JPH0441561A - Polyphenylene sulfide resin composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a polyphenylene sulfide resin composition, and more particularly to a polyphenylene sulfide resin composition having an extremely high crystallization rate.

Polyphenylene sulfide is attracting attention as a material for electrical and electronic equipment and automobile equipment due to its excellent heat resistance and chemical resistance.

Furthermore, it can be molded into various molded parts such as films, sheets, fibers, etc. by injection molding, extrusion molding, etc., and is widely used in fields where heat resistance and chemical resistance are required.

[Prior Art] Polyphenylene sulfide is produced by reacting a dihaloaromatic compound with an alkali metal sulfide such as sodium sulfide in a polar aprotic solvent such as N-methylpyrrolidone as disclosed in Japanese Patent Publication No. 45-3368. It can be obtained by

However, polyphenylene sulfide obtained by this method, especially crystalline poly(p-)unisyl sulfide (hereinafter abbreviated as PPS), has a glass transition temperature of about 90.
℃, and the crystallization rate is also slow, so when trying to obtain a molded product by injection molding, the mold temperature must be set at 130 to 1
Unless the temperature was set at 50°C, a good product with excellent heat resistance and 1-dimensional stability could not be obtained. This is a major drawback of PPS in terms of molding process compared to other general-purpose engineering plastics, such as nylon and PBT, which can be molded at a mold temperature of 100° C. or less, and is considered to be a factor inhibiting the expansion of PPS's applications.

In order to solve this problem, the prior art uses PPS having a melt viscosity of at least 5 Pa.s and a maximum molecular weight of 6.0 Pa.s.
000 oligomeric ester is added (JP-A-62
-45654), adding monomeric carboxylic acid esters (JP-A No. 62-230848), adding other thioethers (JP-A No. 62-230849), adding specific aromatic phosphate esters. (Unexamined Japanese Patent Publication No. 62-2
Methods such as No. 30850 and Japanese Unexamined Patent Publication No. 1-225660 are known. However, in either method, there are problems such as generation of evaporative gas and decomposition gas during molding due to the poor heat resistance of the additives.

[Problems to be Solved by the Invention] The present invention improves the above-mentioned conventional drawbacks by blending cholesterol or a cholesterol derivative with a specific structure into polyphenylene sulfide, and furthermore, the crystallization rate is extremely high, and even a low-temperature mold is sufficient. The present invention provides a polyphenylene sulfide composition that can be crystallized into a polyphenylene sulfide composition.

[Means for Solving the Problems] That is, the present invention provides polyphenylene sulfide 80 to 99.
5% by weight Cholesterol represented by the following formula (1) 0.5 to 20% by weight 26 CH.

Diamond (in the formula, X is an epoxy group, an acid anhydride group, a carboxyl group,
The present invention relates to a polyphenylene sulfide resin composition consisting of an organic group having 1 to 24 carbon atoms containing at least one of an acid amide group, an imide group, a carboxylic acid ester group, and an amino group, or representing hydrogen, and will be described in detail below. do.

The polyphenylene sulfide used in the present invention is not particularly limited as long as it is obtained by a known method as shown in Japanese Patent Publication No. 45-3368, but it contains 70 mol% or more of repeating units represented by the following formula. Preferably. Furthermore, PPS containing 70 mol% or more of p-phenylene sulfide units as repeating units is particularly preferably used. At this time, the remaining repeating units are not limited as long as they are copolymerizable units, such as orthophenylene sulfide units, metaphenylene sulfide units, diphenyl sulfide ether units, diphenyl sulfide sulfone units, diphenyl sulfide ketone units, biphenylsulfide units, Examples include naphthalene sulfide units and trifunctional fluorinated nylene sulfite units.

These copolymerized units may be block copolymerized or random copolymerized. Specific examples of preferable polyphenylene sulfide include poly(p-phenylene sulfide) poly(p-)unisyl sulfide)-poly(m-phenylene sulfide) block copolymer, poly(
p-phenylene sulfide)-polysulfone block copolymer and poly(p-phenylene sulfide)-polyphenylene sulfite sulfone block copolymer.

Furthermore, the PPS suitably used in the present invention has a melt viscosity (0.5 mm in diameter and 2 mm in length at 300°C).
PPS whose value (measured using a Koka type flow tester with a load of 10 using a die) is in the range of 10 to 100,000 poise, preferably 50 to 50,000 poise.
It does not matter if it is linear or oxidatively cross-linked in the presence of oxygen. Furthermore, in order to increase the compatibility with cholesterol used in the present invention, it is preferable to introduce a highly reactive functional group into PPS. The functional group introduced is an amino group.

Carboquine groups, hydroxyl groups, acid anhydride groups, epoxy groups, etc. are suitable, and methods for introducing them include copolymerization of halogen-containing aromatic compounds containing these functional groups, and PP.
Examples include a method of introducing S through a polymer reaction between S and a low molecular weight compound containing a functional group. Furthermore, the above-mentioned PPS may be one in which sodium ions are reduced by performing deionization treatment (acid washing, hot water washing, etc.).

The cholesterol used in the present invention is expressed by the following formula (1
) (wherein X is an epoxy group, an acid anhydride group, a carboxyl group,
Cholesterol is an organic group having 1 to 24 carbon atoms or hydrogen containing at least one of an acid amide group, an imide group, a carboxylic acid ester group, and an amino group. Cholesterol preferable for use in the present invention includes cholesterol in which X in formula (I) is an organic group having 1 to 12 carbon atoms having an acid anhydride group, an epoxy group, a carboxyl group, or hydrogen.

Here, there is an expression that X in the formula is an organic group, but this is not only a hydrocarbon group, but also an ether or a ketone in X.
This means that there is no problem even if it contains a heteroatom-containing functional group such as amide or sulfone.

Although there are no particular limitations on the method for producing the functional group-containing cholesterol, for example, epoxy-modified cholesterol can be obtained by reacting with epichlorohydrin by utilizing the reactivity of hydroxyl groups in cholesterol. Furthermore, acid anhydride-modified cholesterol can be obtained by reacting with trimellitic anhydride chloride.

The amount of cholesterol used in the present invention is 0 to the composition of polyphenylene sulfide and cholesterol.
．． 5-20% by weight, preferably 1-]0% by weight gives good results.

If the amount added is less than 0.5% by weight, the effect of accelerating the crystallization rate will be reduced, which is not preferable. On the other hand, if the amount added exceeds 20%, not only is no further improvement in the crystallization rate observed, but also the physical properties begin to deteriorate, which is not preferable.

When a crystal nucleating agent is used in combination with the composition of the present invention, the -layer crystallization rate becomes faster, so although the addition of an appropriate amount of a crystal nucleating agent is not essential, it gives preferable results.

In addition to inorganic substances such as silica, kaolin, talc, Hytron, and boron nitride, crystal nucleating agents include calcium stearate, aluminum stearate, dipotassium cobaate, dicalcium benzoate, disodium phthalate, trisodium trimellitate, and pyromellitate. Polymers with a higher melting point than organic carboxylic acid metal salts such as tetrapotassium acid or polyphenylene sulfide ketone PS are effective. The amount of these crystal nucleating agents added is preferably 0.05 to 10%, preferably 0.1 to 10%, based on the PPS composition of the present invention.
5 weight 9o.

The crystallization rate of the PPS composition obtained as described above is significantly faster than that of conventional PPS, so even if a low-temperature mold is used, it can be sufficiently crystallized by injection molding, and a molded product with excellent heat resistance can be obtained. be able to.

In addition, if necessary, reinforcing fillers such as glass fibers, carbon fibers, alumina fibers, etc., aramid fibers, wholly aromatic polyester fibers, metal fibers, potassium titanate whiskers, calcium carbonate, mica, talc, phosphoric acid, etc. , barium sulfate, calcium sulfate, kaolin, clay pyroferrite, bentonite, sericite, zeolite nephelinite, attapulgite, wollastonite, PMF, ferrite, calcium silicate,
Magnesium carbonate, dolomite, antimony trioxide, zinc oxide, titanium oxide, magnesium oxide, iron oxide, molybdenum disulfide, graphite 1 gypsum glass beads, glass powder, glass balloon.

Inorganic brighteners such as quartz 2, quartz glass, and organic or inorganic pigments can also be blended.

Also, mold release agents, silane-based, titanate-based strength/twisting agents, lubricants, heat-resistant stabilizers, and weather-resistant stabilizers.

Foaming agents, rust preventives, ion trapping agents, flame retardants, flame retardant aids, etc. may be added as necessary.

Furthermore, polyethylene, polybutadiene,
Polyisoprene, polychloroprene, polystyrene, polybutene, polyα-methylstyrene, polyvinyl acetate,
Polyvinyl chloride, polyacrylic ester, polymethacrylic ester, polyacrylonitrile, nylon 6,
Nylon 66° Nylon 610. Nylon 12. Polyamides such as nylon 11° and nylon 46, polyesters such as polyethylene terephthalate, polybutylene terephthalate, polyarylate, polyurethane, polyacetal, polycarbonate, polyphenylene oxide, polysulfone, polyether sulfone, polyallyl sulfone, polyphenylene sulfide sulfone, polyether ketone, polyphenylene sulfide It is also possible to use a mixture of one or more of homopolymers, random, block, and graft copolymers such as ketones, polyetheretherketones, polyimides, polyamideimides, silicone resins, phenoxy resins, and fluororesins.

[Examples] The present invention will be explained in detail below using Examples, but the present invention is not limited only to these Examples.

The crystallization rate of the PPS composition used in the following examples was determined by heating an amorphous sample obtained by rapidly cooling a molten sample at a heating rate of 10°C/min using DSC. The evaluation was made by measuring the crystallization temperature at the time of the reaction.

Reference Example 1 An example of manufacturing PPS used in Example 1 is shown below.

Sodium sulfide N in a 500 ml autoclave
a S ・2-9 60 mol of H200 and 150 g of N-methyl-2-pyrrolidone (hereinafter abbreviated as NMP) were added, stirred under a stream of nitrogen, and heated to 200°C to obtain 21.2 g of a distillate mainly consisting of water. was removed. After cooling the system to 170°C, 0.60 mol of p-dichlorobenzene (hereinafter abbreviated as p-DCB) was added together with 50 g of NMP, the system was sealed under a nitrogen stream, and the temperature was raised to 250°C. Polymerization was carried out for 3 hours. After the polymerization was completed, the system was cooled and the contents were poured into water to precipitate the polymer.The precipitated polymer was collected in a glass funnel and washed with warm water of about 51 liters.

The filtration was repeated and the polymer was isolated by heating and vacuum drying overnight. The obtained polymer was 61.5 g, yield 95%, melt viscosity (diameter 0.5 m + * at 300°C, length 2
The value measured with a Koka type flow tester using a II11 die and a load of 10)cg was 250 voids. This polymer was placed in an oven set at 250° C. in air and cured for 5 hours to obtain PPS with a melt viscosity of 2,800 voids.

The PPS obtained in this manner is referred to as PP5-1.

Reference Example 2 In Reference Example 1, 0.594 mol of p-dichlorobenzene was used instead of 0.60 mol of p-dichlorobenzene, 3
The same operation as in Reference Example 1 was performed except that 0.006 mol of ,5-dichloroaniline was used. The obtained polymer is 6
1.2g.

The yield was 94%, and the melt viscosities before and after curing were 120 poise and 3,300 poise, respectively. The PPS obtained in this manner is referred to as pps-n.

Reference Example 3 In Reference Example 2, 3,5-dichloroaniline 0.006
The same operation as in Reference Example 2 was performed except that 0.006 mol of 2,4-dichlorobenzoic acid was used instead of mol. The obtained polymer was 62.2 g, yield 96%, and the melt viscosity before and after curing was 240 poise and 2,000 poise, respectively.
It cost 600 poise. The PPS thus obtained is designated as PP5-■.

Reference Example 4 In Reference Example 2, 3,5-dichloroaniline 0.006
2,4-dichlorophenol instead of mole 0.006
The same operation as in Reference Example 2 was performed except that moles were used. The obtained polymer was 60.7 g, yield 93%, and the melt viscosity before and after curing was 110 poise, 3.
It was 400 poise. The pps obtained in this way is referred to as PPS-IV.

Reference Example 5 An example of producing acid anhydride-modified cholesterol used in this example is shown below.

In a two-room separable flask, add 500 ml of anhydrous diethyl ether and trimellitic anhydride chloride (
Add 28 g of TAAC (hereinafter abbreviated as TAAC) and stir under a nitrogen stream.
Dissolve uniformly. After TAAC was uniformly dissolved, 13.7 g of triethylamine and 50 g of cholesterol were dissolved in 500 ml of diethyl ether and added dropwise to the TAAC solution using a dropping funnel. After completion of the dropwise addition, reaction was carried out at room temperature for 4 hours. By-product salts were removed from the reaction slurry by filtration, diethyl ether was removed by evaporation, and 58 g of acid anhydride-modified cholesterol (hereinafter abbreviated as cholesterol AN) was isolated by vacuum drying.

Examples 1 to 7 PPS obtained in Reference Examples 1 to 4 and cholesterol or cholesterol AN obtained in Reference Example 5 were uniformly blended with the composition shown in Table 1, and then blended using Labo Prostomil (Toyo Seiki Gen). The mixture was melt-kneaded at 300° C. for 5 minutes. Approximately 10 mg of the sample after kneading was weighed, placed in a pan for DSC measurement, and the glass transition temperature (Tg) and crystallization temperature (Tc
), and the melting point (Tm) was measured. The results are summarized in Table 1.

Comparative Examples 1 to 4 Using only the PPS obtained in Reference Examples 1 to 4, the Tg and Tc were determined by DSC after melt-kneading in the same manner as in the Examples.

Tm was measured. In all cases, the crystallization temperature was higher than in the examples, and only those with a slow crystallization rate were obtained. (Table 1
Reference) [Effects of the Invention] As is clear from the above explanation, according to the present invention, a PPS composition with a significantly high crystallization rate can be obtained, and even in injection molding using a low-temperature mold, molding with sufficient crystallization can be achieved. You can get the goods.

Patent applicant: Tosoh Corporation - Tosoh Susteel Co., Ltd.

Claims (1)

[Claims] (1) Polyphenylene sulfide 80-99.5% by weight Cholesterol represented by the following formula (I) 0.5-20%
Weight% ▲Mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, X is an epoxy group, an acid anhydride group, a carboxyl group,
A polyphenylene sulfide resin composition comprising an organic group having 1 to 24 carbon atoms or hydrogen containing at least one of an acid amide group, an imide group, a carboxylic acid ester group, and an amino group.