JPH02294331A - Polyarylene sulfide and resin composition - Google Patents

Abstract

PURPOSE:To provide the subject sulfide having specific heat resistance, chemical resistance and dimensional stability and useful as an engineering plastic, etc., by specifying the intrinsic viscosity, the weight-average mol.wt. and the ratio between the intrinsic viscosity and a calculated viscosity thereof, respectively. CONSTITUTION:(A) At least one kind of a metal sulfide selected from the group consisting of alkali metal sulfides and alkali metal hydrosulfides, (B) a dihalogeno aromatic compound and (C) a tri(poly)halogeno nitro aromatic compound are subjected in a B/A molar ratio of 1.03-1.25 to a reaction in a polar solvent (e.g. N-methylpyrrolidone) to provide the objective sulfide having an intrinsic viscosity of 0.1-0.5dl/g, a weight-average mol.wt. of 1X10<4>-2X10<5>, a ratio of intrinsic viscosity/calculated viscosity of 0.4-0.8 and a whiteness degree of >=50.

Description

[Detailed description of the invention]

[Field of Industrial Application] The present invention relates to polyarylene sulfide and resin compositions, and more specifically, the present invention relates to polyarylene sulfide and resin compositions, and more specifically, polyarylene sulfide and resin compositions that have high non-nietonic properties and a high branching density, and in spite of the high branching density, the average molecular weight is not too large. , has a wide molecular weight distribution, has excellent moldability, fluidity, and thermal stability, has no coloring, has high whiteness, and has little generation of flakes during injection molding, and is easily molded by controlling the polymerization system. Polyarylene sulfite can be produced as a resin with stable properties, and in addition to having these characteristics, it also has mechanical strength, heat resistance, and long-term stability. +WRegarding a resin composition with improved chemical properties, etc. [Prior art and problems to be solved by the invention] Polyarylene sulfides such as polyphenylene sulfite are
It is a thermoplastic resin that has some thermosetting properties, and has excellent heat resistance, chemical resistance, and dimensional stability, so it is suitable for use as a molding material for electrical/electronic parts, injection precision molded products, films, etc. It is becoming widely used as an excellent engineering plastic. By the way, as polyarylene sulfide obtained by conventional production methods, thermally crosslinked type and linear high molecular weight type are known. However, the thermally crosslinked type polyarylene sulfide is made by heating polymer powder in the presence of oxygen to achieve a high molecular weight, so it contains an ultra-high molecular weight component and the polymer is heavily colored. ■Also,
In addition to being dark brown with low whiteness, it is extremely brittle due to foaming due to thermal decomposition, excessive branching and crosslinking, and non-uniformity, making it difficult to use as a resin alone, and due to severe coloring. Its uses are extremely limited for reasons such as the difficulty of color matching. On the other hand, although the linear high molecular weight type polyarylene sulfide is superior to the heat-stretched type in physical properties such as mechanical strength, especially toughness, it crystallizes slowly and has low melt tension (extensional viscosity). There is a problem that it is low and that flakes are likely to occur during molding, resulting in poor productivity. Therefore, in order to complementarily solve the problems of the thermally crosslinked type polyarylene sulfite and the linear high molecular weight type polyarylene sulfide, it is necessary to achieve appropriate branching density and crosslinking density, and to improve the molecular weight and molecular weight distribution. Is there a need for optimization? For example, as a means of increasing the molecular weight, a method is conventionally known in which the water-containing alkali metal sulfide is subjected to dehydration treatment prior to the polymerization reaction to adjust the proportion of water in the reaction solution used for polymerization. alone is not sufficient to increase the molecular weight, so a method is used in which a branching agent is added to the reaction solution and the polymerization reaction is carried out to further increase the molecular weight (
U.S. Patent No. 4. See specification No. 0:18,261. ) However, in this conventional method of simply adding a branching agent to increase the molecular weight, although polyarylene sulfide such as polyphenylene sulfite with a sufficiently high molecular weight can be obtained relatively easily, this high molecular weight Molecular weighting reduces the melt flowability of the polymer. Therefore, raising the molding temperature may be an option, but increasing the molding temperature causes decomposition of the polymer, so it is necessary to increase the injection pressure during injection molding, and as a result, the molded product is more likely to have flashes. Furthermore, JP-A-59-22375:I discloses a composition obtained by blending a linear high molecular weight type polyarylene sulfide and a thermally crosslinked type polyarylene sulfide. has the problem of poor thermal stability and coloring, resulting in low whiteness. Furthermore, JP-A-62-240:159 discloses a composition comprising a blend of a linear high molecular weight type polyarylene sulfite and a low molecular weight linear polyarylene sulfite. In this composition, although crystallization is slightly promoted, the melt tension is rather reduced, and the effect of reducing the occurrence of flakes during molding has not been sufficiently achieved. In other words, by achieving appropriate branching density and crosslinking density, and optimizing the molecular weight distribution and molecular weight distribution, the problems of conventional thermally crosslinked type and linear high molecular weight type polyarylene sulfide were complementarily resolved. Polyarylene sulfide is desired. The present invention has been made based on the above circumstances. The object of the present invention is to have a high branching density, high non-Newtonian property and melt tension (extensional viscosity), and a wide molecular weight distribution without having an excessively large average molecular weight despite the high branching density. It is a polyarylene sulfite that produces significantly less flaking during injection molding, has excellent fluidity and moldability, has less impurities, has excellent thermal stability, has less coloring, has high whiteness, and can be toned. The object of the present invention is to provide a resin composition which not only has these features but also has improved mechanical strength, heat resistance, long-term stability, chemical resistance, etc. [!!A thousand steps to solve the problem] In order to solve the above problems, the inventors of the present invention have conducted intensive studies and found that a polyarylene sulfite whose logarithmic viscosity number, weight average molecular weight, ratio of logarithmic viscosity number to calculated viscosity, and whiteness are within a specific range. has a large branching density, non-Newtonian property and melt tension (extensional viscosity), and although the branching density is large, the average molecular weight is not too large.
It has a wide molecular weight distribution, produces significantly less flaking during injection molding, and has excellent fluidity and moldability.
Moreover, in general, it is possible to easily produce resins with stable properties by simply controlling the polymerization system, so they have extremely low impurity content, excellent thermal stability, little coloring, and high whiteness. The inventors have discovered that a filler-containing resin composition using this polyarylene sulfide has further improved mechanical strength, heat resistance, long-term stability, chemical resistance, etc., and has thus arrived at the present invention. The structure of the invention of claim 1 is that the logarithmic viscosity number [η+ahl;
(0.1 to 0.5 djL/g, weight average molecular weight is 1 x 10' to 2 x 10', and logarithmic viscosity ['
? tab]? Calculated viscosity [sword l. 1e (logarithmic viscosity number [η..hl/calculated viscosity [ηl0■.]) is 0.4 to 0.
8 and has a whiteness/chromaticity [JIS P8123] of 50 or more. and/or a powdery filler. The polyarylene sulfide and resin composition of the present invention will be explained below. ? The polyarylene sulfide according to claim 1 (characteristics) The polyarylene sulfide of the present invention has a logarithmic viscosity number [η
▲nh] *Weight average molecular weight, logarithmic viscosity number [η. . h
] and the calculated viscosity [ηlsale (logarithmic viscosity number [kanao.h]/calculated viscosity [η1.■.)] and the whiteness each need to be within specific ranges. That is, the logarithmic viscosity number [ηillh] is usually
0.1 to 0.5 di/g. Preferably 0.2 NO
．． It is 4di/g. This logarithmic viscosity number [η. ．． h] is 0
．． If it is less than 1 djL/g, the strength and moldability such as occurrence of flakes during injection molding may not be sufficient. on the other hand,
If it exceeds 0.5 dl/g, the viscosity during melting will be high and
For example, injection molding requires high temperatures, which can easily lead to resin decomposition and flaking. The weight average molecular weight is I x 10' to 2 x 10
'Preferably 2 x 1G' to 1. It is SX10'.
If the weight average molecular weight is less than 1 x 10', mechanical strength such as impact resistance, long-term stability, chemical resistance, etc. may be significantly reduced. on the other hand. When it exceeds 2 x 105, the viscosity becomes high and moldability is poor, and it may be difficult to obtain a good molded product. In addition, the logarithmic viscosity number [η Todoroki. ] and calculated viscosity

[η1. ．． dish. ratio {branching degree parameter (Bl). Logarithmic viscosity [η+,,hl/
Calculated viscosity [η]. ．． breath. } is 0.4 to 0.8, preferably 0.5 to 0.8. If this ratio is less than 0.4, the crosslinking density will be high and the tree will become stiff, the viscosity will also be high and moldability will be poor, and gel will form during polymerization, making stable production difficult. It may become. On the other hand, 0.
If it exceeds 8, the non-Newtonian property becomes small and it may not be possible to effectively prevent the occurrence of flashing during injection molding. Note that the calculated viscosity [η]eale is as follows for a linear or long chain branched system: [η]aa+a = a. stx 10-'M
In systems with a distribution, it can be calculated from the GPC (gel permeation chromatography) chromatogram using the following formula. (In the above formula, c represents the concentration of the component with the molecular weight M1. ) Moeki whiteness [JIS P8123] is usually 50
or more, preferably 60 or more. Furthermore, the molecular weight distribution of the polyarylene sulfide according to claim 1 is such that the proportion of components with a molecular weight of 2 x 10' or more to the whole is 3% by weight or more, preferably 4% by weight or more, and the proportion of components with a molecular weight of 2 x 1G3 or less is The proportion of the components to the total is 20% by weight or less, preferably 16% by weight
The following is desirable. If the molecular weight distribution is within this range. In particular, moldability is improved, for example, the occurrence of flakes during injection molding is reduced, and sheets and films with uniform thickness and fibers without thread breakage can be obtained. Furthermore, it is desirable that the polyarylene sulfide according to claim 1 has a flow characteristic parameter (El) of 1.2 or more. Flow characteristic parameter (El)
is 1.2 or more. The melt tension increases, making it particularly effective in preventing the occurrence of flashing during injection molding. Here, the flow characteristic parameter (El) is
The following formula; EI=G".b-7G'* {However, in the above formula, G"ob, $5, and G"l are the periods measured at a temperature of 300°C using a cone-disk viscometer. This is the storage modulus obtained by the vibration method, and the angular velocity ω=l
(rad/second). In addition, G''l is the value of a linear polyarylene sulfite having the same logarithmic viscosity number [ηinh] as the sample.} (Production method) Claim l having the above characteristics For example, the polyarylene sulfide described in (A) at least one metal sulfide selected from the group consisting of alkali metal sulfides and alkali metal hydrosulfides and (B) in a polar solvent.
When bringing the dihalogen aromatic compound into contact with the (C) polyhalogen nitroaromatic compound or trihalogen aromatic compound, the formula (^) used for the component. The molar ratio of the component (B) [(B)/(A)] is 1.
．． 03 to 1.25, and a proportionate molar ratio of the component (C) to the component (B) used [(
C)/(B)] within the range of 0.003 to 0.05. Examples of the polar solvent include organic amide compounds, lactam compounds, urea compounds, and cyclic organic phosphorus compounds. Specifically, N,N-dimethylformamide, N
, N-dimethylacetamide F,N,N-diethylacetamide, N,N-dibropylacetamide, N,N-dimethylbenzoic acid amide, Kabuguchi lactam, N-methylcaprolactam, N-ethylcaprolactam, N- Isopropyl caprolactam, N-isobutyl caprolactam, N-normal propyl cabrolactam, N-normal butyl cabrolactam, N-cyclohexyl caprolactam, N-methyl-2-pyrrolidone, N-ethyl-2-
pyrolitone, N-isobrobyl-2-pyrrolitone, N-
Inbutyl-2-pyrrolidone, N-normal propyl-
2-Virrolidone, N-n-n-butyl-2-virolitone, N-cyclohexyl-2-virolitone, N-methyl-
3-Methyl-2-virolitone, N-cyclohexyl-2
-Virrolitone, N-ethyl-3-methyl-2-pyrrolidone, N-methyl-3,4,5-trimethyl-2-pyrrolidone, N-methyl-2-piberitone, N-isopropyl-2-biveridone, N- Methyl-2-piberidone, N-ethyl-2-biperidone, N-isobrobyl-2-biperidone, N-methyl-6-methyl-2-piberitone, N
-Methyl-3-ethyl-2-piveridone, tetramethylurea. N,N'-dimethylethyleneurea, N,N'-dimethylpropyleneurea, l-methyl-1-oxosulfolane, l-ethyl-1-oxosulfolane, 1-phenyl-1-oxosulfolane, l-methyl-l- Oxophosphorane 5 Examples include l-normal brobyl-1-oxophosphorane and l-phenyl-l-oxophosphorane. These solvents may be used alone or in combination of two or more. Among the various polar solvents, aprotic organic amides or lactams can be suitably used, and among these, preferred are N-alkyl lactams and N-alkyl pyrrolidones, and particularly preferred are N-methylpyrrolidone. In the above manufacturing method, at least one selected from the group consisting of alkali metal sulfides is used as the component (^). When using an alkali metal hydrosulfide, it is usually preferable to use a base together. This base is
It is possible to efficiently neutralize or accept hydrogen halide that can be generated by converting an alkali metal hydrosulfide into an alkali metal sulfide or by combining an alkali metal hydrosulfide and a polyhalogen aromatic compound (B). Various types of bases, such as inorganic bases and organic bases, can be used as long as they have acid acceptors that can be used and do not impede the purpose of the invention as claimed in claim 1. In this case, alkali metal hydroxides etc. can be suitably used. Specific examples of the alkali metal hydroxide include lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, and cesium hydroxide. Among these, lithium hydroxide and sodium hydroxide are preferred, and sodium hydroxide is particularly preferred. Note that these bases such as alkali metal hydroxides may be used alone or in combination of two or more. The amount of the base such as alkali metal hydroxide used as required is 1 equivalent (1 equivalent) of the alkali metal hydrosulfide used.
At least 1 equivalent is required per mole). Specific examples of the alkali metal sulfides include, for example,
Examples include lithium sulfide, sodium sulfide, potassium sulfide, rubidium sulfide, and cesium sulfide. Among these, lithium sulfide and sodium sulfide are preferred, and sodium sulfide is particularly preferred. Note that these alkali metal sulfides may be used alone or in combination of two or more. The alkali metal hydrosulfide includes lithium hydrosulfide,
Mention may be made of sodium bisulfide, potassium bisulfide, rubidium bisulfide, calcium bisulfide and cesium bisulfide. Among these, sodium bisulfide and lithium bisulfide are preferred, and sodium bisulfide is particularly preferred. Kikuki alkali metal sulfides and alkali metal hydrosulfides [
Hereinafter, both may be collectively referred to as alkali metal (water) sulfides. ] can be used as an anhydride, or can be used as a commercially available or industrial hydrate or an aqueous mixture. However, if these hydrates or aqueous mixtures contain a large amount of water in the polycondensation system when used as is, a dehydration step can usually be performed prior to the polymerization reaction. Examples of the dihalogen aromatic compound (B) include dihalobenzenes such as m-dihalobenzene and p-dihalobenzene; 2,3-dihalotoluene;
2.5-dihatarotoluene, 2.6-dihalotoluene, 3
．． 4-dihalotoluene, 2.5-dihaloxylene, l-ethyl-2.5-dihalobenzene, l,2,4.5-tetramethyl-3.8-dihalobenzene% 1-n-nhexyl-2.5-dihalobenzene lobenzene, and alkyl-substituted dihalobenzenes or cycloalkyl-substituted benzenes such as l-cyclohexyl-2,5-dihalobenzene: l-phenyl-2,5-dihalobenzene, l-benzyl-2,5-dihalobenzene, and l-benzyl-2,5-dihalobenzene; -Aryl-substituted dioctabenzenes such as -p-tolyl-2,5-dihalobenzene; dihalobiphenyls such as 4,4-dihalobiphenyl; and 1,4-dioctalonaphthalene, 1,6-dihalo Naphthalene. and di-8lonaphthalenes such as 2,6-dihalonaphthalene. The halogen elements in these dihalogen aromatic compounds are fluorine, chlorine, bromine, or iodine, and they may be the same or different. Among the components (B), dihalobenzenes are preferred, and p-dichlorobenzene and m-dichlorobenzene are particularly preferred.
-p-dichlorobenzene containing dichlorobenzene in a proportion of 20 mol% or less. In the above production method, the polyhalogen nitroaromatic compound or trihalogen aromatic compound (C) is, for example, 2,4-
dihalonitrobenzenes such as 22,5-dichlorobenzene; dihalonitrodiphenyl ethers such as 2-nitro4,4°-dichlorodiphenyl ether; 3,3°-dinitro-4,4°-dichloro Dihalonitrodiphenylsulfones such as diphenylsulfone; dihalonitropyridines such as 2,5-dichloro-3-nitropyridine, or various dihalonitronaphthalenes or l,2,4-triclobenzene;
1,3.5-trichlorobenzene such as trichlorobenzene. 1, 4.6-1-Licro-naphthalenes and the like. These may be used alone or in combination of two or more. In the above manufacturing method, the polar solvent [hereinafter referred to as CD]
Sometimes called ingredients. ], at least the metal (
water) sulfide (A) and the polyhalogen aromatic compound (B)
) and the polyhalogenated ditroaromatic compound (C) are brought into contact and reacted to synthesize polyarylene sulfide such as polyphenylene sulfite. However, when carrying out this reaction, the molar ratio [(B)/(A)] of component (A) and component (B) used is 1.03.
~1.25, preferably l. 04 to 1.15, and the molar ratio of the component (B) to the component (C) [ (
C)/(B)l from 0.003 to O. OS. It is important that it is preferably within the range of 0.004 to 0.02. If these molar ratios are out of the above range, polyarylene sulfide with a sufficiently high molecular weight may not be obtained, or even if the molecular weight is sufficiently increased, the obtained polyarylene sulfite may not be melted. Insufficient fluidity leads to insufficient moldability, especially moldability by injection molding, and this molding pressure becomes high, making it easy to generate flakes during injection molding (however, [(B) 1.2 or more and [(C)/(B month is 0.05 or more,
Although it is possible to suppress the generation of paris, it is not practical because the polymer becomes brittle and the yield decreases. ), and in some cases the polymer tends to be colored, making it impossible to obtain the polyarylene sulfide according to claim 1. In the method for producing Moeki, the polymerization reaction can also be carried out in the presence of an appropriate amount of moisture, as is usually carried out. The amount of the polar solvent used in this production method is not particularly limited as long as it is sufficient for the reaction to proceed uniformly, but it is usually used in the above (^). The weight range is 0.1 to 10 times the total weight of components (B) and (C) and other optional components (excluding the solvent). If the amount used is less than 0.1 times the weight, the reaction may not proceed sufficiently. On the other hand, if it exceeds a double star, volumetric efficiency may deteriorate and productivity may decline. Also. In this production method, during the polymerization reaction, catalysts or polymerization aids, molecular weight regulators such as monohalogen aromatic compounds, tetrahalogen aromatic compounds, active hydrogen-containing compounds, alkali metal hydroxides, etc. It is also possible to use appropriately selected liquid regulators, reducing agents, etc., and add them to the reaction system. Moeki catalyst or polymerization aid [hereinafter sometimes referred to as component (E)]. ], various known ones can be used, such as alkali metal halides,
Examples include alkali metal carboxylates, alkali metal carbonates, and alkali metal borates. As the alkali metal octalite, alkali metal fluoride, alkali metal chloride, alkali metal bromide and alkali metal iodide can be used, and specifically, for example, lithium fluoride, sodium fluoride, fluoride Potassium, lithium chloride, sodium chloride, potassium chloride, lupidium chloride, cesium chloride, lithium bromide, sodium bromide, cesium bromide, lithium iodide, sodium iodide, potassium goodide, cesium iodide, etc. can be mentioned. ．． Among these, lithium chloride is particularly suitable. In addition, when employing the dehydration process, this alkali metal halide is usually added to the polar solvent (D) prior to the dehydration. Examples of the alkali metal carboxylates include lithium acetate, sodium acetate, potassium acetate, cesium acetate, lithium benzoate, sodium benzoate, potassium benzoate, lithium formate, sodium formate, lithium probionate, sodium probionate, and Lithium acid, sodium oxalate, lithium acetate, sodium acetate, lithium isoacetate, sodium isoacetate, lithium divalerate, sodium valerate, lithium hexanoate, sodium hexanoate,
Lithium octoate, sodium octoate, lithium fumarate, sodium fumarate, lithium malonate, sodium malonate, lithium tartrate, sodium tartrate, lithium stearate, sodium stearate, lithium phthalate, and sodium phthalate, to name a few. Can be done. Among these, lithium acetate, sodium acetate,
and lithium benzoate are preferred. Examples of alkali metal carbonates include lithium carbonate, sodium carbonate, potassium carbonate, lupidium carbonate, and cesium carbonate. Among these, lithium carbonate and sodium carbonate are preferred, and lithium carbonate is particularly preferred. Examples of the alkali metal borates include lithium borate, sodium borate, potassium borate, and cesium borate. Among these, lithium borate and sodium borate are preferred, and lithium borate is particularly preferred. The catalyst or polymerization aid that is the component (E) is
A) Usually 0.08 to 2.0 mol, preferably 0.5 to 1.0 mol, per 1 mol of metal water sulfide.
Use in a range of 8 mol. If this ratio is less than 0.03 mol, polyarylene sulfite with a sufficiently high molecular weight may not be obtained; If it exceeds O mol,
The metal (water) sulfide mentioned above (^) may be easily decomposed and the polymerization reaction may not proceed smoothly. In addition, in the production method of Moeki, when using the catalyst or polymerization aid as the component (E), use (
^) Molar ratio of component and (B) component [(B)/(A)1
does not necessarily have to be within the range of 1.03 to 1.25. This is because the above range is the polymerization condition for obtaining linear low molecular weight polyarylene sulfide. Examples of the monohalogen aromatic compound include chlorobenzene, bromobenzene, α-bromobenzene, α-chlorotoluene, 0-chlorotoluene, m-chlorotoluene,
Examples include p-chlorotoluene, α-bromotoluene, 0-bromotoluene, m-bromotoluene, and p-bromotoluene. Examples of the active hydrogen-containing compound include thiophenol, phenol, and aniline. In the method for producing curds, these branching agents or molecular weight regulators may be used alone or in combination of two or more. Examples of reducing agents include hydrazine, metal hydrides, alkali formates, and sulfur compounds. Among these, metal hydrides are preferred, with sodium borohydride and calcium hydride being particularly preferred. For example, the polyarylene sulfide according to claim 1 can be produced by the above production method as follows. That is, in order to synthesize the polyarylene sulfite according to claim 1 by the above-mentioned production method, the above-mentioned (A) component, (B) component, (C) component and (D) component, or these and the above-mentioned component The reaction solution obtained by mixing various components used as desired in a predetermined ratio and adjusting the water content as necessary within the above-mentioned predetermined range is usually 180 to 100%
The polymerization reaction is carried out by heating to a temperature in the range of 330°C, preferably 220 to 300°C. If the reaction temperature is less than 180°C, the reaction rate will be slow, making it impractical. On the other hand, if the temperature exceeds 330°C, side reactions and deterioration of the produced polymer will occur, causing coloration and gelation. The reaction time cannot be determined unconditionally because it varies depending on the types and proportions of the components used, the type of catalyst, etc., but it is usually within 20 hours, preferably about 0.1 to 8 hours. In the above production method, this polycondensation reaction can be carried out under an inert gas atmosphere such as nitrogen, argon, and carbon dioxide. There is no particular restriction on the reaction pressure, but it is usually from the autogenous pressure of the polycondensation reaction system such as a solvent to SO kg/c+n' (absolute pressure).Also, the polycondensation reaction may be a one-step reaction carried out at a steady temperature, A multi-stage reaction in which the temperature is raised stepwise or a reaction mode in which the temperature is gradually raised continuously may be used. After the polymerization reaction is completed, the synthesized polyarylene sulfide is subjected to, for example, filtration. Alternatively, it can be isolated by fractionating it directly from the reaction vessel by standard methods such as centrifugation, or by fractionating it from the reaction solution after adding a flocculant such as water and/or diluted acid. Next, the isolated polymer is washed, usually with water, methanol, acetone, etc., to remove alkali metal halides, alkali metal sulfides, polymerization aids, and side reactants attached to the polymer. In addition, without isolating the polymer produced from the reaction-completed liquid, the solvent can be distilled off and recovered, and the remaining liquid can be washed as described above to obtain the polymer. The recovered solvent can be reused.Also, the polyarylene sulfide according to claim 1 can be obtained by, in addition to the above-mentioned production method, for example, modification with an oxidizing agent in a medium, or by the above-mentioned method. It can also be obtained by blending a branched polymer and a linear polymer.In any case, the polyarylene sulfite according to claim 1 can be easily obtained as a stable resin only by controlling the polymerization reaction system. .The polyarylene sulfite obtained in this manner has high non-Newtonian properties and a large branching density, and although the branching density is high, the average molecular weight is not too large and has a wide molecular weight range. It has excellent moldability, fluidity, and thermal stability, has no coloring, has a high degree of whiteness, and has the characteristics of less generation of flakes during injection molding, and is suitable for various molding materials. However, if necessary, various desalting treatments can be carried out to further reduce the salt content such as sodium chloride in the polymer, which can be used to produce, for example, electrical/electronic parts, injection precision parts, etc. Molding,
It can be suitably used in molding materials such as films. 1. The resin composition according to claim 2. 1. The resin composition according to claim 2, at least the resin composition according to claim 1.
Polyarylene sulfide and fibrous and/or polyarylene sulfide
or powdery filler. The polyarylene sulfite is the polyarylene sulfite according to claim 1, and if necessary, components other than the polyarylene sulfite according to claim 1 can be mixed and used. When used in combination with other components, the content of the polyarylene sulfide according to claim 1 is at least SOrfi amount %, preferably at least 70% by weight. Components other than the polyarylene sulfite described in claim 1 include, for example, branched polyarylene sulfite, linear polyarylene sulfide, and other polymers having physical properties other than those described in claim 1. ．． Inorganic fillers can be suitably used as the filigree and/or powdery fillers. Examples of the inorganic filler include calcium carbonate,
Charcoal salts such as magnesium carbonate and dolomite; Sulfates such as calcium sulfate and magnesium sulfate; Sulfite salts such as calcium sulfite; Talc: clay; Mica: titania; Zirconia: ferrite; Asbestos: Glass fiber #I: Silicic acid Silicates such as calcium, montmorillonite, and bentonite; Metal powders such as iron, zinc, copper, aluminum, and nickel; Ceramics such as silicon dicarbide, silicon nitride, and boron nitride; and various whiskers, Rikibon black, graphite, Examples include carbon fiber. These inorganic fillers may be used alone or in combination of two or more. Among these, glass fibers, carbon fibers, or combinations of these with powdered fillers can be preferably used. In addition, the resin composition of the present invention may be used instead of the Moeki inorganic filler or together with the inorganic filler, if necessary.
For example, it may contain organic fillers such as wood flour, coconut shell flour, cork powder, and flock. In addition, the fibrous and/or powdery filler is one whose average fiber diameter or particle diameter is usually 207 mm or less, and a filler having an optimum diameter is selected depending on the purpose of containing the filler. You can select . m Average fiber of fibrous and/or powdery filler! l diameter or particle size is 2
If it is larger than 0 pm, the dispersibility in the composition may decrease. In the resin composition according to claim 2, the blending ratio of the polyarylene sulfide and the fibrous and/or particulate filler is such that the polyarylene sulfide and the fibrous and/or particulate filler are blended in a proportion of 100 parts by weight of the polyarylene sulfide. The amount of the powder/granular filler is usually 5 to 500 parts by weight, preferably 10 to 300 parts by weight. If this blending ratio is less than 5 parts by weight, the effect of blending the fibrous and/or particulate filler will not be sufficient; if it exceeds SOO parts by weight, the crosstalk, dispersibility, and even Mechanical strength may not be sufficient. The resin composition according to claim 2 further contains, in addition to the polyarylene sulfide and the fine and/or particulate filler, for example, a stabilizer, a mold release agent, etc. You can. The resin composition according to claim 2 is. The excellent mechanical strength, long-term durability, and chemical resistance of the polyarylene sulfide described in fJ requirement 1 are further improved, and it can be used, for example, in various molded products such as films and fibers, precision injection molded products, electrical - Can be suitably used as a forming material for electronic parts, etc. [Examples] Next, examples and comparative examples of the present invention will be shown, and the tree invention will be explained in more detail. (Examples 1 to 9, Comparative Examples 1 to 6) In the autoclave of 101, sodium sulfide pentahydrate 1
, 370g. 345 g of lithium chloride (however, lithium chloride was not added in Example 9), and N
- Add 4,160 methyl pyrrolidone (NliP) and heat to 200℃ under nitrogen atmosphere, then add water and NliP.
The il compound was distilled out using 1J30 s. 10 residue
After cooling to 0°C, paradichlorobenzene (PDCB) dissolved in NIIP 1,500 an. Dichloronitrobenzene (DCNB) or trichlorobenzene (
TCB) was added to the remaining sodium sulfide at the specified molar ratio. Thereafter, the mixture was allowed to react at 268°C for 3 hours.
After cooling to room temperature, the solid matter was separated, washed sequentially with 4,500 ml of pure water and acetone, and vacuum-dried for 20 hours while heating to 100°C. Regarding the obtained polyarylene sulfide, logarithmic viscosity number [η1h], molecular weight distribution, calculated viscosity [ηl calc
+ Logarithmic viscosity number [ηinh ] and calculated viscosity [η] aa
ratio with le {branching degree parameter (Bl); logarithmic viscosity number [η. ．． %hl/calculated viscosity [η] ealc) *Evaluations were made for each item of flow characteristic parameter (E!) and whiteness. The results are shown in Table 1. Further, the molecular weight distribution measurement results of Example 1, Example 5, Comparative Example 4, and Comparative Example 5 are shown in FIGS. 1 to 4, respectively. The evaluation of each item was performed as follows. Solvent: α-chlornaphthalene concentration 2 0.2±0.01 (g/d) separation column;
AT800P+ AT80M/S x 2 [manufactured by Showa Denko ■] Column temperature; Flow rate: Detector: Molecular welfare determination: 210"C l l/min UV detector (detection wavelength input = 356 n) About width-dispersed polystyrene with known molecular weight Measured under the same conditions, using a universal calibration curve.
ncurve). Logarithmic viscosity number [ηinh]: Measured using α-chlornaphthalene solvent at a concentration of 0.4 g/di at a temperature of 208°C. Molecular weight distribution: Measurements were performed under the following measurement conditions. Equipment used: Gel permeation chromatography with high temperature UV detector Branch degree parameter (Bl); Logarithmic viscosity number [η, nh]/Calculated viscosity [η]. Calculated using 1e. Note that the calculated viscosity [η] galc is [q]e−1 for a linear or long chain branched system. = 8.91x 10-'M 0''
'In addition, for systems with a distribution, the following formula is used to calculate from the GPC chromatogram. Flow characteristic parameter (El). It was calculated using the following formula. EI=G''.b-/G' where G'.b. and G'l are the storage modulus determined by the periodic vibration method using a cone-disk viscometer at a temperature of 300°C. and the angular velocity ω=1 (rad/sec)
This is the value of Incidentally, G'1 is the value of a linear polyarylene sulfite having the same logarithmic viscosity number [η▲nh] as that of the sample. The fixed results are shown in the t51 table. However, in Comparative Example 6, a test piece was prepared in the same manner as described above using a blend of unbranched polyphenylene sulfite with a different molecular structure, and the tip of the paris was prepared as described above. The length was measured. 《This page, hereafter in the margins》 Furthermore, glass fibers blended with the aforementioned polyarylene sulfite at a ratio of 4[lfi amount%]! 1 [rO:IM^497, manufactured by Asahi Fiberglass Co., Ltd.] was prepared. 127x 12.7x co. Measurement using a microscope of the length of the tip end when a test piece of 18 weight 1 was injection molded (1 market price) According to Table 1, the polyarylene sulfide described in claim 1 has high non-Newtonian properties. The branching density is large,
Although the branch density is high, the average molecular weight is not too large, and it is clear that it has a wide molecular weight distribution. Also. a In the resin composition according to claim 2,
It is clear that the occurrence of flakes during injection molding is significantly suppressed. [Effects of the Invention] (1) According to the invention of claim 1, the logarithmic viscosity number, the weight average molecular weight, the ratio of the logarithmic viscosity number to the calculated viscosity, and the whiteness are within specific ranges, so the non-Newtonian property is high. Despite the high branching density, the average molecular weight is not too large and has a wide molecular weight distribution, and it has excellent moldability, fluidity, and thermal stability, and has no coloration and low whiteness. It is possible to provide an industrially useful polyarylene sulfide that has various advantages, such as high yield, low generation of paris during injection molding, and ease of production simply by controlling the polymerization system. (2) According to the invention of claim 2, the polyarylene sulfide resin containing the polyarylene sulfite as a main component according to claim 1, which has the various advantages described above, and a fibrous and/or powdery filler are combined. By containing the polyarylene sulfite, it is possible to provide an industrially useful resin composition in which the excellent mechanical strength, long-term stability, chemical resistance, etc. of the polyarylene sulfite according to claim 1 are further improved.

[Brief explanation of the drawing]

Claims (2)

[Claims] (1) Logarithmic viscosity number [η_i_n_h] is 0.1 to 0.5
dl/g, and the weight average molecular weight is 1×10^4 to 2×
10^5, and the ratio of the logarithmic viscosity number [η_i_n_h] to the calculated viscosity [η]_c_a_i_c (logarithmic viscosity number [η]
___i_n_h/calculated viscosity [η]_c_a_i_c) is 0
．． 4 to 0.8, and the whiteness [JISP8123] is 5.
A polyarylene sulfide characterized by having a polyarylene sulfide of 0 or more. (2) the polyarylene sulfide according to claim 1;
A resin composition characterized by containing a fibrous and/or powdery filler.