JPH0627260B2 - Resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial field of application) The present invention is excellent in blend compatibility including a block copolymer composed of a polyphenylene sulfide (hereinafter abbreviated as PPS) portion and a polysulfone portion, and is excellent in impact resistance. It relates to an improved resin composition. More specifically, various molded products with improved mechanical properties related to toughness such as impact resistance and flexibility, which contain a block copolymer formed by chemically bonding polysulfone as a soft segment to PPS as an essential component. The present invention relates to a resin composition that can be used in.

(Prior art and problems) PPS resin has been attracting attention as a high-performance engineering plastic having excellent heat resistance, chemical resistance, and rigidity as compared with engineering plastics such as nylon, polycarbonate, polybutylene terephthalate, and polyacetal. However, this resin has the serious drawback of being relatively poor in toughness and fragile. In recent years, a linear PPS different from the conventional heat-crosslinked PPS is being developed, but even in that case, impact resistance and toughness such as elongation are poor in a crystallized state.

Conventionally, a filler such as glass fiber has been blended in order to improve the impact resistance of PPS, but since it is not sufficient, it is not effective in preventing crack generation due to molding shrinkage strain, for example. On the other hand, polymer blending with a flexible polymer is an effective method, but there are few polymers that are flexible and have excellent heat resistance and chemical resistance, or because compatibility with PPS is insufficient, bending strength, etc. It has problems such as a decrease in mechanical strength and deterioration of the surface condition of a molded product, and it has not yet been possible to obtain a PPS having improved impact resistance and flexibility without impairing the characteristics of PPS.

(Means for Solving Problems) In view of the situation as described above, the present inventors have found that PPS having improved mechanical properties such as impact resistance and excellent blend compatibility.
As a result of intensive studies to obtain a resin, the present invention has been achieved by mixing PPS and / or polysulfone with a block copolymer composed of a PPS portion and a polysulfone portion.

That is, the present invention provides a resin composition comprising a block copolymer having a PPS portion and a polysulfone portion, PPS and / or polysulfone, and optionally a filler.

The components of the block copolymer of the present invention and PPS that can be mixed with the copolymer have the general formula Those containing 70 mol% or more of the structural unit represented by are preferable because they provide a composition having excellent characteristics. Further, such PPS has a logarithmic viscosity [η] (where [η] is 0.4
It is a value calculated according to the following formula [η] = ln (relative viscosity) / polymer concentration, measured at 206 ° C. in α-chlornaphthalene at a polymer concentration of a solution of g / 100 ml. Is preferably in the range of 0.03 to 0.80.

The PPS may be polymerized by polymerizing p-dichlorobenzene in the presence of sulfur and sodium carbonate, sodium sulfide or sodium hydrosulfide and sodium hydroxide or hydrogen sulfide and sodium hydroxide or sodium amino in a polar solvent. A method of polymerizing in the presence of an alkanoate, a self-condensation of p-chlorothiophenol and the like can be mentioned. However, sodium sulfide and p can be added in an amide solvent such as N-methylpyrrolidone or dimethylacetamide or a sulfone solvent such as sulfolane. -A method of reacting dichlorobenzene is suitable. At this time, it is a preferable method to add an alkali metal salt of carboxylic acid or sulfonic acid or to add an alkali hydroxide in order to adjust the degree of polymerization. If it is less than 30 mol% as a copolymerization component, a meta bond Ortho-join Ether bond Sulfone bond Biphenyl bond Substituted phenyl sulfide bond Here, R represents an alkyl group, a nitro group, a phenyl group, an alkoxy group, a carboxylic acid group or a metal base of carboxylic acid), trifunctional bond It does not matter if it contains such a compound as long as it does not significantly affect the crystallinity of the polymer, but preferably the copolymerization component is 1
It is preferably 0 mol% or less. Particularly, when a phenyl, biphenyl, naphthyl sulfide bond or the like having a functionality of 3 or more is selected for the copolymerization, the content is preferably 3 mol% or less, more preferably 1 mol% or less.

Specific methods for producing such PPS include, for example, (1) reaction of a halogen-substituted aromatic compound with an alkali sulfide (see US Pat. No. 2,513,188, JP-B-44-27671 and JP-B-45-3368), 2) Condensation reaction of thiophenols in the presence of alcal catalysts or copper salts (see US Pat. No. 3,274,165 and British Patent No. 1160660), (3) aromatic compounds in the presence of a sulfur acid catalyst with a Lewis acid catalyst Examples of the condensation reaction (see Japanese Patent Publication No. 46-27255 and Belgian Patent No. 29437) and the like.

The block copolymer in the present invention can be obtained, for example, by reacting the end group of polysulfone with the end group of PPS. Therefore, for example, the end group of polysulfone has a chlorophenyl group (structural formula: When it is, 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, a method of previously reacting the amount of the sodium sulfide component of the monomer in an excess of 1 to 20 mol% with respect to the p-dichlorobenzene component during the polymerization reaction, or a third method during the copolymerization reaction with polysulfone Examples include a method of adding a binder such as sodium sulfide as a component.

On the other hand, the component of the block copolymer and the polysulfone that can be mixed with the copolymer in the present invention are defined as a polyarylene compound in which the arylene unit is located randomly or in an ordered manner together with an ether and a sulfone bond. The compound represented by the structural formula (wherein n represents an integer of 10 or more) can be mentioned, and it is preferable to have the structure of or.

The above polysulfone has a reduced viscosity of η _sp / C (where η _sp
sp / C is a value calculated according to the following formula η _sp / C = (relative viscosity-1) / polymer concentration, measured at 25 ° C. in chloroform at a polymer concentration of 0.2 g / 100 ml of solution. Is preferably in the range of 0.05 to 1.0. As a method of polymerizing this polymer, for example, a method of reacting 4,4'-dichlorodiphenyl sulfone with a sodium salt of 2,2-bis (4-hydroxyphenyl) -propane is disclosed in Japanese Patent Publication No. 42-7799. It is disclosed.

The block copolymer of the present invention is used as a polysulfone terminal group.
In the case of synthesizing by reacting with the end group of PPS, the amount of dichlorodiphenyl sulfone component is reacted in advance in an amount of 1 to 20 mol% excess with respect to the amount of bis (4-hydroxyphenyl) -propane component during polysulfone synthesis. It is preferable to use a method or a method of adding a binder such as dichlorodiphenyl sulfone as the third component during the copolymerization reaction with PPS.

In addition, the ratio of PPS and polysulfone during the copolymerization reaction varies depending on the desired characteristics.
The weight ratio with the PPS component is generally 1 to 99/99 to 1,
The range is preferably 5 to 90/95 to 10. If the weight ratio is less than 1/99, the effects such as impact resistance imparted by polysulfone cannot be exhibited, and 99/1
If it exceeds, it is not preferable because the intended effect of this patent cannot be obtained.

The solvent used in the block copolymerization reaction is preferably an organic polar solvent that is substantially liquid at the temperature and pressure. Specifically, formamide, acetamide, N-methylformamide, N, N-dimethylformamide, N, N-dimethylacetamide, 2-pyrrolidone,
N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, ε-caprolactam, N-methyl-ε-caprolactam, hexamethylphosphoramide, tetramethylurea, 1,3-dimethyl-2-imidazolidinone, etc. Amides, ureas and lactams; sulfones such as sulfolane and dimethylsulfolane; nitriles such as benzonitrile; ketones such as methylphenylketone; and mixtures thereof. Among these solvents, it is particularly preferable to use an aprotic organic polar solvent such as amides, lactams or sulfones.
The amount of the organic polar solvent used is in the range of 2 to 20 and preferably in the range of 3 to 10 by weight ratio to the amount of the polymer component.

The block copolymer used in the present invention has a logarithmic viscosity [η] (where [η] is a polymer concentration of 0.4 g / 100 ml at a concentration of 206 ° C. in α-chloronaphthalene).
Is a value calculated according to the following formula [η] = ln (relative viscosity) / polymer concentration. ) Is preferably in the range of 0.03 to 1.0.

The resin composition of the present invention is the block copolymer 3-10.
0 parts by weight, more preferably 10 to 100 parts by weight
When PPS is used in combination, PPS is preferably 1 to 97 parts by weight, more preferably 10 to 90 parts by weight, and when polysulfone is used in combination, polysulfone is preferably 1 to 60 parts by weight, more preferably 10 to 40 parts by weight. Part is included. The resin composition of the present invention contains 3 to 100 parts by weight of the block copolymer, whereby the impact resistance is greatly improved and the compatibility is further improved.

Further, the resin composition of the present invention can be obtained by reacting an excess amount of either the PPS component or the polysulfone component during the production of the block copolymer. At that time, it was confirmed that free PPS and polysulfone were contained by the fact that a certain amount of polysulfone was contained in the polymer after repeated extraction with N-methylpyrrolidone which is a good solvent for polysulfone and chloroform. On the other hand, whether or not PPS homopolymer is mixed can be confirmed by a fractional precipitation experiment using α-chlornaphthalene.

The composition of the present invention may contain 70% by weight or less of an arbitrary filler in the composition in order to improve the performance as an engineering plastic such as strength, heat resistance and dimensional stability. Specific examples of the filler include glass fiber, carbon fiber, potassium titanate, asbestos, silicon carbide, ceramic fiber, metal fiber, fibrous reinforcing agent such as silicon nitride barium sulfate, calcium sulfate, kaolin, and the like.
Clay, pyrofluoride, bentonite, sericite, zeolite, mica, mica, nepheline sinite,
Talc, Phthalbargite, Wollastonite, PM
F, ferrite, calcium silicate, calcium carbonate, magnesium carbonate, dolomite, ammonium trioxide, zinc oxide, titanium oxide, magnesium oxide, iron oxide, molybdenum dioxide, graphite, gypsum, glass beads, glass balloons, quartz powder, etc. Inorganic fillers Organic reinforcing agents such as aramid fibers are included. When adding these reinforcing agents or fillers, known silane coupling agents can be used.

Further, the composition of the present invention includes a thermoplastic resin such as polyphenylene oxide, polyarylate, polyamide, polybutylene terephthalate, polyether ether ketone, polyimide, etc., and an epoxy resin such as a novolac type epoxy resin, etc. within a range not departing from the object of the present invention. Polyolefins such as polyethylene and polypropylene, α-off fin copolymers such as maleic acid-modified polypropylene, and thermoplastic elastomers such as nylon 11 / polyale polyamide elastomers can be contained.

The composition of the present invention can be prepared by various known methods. For example, a method of uniformly mixing the raw materials in advance with a mixer such as a tumbler or a Henschel mixer, feeding the mixture to a single-screw or twin-screw extruder, melt-kneading at 230 to 400 ° C., and then pelletizing You can

(Effect of the invention) Since the resin composition of the present invention contains a block copolymer composed of a PPS part and a polysulfone part, it has excellent mechanical properties such as impact resistance, and is suitable for conventional applications of PPS such as electric and electronic parts. It can be used not only for certain injection molded products or compression molded products but also for extrusion molded products such as fibers, sheets, films and tubes, blow molded products, transfer molded products and the like.

(Examples) Next, the present invention will be specifically described with reference to Examples, but the present invention is not limited thereto.

Example 1, Comparative Examples 1-2 Synthesis of (A) -terminal chlorophenyl group-type polysulfone 5
In a glass flask, 366 g of bis (4-hydroxyphenyl) -propane (hereinafter abbreviated as bisphenol A) (1.
(60 mol), 1000 ml of dimethyl sulfoxide and 2000 ml of monochlorobenzene were charged and heated to 60 to 80 ° C.
The system was purged with nitrogen. Next, 256 g (3.20 mol) of 50% caustic soda aqueous solution was added dropwise over 10 minutes with vigorous stirring. The system was separated into a chlorobenzene phase and an aqueous phase of the disodium salt of bisphenol A dissolved in dimethylsulfoxide. Then, the reaction mixture was refluxed while being replaced with nitrogen, water was expelled by azeotropy and chlorobenzene was returned to the system. The internal temperature rose from 120 ° C to 140 ° C, most of the water in the system was distilled off, and the disodium salt of bisphenol A was deposited as a precipitate. Set the system temperature to 155
Chlorobenzene was distilled by raising to ~ 160 ° C to redissolve the precipitate. Then, 478 g (1.66 mol) of dried 4,4'-dichlorodiphenyl sulfone was added to 50 wt.
% Chlorobenzene solution was added over 10 minutes while maintaining at 110 ° C. At that time, the inside of the system was controlled at 150 to 160 ° C. After the addition of dichlorodiphenyl sulfone was completed, the reaction was carried out at 160 ° C. for 3 hours, and an amber viscous polymer solution was obtained. The solution was cooled, diluted with 1000 ml of chlorobenzene to remove by-product salt by filtration, and then poured into 5 times the amount of methanol of the polymer solution to precipitate the polymer. The obtained white precipitate was dissolved in chloroform, washed with water, reprecipitated again with chloroform and methanol, and the precipitate was dried under reduced pressure at 130 ° C. to obtain 668 g of white polysulfone (yield 95.0%). The reduced viscosity η _sp / C of this polymer (polymer concentration 0.2 / 100 ml, measured in chloroform at 25 ° C., value calculated according to the formula η _sp / C = specific viscosity / polymer concentration) was 0.34.

(B) Synthesis of terminal sodium sulfide group-type PPS 10 An autoclave was charged with 3300 g of N-methylpyrrolidone, 1153 g (8.80 mol) of sodium sulphide 2.7-hydrate and 4.0 g (0.10 mol) of sodium hydroxide and heated to 200 ° C. under a nitrogen atmosphere. The temperature was raised while stirring for about 2.5 hours to distill 250 ml of water. After cooling the reaction system to 150 ° C., 1176 g (8.0 mol) of p-dichlorobenzene and 800 g of N-methylpyrrolidone were added, and the mixture was heated to 230 ° C.
For 1 hour and then at 260 ° C. for 2 hours. The internal pressure at the end of the polymerization was 7.5 kg / cm ² . After cooling the reaction vessel,
After sampling and separating a portion of the contents, the solid content was washed with boiling water three times, and then washed with acetone twice.
It was dried at 120 ° C. to obtain a light grayish brown powdery PPS polymer (yield about 94%). Logarithmic viscosity [η] of polymer (polymer concentration 0.4 g / 100 ml, in α-chlornaphthalene 206 ° C)
And [η] = ln (relative viscosity) / value calculated according to the polymer concentration) was 0.14.

(C) Synthesis of Block Copolymer 2350 g of the above PPS polymerization mixture, 290 g of the above polysulfone and 1300 g of N-methylpyrrolidone were added, and after nitrogen purging, the mixture was sealed, heated to 230 ° C., and reacted at this temperature for 2 hours. After cooling the reaction vessel, 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 cake obtained is heated at 120 ° C. for 5
After drying for an hour, 510 g of an off-white powdery polymer was obtained.
[Η] of this polymer was 0.25. In addition, when the infrared absorption spectrum was measured, no peak other than the absorptions of the PPS and polysulfone was observed, and 1390 cm ^-1
When polysulfone was quantified from the intensity of characteristic absorption observed at 1240 cm ^-1 and 48.0% by weight in the polymer. At the same time, the elemental analysis of the polymer was carried out, and when the amount of sulfur was quantified, the value was 18.89%, and it was confirmed that the polymer contained 48.0% by weight of polysulfone.

Furthermore, the solvent extraction experiment of the said polymer was conducted. That is, 200 g of chloroform, which is a good solvent for polysulfone, was used for 10 g of the above polymer, and Soxhlet extraction was carried out for 2 hours. However, polysulfone did not elute at all, and the infrared absorption spectrum of the above polymer recovered by the extraction experiment was measured to determine that polysulfone The content was 48.0% by weight.

From these results, the copolymerization reaction product of the present example is PPS.
It was confirmed that and polysulfone were chemically bonded block copolymers.

(D) Preparation of Composition After heat-treating the above block copolymer at 260 ° C. for 3 hours, a mixture of 50 parts by weight of 50 parts by weight of PPS Ryton P-4 manufactured by Philips Petroleum Co., USA was added to a mixture of 30 mm. Using a twin-screw extruder, the mixture was heated and kneaded to form pellets. This pellet was injection molded at 330 ° C. to prepare a test piece. ASTM D-1238 (315 ° C, 5
Melt flow index (MI)
(Abbreviated as “value”), bending strength, ASTM D-790
The Izod impact strength was measured by the method of D-256.
The appearance compatibility was visually observed, and the peeled state of the molded product was visually observed after a peeling test by a method in which an adhesive tape was attached to the fracture surface of the test piece and then removed.

In Comparative Example 1, 50 parts by weight of the polysulfone synthesized in this example and PPS powder were mixed so as to have a polysulfone content of 48.0% by weight and Ryton P.
According to the above method, a test piece was prepared by mixing 50 parts by weight of -4 and the physical properties were measured.

Further, in Comparative Example 2, the same test piece was prepared and the physical properties of the PPS powder obtained by the same method as in this Example were measured. The results are shown in Table-1.

In the case of the composition of the present invention, its M1 value is lower than that of PPS alone or the like, which shows an increase in melt viscosity due to the inclusion of the block copolymer. Further, from the appearance and the peeled state of the molded product, it is assumed that the block copolymer has good dispersibility and causes microphase separation. As a result, the composition of the present invention is significantly improved in both bending strength and impact strength as compared with the mixture, indicating that the composition has improved impact resistance.

Example 2 The block copolymer obtained in Example 1 was heat treated at 260 ° C. for 3 hours to 80 parts by weight of the US Union.
Carbide Polysulfone (Udel P-3703)
20 parts by weight of the mixture was pelletized and injection-molded in the same manner as in Example 1 to prepare a test piece, and its physical properties were measured. The results are shown in Table-2.

Example 3 1152 g (8.0% sodium benzoate with sodium sulfide
A terminal sodium sulfide group-type PPS polymerization mixture was synthesized in the same manner as in Example 1 except that the amount of (mol) was added. It was 0.29 when partly sampled and [η] was measured.

A part of this polymerization mixture (3690 g) was mixed with 210 g of a terminal chlorophenyl group-type polysulfone (η _sp /C=0.35) synthesized in the same manner as in Example 1 and 800 g of N-methylpyrrolidone, and after nitrogen purge, the mixture was sealed at 230 ° C. The temperature was raised to, and the reaction was carried out at this temperature for 2 hours. The same treatment as in Example 1 was carried out to obtain 489 g of a grayish brown powdery polymer. The inherent viscosity [η] of this polymer was 0.37. In addition, when the infrared absorption spectrum was measured, polysulfone
It contained 2.4% by weight. As a result of performing the chloroform extraction experiment and the α-chlornaphthalene fractional precipitation experiment described in Example 1, almost no homopolymers of PPS and polysulfone were recovered. Therefore, most of the polymers obtained in this Example were obtained. It was confirmed that most of them were block copolymers.

A test piece was prepared by mixing 68 parts by weight of PPS Ryton P-4 and 12 parts by weight of polysulfone (Udel P-3703) with 20 parts by weight of the above-mentioned copolymer to prepare a test piece and measuring the physical properties. did. The results are shown in Table-2.

Example 4, Comparative Example 3 To 24 parts by weight of the block copolymer obtained in Example 1 which was heat-treated at 260 ° C. for 3 hours, 36 parts by weight of PPS Ryton P-4 and commercially available glass fiber ( Asahi Fiber Glass CS-03MA419) 40 parts by weight are mixed, and 2
A test piece was prepared by heat-kneading with a shaft extruder, pelletizing, and injection molding at 330 ° C.

On the other hand, as Comparative Example 3, a mixture of PPS and polysulfone containing 19.2 wt% of the polysulfone obtained in Example 1 was used in place of the resin component of this example, and a test piece was prepared in the same manner to measure the physical properties. .

As shown in Table 2, the copolymer composition of the present invention showed good bending strength and impact resistance even when compounded with glass fiber.

Example 5, Comparative Example 4 400 g (1.60 mol) of bis (4-hydroxyphenyl) -sulfone was used instead of bisphenol A, and 359 g (3.20 mol) of 50% potassium hydroxide aqueous solution was used instead of caustic soda aqueous solution. A terminal chlorophenyl group type polyether sulfone (η _sp /C=0.46) was obtained in the same manner as in Example 1 except for the above. Copolymerization of this polymer with the PPS polymerization mixture obtained in Example 1 yielded 858 g of a powdered polymer. [Η] of this polymer was 0.17, the content of polyethersulfone was 10.7% by weight, the polysulfone component was almost block copolymerized, and the block copolymer component was 19% by weight and the PPS component was It was 81% by weight of the composition.

After the copolymer composition was heat treated at 260 ° C. for 5 hours,
A test piece was prepared by pelletizing and injection molding.

As Comparative Example 4, 10.7% of the polyersulfone of this Example was used.
A test piece was prepared in the same manner using a mixture of PPS and polyether sulfone containing wt% to measure the physical properties.

The results are shown in Table-3.

Example 6, Comparative Example 5 A terminal chlorophenyl group-type polysulfone (η _sp /C=0.65) was synthesized in the same manner as in Example 1. On the other hand, a terminal sodium sulfide group-type PPS polymerization mixture was synthesized in the same manner as in Example 1 except that 722 g (8.80 mol) of sodium acetate was added together with sodium sulfide. It was 0.30 when partly sampled and [η] was measured. A powdery polymer having an [η] of 0.40 was obtained by a copolymerization reaction between a part of the polymerization mixture and the polysulfone. This polymer is
48% by weight of PPS / polysulfone block copolymer component
And a PPS component of 52% by weight.

The above copolymer composition was pelletized and injection molded to prepare a test piece. On the other hand, as Comparative Example 5, so that the polysulfone content in the copolymer composition is the same as
The PPS of this example and polysulfone were mixed, and a test piece was prepared in the same manner to measure the physical properties.

The results are shown in Table-3.

Example 7 With respect to 40 parts by weight of the copolymer composition obtained in Example 6, 30 parts by weight of commercially available glass fiber and 30 parts of calcium carbonate were used.
By mixing the parts by weight, a test piece was prepared in the same manner and the physical properties were measured.

The results are shown in Table-3.

Claims (1)

[Claims] 1. A block copolymer comprising a polyphenylene sulfide moiety and a polysulfone moiety, and a polyphenylene sulfide and / or polysulfone,
A resin composition which optionally contains a filler.