JPS61225218A - Block copolymer - Google Patents

Abstract

PURPOSE:A block copolymer improved in impact resistance and flexibility, prepared by chemically bonding a polysulfone as a soft segment to a polyphenylene sulfide. CONSTITUTION:A halogen-substituted aromatic compound (e.g., p-dichloro benzene) is polymerized with Na2S in an amide or sulfone solvent (e.g., sulfolane) to obtain a polyphenylene sulfide containing at least 70mol% structural units of formula I. This polyphenylene sulfide is graft-copolymerized with a polysulfone of one of formulas II-IV, etc. (wherein n>=10) having a reduced viscosity (as measured in 0.2g/100ml chloroform solution at 25 deg.C) of 0.05-1.0 in an organic polar solvent (e.g., formamide) to obtain a block copolymer having a relative viscosity [eta] (as measured in a 0.4g/100ml alpha-chloronaphthalene solu tion at 206 deg.C and calculated according to the equation of formula V) of 0.03-1.0.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a block copolymer comprising a /rifhenylene sulfide (hereinafter abbreviated as PPS) moiety and a 4-resulfone moiety. More specifically, the present invention relates to a block resin with improved mechanical properties related to toughness such as impact resistance and flexibility, which is produced by chemically bonding polysulfone as a ppsK soft segment.

(Conventional technology and problems) PPS has attracted attention as a high-performance engineering plastic that has excellent heat resistance, chemical resistance, and rigidity compared to engineering plastics such as nylon, polycarbonate, polybutylene terephthalate, and polyacetal. There is. However, this resin has serious drawbacks in that it has poor toughness and is brittle compared to the above-mentioned engineering plastics. In recent years, linear PPS, which is different from conventional thermally crosslinked PPS, is being developed, but even in this case, it is poor in impact resistance and toughness such as elongation in a crystallized state.

Conventionally, fillers such as glass fibers have been added to improve pps impact resistance, but this is insufficient and is therefore ineffective in preventing cracks caused by, for example, molding shrinkage distortion.

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, and the compatibility with PPS is insufficient.
It has problems such as a decrease in mechanical strength such as bending strength and deterioration of the surface condition of molded products, and it has not yet been possible to obtain PPS with improved impact resistance and flexibility without impairing the characteristics of PPS. Not yet.

(Means for Solving the Problems) In view of the above-mentioned circumstances, the present inventors have developed a ppm with improved mechanical properties such as impact resistance and excellent blend compatibility.
As a result of intensive studies to obtain S resin, it was discovered that a block resin obtained by carrying out a copolymerization reaction of pps having a terminal reactive group and polysulfone and chemically bonding the two was effective. 1. The present invention has been made. It has been reached.

That is, the present invention consists of a pps part and a polysulfone part, and has a logarithmic viscosity [η] (here, [η] is 0.41/10
The value was measured at 206° C. in α-chlornaphthalene at a polymer concentration of 0−1 solution, and calculated according to the following formula: [η) = tn (relative viscosity)/polymer concentration. ) is in the range of 0.03 to 1.0.

It is preferable that the block copolymer of the present invention contains more than 100% of the pps mole, and if the amount is less than 700%, it is difficult to obtain a block copolymer with excellent properties. Also, that P
Logarithmic viscosity of PS [η] (here [η] is 0.41!/1
Measured at 206°C in α-chlornaphthalene at a polymer concentration of 00- solution, and the following formula [η) = -tn
This is a value calculated according to (relative viscosity)/polymer concentration.

) is preferably in the range of 0.03 to 0.80.

This/IJ polymerization method includes polymerizing a halogen-substituted aromatic compound, such as p-dichlorobenzene, in the presence of sulfur and sodium carbonate, or polymerizing sodium sulfide or sodium hydrosulfide and sodium hydroxide or Methods include polymerization in the presence of hydrogen sulfide and sodium hydroxide or sodium aminoalkanoate, self-condensation of p-chlorothiophenol, etc.
- A method in which sodium sulfide and p-dichlorobenzene are reacted in an amide solvent such as methylpyrrolidone or dimethylacetamide or a sulfone solvent such as sulfolane is suitable. At this time, in order to adjust the degree of polymerization, it is a preferable method to add an alkali metal salt of carboxylic acid or sulfonic acid, or to add alkali hydroxide. As a copolymerization component, 30 Hifonic di# bond ((■H original ΣS-), substituted phenyl nitro group, phenyl group, alkoxy group, carbic acid group or metal base of carboxylic acid), trifunctional mer crystallinity The amount of the copolymerized component is preferably 10 mol or less, although it may be within a range that does not significantly affect the amount. Especially phenyl and biphenyl having trifunctionality or more.

When a naphthyl sulfide bond or the like is selected for copolymerization, the amount is preferably 3 molar or less, more preferably 1 molar or less.

A specific method for producing such PPS is 1, for example (1).
Production method using halogen-substituted aromatic compound and alkali sulfide (U.S. Patent No. 2513188, Japanese Patent Publication No. 44-2767)
(See No. 1 and Special Publication No. 45-3368).

(2) Production method by condensation reaction of thiophenols in the coexistence of an alkali catalyst or copper salt (US Patent No. 3274)
165 and British Patent No. 1160660),
(3) Production method by condensation reaction of aromatic compounds with sulfur chloride in the coexistence of a Lewis acid catalyst (Japanese Patent Publication No. 46-2725
No. 5 and Belgian Patent No. 29437).

The block copolymer in the present invention can be obtained by, for example, reacting the terminal group of polysulfone with the terminal group of PPS. Case PP
The terminal group of S is a sodium sulfide group (structural formula: Na
It is necessary to use a reactive group such as p-). It takes p
As a method for obtaining ps, there is a method in which the monomer is sulfurized in advance during the polymerization reaction, and the amount of the IJium component is 1 to 20 molar excess relative to the p-dichlorobenzene component. Examples include a method of adding a binder such as sodium sulfide as the third component.

On the other hand, the polysulfone moiety constituting the block copolymer of the present invention is defined as a polyarylene compound in which arylene units are positioned randomly or orderly together with ether and sulfone bonds.

For example, those having the following structural formulas (1) to (phase) (n in the formula represents an integer of 10 or more) may be mentioned, but those having the structure (1) or (2) are preferable.

■(soKto(filter 0□QCH2C＼ ■Can)0M2QOte＞so2℃allow■ 壬0(叉he7J),,B02α ze・G"o-G(X @ c o so□Reduced viscosity of the above polysulfone part ηsp/C (where ηll
p/c is 0.2! The value was measured at 25°C in chloroform at a polymer concentration of a solution of i/100-, and was calculated according to the following formula: 'l sp/c = (relative viscosity-1)/polymer concentration. ) is preferably in the range of 0.05 to 1.0. As a method for polymerizing this 4-limer, for example, dichlorodiphenylsulfont 2゜2-bis(
Examples include a method of reacting sodium salt of (4-hydroxyphenyl)-propane (Japanese Patent Publication No. 7799/1983).

The terminal group of I resulfone and p
When synthesizing by reacting with the terminal group of ps, the amount of dichlorodiphenyl sulfone component is adjusted in advance to be in excess of 1 to 20 moles relative to the amount of bis(4-hydroxyphenyl)-pronobenzene component during polysulfone synthesis. How to react with
Alternatively, it is preferable to use a method in which a binder such as dichlorodiphenyl sulfone is added as a third component during the copolymerization reaction with pps.

Furthermore, during the copolymerization reaction, it is most preferable to make the number of terminal reactive groups of PPS and polysulfone the same, since a pro- and poly-copolymer can be obtained in good yield. On the other hand, if the number of terminal groups of either component is excessive, only the pro-copolymer can be recovered by fractionating or extracting only the unreacted photo-polymer component after the reaction is completed.

The solvent used in the copolymerization reaction has a substantially 1c! Preferred are organic polar solvents that are Specifically, formami-P.

Acetamide, N-methylformamide, N,N-dimethylformamide, N,N-dimethylacetamide, 2
-pyrrolidone, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, ε, -caprolactam, N-methyl-6-caprolactam, hexamethylphosphoramide, tetramethylurea, 1,3-dimethyl-2- Amides such as indasilidinone, urea and lactams; sulfones such as sulfolane and dimethylsulfolane; nitrites such as benzonitrile; ketones such as methylphenylketone; and mixtures thereof.

Among these solvents, it is particularly preferable to use aprotic organic solvents such as amides, lactams, or sulfones. The amount of the organic polar solvent used is in the range of 2 to 20, preferably 3 to 10, in weight ratio to the amount of the polymer component.

The fact that the copolymerization reaction product resulting from the pro- and polysulfone reaction is a pro- and polysulfone copolymer of chemically bonded PPS and polysulfone means that the resulting polymer can be used in N-methylpyrrolidone or chloroform, which is a good solvent for polysulfone. This is confirmed by the fact that the amount of polysulfone contained in the polymer cake does not decrease after repeated extractions. On the other hand, whether unreacted pps is contained in the copolymerization reaction product can be determined by mixing the product with α-chlornaphthalene, dissolving it at 210°C, and cooling it to 160°C. K PPS precipitates. You can check whether it is or not.

The block copolymer of the present invention includes I-riphenylene oxide, I-realylate, I-lyamide, ? Thermoplastic resins such as littylene terephthalate, polyetheretherketone, polyimide, epoxy resins such as Nogalac type epoxy resin, polyolefins such as polyethylene, polyethylene, α-olefin copolymers such as maleic acid-modified polypropylene, or nylon. 11/f! Liether I lyamide elastomer can be applied to compositions with thermoplastic elastomers. Furthermore, it is also possible to apply the present invention to a container using a fibrous reinforcing material such as glass fiber or carbon fiber, or an inorganic filler such as Merck, mica, or calcium carbonate.

Therefore, the block copolymer of the present invention can be used not only for injection molded products or compression molded products, which are the main uses of conventional PPS products such as electrical and electronic parts, but also for fibers, sheets, films,
It can be used for extrusion molded products such as tubes, blow molded products, transfer molded products, etc.

(Effects of the Invention) The pro-copolymer of the present invention differs from a composition that is simply a blend of PPS and polysulfone, which has poor compatibility, because it is a block copolymer of polymer chains of PPS and polysulfone. It has excellent mechanical properties such as bending strength and impact resistance, and is also excellent in compatibility with 228% polysulfone and the like.

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

Example 1. Comparative Example 1 First, a terminal chlorphenyl group type polysulfone was synthesized as follows. 51 In a glass flask, add bis(4-hydroxyphenyl)-propane (hereinafter abbreviated as bisphenol A) 343 # (1,50 mol), 10,100 O of dimethyl sulfoxide, and 2,000 O of monochlorobenzene.
rLt1, heated to 60-80°C, and purged the system with nitrogen. Then, 5Ots caseinida aqueous solution 2411
(3.0 mol) was added dropwise over 10 minutes with vigorous stirring. The system was separated into a chlorobenzene phase and an aqueous solution phase of the Nina)IJium salt of bisphenol A dissolved in dimethyl sulfoxide. Next, the reaction mixture is refluxed while purging with nitrogen, water is removed by azeotropy, and chlorobenzene is 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 precipitated. The temperature in the system is 15
By increasing the temperature from 5 to 160°C, chlorobenzene was distilled and the precipitate was redissolved. Next, dry 4,4'
- A solution of 448 g (1.56 mol) of dichlorodiphenyl sulfone in 50 cyclobenzene was added over 10 minutes while maintaining the temperature at 110°C. At that time, the temperature inside the system is 150 to 160℃.
GC:ry) Roll sita. After the addition of dichlordiphenyl sulfone was completed, the reaction was carried out at 160° C. for 3 hours, and an amber viscous polymer solution was obtained. Cool this solution and
After diluting with 000-chlorobenzene and removing by-product sodium chloride by t-filtration, the polymer was poured into methanol in an amount 5 times the amount 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 f: dried under reduced pressure at 130°C to obtain white polysulfone 633I (yield: 96
．． 0%).

The reduced viscosity of this polymer is η, /C (poly, -5iO,
2,9/100a/, measured at 25°C in chloroform,
The value calculated according to the formula η8p/C=specific viscosity/polymer concentration) was 0.34.

Next, terminal sodium sulfide group type ppst was synthesized as follows. 101 In an autoclave, add 350011 N-methylpyrrolidone and 11 sodium sulfide 2.7 hydrate.
153.9 (8.80 mol) and sodium hydroxide 4.0.9 (0.10 mol), under nitrogen atmosphere,
Raise the temperature to 200°C while stirring for about 2 hours.
0 d of water was distilled off. After cooling the reaction system to 150°C, p-dichlorobenzene 117611 (8.0 mol),
Add N-methylpyrrolidone 800Ii and heat at 230℃ for 1
The reaction was then carried out at 260° C. for 2 hours. The internal pressure at the end of 1 cup was 7.1 to 9/cm''. After cooling the reaction vessel, a part of the contents was sampled and separated, and the solid content was boiled and washed three times with hot water. Furthermore, it was washed twice with acetone and then dried at 120°C to obtain a pale gray-brown powdery PPS polymer (yield: 94%). Logarithmic viscosity of the polymer [η] (
Measured at 206° C. in α-chlornaphthalene at a polymer concentration of 0.4 g/100 mt, [η) = An (value calculated according to relative viscosity)/polymer concentration) was 0.1 cow.

Subsequently, the above PPS polymerization mixture 2360# and the above polysulfone 30011 and N-methylpyrrolidone 13 were added.
00.9 was added, the mixture was sealed, the temperature was raised to 230°C, and the reaction was carried out at this temperature for 2 hours. After cooling the reaction vessel,
Separate the contents and reduce the solid content by 2 with N-methylpyrrolidone.
After washing twice, it was boiled and washed three times with hot water. The resulting cake was dried at 120° C. for 5 hours to obtain 5281 gray-brown powdery polymer.

[η] of this polymer was 0.27. In addition, when the infrared absorption spectrum was measured, no peaks other than the absorption of the PPS and polysulfone were observed, and 139
Polysulfone was quantified from the intensity of the characteristic absorption seen at 0 cIn and 1240 cm, and was found to contain 49.6% by weight in the polymer. At the same time, elemental analysis of the polymer was carried out, and the sulfur content was determined to be 18.52%.
Confirmed that it is included.

Furthermore, K. conducted a solvent extraction experiment on the above polymer. That is, Soxhlet extraction was performed for 2 hours using chloroform, a good solvent for polysulfone, for 10 g of the polymer for 2 hours, but no polysulfone was eluted. The content of cypolysulfone was determined to be 49.6% by weight. At the same time, a similar extraction experiment was conducted on the PPS blend containing 49.6% by weight of polysulfone.

The polysulfone was completely eluted from the PPS blend.

On the other hand, the above polymer and the above polysulfone were 49.6
Fractional precipitation experiments in α-chlornaphthalene were performed on PPS blends containing % by weight.

Each sample 21 was mixed with 100% α-chlornaphthalene, dissolved at 210°C, and then gradually cooled. At 160°C, all of the PPS in the blend precipitated, whereas the PPS from the solution of the polymer No PPS precipitate was observed, indicating that the above polymer did not contain PPS homopolymer.

From these results, it is clear that the copolymerization reaction product of this example is PP.
It was confirmed that S and polysulfone are chemically bonded to form a block copolymer.

The copolymer obtained in this example was heat-treated at 1260° C. for 5 hours, and then heated and kneaded using a 30 m twin-screw presser to form pellets. This pellet was injection molded at 330°C to prepare a test piece. ASTM D-1238 (315℃
The melt flow index (abbreviated as MI value) was measured by the method of , 5 to 9 loads), the bending strength was measured by the method of ASTM D-790, and the Izot impact strength was measured by the method of ASTM D-256.

In addition, appearance compatibility was observed with the naked eye, and the peeling state of the molded product was visually observed after a peel test was conducted using a sampling method in which an adhesive tape was attached to the fractured surface of the test piece.

In Comparative Example 1, 72 p was obtained by the above-mentioned treatment after the polymerization reaction of the polysulfone synthesized in this example and PPS.
Using PS powder, the polysulfone content is 49.6 weight tS.
Following the above method, a test piece was prepared and the physical properties were measured.

Furthermore, in Comparative Example 2, a similar test piece was prepared using only PPS powder obtained by the same method as in this example, and the physical properties were measured.

The results are shown in Table-1. In the case of copolymers, the MI value is significantly lower than that of pps alone or as a mixture.
This shows an increase in melt viscosity due to block copolymerization. It is inferred from the appearance and peeling state of the molded product that the copolymer has good dispersibility between the two, causing microphase separation.

Furthermore, both the bending strength and the impact strength were significantly improved compared to the mixture, indicating that this copolymer is a resin with improved impact resistance.

Example 2. Comparative Example 3 Sodium benzoate with sodium sulfide 1152.9
An IJ umsulfide group type PPS polymerization mixture was synthesized in the same manner as in Example 1, except that (8.0 mol) was added. When some samples were taken and [η] was measured, it was 0.30.

A portion of 3710 g of this polymerization mixture and a terminal chlorphenyl group type polysulfone synthesized in the same manner as in Example 1 (
ηsp/C=0.35) 210# and N-methylpyrrolidone 8009 were mixed, sealed after snow removal, and heated at 230°C.
The temperature was raised to 100.degree. C., and the reaction was continued at this temperature for 2 hours. Processed in the same manner as in Example 1, yielding 489. A gray-brown powdery 4rimer of F was obtained. The logarithmic viscosity [η] of this polymer was 0.36. Further, when an infrared absorption spectrum was measured, it was found that 30.4% by weight of polysulfone was contained. As a result of conducting the chloroform extraction experiment and the fractional precipitation experiment using α-chlornaphthalene as described in Example 1, almost no homopolymer of pps and polysulfone was recovered. It was confirmed that most of the polymers were block copolymers.

A test piece was prepared by pelletizing and injection molding the above copolymer. Also, as Comparative Example 3.

The physical properties were measured using a mixture of the polysulfone synthesized in this example and PPS powder so that the polysulfone content was 30.4% by weight.

The results are shown in Table-2. Similar to Example 1, this copolymer has significantly improved impact strength and bending strength compared to the mixture, and is a resin with improved impact resistance.

Claims (1)

[Claims] Consists of a polyphenylene sulfide part and a polysulfone part, and has a logarithmic viscosity [η] (here, [η] is 0.4 g/
The value was measured at 206° C. in α-chlornaphthalene at a polymer concentration of 100 ml of solution, and calculated according to the following formula [η]=ln (relative viscosity)/polymer concentration. ) is in the range of 0.03 to 1.0.