooling the reaction system to 150°C, p-dichlorobenzene 10
29 g (7.0 mol), N-methylpyrrolidone 700.
! 9 was added, and the mixture was reacted at 230°C for 1.5 hours and then at 260°C for 2 hours. The internal pressure at the end of polymerization is 7.0 J/
It was cm2. After cooling the reaction vessel, a portion of the contents was sampled and distributed from house to house, and the cake was boiled and washed three times with hot water, further washed twice with acetone, and then dried at 120°C to form a pale gray-brown powder of PPS. Polymer was obtained (yield approx. 9
4ch). The logarithmic viscosity of this polymer [η] (where, [η
] was measured at 206°C in α-chlornaphthalene with a polymer concentration of 14 g and 7100 ml, and [η) = tn (relative viscosity) / the value calculated according to polymer concentration) was 0.14
Met.

(C) Synthesis of block copolymer Add the terminal chlorophenyl group fiPPs 8300 F and N-methylpyrrolidone 1200.9 to the above PPS polymerized polymer mixture 2370#, and seal after nitrogen purge.
The temperature was raised to 20°C, and the reaction was continued at this temperature for 3 hours. After the reaction vessel was cooled, the contents were separated and the solid content was washed twice with N-methylpyrrolidone and then boiled and washed three times with hot water.

The resulting cake was dried at 120° C. for 5 hours to obtain 486 g of light brown powdery polymer. The [η] of the polymer was 0.19.

Furthermore, when the infrared absorption spectrum of this polymer was measured, no peaks other than pps and ppss absorption were observed, and peaks at 1320 cm-1,620 cm-1 and 4
When PP5S was quantified from the intensity of characteristic absorption observed at 80 crn, it was found that 46.0% by weight of PP5S was contained in the polymer. At the same time, the polymer was subjected to elemental analysis and the sulfur content was determined to be 27.87%, confirming that the polymer contained 46.0% by weight of PP5S.

The melt viscosity of the obtained polymer was 520 poise, and this polymer was designated as Polymer D.

When Polymer E was crosslinked in air at 270°C for 2.5 hours, Polymer E with a melt viscosity of 3100 poise was obtained.

Examples-1 to 4. Comparative examples 1-2 Polymers A, B, and D obtained in Reference Examples-1 and 2.

After uniformly premixing E Oyohi N, N'-(methylenedi-p-phenylene) simaleimide in the proportions shown in Table 1, 30
The mixture was kneaded and pelletized using a 40 mm extruder heated to 0°C.

This pellet was heated to 300°C in a 40-tone extruder to a thickness of 2Wr! A sheet-like extrusion molded product with a width of 100 tan and a width of 100 tan was obtained. The extrusion properties and bending strength of the obtained sheet were measured by cutting test pieces. The results are shown in Table-1.

Examples 5-6. Comparative Examples 3 to 4 The pellets obtained in Example 2 and Comparative Example 1 were designated as hard pellets A and B, respectively, and similarly polymer C100
Phr and N, N'-(methylenedi-p-phenylene) simaleimide 4 The pellets obtained by Phr)k pellets C, and the pellets obtained by using only polymer C and tf pellets D. Each pellet epoxy silane treated 3m
Cut glass fibers were uniformly premixed according to the formulation shown in Table 2 and kneaded in a 40m+ extruder heated to 300°C to form pellets.

A test piece was made from this pellet using an injection molding machine, and its bending properties were measured.

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Claims (1)

Scope of Claims: (a) 100 parts by weight of polyphenylene sulfide and/or a block copolymer consisting of a polyphenylene sulfide moiety and a polyphenylene sulfide sulfone moiety (b) 0 maleimide compound represented by the following general formula (1)
．． 1 to 20 parts by weight ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼... (1) (In the formula, R is an aromatic, alicyclic, or aliphatic organic group, and X_1 and X_2 are hydrogen, halogen, or alkyl groups. and n is 1 to 10. A thermoplastic resin composition comprising: