JPS6366862B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a polyarylene sulfide polymer composition with improved impact resistance, and more particularly, to a polyarylene sulfide polymer or a modified product thereof, a vinyl aromatic compound and a conjugated diene compound are added as monomers. The present invention relates to a composition comprising a block copolymer having the following structure. Polyarylene sulfide polymers are heat resistant,
It is widely used as an engineering resin for electrical parts, precision equipment parts, chemical equipment parts, automobile parts, etc. because it has excellent hardness, chemical resistance, and extremely high rigidity. However, despite having such excellent properties, polyarylene sulfide polymers have poor impact resistance, which is a major hindrance to further expanding their range of applications. The inventors of the present application have conducted intensive studies to improve the impact resistance of polyarylene sulfide polymers and to find more useful materials. The inventors have discovered that the object can be achieved by combining block copolymers composed of compounds as monomers, and have arrived at the present invention. That is, the present invention comprises: 1 (i) 100 parts by weight of a polyarylene sulfide polymer or a modified material thereof; (ii) one or more polymer blocks mainly composed of a vinyl aromatic compound; and a conjugated diene compound. A block copolymer containing at least one polymer block as a main component and having a weight ratio of a vinyl aromatic compound to a conjugated diene compound of 5/95 to 95/5, which comprises the following (a) and (b) 1 part by weight or more and less than 100 parts by weight of a block copolymer that satisfies at least one of the requirements in (b) (b) More than 75% by weight of the vinyl aromatic compound in the copolymer is a block homopolymer segment (b) Impact-resistant resin composition 2 consisting of 1,2-vinyl bond content exceeding 15% The polyarylene sulfide polymer of component (i) has the general formula [-Ar-S ] - (In the above formula, Ar represents a phenylene group or a phenylene group substituted with an alkyl group or a substituted alkyl group.) An arylene sulfide polymer, copolymer, or modified product thereof having the structural unit Composition 3 according to Item 1, wherein the modified polyarylene sulfide polymer of component (i) has the general formula [-Ar-S]- (in the above formula, Ar is a phenylene group, an alkyl group, or Composition 4 according to item 2 above, which is a mixture of an arylene sulfide polymer or copolymer having the structural unit (representing a phenylene group substituted with a substituted alkyl group) and a styrene polymer. The system polymer is polystyrene, impact-resistant rubber-modified styrene polymer, acrylonitrile-butadiene-styrene copolymer, methacrylic acid ester-butadiene-styrene copolymer,
Composition 5 according to item 3 above, which is a styrene-maleic anhydride copolymer and any mixture thereof; component (ii) has a vinyl aromatic compound content of 5 to 5;
Composition 6 according to item 1 above, which is a block copolymer having a content of 95% by weight, wherein component (ii) has a vinyl aromatic compound content of 10 to 10% by weight.
Composition 7 according to item 5, which is a block copolymer having a content of vinyl aromatic compound of more than 60% by weight and not more than 90% by weight of component (ii). Composition 8 according to item 5 above, which is based on 100 parts by weight of the total amount of component (i) and component (ii),
Glass fiber, carbon fiber or powdered inorganic filler
There is provided a composition according to items 1 to 8 above, which contains 150 parts by weight or less. The present invention will be explained in detail below. The polyarylene sulfide polymer used in the present invention has the general formula [-Ar-S]- (In the above formula, Ar represents a phenylene group, or a phenylene group substituted with an alkyl group or a substituted alkyl group. ) is an arylene sulfide polymer or copolymer having the structural unit. Suitable examples include polyphenylene sulfide and poly4,4-diphenylene sulfide. In addition, a modified polyarylene sulfide polymer is a product obtained by blending a styrene polymer into an arylene sulfide polymer or copolymer having the structural unit of the above general formula to modify its properties. be.
Styrenic polymers used for modification include polystyrene, styrene-α-methylstyrene copolymer, butadiene-styrene block copolymer, impact-resistant rubber-modified styrene polymer, acrylonitrile-styrene copolymer, and styrene-methacrylate. Acid ester block copolymers, styrene-maleic anhydride copolymers, acrylonitrile-butadiene-styrene copolymers, acrylic ester-butadiene-styrene copolymers, methacrylic ester-butadiene-styrene copolymers, and these polystyrene-based Mixtures of polymers may be mentioned. The content of the styrene polymer constituting the modified polyarylene sulfide polymer is 70% by weight or less, more generally 50% by weight or less. Next, a block copolymer (hereinafter referred to as component (ii)) containing one or more polymer blocks mainly composed of a vinyl aromatic compound and one or more polymer blocks mainly composed of a conjugated diene compound , simply referred to as "block copolymer"), the weight ratio of the vinyl aromatic compound to the conjugated diene compound is 5/95.
The composition range is from 10/90 to 90/10, more preferably from 15/85 to 85/15. If the above weight ratio is less than 5/95, the properties of the block copolymer as a thermoplastic elastomer will be poor, and the weight ratio will be too low.
If it exceeds 95/5, the effect of improving impact resistance will be poor, which is not preferable. In the composition of the present invention, when the vinyl aromatic compound content of the block copolymer is in the range of 10 to 60% by weight, a composition with particularly excellent impact resistance can be obtained; In a range of more than 60% by weight and less than 95% by weight, a substantially transparent composition can be obtained. Therefore, in the present invention, the content of the vinyl aromatic compound can be arbitrarily changed within the above range depending on the required properties. The polymer block mainly composed of vinyl aromatic compounds in the above block copolymer is the hard segment of the block copolymer, and its glass transition point is
The temperature is 40°C or higher, preferably 60°C or higher. In this block, the weight ratio of the vinyl aromatic compound and the conjugated diene compound is 60/40 to 100/0, preferably
Composition range from 80/20 to 100/0, more preferably
It is 100/0. The distribution of the minor component conjugated diene compound in this block may be random, tapered (increasing or decreasing monomer component along the molecular chain), partially block-like, or a combination thereof. On the other hand, a polymer block mainly composed of a conjugated diene compound is a soft segment of a block copolymer, and its glass transition point is 0°C or lower, preferably -20°C or lower. In this block, the weight ratio of the vinyl aromatic compound to the conjugated diene compound is 0/100 to 40/60, preferably 0/100 to 40/60.
The composition range is 30/70. The distribution of the minor vinyl aromatic compound in this block may be random, tapered, partially block-like, or a combination thereof. When containing two or more polymer blocks mainly composed of vinyl aromatic compounds or polymer blocks mainly composed of conjugated diene compounds, each block may have the same structure or different structures. In the above block copolymer, the weight ratio of the polymer block mainly consisting of a vinyl aromatic compound to the polymer block mainly consisting of a conjugated diene compound is 5/95 to 95/5, preferably 10/90 to 90. /10 range. The vinyl aromatic compounds constituting the block copolymer include styrene, o-methylstyrene, p-methylstyrene, p-tert-butylstyrene, 1,3 dimethylstyrene, α-methylstyrene,
Among vinylnaphthalene, vinylanthracene, etc., styrene is particularly common.
These may be used not only as a single type but also as a mixture of two or more types. Examples of conjugated dienes include diolefins having 4 to 8 carbon atoms and a pair of conjugated double bonds, such as 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), and 2,3-butadiene. dimethyl 1,3 butadiene, 1,3 pentadiene,
Examples include 1,3-hexadiene, and particularly common ones include 1,3-butadiene and isoprene. These are not only one type but two types.
It may be used as a mixture of more than one species. The average molecular weight of the block copolymer is 10,000~
The range is 1,000,000, preferably 20,000 to 800,000, and more preferably 30,000 to 500,000. Furthermore, the molecular structure of the block copolymer may be linear, branched, radial, or any combination thereof. Examples of such structures include the following. (A-B)n, A(-B-A)n, B(-A-
B)n [(A-B)n]-n ₊₂ C [(B-A) _-o B]-n ₊₂
C (wherein A is a polymer block mainly composed of a vinyl aromatic compound, B is a polymer block mainly composed of a conjugated diene compound, C is a coupling agent residue or a polyfunctional organolithium compound residue, m and n
is an integer greater than or equal to 1. ) The block copolymer used in the present invention is usually prepared by polymerizing a vinyl aromatic compound and a conjugated diene compound as an anion in an inert hydrocarbon solvent such as benzene, hexane, or cyclohexane using an organic lithium compound such as butyllithium as a polymerization catalyst. Branched,
A radial block copolymer is obtained. others,
Any vinyl aromatic compound-conjugated diene compound block copolymer obtained by any production method can be used as long as it falls within the range of the above limitations. The above-mentioned block copolymer is not limited to only one type, but also has a polymer structure, such as styrene content, molecular weight,
It is also possible to combine two or more types of block copolymers having different numbers of blocks. The block copolymer used in the present invention is one in which more than 75% by weight of the vinyl aromatic compound in the copolymer exists as a block homopolymer segment, or a 1,2-vinyl bond in the copolymer. It is necessary to have a content of more than 15% in order to obtain a composition with excellent processability. Block-like homopolymer segments of vinyl-substituted aromatic compounds in copolymers can be obtained by oxidative decomposition of the copolymers with di-tertiary butyl hydroperoxide catalyzed by osmium tetroxide (e.g., LMKolthoff et al., J. Polymer Sci.
1429 (1946)). Therefore, the proportion of vinyl-substituted aromatic compounds present as block-like homopolymer segments in a copolymer can be determined by calculating the amount of block-like homopolymer segments in a block copolymer determined by such a method. It can be determined by dividing by the amount of all vinyl-substituted aromatic compounds contained. The content of 1,2-vinyl bonds in copolymer (i) can be measured using an infrared spectrophotometer according to the method described in Analytical Chemistry, Vol. 21, p. 923 (1949). can. The impact-resistant resin composition of the present invention contains component (ii) in an amount of 1 part by weight or more and less than 100 parts by weight, preferably 3 to 70 parts by weight, per 100 parts by weight of component (i). Ingredient (i)
If the ratio of component (ii) to 100 parts by weight is less than 1 part by weight, the effect of improving impact resistance will be small, and if it is more than 100 parts by weight, the tensile strength and rigidity of the composition will be lost, which is not preferred. Other additives can be added to the composition of the present invention as necessary. The type of additive is not particularly limited as long as it is commonly used in plastic formulations, but examples include glass fiber, glass beads, inorganic reinforcing agents such as silica, charcoal, and talc, organic fibers, coumaron indene resin, etc. organic reinforcing agents, crosslinking agents such as organic peroxide and inorganic peroxide, titanium white, carbon black,
Pigments such as iron oxide, dyes, flame retardants, antioxidants,
Examples include ultraviolet absorbers, antistatic agents, lubricants, plasticizers, other fillers, and mixtures thereof. In particular, a composition containing 150 parts by weight or less, preferably 10 to 100 parts by weight, of glass fiber, carbon fiber, or powdered inorganic filler per 100 parts by weight of the thermoplastic polymer composition of the present invention has heat resistance, Rigidity and mechanical strength are further improved, providing an excellent material for molded products. As the glass fiber, those having a diameter of about 2 to 100 microns and a length of about 50 to 30,000 microns, which are usually used for resin mixing, are used. In addition, as a powdered inorganic filler,
Those used for resin mixing, such as calcium carbonate, finely divided silicic acid, synthetic silicic acid, and clay, can be used. The block copolymer composition of the present invention comprising component (i) and component (ii) can be produced by any conventional compounding method. For example, melt kneading methods using general kneading machines such as open rolls, intensive mixers, internal mixers, co-kneaders, continuous kneaders with twin-screw rotors, extruders, etc., after dissolving or dispersing each component in a solvent. A method of removing the solvent by heating, etc. is used. The impact-resistant resin composition of the present invention thus obtained can be easily molded into molded products of various shapes by any conventionally known molding method such as extrusion molding, injection molding, etc. Can be used for parts, precision equipment parts, automobile parts, etc. Some Examples will be shown below, but these are intended to explain the present invention more specifically, and it goes without saying that the scope of the present invention is not limited thereto. Examples 1 to 3 (and Comparative Examples 1 and 2) Production of block copolymer The inside of a dry polymerization vessel with an internal volume of 30 mm was sufficiently purged with nitrogen gas, and 4.2 g of precisely dehydrated hexane and 0.8 kg of hexane were added to it. of styrene and 0.6 kg of butadiene were added, and then a hexane solution containing 4 g of n-butyllithium as a polymerization initiator was added, and the internal temperature was raised to 70° C. to carry out polymerization. After the polymerization is substantially complete, 7.8Kg hexane, 0.8Kg
of styrene and 1.8 Kg of butadiene were added and polymerized at 70°C. After the polymerization was substantially complete, a small amount of methanol was added to stop the polymerization. Then 40 g of 2,6-di-tert-butyl-
After adding 4-methylphenol and 40 g of trisnonylphenyl phosphate, the solvent cyclohexane was distilled off under heating to obtain a block copolymer (Sample 1). The styrene content of this block copolymer is 40% by weight, and approximately 80% of the styrene is
existed as block polystyrene. Production of impact-resistant resin composition Polyphenylene sulfide (hereinafter abbreviated as PPS), Sample 1, and polystyrene (hereinafter abbreviated as PS) were each mixed in a Henschel mixer according to the blending ratios shown in Table 1. After thorough mixing, 30
Pelletization was performed using a mm extruder in a conventional manner. This pellet was injection molded to prepare a test piece, and its tensile strength and impact strength were measured. The results are shown in Table 1, and it can be seen that a composition with improved impact resistance can be obtained by blending a block copolymer with PPS. It is also clear from Table 1 that if the blending amount of the block copolymer exceeds the range of the present invention, the tensile strength will decrease, which is undesirable.

[Table] Examples 4 and 5 Examples 1 to 3 were prepared according to the blending ratios of PPS, Sample 1, PS, and high impact rubber modified polystyrene (hereinafter abbreviated as HIPS) shown in Table 2.
A composition of the present invention was prepared in the same manner as above, and its impact strength was measured. The results are shown in Table 2.

[Table] Used.
Comparative Example 3 In the production of the block copolymers shown in Examples 1 to 3, except that a mixture of hexane, styrene and butadiene was fed in conjunction to a polymerization vessel at a rate of 200 ml/min for polymerization. A block copolymer (sample 2) was obtained in the same manner as the block copolymer. The styrene content of this copolymer is 40
Approximately 23% by weight of the styrene is present as block polystyrene and 1,2-
The content of vinyl bonds was 11%. Sample 2 was subjected to PPS in the same manner as Examples 1 to 3.
When injection molding was performed, it became clear that the surface texture of the molded pieces was poor and the processability was poor. Examples 6 to 10 (and Comparative Example 4) Production of block copolymer 4.5 kg of purified and dehydrated cyclohexane and 1.5 kg of styrene were charged into the same polymerization vessel as used in Examples 1 to 3, and then polymerization was started. After adding a hexane solution containing 2.8 g of 2-butyllithium as an agent, the internal temperature was raised to 70°C to carry out polymerization. After the polymerization of styrene is substantially completed, 1 kg
of butadiene, 1.5 Kg of styrene and 7.5 Kg of cyclohexane were added and polymerized at 70°C. After the polymerization was substantially completed, a block copolymer was obtained by the same treatment as described above (Sample 3).
The styrene content of this copolymer was 75% by weight, and about 85% of the styrene was present as block polystyrene. Next, the purified and dehydrated 4.5
Prepare Kg of cyclohexane and 1.5Kg of styrene,
Next, n-butyllithium was added as a polymerization initiator.
After adding a hexane solution containing 2.4 g, the internal temperature was raised to 60°C to carry out polymerization. After the styrene polymerization is substantially completed, 0.8Kg of butadiene,
1.7Kg styrene, 7.5Kg cyclohexane and 8
g of tetrahydrofuran mixture and heated to 60 °C.
Polymerized with After the polymerization was substantially completed, a block copolymer was obtained (Sample 4) by the same treatment as above. The styrene content of this copolymer is 80
The content of 1,2-vinyl bonds in weight percent was about 25%. Production of impact-resistant resin composition Example 1 was prepared using sample 3 or sample 4, PPS, and PS according to the compounding ratios shown in Table 3.
A test piece was prepared in the same manner as in 3 to 3, and its tensile strength and impact strength were measured. The results are shown in Table 3. All compositions of the present invention were substantially transparent compositions.

[Table] Used.
Example 11 (and Comparative Example 5) A composition of the present invention containing glass fibers was pelletized according to the process shown in Table 4. This pellet was injection molded to prepare a test piece, and the impact strength was measured. The results are shown in Table 4. In this experiment, the block copolymer used was S-411 (manufactured by Philips Petroleum) (sample 5), which is a radial type block copolymer.
was used.

【expressed.

Claims (1)

[Scope of Claims] 1. (i) 100 parts by weight of a polyarylene sulfide polymer or its modified material; (ii) one or more polymer blocks mainly composed of a vinyl aromatic compound; and a conjugated diene compound. A block copolymer containing at least one polymer block as a main component and having a weight ratio of a vinyl aromatic compound to a conjugated diene compound of 5/95 to 95/5, which comprises the following (a) and (b) 1 part by weight or more and less than 100 parts by weight of a block copolymer that satisfies at least one of the requirements in (b) (b) 75% by weight of the vinyl aromatic compound in the copolymer
(b) an impact-resistant resin composition comprising a 1,2-vinyl bond content of more than 15%;