JPS61225217A - Removal of impurity from polyphenylene sulfide resin - Google Patents

Abstract

PURPOSE:To obtain a highly pure polyphenylene sulfide resin, by partially dissolving a powdered polyphenylene sulfide resin in a specified solvent, filtering this solution and washing the resin with a solvent in which the resin is insoluble. CONSTITUTION:A slurry of a powered polyphenylene sulfide resin (concentration <=50%) in a solvent selected from among at least one solvent (A) selected from among benzyl alcohol, sulfolane, glycerin and (di)ethylene glycol, a mixed solvent (B) comprising solvent A and a solvent selected from among alpha-halonaphthalene, (halo)biphenyl and o- or m-terphenyl and a mixed solvent (C) comprising solvent A or solvent B and N-methyl-2-pyrrolidone is heated at 100-270 deg.C for 1-10hr to dissolve the resin partially. After cooling, this solution is filtered and washed with a solvent in which the resin is insoluble (e.g., water) to remove impurities, chiefly sodium chloride.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to polyphenylene sulfide resin (hereinafter referred to as PPS).
[Conventional technology] PPS has excellent properties such as heat resistance, high dimensional stability, and low melt viscosity. Although it is expected to be used in the field of encapsulation materials for LSIs and LSIs, it is hardly used in reality. The biggest reason for this is that ordinary PPS contains impurities, mainly salt, and due to these impurities, products using PPS do not have sufficient moisture resistance reliability. In order to improve this moisture resistance reliability, it is necessary to remove impurities in PPS.
As shown in the issue, PPS was mixed with ethylene glycol and N-
A method of treating with a mixed solvent with methyl-2-pyrrolidone, and a method of treating PPS as shown in JP-A-57-108136
A known method is to add a chemical such as sodium carbonate to a water slurry and treat it under high temperature and pressure. However, the former method not only requires a large amount of solvent, but also requires repeating the same operation at least twice, preferably three to five times, to remove impurities to the required extent. Furthermore, the latter method is aimed not only at removing impurities but also at stabilizing the melt flow, and is not sufficiently effective in removing impurities. As described above, it has often been impossible to obtain satisfactory results with conventional techniques.

[Problem that the invention seeks to solve]

The present invention is a book that attempts to provide a simple and efficient method for removing impurities in PPS, which was time-consuming and did not produce sufficient effects using conventional techniques.

[Means for solving problems]

The present invention solves the above problems by heating and mixing powdered polyphenylene sulfide resin and a solvent selected from the following (I) to (buttons), bringing the two into sufficient contact in a partially dissolved state, and then cooling and filtering. This is a method for removing impurities from polyphenylene sulfide resin, which is characterized by washing with a solvent that does not dissolve polyphenylene sulfide resin.

α) Single or mixed solvent selected from benzyl alcohol, sulfolane, glycerin, ethylene glycol, diethylene glycol ■ Benzyl alcohol, sulfolane, glycerin,
A solvent selected from ethylene glycol and diethylene glycol and α-halogenated naphthalene, hyphenyl, 0-
A mixed solvent with a solvent selected from terphenyl, m-terphenyl, and halogenated hyphenyl; A single or mixed solvent selected from benzyl alcohol, sulfolane, and glycerin; or a mixed solvent of (2) above and N-methyl-2-pyrrolidone; Mixed solvent (IV) A mixed solvent of N-methyl-2-pyrrolidone and water in the amount of the above-mentioned solvent. In the present invention, the amount of solvent (weight ratio) brought into contact with PPS in a partially dissolved state is approximately 1.0 to PPS. ~15 times is sufficient. That is, the above solvent may be used so that the PPS slurry concentration is 50% or less. In addition, an appropriate amount of water may be added to the above solvent.The temperature at which oPPs is partially dissolved may vary depending on the type of PPS and the type and amount of solvent used, but is usually 100-270°C, preferably 150-270°C.
The contact time with the solvent in a partially dissolved state is preferably 1 to 10 hours, but 2 to 4 hours is sufficient.

Solvents that do not dissolve 1 ft of pps include water, aromatic or aliphatic hydrocarbons, ketone-based finishing agents, alcohol-based solvents, and mixed solvents thereof. In addition, PPSTI is in the form of powder obtained through normal manufacturing processes, but it is preferable to make it into fine powder by a dry method or wet method in order to increase the contact area. In the method of the present invention, PPS in a partially dissolved state is The contact with the solvent is usually sufficient to remove impurities to the desired extent in 1 time, but if necessary, the impurities can be further reduced by repeating the contact 2 times or 3 times.

[Effect]

ll1p around crystals of salt, etc., which are impurities in PPS.
It has PS attached to it and cannot be removed by simple washing with water. Therefore, it is possible to elute salt etc. with pps'
It must be dissolved or swollen to expose the salt, etc. In the present invention, PPS is not completely dissolved or melted, but only partially dissolved. Therefore, PPS needs to be in powder form,
Furthermore, it is preferable to make the powder as fine as possible for elution of crystals such as common salt.

The solvents used in the present invention, such as benzyl alcohol, sulfolane, glycerin, ethylene glycol, and diethylene glycol, have the effect of dissolving a portion of PPS at high temperatures and also dissolving common salt and the like. Therefore P
Impurities such as common salt existing inside the PS can be easily extracted.

In addition, most of the impurities such as common salt are dissolved in the above-mentioned solvent, so one high temperature treatment is usually sufficient. However, after being cooled and solidified, the above-mentioned solvent from which impurities were extracted remains in the 9PPS particles.
Since there is a risk of increasing the concentration of impurities, cleaning is performed with a solvent that does not dissolve PPS. By washing with a solvent that does not dissolve PPS, it is sufficient to extract impurities such as common salt once at a high temperature.

[Example, comparative example]

The present invention is explained in detail by Examples and Comparative Examples.The respective results are listed in Table 2.

Example 1 pps-i (powdered polymer obtained by reacting baladichlorobenzene and sodium sulfide by a known method, melting point 28
Melt viscosity at 6°C and 300°C: 52 voids, particle size: 10-1
50μ average 35μ>20? and benzyl alcohol ZOO
The mixture was charged into a 91'5rl autoclave and treated at 190°C for 4 hours with stirring.

After cooling, the filtered cake was mixed with methyl ethyl ketone (MEK).
) 100- and twice with 100 tnl of ion-exchanged water. The polymer was dried under a vacuum of 90" C15 Torr. The following examples were similarly dried.

Examples 2 to 5 PPS-11 (powdered polymer obtained in the same manner as PPS-I, melting point 284°C, melt viscosity at 300"C 63
Particle size] 0° to 170 μm (average 40 μm) and benzyl alcohol were charged into a 17 autoclave in the proportions shown in Table 1 and treated at 210”C with stirring for 2 hours. After cooling, the filtered cake was prepared in the same manner as in Example]. Washed and dried using the method.

Table 1 Example 2 Example 3 Example 4 Example 5 PPS-II
20y 40y 60P 60?
Benzilua A/, -2180F 160F 1409 1
11.49 Slurry → 1 degree 10% 20% 3
0% 35% Example 6 PPS-In (Powdered polymer obtained in the same manner as PPS-I, melting point 288°C, melt viscosity at 300"C [
112 poise, particle size 5-130μ average 32μ) 2Qy and 3% moisture added sulforan (@'i Nippon Rika! 1iL/
N8159124) 200yel 1yF-1 The mixture was charged into a crepe and treated at 190°C for 4 hours with stirring. 60″
It was cooled with C1 and filtered at 60°C. p overkey *fMEK
] Washed twice with OOd and twice with 100% ion-exchanged water, and dried.

Example 7 The same treatment as in Example 1 was carried out using PPS-I 2 (l) and 2 oz of glycerin. It was cooled to 60°C and filtered at 60°C. The filter cake was washed twice with 100 d of distilled water and dried.

Example 8 The same treatment as in Example 7 was carried out using PPS-W (Rydon V-1 manufactured by Phillips Petroleum) 209 and glycerin 2002, and the filter cake was prepared using MEKlooWI.
It was washed once with 100 ml of distilled water and once with 100 ml of distilled water, and dried.

Example 9 Using PPS-I 20y and ethylene glycol 2002, the same treatment, washing and drying as in Example 1 was carried out.

Example: 0 PPS-I 20y and diethylene glycol 2002
The same treatment as in Example 1 was carried out using . p over cake FiM
Washed twice with EK ] 00-, twice with ion-exchanged water]00-, and dried.

Example 1: PPS-N zoy, 100y of sulforane and 1002y of glycerin were placed in a ]l autoclave and stirred for 2 hours.
It was treated at 10°C for 4 hours. The filter cake containing the solvent was washed twice with 100 d of methanol, once with 00 d of ion-exchanged water, and dried.

Example 12 20y of PPS-I, 1002y of benzyl alcohol, and 100y of α-chlornaphthalene were charged into a 11 autoclave and treated at 230°C for 4 hours with stirring. The filter cake is MFJK]001n! , 2 times, ion exchange water 100
d twice and dried.

Example 13 PPS-I 21', glycerin 100y and α-chlornaphthaline 1002 in 1! The mixture was charged into an autoclave and treated at 230 to 240°C for 4 hours while stirring. The filter cake was washed twice with MEK]00111/, once with distilled water]00-, and dried.

Example 14 PPS-I 30y, glycerin 150y and α-chlornaphthalene 1501t? 11 Place in an autoclave and treat at 230°C for 4 hours with stirring. Filter at 080°C.
Washed twice with m/ and dried.

Example 15 The desalted PPS-1179 obtained in Example 14 above, 85y of glycerin and 85y of α-chlornaphthalene were mixed with lI
! The mixture was charged into an autoclave and treated at 230° C. with stirring.

Filter at 60°C and add the filter cake to MEK100+ytt'
Wash twice with 100 d of deionized water and dry 1. Ta.

Example】6 PPS-I? Grinded with a dry lab jet mill, particle size: 7μ
Below (average 6μ) 30y1 glycerin 150
f and α-chlornaphthalene 1502 were charged into an autoclave and treated at 240° C. for 4 hours with stirring. Filter cake with MEK 150mt' twice, ion-exchanged water】5
It was washed twice at 0d and dried.

Example 17 PPS-U 20f, ethylene glycol 1002,
α-bromnaphthalene 100y II! The mixture was charged into an autoclave and treated at 210° C. for 4 hours with stirring. The filter cake containing the solvent after filtration at 50°C was washed with acetone twice at 50°C.
Washed twice with ion-exchanged water and dried.

Example 8 The same treatment, washing and drying as in Example 1 was carried out using PPS-I 2 (1, 100 yt of benzyl alcohol) and 100 yt of N-methyl-2-pyrrolidone (NMP).

Example] 9 PPS-I 20P, Glycerin] 002 and NMP1
The same treatment as in Example 1 was carried out using 00yf, and filter cake #
-tMEK] 00- twice, ion-exchanged water] 00-
Washed twice and dried.

Example 20 After premixing pps-m zooy and glycerin 300y, the mixture was dispersed and pulverized using a 6-inch three-roll mill to form a paste. This paste 212.9 y (PPS-fu85
．． 2y, glycerin 127.7y) and NMP127.7
y was treated in the same manner as in Example], and distilled water 3001n was added.
It was washed twice with l and dried.

Example 2] Pulverized PP5-I20y used in Example 16.

Example 1 using 100y of glycerin and 100y of NMP
The same treatment, washing and drying as above was carried out.

Example 22 PPS-I20y, glycerin 66.7f! , α-chlornaphthalene 66.79, NMP 66.7 p to l!
The mixture was placed in an autoclave and treated at 230° C. for 4 hours with stirring. Filter cake with 100 ml of MEK! twice with ion-exchanged water] and once with 00 me and dried.

Example 23 PPS-■ 202, 5 oy of sulfolane, benzyl alcohol say and NMP loo were placed in an autoclave and treated in the same manner as in Example], and the filter cake containing the solvent was washed twice with 100 gl of methanol and 100 gl of ion-exchanged water. Washed twice and dried.

Example 24 PPS-I 20y, glycerin 66.79. 66.7 y of biphenyl and 66.7 y of NMP were placed in a 11 autoclave and treated at 230"C for 4 hours with stirring. After cooling, 100 y of xylene was added and filtered. The filter cake was treated with 200 y of xylene twice and ion-exchanged water. 200
d twice and dried.

Example 25 PP5-So paste (PPS-11) prepared in Example 20
120y, glycerin 30y) 50y, glycerin 7Q
The same treatment as in Example 1 was carried out using y and NMPlooy, and the filter cake was treated once with HMEK100- and distilled water 100 d.
Washed once and dried.

Example 26 20 y of PPS-I, 150 y of glycerin, and 50 y of distilled water were placed in an autoclave 11 and subjected to the same treatment as in Example 1. Permissive Cake #-iMEK] 00 servings twice, 100 I of distilled water! lI! Example 27 PPS-■ 20g! , NMPlooy and distilled water 10
02] I! The mixture was charged into an autoclave and treated at 160° C. for 4 hours with stirring. The filter cake was washed twice with MEKloo- and dried.

Comparative Example 1 PP5-I 21' and 200 y of distilled water were placed in a 11 autoclave and treated at 190"C for 4 hours with stirring. The filter cake was washed twice with 100 y of distilled water and dried.

Next, Table 2 shows the PPS used and the analysis results after treatment. For analysis of NaCl, the sample was pretreated by sulfuric acid ashing, quantified by flame light analysis, and the results were expressed as Na2O. The ash content was measured by a conventional method using a Matsufuru furnace.

〔Effect of the invention〕

The present invention shows the effect that by using a specific solvent, impurities can be removed from PPS containing impurities such as common salt with a high efficiency of 80 to 98% in one heat treatment. This has the excellent effect of making it possible to use PPS, which was difficult to use for parts and IC+LSI.

ys2 table

Claims (3)

[Claims] (1) Powdered polyphenylene sulfide resin and the following (
A polyphenylene sulfide resin characterized by heating and mixing the solvents selected from I) to (IV), bringing them into sufficient contact in a partially dissolved state, cooling and filtering, and washing with a solvent that does not dissolve the polyphenylene sulfide resin. Method for removing impurities from enylene sulfide resin. (I) Single or mixed solvent selected from benzyl alcohol, sulforane, glycerin, ethylene glycol, diethylene glycol (II) Solvent selected from benzyl alcohol, sulforan, glycerin, ethylene glycol, diethylene glycol and α-halogenated naphthalene, biphenyl, o- A mixed solvent with a solvent selected from terphenyl, m-terphenyl, and halogenated biphenyl (III) A single or mixed solvent selected from benzyl alcohol, sulfuran, and glycerin, or a mixed solvent of the above (II) and N-methyl-2-pyrrolidone. (IV) A mixed solvent of the above (I) or a mixed solvent of N-methyl-2-pyrrolidone and water. (2) The method for removing impurities according to claim 1, wherein the polyphenylene sulfide resin is pulverized by a dry method. (3) The method for removing impurities according to claim 1, wherein the polyphenylene sulfide resin is pulverized by a wet method.