JPH0521136B2 - - Google Patents
Info
- Publication number
- JPH0521136B2 JPH0521136B2 JP60109413A JP10941385A JPH0521136B2 JP H0521136 B2 JPH0521136 B2 JP H0521136B2 JP 60109413 A JP60109413 A JP 60109413A JP 10941385 A JP10941385 A JP 10941385A JP H0521136 B2 JPH0521136 B2 JP H0521136B2
- Authority
- JP
- Japan
- Prior art keywords
- pps
- melt viscosity
- formula
- powder
- polyphenylene sulfide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000011777 magnesium Substances 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 8
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 7
- 229910052749 magnesium Inorganic materials 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 150000003857 carboxamides Chemical class 0.000 claims description 4
- 239000004734 Polyphenylene sulfide Substances 0.000 claims 3
- 229920000069 polyphenylene sulfide Polymers 0.000 claims 3
- 238000000034 method Methods 0.000 description 12
- 239000000843 powder Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 239000000155 melt Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- -1 polyphenylene sulfite Polymers 0.000 description 4
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229910052979 sodium sulfide Inorganic materials 0.000 description 2
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 description 1
- 235000010893 Bischofia javanica Nutrition 0.000 description 1
- 240000005220 Bischofia javanica Species 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012765 fibrous filler Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
Description
〔産業上の利用分野〕
本発明は、溶融成形可能な淡白色の高溶融粘度
ポリフエニレンサルフアイト（以下PPSと略す）
の製造方法に関するものである。
PPSは、その優れた耐熱性、耐薬品性をいかし
て電子機器部材，自動車機器部材として注目を集
めている。また、射出成形、押出成形等により各
種エンジニアリングプラスチツク部品，フイル
ム，シート，繊維等に成形可能であり、耐熱性の
要求される分野に幅広く用いられている。
〔従来の技術〕
高溶融粘度のPPSの製造方法としては、従来次
のようなものが知られている。
(1) Ｎ−メチルピロリドン等の有機極性溶媒中で
Ｐ−ジクロルベンゼンと硫化ナトリウムを反応
させる方法（特公昭45−3368号）によつて得ら
れた低溶融粘度PPSを空気中で加熱し、酸化架
橋させて高溶融粘度とする方法、
(2) 上記(1)法において、重合助剤として、アルカ
リ金属カルボン酸塩を添加する方法（特公昭52
−12240号）、
(3) 上記(2)法においてＰ−ジクロルベンゼンに加
えて、少量のトリクロルベンゼンを添加共重合
させる方法（特公昭57−334号）。
しかし、(1)の方法では、250℃以上の高温で数
時間加熱処理することが必要であり、また溶融粘
度のコントロールが難しいなどの設備および生産
性などの問題がある。
また、被処理物は著しく茶褐色に着色するた
め、顔料等の添加により任意に着色することが困
難となる。
(2)，(3)の方法は、(1)の方法を改良し、上記の加
熱処理をすることなしに成形用途に使用し得る程
度に高められた溶融粘度を有するPPSを得る方法
である。しかしながら、これらの方法において
は、アルカリ金属カルボン酸塩は硫化ナトリウム
とほぼ等モル量必要とされており、特に高溶融粘
度化に有効な酢酸リチウムは、高価なためPPSの
製造コストが高くなる。また、多量のアルカリ金
属カルボン酸塩を使用するため、処理廃水に多量
の有機酸が混入することになり、公害上の問題を
生ずる恐れがあり、また、それを除外するために
は、多大の費用を必要とすることなど問題があり
工業的でない。
〔発明が解決しようとする問題点〕
本発明は、上記欠点を改良した溶融成形可能な
淡白色の高溶融粘度PPSの製造法を提供するもの
である。
〔問題を解決するための手段〕
本発明の要旨は、一般式
[Industrial Application Field] The present invention is a melt-mouldable pale white high melt viscosity polyphenylene sulfite (hereinafter abbreviated as PPS).
The present invention relates to a manufacturing method. PPS is attracting attention as a material for electronic equipment and automobile equipment due to its excellent heat resistance and chemical resistance. Furthermore, it can be molded into various engineering plastic parts, films, sheets, fibers, etc. by injection molding, extrusion molding, etc., and is widely used in fields where heat resistance is required. [Prior Art] The following methods are conventionally known as methods for producing PPS with high melt viscosity. (1) Low melt viscosity PPS obtained by the method of reacting P-dichlorobenzene with sodium sulfide in an organic polar solvent such as N-methylpyrrolidone (Japanese Patent Publication No. 3368/1982) was heated in air. (2) A method in which an alkali metal carboxylate is added as a polymerization aid in the method (1) above (Japanese Patent Publication No. 52
-12240), (3) A method in which a small amount of trichlorobenzene is added to and copolymerized in addition to P-dichlorobenzene in the above method (2) (Japanese Patent Publication No. 57-334). However, method (1) requires heat treatment at a high temperature of 250° C. or higher for several hours, and also has problems with equipment and productivity, such as difficulty in controlling melt viscosity. In addition, since the object to be treated is significantly colored brown, it is difficult to arbitrarily color the object by adding pigments or the like. Methods (2) and (3) are improvements on method (1) to obtain PPS with a melt viscosity that is high enough to be used for molding applications without the above heat treatment. . However, in these methods, the alkali metal carboxylate is required in an approximately equimolar amount as that of sodium sulfide, and lithium acetate, which is particularly effective in increasing melt viscosity, is expensive, which increases the production cost of PPS. Furthermore, since a large amount of alkali metal carboxylate is used, a large amount of organic acid will be mixed into the treated wastewater, which may cause pollution problems. There are problems such as the cost involved, and it is not industrially viable. [Problems to be Solved by the Invention] The present invention provides a method for producing a pale white, high melt viscosity PPS that can be melt molded and that improves the above-mentioned drawbacks. [Means for solving the problem] The gist of the present invention is that the general formula
【式】
なる構造単位で示されるPPSを有機アミド溶媒
中、かつPPSに対し0.01〜5.0重量％の金属マグネ
シウム存在下で加熱することを特徴とする淡白色
の高溶融粘度PPSの製造法にあり、以下その詳細
について説明する。
本発明において使用するPPSは、一般式[Formula] A method for producing pale white high melt viscosity PPS characterized by heating PPS represented by the structural unit in an organic amide solvent and in the presence of metallic magnesium in an amount of 0.01 to 5.0% by weight relative to PPS. The details will be explained below. The PPS used in the present invention has the general formula
【式】で示される繰り返し単位を
もつた構造のものが70モル％以上、好ましくは90
モル％以上含まれるものであれば他の成分が共重
合されたものであつてもよく、その粘度も特に特
定されない。この場合、他の成分としては例えば70 mol% or more, preferably 90 mol% or more of a structure having a repeating unit represented by [Formula]
It may be copolymerized with other components as long as it is contained in a mole % or more, and its viscosity is not particularly specified. In this case, other ingredients include, for example
【式】【formula】
【式】【formula】
【式】【formula】
【式】【formula】
【式】【formula】
【式】【formula】
【式】【formula】
以上の説明から明らかなように本発明によれ
ば、茶褐色に着色させることなく、成形可能な程
度に高められた溶融粘度を有するPPSが得られ、
射出成形のみならず押出し成形等によつてパイ
プ，シート等が成形可能である。
更に本発明のPPSに熱安定剤，顔料，粉末状充
填剤，繊維状充填剤等を充填して使用すること
も、もちろん可能である。
〔実施例〕
以下の実施例及び比較例でのPPSの溶融粘度の
測定は、高化式フローテスター（ダイス；φ＝
0.5mm，Ｌ＝１mm）を使用し、300℃，10Kg荷重で
測定した。
また、PPS中のマグネシウム含量は、約0.5ｇ
の試料を石英ビーカー中で約10mlの硫酸および約
10mlの硝酸で湿式分解させた後、脱イオン水を加
えて一定容量に調整した液を原子吸光分光分析に
より求めたものであり、ポリマーの色はポリマー
乾燥後、目視により判別した。
実施例 １
15容量のオートクレーブにNa2S・
28H2O14.8モル，Ｎ−メチルピロリドン4.9を
入れ、窒素気流下撹拌して210℃まで昇温し、424
ｇの主に水からなる留出液を留去した。系を170
℃まで冷却した後、Ｐ−ジクロルベンゼン14.8モ
ルを添加し、窒素気流下に系を封入，昇温して
250℃にて３時間重合した。冷却後内容物を水中
にあけ、温水で３回洗浄，過をくり返した後、
メタノールで１回洗浄し、一晩加熱乾燥を行つて
灰白色の粉体を得た。得られた重合体の収量は
1.470ｇ，収率は94％であり、溶融粘度は10Kg荷
重で100ポイズであつた。
次いで、得られたPPS粉末50ｇ，Mg粉末0.34
ｇおよびＮ−メチル−２−ピロリドン300ｇを仕
込み、窒素で系内を置換した後、昇温し、240℃
で２時間加熱撹伴した。オートクレーブを冷却
後、ポリマーを熱水で３回洗浄した。80℃で一日
間乾燥後、溶融粘度およびマグネシウム含量の測
定を行つた。結果を第一表に示す。
実施例 ２
実施例１の重合において得られたポリマーを
Mg粉末0.085ｇと加熱処理した以外は、実施例１
と同様の操作を行つた。結果を第一表に示す。
実施例 ３
240℃で30分加熱処理した以外は、実施例２と
同様の操作を行つた。結果を第１表に示す。
比較例 １
Mg粉末0.003ｇを用いた以外は、実施例２と同
様の操作を行つた。結果を第１表に示す。
比較例 ２
Mgの代わりにZn粉末0.92ｇを用いた以外は、
実施例２と同様の操作を行つた。結果を第１表に
示す。
比較例 ３
Mgの代わりにAl粉末0.19ｇを用いた以外は、
実施例２と同様の操作を行つた。結果を第１表に
示す。
比較例 ４
実施例１の重合において得られたポリマー50ｇ
とMg粉末0.34ｇとを、ボールミル中で２時間粉
砕混合し、実施例１と同様の評価を行つた。結果
を第１表に示す。
As is clear from the above description, according to the present invention, PPS can be obtained which has a melt viscosity that is high enough to be moldable without being colored brown.
Pipes, sheets, etc. can be formed not only by injection molding but also by extrusion molding. Furthermore, it is of course possible to use the PPS of the present invention by filling it with a heat stabilizer, pigment, powder filler, fibrous filler, etc. [Example] In the following examples and comparative examples, the melt viscosity of PPS was measured using a Koka type flow tester (dice; φ=
0.5 mm, L=1 mm), and was measured at 300°C and a load of 10 kg. In addition, the magnesium content in PPS is approximately 0.5g.
sample in a quartz beaker with approximately 10 ml of sulfuric acid and approx.
After wet decomposition with 10 ml of nitric acid, deionized water was added to adjust the volume to a constant volume, which was determined by atomic absorption spectrometry. The color of the polymer was visually determined after drying the polymer. Example 1 Na 2 S in a 15 capacity autoclave.
Add 14.8 mol of 28H 2 O and 4.9 mol of N-methylpyrrolidone, stir under a nitrogen stream and raise the temperature to 210°C.
A distillate consisting mainly of water was distilled off. 170 system
After cooling to ℃, 14.8 mol of P-dichlorobenzene was added, the system was sealed under a nitrogen stream, and the temperature was raised.
Polymerization was carried out at 250°C for 3 hours. After cooling, pour the contents into water, wash with warm water three times, and repeat the process.
It was washed once with methanol and dried by heating overnight to obtain an off-white powder. The yield of the obtained polymer is
The yield was 1.470 g, 94%, and the melt viscosity was 100 poise at a load of 10 kg. Next, 50g of the obtained PPS powder, 0.34g of Mg powder
After charging 300 g of N-methyl-2-pyrrolidone and purging the system with nitrogen, the temperature was raised to 240°C.
The mixture was heated and stirred for 2 hours. After cooling the autoclave, the polymer was washed three times with hot water. After drying at 80°C for one day, melt viscosity and magnesium content were measured. The results are shown in Table 1. Example 2 The polymer obtained in the polymerization of Example 1 was
Example 1 except for heat treatment with 0.085g of Mg powder
I performed the same operation as . The results are shown in Table 1. Example 3 The same operation as in Example 2 was performed except that heat treatment was performed at 240° C. for 30 minutes. The results are shown in Table 1. Comparative Example 1 The same operation as in Example 2 was performed except that 0.003 g of Mg powder was used. The results are shown in Table 1. Comparative Example 2 Except for using 0.92g of Zn powder instead of Mg,
The same operation as in Example 2 was performed. The results are shown in Table 1. Comparative Example 3 Except for using 0.19g of Al powder instead of Mg,
The same operation as in Example 2 was performed. The results are shown in Table 1. Comparative Example 4 50 g of polymer obtained in the polymerization of Example 1
and 0.34 g of Mg powder were pulverized and mixed in a ball mill for 2 hours, and the same evaluation as in Example 1 was performed. The results are shown in Table 1.
【表】
第１表よりPPSとPPSに対して0.01重量％以上
の金属マグネシウムとを有機アミド系溶媒中で加
熱処理することにより、淡白色で、かつ溶融粘度
が著しく高められたPPSが得られることがわか
る。
また比較例２，３から亜鉛や、アルミニウム等
の金属を用いた場合は、溶融粘度の増大効果が見
られず、本発明においては金属マグネシウムのみ
が有効であることがわかる。
さらに、比較例４から明らかなように、PPSと
金属マグネシウムとをただ単に混合しただけで
は、溶融粘度の増加は見られず、有機アミド系溶
媒中で加熱することが有効であることがわかる。[Table] From Table 1, by heat-treating PPS and metallic magnesium in an amount of 0.01% by weight or more based on PPS in an organic amide solvent, a pale white PPS with a significantly increased melt viscosity can be obtained. I understand that. Further, from Comparative Examples 2 and 3, when metals such as zinc and aluminum were used, no effect of increasing the melt viscosity was observed, and it is understood that only metallic magnesium is effective in the present invention. Furthermore, as is clear from Comparative Example 4, no increase in melt viscosity was observed by simply mixing PPS and magnesium metal, indicating that heating in an organic amide solvent is effective.
Claims (1)
ド中、かつポリフエニレンサルフアイドに対し、
0.01〜5.0重量％の金属マグネシウム存在下で加
熱することを特徴とする淡白色の高溶融粘度ポリ
フエニレンサルフアイドの製造法。[Claims] 1. Polyphenylene sulfide represented by the structural unit of the general formula [formula] in an organic amide and for polyphenylene sulfide,
A method for producing pale white, high melt viscosity polyphenylene sulfide, which is characterized by heating in the presence of 0.01 to 5.0% by weight of metallic magnesium.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60109413A JPS61268728A (en) | 1985-05-23 | 1985-05-23 | Production of high-melt viscosity polyphenylene sulfide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60109413A JPS61268728A (en) | 1985-05-23 | 1985-05-23 | Production of high-melt viscosity polyphenylene sulfide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61268728A JPS61268728A (en) | 1986-11-28 |
| JPH0521136B2 true JPH0521136B2 (en) | 1993-03-23 |
Family
ID=14509616
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60109413A Granted JPS61268728A (en) | 1985-05-23 | 1985-05-23 | Production of high-melt viscosity polyphenylene sulfide |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61268728A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0653735U (en) * | 1992-12-28 | 1994-07-22 | 株式会社ゼクセル | Stop lever shaft support device |
-
1985
- 1985-05-23 JP JP60109413A patent/JPS61268728A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0653735U (en) * | 1992-12-28 | 1994-07-22 | 株式会社ゼクセル | Stop lever shaft support device |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61268728A (en) | 1986-11-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP3646737B2 (en) | Reactive polyarylene sulfide | |
| TW412569B (en) | Polyarylene sulfide composition | |
| JPS62143932A (en) | Production of polyphenylene sulfide | |
| JP2021507035A (en) | A method for producing a polyphenylene sulfide resin, and a polyphenylene sulfide resin produced by the method. | |
| CN110615915A (en) | Composite polypropylene nucleating agent and preparation method and application thereof | |
| DD258021A5 (en) | PROCESS FOR PREPARING POLYMERS WITH CONJUGATED DOUBLE BONDINGS | |
| JPH0521136B2 (en) | ||
| DE4208005A1 (en) | AROMATIC POLYAMIDES AND METHOD FOR THE PRODUCTION THEREOF | |
| CN109337340A (en) | A kind of acetylation polyester modification conductive film and preparation method thereof | |
| JPH0798901B2 (en) | Polyphenylene sulfide composition | |
| JP3190071B2 (en) | Polyarylene thioether composition | |
| CN108424645A (en) | A kind of fire prevention battery conductive material and preparation method thereof | |
| JPS62138528A (en) | Production of polyphenylene sulfide | |
| JPS59115331A (en) | Production of polyphenylene sulfide polymer | |
| JPH0240251B2 (en) | ||
| JP2611379B2 (en) | Polyphenylene sulfide film | |
| US4945153A (en) | Method of producing prepolymer of aromatic polythiazole in the presence of a phosphoric acid compound | |
| JPS6361963B2 (en) | ||
| JPH0254370B2 (en) | ||
| JPH04225063A (en) | Method for treating polyarylene sulfide resin | |
| JPS62288630A (en) | Photo-stabilized polyarylene thioether | |
| JPH0573773B2 (en) | ||
| JP2535509B2 (en) | Polyphenylene sulfide resin composition | |
| DONARUMA | A New Group of Oxime Esters | |
| JP3307018B2 (en) | Method for producing polyarylene sulfide resin and polyphenylene sulfide resin |