JPS63125531A - Carbon fiber-reinforced resin composition - Google Patents

Abstract

PURPOSE:To obtain the title composition excellent in heat and chemical resistance, flexibility, etc., by impregnating a carbon fiber with a resin containing a block copolymer consisting of chemically bonded polyphenylene sulfide and polyphenylene sulfide sulfone. CONSTITUTION:A carbon fiber-reinforced resin composition prepared by impregnating a carbon fiber with a mixture of a block copolymer consisting of chemically bonded polyphenylene sulfide (PPS) and polyphenylene sulfide sulfone (PPSS) as soft segments with at least either PPS or PPSS. Since, instead of a resin obtained by merely blending PPS with PPSS of poor compatibility with PPS, a block copolymer consisting of chemically bonded chains of the both components is used, a high-performance carbon fiber-reinforced plastic freed from thermal crack and deterioration of carbon fiber due to PPS and excelling in heat and chemical resistance and adhesion to carbon fiber in which PPS is inherently excellent can be obtained, and this plastic can be applied to aircraft and aerospace use.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention is directed to carbon fiber reinforced glass (hereinafter referred to as CFRP), which has the excellent physical properties of carbon fiber and has excellent heat resistance, chemical resistance, mechanical strength, etc. VC).More specifically, the essential component is a copolymer made by chemically bonding polyphenylene sulfide (hereinafter referred to as PPS) with polyphenylene sulfide sulfone (hereinafter referred to as PP5S) as a soft segment. It relates to CFRP which is completely impregnated with a resin composition and has excellent mechanical properties such as heat resistance, chemical resistance, and flexibility.

(Prior Art and Problems) CFRP is lightweight and has excellent mechanical, chemical, and electrical properties, so it is widely used as a variety of structural members. The performance of CFRP is not always satisfactory due to the adhesion between the carbon fibers and matrix resin, and the heat resistance and mechanical properties of the matrix and resin. is required.

Among the performances required of this CFRP, heat resistance, chemical resistance, etc. are largely influenced by the type of matrices and resins. For example, epoxy resins that have good adhesion to carbon fibers may have insufficient heat resistance. On the other hand, polyimide resins which have excellent heat resistance have poor moldability and are unsuitable for industrial use in terms of productivity and cost.

PPS resin is attracting attention as a high-performance thermoplastic resin with excellent heat resistance, chemical resistance, and rigidity, but this resin impregnates carbon fiber with uncrosslinked PPS resin and cross-links the PPS during post-heat treatment. The radicals generated during the reaction deteriorate the carbon fiber, and because the elongation is small, thermal cracks are likely to occur in CFRP after molding, and the strength or glabella shear strength (hereinafter abbreviated as ILSS) is low. In addition, the heat treatment for crosslinking mentioned above increases the molding time, which reduces productivity.
It has not yet been put into practical use as IJ Fuchs resin for FRP.

On the other hand, in order to improve the above-mentioned drawbacks, a method using a pps resin composition mixed with polysulfone in a specific range as a matrix resin is disclosed in Japanese Patent Publication No. 82130/1982, but the interaction between PPS and polysulfone is Due to insufficient solubility, the flexibility or mechanical strength of pps cannot be sufficiently improved, and it is not always possible to provide a satisfactory CFRP.

(Ninth Means for Solving the Problems) The present inventors have developed a resin that has the advantages of PPS, improves its disadvantage of flexibility, and substantially eliminates deterioration of carbon fibers, thermal cracks of CFRP, etc. As a result of intensive studies to obtain compositions, we found that pps and ppss, which have terminal reactive groups.
The inventors have discovered that it is effective to use as a matrix resin a resin formed by chemically bonding the two through a copolymerization reaction, and have thus arrived at the present invention.

That is, the present invention uses CFRP, which has excellent mechanical properties such as heat resistance, chemical resistance, and flexibility, and is made by impregnating carbon fibers with a resin composition containing as an essential component a block copolymer composed of PPS and ppss. This is what we provide.

In the present invention, components of the pro-copolymer and PPS that can be mixed with the copolymer are preferably those included in the general formula because they provide a composition with excellent properties. However, such PPS has a logarithmic viscosity [η] (where [η] is 0.4
．． 9/Zoo Go's m liquid? At the reamer concentration, α-
Measured in chlornaphthalene at 206°C, using the following formula [η) = An (relative viscosity)/? This is the value calculated according to the terry concentration. ] is preferably in the range of 0.03 to 0.80.

Polymerization methods for this tellimer include a method in which a halodane-substituted aromatic compound, such as p-dichlorobenzene, is polymerized in the presence of sulfur and sodium carbonate, and a method in which a halodane-substituted aromatic compound, such as p-dichlorobenzene, is polymerized in the presence of sulfur and sodium carbonate; Examples include polymerization in the presence of sodium hydroxide or sodium aminoalkanoate, and self-condensation of p-chlorothiophenol. A suitable method is to react sodium sulfide and p-dichlorobenzene in a medium. At this time, to adjust the degree of polymerization, carmenic acid, sulfonic acid, or an alkali metal salt of phosphoric acid may be added.
Adding alkali hydroxide is a preferred method.

As copolymerization components, if the molar width is less than 30, meta-bonding groups, phenyl groups, alkoxy groups, carnoic acid groups (indicates metal bases of carmenic acid), within a range that does not significantly affect the crystallinity of the trifunctional bond. However, preferably the copolymerization component is 10 molar or less.

In particular, when a trifunctional or more functional phenyl, biphenyl, naphthyl sulfide bond, etc. is selected for copolymerization, the molar ratio is preferably 3 or less.

As a specific method for producing such PPS, for example, (1)
Production method using halodane-substituted aromatic compound, alkali sulfide and K (US Pat. No. 2,513,188, Japanese Patent Publication No. 44-2767)
1, Special Publication No. 45-3368 and Special Publication No. 52-12
240), (2) A method for producing thiophenols by condensation reaction in the presence of an alkali catalyst or copper salt (US Pat. No. 3,274,165 and British Pat. No. 11,606)
(Refer to No. 60), (3) Production method by condensation reaction of an aromatic compound with sulfur chloride in the coexistence of a Lewis catalyst (Special Publication No. 4)
6-27255 and Belgian Patent No. 29437].

The block copolymer in the present invention is, for example, pps s
It is obtained by reacting the terminal group of ppss with the terminal group of PPS, so for example, if the terminal group of ppss is
The terminal group of S is a sodium sulfide group (structural formula: Na
It is necessary to use a reactive group such as 5-). An example of a method for obtaining such pps 1 is to react the sodium sulfide component of the monomer in advance in a 1 to 20 molar excess with respect to the p-dichlorobenzene component during the polymerization reaction.

On the other hand, it is defined as a polymer constituting the block copolymer of the present invention. The molecular solution of this polymer has a logarithmic viscosity η1nh (where ηinh is a solution of 0.5/100 phenol/1.1, 2.2
-30% in tetrachloroethane (3:2 weight ratio) mixed solvent
The original value is calculated according to the following formula: η1nh=tn (relative viscosity)/polymer concentration. ] is preferably in the range of O, OS to 1.0. Examples of polymerization methods for this polymer include a method in which a dihaloaromatic sulfone and an alkali metal sulfide are reacted in an organic amide bath medium (see US Pat. No. 4,102,875).

It is useful when synthesizing the block copolymer of the present invention, and the method for obtaining it is such that, during the polymer synthesis reaction, the amount of Dino-Kuchi aromatic sulfone is, for example, 5% relative to the amount of alkali metal sulfide. A method of reacting in a molar excess state (see US Pat. No. 4,301,274) can be mentioned.

When performing the copolymerization reaction of ppss and PPS in the method of the present invention, it is also possible to use a method of adding a binder such as dihaloaromatic sulfone or sodium sulfide as a third component. Ninth, without departing from the purpose of the present invention, which is a block copolymer, there is a method of polymerizing either PPS or ppss in the presence of the other monomer component to finally obtain a copolymer. It can also be used.

However, 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 in good yield. On the other hand, if the number of terminal groups of either component is excessive, after the reaction is completed, unreacted homozygotes remain? By separating or extracting only the remer component, only the block copolymer can be completely recovered.

The solvent used in the copolymerization reaction is preferably an organic polar solvent that is substantially liquid at that temperature and pressure. Specifically, formamide, acetamide, N-methylformamide, N,N-dimethylformamide, N
, N-trimethylacetamide, 2-pyrrolidone, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone,
! -caglolactam, N-methyl-ε-caprolactam, hexamethylphosphoramide, tetramethylurea, 1
．． Amides such as 3-dimethyl-2-imidazolidinone,
Examples include urea and lactams; sulfones such as sulfolane and dimethylsulfolane; nitriles such as benzonitrile; ketones such as methylphenyl ketone; and mixtures thereof.

Among these solvents, it is particularly preferable to use aprotic organic polar solvents such as amides, lactams, or sulfones. The amount of organic polar solvent used is j? '
The weight ratio to the amount of lJmer component is in the range of 2 to 20,
Preferably it is in the range of 3 to 1o.

Copolymerization reaction by block reaction 't=nose is chemically bonded to form a block copolymer of epps and ppss. :2 weight ratio] Even though ppss is no longer contained in the extract after repeated extraction with a mixed solvent, the presence of this component in the polymer is confirmed.On the other hand, the copolymerization reaction product Whether or not unreacted PPS is contained in the product can be confirmed by performing fractional precipitation of the product using α-chlornaphthalene, which is a good solvent for PPS, and checking whether PPS homopolymer is present.

Please note that when performing a copolymerization reaction, the ratio of pps and ppss varies depending on the desired properties, but the ppss component and PP
The weight ratio with the S component is generally in the range of 1 to 99/99 to 1, preferably 5 to 90/95 to 10. If the weight ratio is less than 1799, the effects such as flexibility imparted by ppss cannot be achieved, and if it exceeds 99/1, the effects aimed at in this patent cannot be obtained, which is not preferable.

The block copolymer used in the present invention has a logarithmic viscosity [
η] (where [η] is 206 in α-chlornaphthalene at a polymer concentration of 0.4 N/100g solution)
It is a value calculated according to the following formula [η)=Afl(relative viscosity]/−limer concentration] in the range of 0.03 to 1.0 when measured at ℃.

The resin composition of the present invention comprises the block copolymers 3 to 10
．． When PPS is used in combination with 0 parts by weight, more preferably 10 to 100 parts by weight, PPS is preferably 1 to 9 parts by weight.
7 parts by weight, more preferably 10 to 90 parts by weight, ppss
When used together, ppss is preferably contained in an amount of 1 to 60 parts by weight, more preferably 10 to 40 parts by weight. Incidentally, the resin composition of the present invention is a monomer t-
It is preferable that the resin composition of the present invention contains 3 to 100 parts by weight because it has a great effect of improving flexibility and is less likely to cause thermal cracking, cracking, etc. of CFRP. The PPS component i& can be obtained by reacting one of the ppss components in excess. At that time, the presence of free PPS and ppss means that a certain amount of ppss is contained in the polymer after repeated extraction with N-methylpyrrolidone or a mixed solvent of phenol/tetrachloroethane, which is a good solvent for ppss. On the other hand, whether or not PPS homopolymer is present can be confirmed by a fractional precipitation experiment using α-chlornaphthalene.

The carbon fibers used in the present invention are relatively long fibers, usually having a length of 7 days or more, preferably 1 or more days, and may be of any type such as rayon type, I-lyacrylonitrile type, or pitch type. The carbon fiber may be in any form such as yarn, roving, cut fiber, woven fabric, knitted fabric, or braided fabric.

TFC, the resin composition of the present invention may contain other types of polymers such as thermoplastic resins and epoxy resins, additives, and fillers without departing from the purpose of the present invention. Furthermore, as reinforcing fibers, other reinforcing fibers such as glass fibers and organic fibers such as aramid fibers and aromatic polyester fibers may be used in combination.

In the resin composition of the present invention, the solid content weight ratio of the resin component and carbon fiber is usually 20/80 to 80/20, preferably 30/80 to 80/20.
/70 to 60/40.

The means for impregnating carbon fibers with the resin composition of the present invention is not particularly limited, and there are various methods. For example, a method of impregnating resin powder, slurry, resin solution, etc. using a spray can be mentioned. Furthermore, the resin composition of the present invention may be melted by heating preferably to 300 to 360° C., and carbon fibers may be impregnated with this in stages or continuously and molded. As a heating method, there is a method of high-frequency heating of the resin in the presence of a sensitizer. Molding is usually 300
~360℃ to at least 100! It can be carried out under a pressure of g/α8, and then slowly or rapidly cooled.

(Effects of the Invention) The feature of the present invention is that, unlike resins obtained by simply blending PPS and ppss, which have poor compatibility, the polymer chains of both components are chemically bonded as a matrix resin to be impregnated with carbon fibers. The point is that a resin containing a polypropylene copolymer is used.

In other words, the heat resistance and chemical resistance of PPS are maintained, the flexibility is improved, and the occurrence of thermal cracks in CFRP is suppressed by using the matrix resin.
Decrease in strength or ILSS caused by deterioration C of carbon fibers during the thermal crosslinking process of pps is prevented.

Therefore, the CFRP of the present invention is PPS! /C-induced carbon fiber deterioration and thermal cracking, and PPS
It is a high-performance CFRP with excellent heat resistance, chemical resistance, and adhesion to carbon fibers, and can be applied to aerospace and other applications.

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

Example 1. Comparative Examples 1 and 2 First, N-methylpyrrolidone 1 was placed in a 107 autoclave.
980I! , sodium sulfide hemihydrate 65511 (5
,0 mol], sodium hydroxide 2.0. F, and bis(p-chlorophenyl)sulfone 1436, p(s, o
mol], heated to 200°C under a nitrogen atmosphere, and allowed to react at that temperature for 6 hours with stirring.

Next, bis(p-chlorophenyl)sulfone 7 was added to this system.
2g (0.25 mol) t-N-methylpyrrolidone 200
A solution containing gK 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. 8 pieces of this cake
Dry under reduced pressure at 0 to 150°C to obtain light brown polymer 119O.
N was obtained (yield: 96 cm). Logarithmic viscosity η1 of this polymer
nh (where ηinh is phenol/1,1,2 at a polymer concentration of 0.5y100 rnt solution)
．． The value was measured in a mixed solvent of 2-tetrachloroethane (3:2 weight ratio) at 30°C and calculated according to the following formula η1nh=tn (relative viscosity)/polymer concentration.] is 0.22, which is 7t.

Subsequently, add N-methylpyrrolidone 3100 # and sodium sulfide 2.7 hydrate to 101 autoclave 1009 F.
(7.7 mol) and sodium hydroxide 3.5.9 (
0.09 mol] was charged, the temperature was raised to 200°C under nitrogen atmosphere with stirring for about 2 hours, water of 2201d was distilled out, and the t0 reaction system was cooled to 150°C, and then p-dichlorobenzene was added. 102911 (7.0 mol) and N-methylpyrrolidone 700I were added and reacted at 230°C for 1.5 hours and then at 260°C for 2 hours.The internal pressure at the end of the polymerization was 7.0 kg/i. After cooling the container, a portion of the contents was sampled and distributed from house to house, and the case Φ was boiled and washed three times with hot water, and then twice with acetone.
It was dried at 0.degree. C. to obtain a light grayish brown powder of pps,x remer (yield: about 94%). Logarithmic viscosity of this polymer [η] (
Here, [η] is polymer concentration 0.4, F/100d
, measured in α-chlornaphthalene at 206°C, [η)=
The ratio value calculated according to tn (relative viscosity)/polymer concentration was 0.14.

Next, 2370 g of the above-mentioned PPS polymerized polymer mixture, the terminal chlorphenyl group type PPSS3QOg and 1200 # of N-methylpyrrolidone were added, and after nitrogen gas, the mixture was sealed, heated to 220°C, and reacted at this temperature for 3 hours. Nine.

After cooling the reaction vessel, the contents were separated by sieve, the solid content was washed twice with N-methylpyrrolidone, and then boiled and washed three times with hot water.The nine cakes obtained were dried at 120°C for 5 hours. 486
A light brown powdery polymer of I was obtained. This polymer [η]
was 0.19.

In addition, when we measured the infrared absorption coefficient of this polymer, no peaks other than pps and ppss absorption were observed, and 1320 (7FI, 620 return and 48
The ppss was determined from the intensity of the characteristic absorption observed at 0 cm-1, and was found to be 46.0% by weight in the polymer. At the same time, elemental analysis of the polymer was carried out: the sulfur content was quantified and showed a value of 27.87%, confirming that the polymer contained 46.0 parts by weight of ppss.

Furthermore, a solvent extraction experiment of the above polymer was conducted. That is, an attempt was made to disperse the above polymer in N-methylpyrrolidone, which is a good solvent for ppss, and extract and remove unreacted ppss at 100°C. However, ppss was not eluted at all, and the infrared absorption spectrum measurement of the 41J mer recovered after the extraction experiment revealed that the ppss content was 46.
From these results, we can confirm that PPS and ppss are chemically bonded in the copolymerization reaction product of this example!
Be sure to confirm that it is a lock copolymer.

Next, this polymer was dispersed in chloroform to prepare a snow fat solution, and after a meal, this was poured into Toshiku Co., Ltd.)j! ! ! Using carbon fiber Trading Card T-300, a carbon fiber cloth with length/width ratio of 1/1 was impregnated, and chloroform was further removed by drying to create Gripreg. This Gripreg was laminated and put into a mold, and after heating and crosslinking at 350℃ for 40 minutes,
Pressure is applied in the range of 20-7 cm” and then cooled, and the mold becomes 14 cm.
The molded product was cooled to 0° C. and taken out at time t. The carbon fiber content of the molded product was adjusted to 60% by weight. After step 7 of annealing the molded product at 150°C for 1.5 hours, A
Bending strength and ILSS were measured in accordance with STMD-2344 and ASTM D-790. Display the results -
Shown in 1.

In Comparative Example 1, the e ppss powder obtained in Example 1 and the ppss powder obtained in Example 1 were used.
A molded article was obtained in the same manner as in Example 1 using a mixture containing PPS powder obtained by conventional treatment of the polymerization product with a ppss of 46.0 in the polymer. Seriously, in Comparative Example 2,
Impregnate only the above PPS powder and take out the molded product in the same manner. As shown in Table 1, the molded product obtained using the polymer containing the PPS/PP5S block copolymer was more bendable than the case without the addition of ppss or when a mixture of PPS and ppss was used. Strength and ILS
S is large in all cases, and the physical properties are good.

Table 1 Example 2 In the same manner as in Example 1, ppss was added to 1 in the polymer mixture.
A mixture of pps containing 8.0 weight + i width and a block copolymer of PPS/PP5S (weight of PPS/block copolymer = 15/85) was synthesized. This polymer [η
] is 0.18, just in case. pps synthesized in advance in Example 1
s homo? The above copolymer mixture was dispersed by dissolving the reamer in chloroform so that 5.0% by weight of the reamer was incorporated in the resin component, and the total ppss in the resin component was 23.0% by weight.
Make sure to adjust the resin solution for 0 weight. The following procedure was repeated in the same manner as in Example 1 except that the heating crosslinking time was changed to 30 minutes, and when the physical properties were evaluated, the bending strength at 23°C and 150°C was 77 kg/rrm, respectively.
kg/m” to'4VCK'IN Good physical properties, and ILSS at 23℃ is 6.7Kg/ms
“It was good.

Claims (1)

[Claims] A carbon fiber reinforced resin composition obtained by impregnating carbon fibers with a mixture of a block copolymer in which polyphenylene sulfide and polyphenylene sulfide sulfone are chemically bonded, and at least one of polyphenylene sulfide and polyphenylene sulfide sulfone.