JPH038655B2 - - Google Patents
Info
- Publication number
- JPH038655B2 JPH038655B2 JP26966284A JP26966284A JPH038655B2 JP H038655 B2 JPH038655 B2 JP H038655B2 JP 26966284 A JP26966284 A JP 26966284A JP 26966284 A JP26966284 A JP 26966284A JP H038655 B2 JPH038655 B2 JP H038655B2
- Authority
- JP
- Japan
- Prior art keywords
- polyvinylene
- sulfide
- chloride
- alkali metal
- selenide
- 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
Links
- -1 alkali metal selenide Chemical class 0.000 claims description 40
- 229920001197 polyacetylene Polymers 0.000 claims description 30
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 125000004122 cyclic group Chemical group 0.000 claims description 9
- 229920000570 polyether Polymers 0.000 claims description 9
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 8
- 150000003346 selenoethers Chemical class 0.000 claims description 7
- 229910052783 alkali metal Inorganic materials 0.000 claims description 6
- 229910052977 alkali metal sulfide Inorganic materials 0.000 claims description 4
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 3
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 3
- 229910001510 metal chloride Inorganic materials 0.000 claims description 2
- 150000004714 phosphonium salts Chemical group 0.000 claims description 2
- 125000003367 polycyclic group Chemical group 0.000 claims 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 14
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 12
- 238000005979 thermal decomposition reaction Methods 0.000 description 12
- 239000007788 liquid Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 8
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 7
- 150000004770 chalcogenides Chemical class 0.000 description 7
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 7
- 239000002244 precipitate Substances 0.000 description 7
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 7
- 229910052786 argon Inorganic materials 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 229940045803 cuprous chloride Drugs 0.000 description 4
- 239000003444 phase transfer catalyst Substances 0.000 description 4
- 229910052979 sodium sulfide Inorganic materials 0.000 description 4
- KFUSEUYYWQURPO-OWOJBTEDSA-N trans-1,2-dichloroethene Chemical group Cl\C=C\Cl KFUSEUYYWQURPO-OWOJBTEDSA-N 0.000 description 4
- UKDOTCFNLHHKOF-FGRDZWBJSA-N (z)-1-chloroprop-1-ene;(z)-1,2-dichloroethene Chemical group C\C=C/Cl.Cl\C=C/Cl UKDOTCFNLHHKOF-FGRDZWBJSA-N 0.000 description 3
- AUFVJZSDSXXFOI-UHFFFAOYSA-N 2.2.2-cryptand Chemical compound C1COCCOCCN2CCOCCOCCN1CCOCCOCC2 AUFVJZSDSXXFOI-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000011669 selenium Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 2
- ZVQOOHYFBIDMTQ-UHFFFAOYSA-N [methyl(oxido){1-[6-(trifluoromethyl)pyridin-3-yl]ethyl}-lambda(6)-sulfanylidene]cyanamide Chemical compound N#CN=S(C)(=O)C(C)C1=CC=C(C(F)(F)F)N=C1 ZVQOOHYFBIDMTQ-UHFFFAOYSA-N 0.000 description 2
- UDYGXWPMSJPFDG-UHFFFAOYSA-M benzyl(tributyl)azanium;bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CC1=CC=CC=C1 UDYGXWPMSJPFDG-UHFFFAOYSA-M 0.000 description 2
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 description 2
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- VPQBLCVGUWPDHV-UHFFFAOYSA-N sodium selenide Chemical compound [Na+].[Na+].[Se-2] VPQBLCVGUWPDHV-UHFFFAOYSA-N 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 125000000101 thioether group Chemical group 0.000 description 2
- 150000003568 thioethers Chemical class 0.000 description 2
- FIGVVZUWCLSUEI-UHFFFAOYSA-N tricosane Chemical compound CCCCCCCCCCCCCCCCCCCCCCC FIGVVZUWCLSUEI-UHFFFAOYSA-N 0.000 description 2
- UWTUEMKLYAGTNQ-OWOJBTEDSA-N (e)-1,2-dibromoethene Chemical group Br\C=C\Br UWTUEMKLYAGTNQ-OWOJBTEDSA-N 0.000 description 1
- NLMDJJTUQPXZFG-UHFFFAOYSA-N 1,4,10,13-tetraoxa-7,16-diazacyclooctadecane Chemical compound C1COCCOCCNCCOCCOCCN1 NLMDJJTUQPXZFG-UHFFFAOYSA-N 0.000 description 1
- STHIZMRUXPMSCW-UHFFFAOYSA-N 1,4,10-trioxa-7,13-diazacyclopentadecane Chemical compound C1COCCNCCOCCOCCN1 STHIZMRUXPMSCW-UHFFFAOYSA-N 0.000 description 1
- AKAIWNDBVZJOAJ-UHFFFAOYSA-N 1,4-dithiine Chemical compound S1C=CSC=C1 AKAIWNDBVZJOAJ-UHFFFAOYSA-N 0.000 description 1
- XQQZRZQVBFHBHL-UHFFFAOYSA-N 12-crown-4 Chemical compound C1COCCOCCOCCO1 XQQZRZQVBFHBHL-UHFFFAOYSA-N 0.000 description 1
- VFTFKUDGYRBSAL-UHFFFAOYSA-N 15-crown-5 Chemical compound C1COCCOCCOCCOCCO1 VFTFKUDGYRBSAL-UHFFFAOYSA-N 0.000 description 1
- XEZNGIUYQVAUSS-UHFFFAOYSA-N 18-crown-6 Chemical compound C1COCCOCCOCCOCCOCCO1 XEZNGIUYQVAUSS-UHFFFAOYSA-N 0.000 description 1
- LVNQVIZBPSRXAN-UHFFFAOYSA-N 4,7,13,18-tetraoxa-1,10-diazabicyclo[8.5.5]icosane Chemical compound C1COCCOCCN2CCOCCN1CCOCC2 LVNQVIZBPSRXAN-UHFFFAOYSA-N 0.000 description 1
- WUHOJKXEIIYUSL-UHFFFAOYSA-N 7,16-didecyl-1,4,10,13-tetraoxa-7,16-diazacyclooctadecane Chemical compound CCCCCCCCCCN1CCOCCOCCN(CCCCCCCCCC)CCOCCOCC1 WUHOJKXEIIYUSL-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 description 1
- 229910001508 alkali metal halide Inorganic materials 0.000 description 1
- 150000008045 alkali metal halides Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- FNEPSTUXZLEUCK-UHFFFAOYSA-N benzo-15-crown-5 Chemical compound O1CCOCCOCCOCCOC2=CC=CC=C21 FNEPSTUXZLEUCK-UHFFFAOYSA-N 0.000 description 1
- KXHPPCXNWTUNSB-UHFFFAOYSA-M benzyl(trimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1=CC=CC=C1 KXHPPCXNWTUNSB-UHFFFAOYSA-M 0.000 description 1
- USFRYJRPHFMVBZ-UHFFFAOYSA-M benzyl(triphenyl)phosphanium;chloride Chemical compound [Cl-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)CC1=CC=CC=C1 USFRYJRPHFMVBZ-UHFFFAOYSA-M 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- KFUSEUYYWQURPO-UPHRSURJSA-N cis-1,2-dichloroethene Chemical group Cl\C=C/Cl KFUSEUYYWQURPO-UPHRSURJSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 150000003983 crown ethers Chemical class 0.000 description 1
- 229960003280 cupric chloride Drugs 0.000 description 1
- YSSSPARMOAYJTE-UHFFFAOYSA-N dibenzo-18-crown-6 Chemical compound O1CCOCCOC2=CC=CC=C2OCCOCCOC2=CC=CC=C21 YSSSPARMOAYJTE-UHFFFAOYSA-N 0.000 description 1
- UNTITLLXXOKDTB-UHFFFAOYSA-N dibenzo-24-crown-8 Chemical compound O1CCOCCOCCOC2=CC=CC=C2OCCOCCOCCOC2=CC=CC=C21 UNTITLLXXOKDTB-UHFFFAOYSA-N 0.000 description 1
- BBGKDYHZQOSNMU-UHFFFAOYSA-N dicyclohexano-18-crown-6 Chemical compound O1CCOCCOC2CCCCC2OCCOCCOC2CCCCC21 BBGKDYHZQOSNMU-UHFFFAOYSA-N 0.000 description 1
- RIYVKHUVXPAOPS-UHFFFAOYSA-N dithiine Chemical compound S1SC=CC=C1 RIYVKHUVXPAOPS-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- JHYNXXDQQHTCHJ-UHFFFAOYSA-M ethyl(triphenyl)phosphanium;bromide Chemical compound [Br-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CC)C1=CC=CC=C1 JHYNXXDQQHTCHJ-UHFFFAOYSA-M 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- YTGHXYPZJCPPQS-UHFFFAOYSA-N hexadecylphosphanium;bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[PH3+] YTGHXYPZJCPPQS-UHFFFAOYSA-N 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- LSEFCHWGJNHZNT-UHFFFAOYSA-M methyl(triphenyl)phosphanium;bromide Chemical compound [Br-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(C)C1=CC=CC=C1 LSEFCHWGJNHZNT-UHFFFAOYSA-M 0.000 description 1
- JXTPJDDICSTXJX-UHFFFAOYSA-N n-Triacontane Natural products CCCCCCCCCCCCCCCCCCCCCCCCCCCCCC JXTPJDDICSTXJX-UHFFFAOYSA-N 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- REJGOFYVRVIODZ-UHFFFAOYSA-N phosphanium;chloride Chemical group P.Cl REJGOFYVRVIODZ-UHFFFAOYSA-N 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- DPKBAXPHAYBPRL-UHFFFAOYSA-M tetrabutylazanium;iodide Chemical compound [I-].CCCC[N+](CCCC)(CCCC)CCCC DPKBAXPHAYBPRL-UHFFFAOYSA-M 0.000 description 1
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 description 1
- YMBCJWGVCUEGHA-UHFFFAOYSA-M tetraethylammonium chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC YMBCJWGVCUEGHA-UHFFFAOYSA-M 0.000 description 1
- UQFSVBXCNGCBBW-UHFFFAOYSA-M tetraethylammonium iodide Chemical compound [I-].CC[N+](CC)(CC)CC UQFSVBXCNGCBBW-UHFFFAOYSA-M 0.000 description 1
- RXMRGBVLCSYIBO-UHFFFAOYSA-M tetramethylazanium;iodide Chemical compound [I-].C[N+](C)(C)C RXMRGBVLCSYIBO-UHFFFAOYSA-M 0.000 description 1
- HHTRNOOZEBPETC-UHFFFAOYSA-M triethyl(3-phenylpropyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CCCC1=CC=CC=C1 HHTRNOOZEBPETC-UHFFFAOYSA-M 0.000 description 1
- WPPGURUIRLDHAB-UHFFFAOYSA-M triethyl(hexadecyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](CC)(CC)CC WPPGURUIRLDHAB-UHFFFAOYSA-M 0.000 description 1
Landscapes
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
Description
【発明の詳細な説明】
(産業上の利用分野)
本発明は、ポリビニレンスルフイドまたはポリ
ビニレンセレニドの製造方法に関するものであ
る。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a method for producing polyvinylene sulfide or polyvinylene selenide.
(従来の技術)
ポリビニレンカルコゲナイドは、高分子主鎖に
カルコゲナイド原子を含んだ一次元高分子であ
り、特にカルコゲナイド原子が硫黄原子であるも
のがポリビニレンスルフイドである。これらの含
カルコゲナイド系高分子は、その構造に特有の電
気的特性および熱的特性を有しており、有機高分
子半導体あるいは耐熱性高分子として有用であ
る。(Prior Art) Polyvinylene chalcogenide is a one-dimensional polymer containing a chalcogenide atom in its main chain, and polyvinylene sulfide is particularly one in which the chalcogenide atom is a sulfur atom. These chalcogenide-containing polymers have electrical and thermal properties specific to their structure, and are useful as organic polymer semiconductors or heat-resistant polymers.
本発明者等は、先にポリビニレンカルコゲナイ
ドを製造する方法として、XHC=CHX′、ただ
しX,X′はF,Cl,Br,Iにアルカリ金属カル
コゲナイドを反応させる方法を提案した(特願昭
57−60943号(特開昭58−179233号公報)、以下
“先願1”という)。また、本発明者等は、先にポ
リビニレンスルフイドを製造する方法として、
1,2−ジクロルエチレンと硫化ナトリウムとを
反応させる方法を提案した(特願昭58−19821号
(特開昭59−147021号公報)、特願昭59−62157号
(特開昭60−206833号公報)、以下“先願2”,“先
願3”という)。 The present inventors previously proposed a method of reacting an alkali metal chalcogenide with XHC=CHX', where X, X' are F, Cl, Br, and I as a method for producing polyvinylene chalcogenide (patent application
No. 57-60943 (Japanese Unexamined Patent Publication No. 58-179233, hereinafter referred to as "Prior Application 1"). In addition, the present inventors first developed a method for producing polyvinylene sulfide.
proposed a method of reacting 1,2-dichloroethylene with sodium sulfide (Japanese Patent Application No. 19821/1982 (Japanese Unexamined Patent Publication No. 147021/1982), Japanese Patent Application No. 62157/1983 (Japanese Unexamined Patent Publication No. 60/1983) 206833), hereinafter referred to as "Prior Application 2" and "Prior Application 3").
(発明が解決しようとする問題点)
しかしながら、先願1〜先願3の方法で得られ
るポリマーは耐熱性が低いという欠点を有してい
る。たとえば、先願3の方法で得られるポリビニ
レンスルフイドは、原料として1,2−ジクロル
エチレンのシス型またはトランス型のいずれかを
用いることにより、それぞれ120℃,150℃の温度
で収縮、黒化が生じる。さらに、180℃に達する
といずれのポリビニレンスルフイドも熱分解を起
こし、黄色の液体を放出し始める。このように、
先願の製造方法により得られるポリマーは低耐熱
性という点で、さらに検討を重ねる必要がある。(Problems to be Solved by the Invention) However, the polymers obtained by the methods of Prior Applications 1 to 3 have a drawback of low heat resistance. For example, polyvinylene sulfide obtained by the method of Prior Application 3 shrinks at temperatures of 120°C and 150°C, respectively, by using either the cis or trans form of 1,2-dichloroethylene as a raw material. , darkening occurs. Furthermore, when the temperature reaches 180°C, both polyvinylene sulfides undergo thermal decomposition and begin to release a yellow liquid. in this way,
Since the polymer obtained by the manufacturing method of the previous application has low heat resistance, it is necessary to conduct further studies.
(問題点を解決しようとする手段)
そこで本発明者等は、1,2−ジハロゲン化エ
チレンとアルカリ金属カルコゲナイドとからポリ
ビニレンカルコゲナイドを製造する方法について
研究を重ねた結果、反応系中に第B族金属の塩
化物または相間移動触媒を添加することにより、
耐熱性を向上させることができることを見いだ
し、この知見に基いて本発明をなすに至つた。(Means for Solving the Problems) Therefore, the present inventors have conducted repeated research on a method for producing polyvinylene chalcogenide from 1,2-dihalogenated ethylene and alkali metal chalcogenide. By adding group metal chlorides or phase transfer catalysts,
It was discovered that heat resistance could be improved, and the present invention was completed based on this knowledge.
本発明は、1,2−ジハロゲン化エチレンとア
ルカリ金属硫化物またはアルカリ金属セレン化物
との反応系中に第B族金属の塩化物または相間
移動触媒である第4級アンモニウム塩、第4級ホ
スホニウム塩、環状ポリエーテル、多環性環状化
合物、環状ポリエーテルアミン及び環状ポリエー
テルスルフイドのうちの1種を添加することを特
徴とする耐熱性の向上したポリビニレンスルフイ
ドまたはポリビニレンセレニドを製造する方法で
ある。また第B族金属の塩化物と相間移動触媒
である前記化合物を併用することも可能である。 The present invention provides a method for preparing quaternary ammonium salts, quaternary phosphonium chlorides or phase transfer catalysts of group B metals in the reaction system of 1,2-dihalogenated ethylene and alkali metal sulfides or alkali metal selenides. Polyvinylene sulfide or polyvinylene selenium with improved heat resistance characterized by adding one of a salt, a cyclic polyether, a polycyclic cyclic compound, a cyclic polyether amine, and a cyclic polyether sulfide. This is a method for producing Nido. It is also possible to use a chloride of Group B metal and the above-mentioned compound which is a phase transfer catalyst in combination.
本発明で用いられる1,2−ジハロゲン化エチ
レンとしては、構造式
XHC=CHX′
(ただし、X,X′はフツ素F、塩素Cl、臭素
Br、ヨウ素Iのいずれかを示す)で表わされ、
これらはシス型、トランス型の各異性体、および
それらの混合物が使用可能である。好ましくは、
1,2−ジクロルエチレンのシス型またはトラン
ス型を用いる。アルカリ金属硫化物またはアルカ
リ金属セレン化物としては、一般式 M2L
(ただし、MはNa,K,Li,Rb,Csのいずれ
かを示し、LはSまたはSeを示す)で表わされ
る化合物を用いる。アルカリ金属硫化物またはア
ルカリ金属セレン化物には、無水塩よび含水塩の
2種類が存在することがあり、純粋な構造を有す
るポリビニレンスルフイドまたはポリビニレンセ
レニドを得るためには、無水塩を用いることが好
ましい。さらに好ましくは、硫化ナトリウムの無
水塩Na2Sを用いる。 The 1,2-dihalogenated ethylene used in the present invention has the structural formula:
Br, iodine I),
These can be used in the form of cis isomers, trans isomers, or mixtures thereof. Preferably,
The cis or trans form of 1,2-dichloroethylene is used. As alkali metal sulfides or alkali metal selenides, compounds represented by the general formula M 2 L (where M represents either Na, K, Li, Rb, or Cs, and L represents S or Se) are used. use Alkali metal sulfides or alkali metal selenides may exist in two types: anhydrous salts and hydrated salts. In order to obtain polyvinylene sulfide or polyvinylene selenide with a pure structure, the anhydrous salt is It is preferable to use More preferably, the anhydrous salt of sodium sulfide, Na 2 S, is used.
ここで、硫化ナトリウムを用いて製造される生
成物は、特にポリビニレンスルフイドとして知ら
れるものである。 The products produced here using sodium sulfide are, in particular, those known as polyvinylene sulfides.
第B族金属の塩化物としては、塩化第一銅
CuCl、塩化第二銅CuCl2、塩化銀AgCl等が挙げ
られるが、好ましくは塩化第一銅CuClを用いる。 As the chloride of group B metal, cuprous chloride
Examples include CuCl, cupric chloride CuCl 2 , silver chloride AgCl, and preferably cuprous chloride CuCl is used.
相間移動触媒である化合物としては、ベンジル
トリメチルアンモニウムクロリド、ベンジルトリ
エチルアンモニウムクロリド、セチルトリメチル
アンモニウムクロリド、セチルトリエチルアンモ
ニウムクロリド、テトラメチルアンモニウムクロ
リド、テトラエチルアンモニウムクロリド、テト
ラn−ブチルアンモニウムブロミド、ベンジルト
リブチルアンモニウムブロミド、テトラエチルア
ンモニウムブロミド、テトラメチルアンモニウム
イオダイド、テトラエチルアンモニウムイオダイ
ド、テトラn−ブチルアンモニウムイオダイド等
の第4級アンモニウム塩、またはベンジルトリフ
エニルホスホニウムクロリド、エチルトリフエニ
ルホスホニウムブロミド、メチルトリフエニルホ
スホニウムブロミド、トリブチルヘキサデシルホ
スホニウムブロミド等の第4級ホスホニウム塩、
または12−クラウン−4,15−クラウン−5,ベ
ンゾ−15−クラウン−5,18−クラウン−6,ジ
ベンゾ−18−クラウン−6,ジシクロヘキシル−
18−クラウン−6,ジベンゾ−24−クラウン−
8,ジベンゾピリジノ−18−クラウン−6等の環
状ポリエーテル(クラウンエーテル)、またはク
リプトフイクス211(エー・メルク社商標名,4,
7,13,18−テトラオキサ−1,10−ジアザビシ
クロ〔8,5,5〕エイコサン),クリプトフイ
クス221(エー・メルク社商標名,4,7,13,
16,21,−ペンタオキサ−1,10−ジアザビシク
ロ〔8,5,5〕トリコサン),クリプトフイク
ス222(エー・メルク社商標名,4,7,13,16,
21,24−ヘキサオキサ−1,10−ジアザビシクロ
〔8,8,8〕ヘキサコサン),クリプトフイクス
222BB(エー・メルク社商標名,5,6−14,15
−ジベンゾ−4,7,13,16,21,24−ヘキサオ
キサ−1,10−ジアザビシクロ〔8,8,8〕ヘ
キサコサン)等の多環性環状化合物、またはクリ
プトフイクス21(エー・メルク社商標名1,4,
10−トリオキサ−7,13−ジアザシクロペンタデ
カン),クリプトフイクス22(エー・メルク社商標
名1,7,10,16−テトラオキサ−4,13−ジア
ザシクロオクタデカン),クリプトフイクス
22DD,(エー・メルク社商標名,4,13−ジデ
シル−1,7,10,16−テトラオキサ−4,13−
ジアザシクロオクタデカン),クリプトフイクス
23(エー・メルク社商標名,1,7,10,13,19
−ペンタオキサ−4,16−ジアザシクロヘンエイ
コサン)等の環状ポリエーテルアミン、または環
状ポリエーテルスルフイド等を用いることが可能
である。 Compounds that are phase transfer catalysts include benzyltrimethylammonium chloride, benzyltriethylammonium chloride, cetyltrimethylammonium chloride, cetyltriethylammonium chloride, tetramethylammonium chloride, tetraethylammonium chloride, tetra n-butylammonium bromide, benzyltributylammonium bromide, Quaternary ammonium salts such as tetraethylammonium bromide, tetramethylammonium iodide, tetraethylammonium iodide, tetra n-butylammonium iodide, or benzyltriphenylphosphonium chloride, ethyltriphenylphosphonium bromide, methyltriphenylphosphonium bromide, tributyl Quaternary phosphonium salts such as hexadecylphosphonium bromide,
or 12-crown-4, 15-crown-5, benzo-15-crown-5, 18-crown-6, dibenzo-18-crown-6, dicyclohexyl-
18-crown-6, dibenzo-24-crown-
8. Cyclic polyethers (crown ethers) such as dibenzopyridino-18-crown-6, or Cryptofix 211 (trademark name of A-Merck Co., Ltd., 4,
7,13,18-tetraoxa-1,10-diazabicyclo[8,5,5]eicosane), Cryptofix 221 (trademark name of A-Merck Co., Ltd., 4,7,13,
16,21,-pentaoxa-1,10-diazabicyclo[8,5,5]tricosane), Kryptofix 222 (trademark name of A-Merck Co., Ltd., 4,7,13,16,
21,24-hexaoxa-1,10-diazabicyclo[8,8,8]hexacosane), cryptofix
222BB (trade name of A-Merck Co., Ltd., 5, 6-14, 15
- polycyclic cyclic compounds such as -dibenzo-4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo[8,8,8]hexacosane), or Cryptofix 21 (trademark of A-Merck & Co., Ltd.) Name 1, 4,
10-trioxa-7,13-diazacyclopentadecane), Cryptofix 22 (A Merck & Co., Ltd. trade name 1,7,10,16-tetraoxa-4,13-diazacyclooctadecane), Cryptofix 22
22DD, (trade name of A-Merck Co., Ltd., 4,13-didecyl-1,7,10,16-tetraoxa-4,13-
diazacyclooctadecane), cryptofix
23 (A-Merck trademark name, 1, 7, 10, 13, 19
It is possible to use a cyclic polyether amine such as (-pentaoxa-4,16-diazacycloheneicosane) or a cyclic polyether sulfide.
本発明の製造方法において、重合反応は溶媒の
存在が好ましく、その溶媒としてジメチルスルホ
キシドが好ましい。 In the production method of the present invention, the presence of a solvent is preferred for the polymerization reaction, and dimethyl sulfoxide is preferred as the solvent.
また、本発明においては、10〜60℃の温度範囲
で反応を行うことが好ましい。 Moreover, in the present invention, it is preferable to carry out the reaction at a temperature range of 10 to 60°C.
反応時間に関しては特に限定しないが、生成物
の溶媒中での安定性、反応温度、原料物質の反応
溶媒への溶解性との兼ね合いにより、最適反応時
間が決められる。10〜60℃の温度範囲では、少な
くとも1時間以上の反応時間が必要である。 Although the reaction time is not particularly limited, the optimum reaction time is determined by balancing the stability of the product in the solvent, the reaction temperature, and the solubility of the raw materials in the reaction solvent. In the temperature range of 10 to 60°C, a reaction time of at least 1 hour is required.
生成した目的ポリマーは、反応液から副生物の
アルカリ金属ハロゲン化物を過により除去した
あと、液を大量のメタノールに注ぐことによ
り、沈殿物として得ることができる。 The produced target polymer can be obtained as a precipitate by removing by-product alkali metal halide from the reaction solution by filtration and then pouring the solution into a large amount of methanol.
得られたポリマーの耐熱性は次のようにして容
易に調べることができる。まず、ポリマーの粉末
を融点測定用のキヤピラリー管につめ、これを融
点測定器に取付け、徐々に加熱していく。ある温
度に達すると、充填したポリビニレンカルコゲナ
イドの粉末は収縮し、黒化が始まる。さらに昇温
していくと、熱分解し黄色ないし赤黄色の液体が
キヤピヤラリー管壁に付着してくる。 The heat resistance of the obtained polymer can be easily examined as follows. First, polymer powder is packed into a capillary tube for measuring the melting point, which is then attached to a melting point meter and gradually heated. Once a certain temperature is reached, the filled polyvinylene chalcogenide powder shrinks and begins to darken. As the temperature rises further, it thermally decomposes and a yellow to reddish-yellow liquid adheres to the capillary tube wall.
(発明の効果)
従来の製造方法で製造されたポリビニレンスル
フイドでは、収縮・黒化の温度が120〜150℃、熱
分解により黄色液体が発生する温度が180℃であ
る。これに対し、同じポリビニレンスルフイドで
も、本発明の製造方法によると収縮・黒化温度お
よび熱分解による黄色液体の発生温度を大巾に上
昇させることができた。(Effects of the Invention) In polyvinylene sulfide produced by conventional production methods, the temperature at which shrinkage and blackening occurs is 120 to 150°C, and the temperature at which yellow liquid is generated by thermal decomposition is 180°C. On the other hand, even with the same polyvinylene sulfide, according to the production method of the present invention, the shrinkage/blackening temperature and the temperature at which yellow liquid is generated due to thermal decomposition could be significantly increased.
(実施例)
ポリビニレンスルフイドの熱分解により生じる
黄色液体は、ガスクロマトグラフイー・マススペ
クトロメトリーによる解析から、1,4−ジチイ
ンであることがわかつた。ポリビニレンスルフイ
ド鎖が熱分解により切断され、6員環のジチイン
となつて発生するものと考えられる。(Example) Analysis by gas chromatography/mass spectrometry revealed that the yellow liquid produced by thermal decomposition of polyvinylene sulfide was 1,4-dithiine. It is thought that the polyvinylene sulfide chain is cleaved by thermal decomposition and a six-membered ring dithiine is generated.
本発明により製造されたポリビニレンスルフイ
ドは、従来の方法により製造されたものに比べ
て、熱分解開始温度が高く、耐熱性が上昇してい
る。 The polyvinylene sulfide produced by the present invention has a higher thermal decomposition initiation temperature and improved heat resistance than that produced by conventional methods.
次に実施例によつて本発明をより具体的に説明
する。 Next, the present invention will be explained in more detail with reference to Examples.
実施例 1
容量1000mlのオートクレーブ内をアルゴンガス
で置換し、硫化ナトリウム無水塩40.5gと塩化第
一銅2gを入れた。オートクレーブを密閉後、ト
ランス−1,2−ジクロルエチレン40mlとジメチ
ルスルホキシド500mlとの混合液を滴下し、反応
温度40℃で96時間激しく攪拌した。反応液を過
したあと、液を大量のメタノール中に注ぐこと
により、黒褐色沈殿物が生じた。収量は6gであ
つた。IRスペクトルの測定により、シス、トラ
ンス両構造の混在した純粋なポリビニレンスルフ
イド構造であることが確認された。Example 1 The inside of a 1000 ml autoclave was purged with argon gas, and 40.5 g of anhydrous sodium sulfide and 2 g of cuprous chloride were placed therein. After sealing the autoclave, a mixed solution of 40 ml of trans-1,2-dichloroethylene and 500 ml of dimethyl sulfoxide was added dropwise, and the mixture was vigorously stirred at a reaction temperature of 40° C. for 96 hours. After filtering the reaction solution, the solution was poured into a large amount of methanol, producing a dark brown precipitate. The yield was 6g. IR spectrum measurement confirmed that it was a pure polyvinylene sulfide structure containing both cis and trans structures.
このポリビニレンスルフイドをキヤピラリー管
につめ、加熱実験を行つたところ、150〜200℃で
収縮が始まつたが、250℃までは熱分解による黄
色液体の発生は見られなかつた。 When this polyvinylene sulfide was packed in a capillary tube and a heating experiment was performed, it began to shrink at 150-200°C, but no yellow liquid was observed due to thermal decomposition up to 250°C.
実施例 2
容量50mlのオートクレーブ内をアルゴンガスで
置換し、硫化ナトリウム無水塩Na2S5gと、18−
クラウン−6を0.5g入れた。オートクレーブを
密閉後、トランス−1,2−ジクロルエチレン2
gとジメチルスルホキシド30mlとの混合液を滴下
し、40℃で96時間激しく攪拌し。反応液を600
mlのメタノールに注いだところ、ただちに白褐色
沈殿が生じた。収量は0.86gであつた。Example 2 The inside of an autoclave with a capacity of 50 ml was replaced with argon gas, and 5 g of sodium sulfide anhydrous salt Na 2 S and 18-
0.5g of Crown-6 was added. After sealing the autoclave, trans-1,2-dichloroethylene 2
A mixture of g and 30 ml of dimethyl sulfoxide was added dropwise, and the mixture was vigorously stirred at 40°C for 96 hours. 600 ml of reaction solution
When poured into ml of methanol, a whitish brown precipitate immediately formed. The yield was 0.86g.
得られたポリビニレンスルフイドについて加熱
実験を行つたところ、220℃まで熱分解による黄
色液体の発生は見られなかつた。 When a heating experiment was conducted on the obtained polyvinylene sulfide, no yellow liquid was observed to be generated due to thermal decomposition up to 220°C.
実施例 3
容量50mlのオートクレーブ内をアルゴンガスで
置換し、硫化ナトリウム無水塩5gと、ベンジル
テトラエチルアンモニウムクロライド0.3gとを
入れ、トランス−1,2−ジクロルエチレン2g
とジメチルスルホキシド30mlの混合液を滴下し、
反応温度40℃で92時間激しく攪拌した。反応液
を600mlのメタノールに注いだところ、ただちに
白褐色沈殿が生じた。収量は0.74gであつた。Example 3 The inside of a 50 ml autoclave was replaced with argon gas, and 5 g of anhydrous sodium sulfide and 0.3 g of benzyltetraethylammonium chloride were added, followed by 2 g of trans-1,2-dichloroethylene.
Drop a mixture of 30 ml of dimethyl sulfoxide and
The reaction mixture was stirred vigorously for 92 hours at a reaction temperature of 40°C. When the reaction solution was poured into 600 ml of methanol, a whitish brown precipitate was immediately formed. The yield was 0.74g.
このポリビニレンスルフイドについて加熱実験
を行つたところ、220℃まで熱分解による黄色液
体の発生は見られなかつた。 When heating experiments were conducted on this polyvinylene sulfide, no yellow liquid was observed to be generated due to thermal decomposition up to 220°C.
実施例 4
容量300mlのオートクレーブ内をアルゴンガス
で置換し、硫化ナトリウム無水塩30gと、セチル
トリメチルアンモニウムクロライド2.4gとを入
れ、トランス−1,2−ジクロルエチレン12gと
ジメチルスルホキシド180mlの混合液を滴下し、
反応温度40℃で95時間激しく攪拌した。反応液
を4のメタノール中に注いだところ、白褐色沈
殿が生じた。収量は4.7gであつた。Example 4 The inside of an autoclave with a capacity of 300 ml was replaced with argon gas, 30 g of anhydrous sodium sulfide and 2.4 g of cetyltrimethylammonium chloride were added, and a mixed solution of 12 g of trans-1,2-dichloroethylene and 180 ml of dimethyl sulfoxide was added. dripping,
The mixture was stirred vigorously for 95 hours at a reaction temperature of 40°C. When the reaction solution was poured into methanol from Step 4, a whitish brown precipitate was produced. The yield was 4.7g.
このポリビニレンスルフイドについて加熱実験
を行つたところ210℃まで熱分解による黄色液体
の発生は見られなかつた。 When heating experiments were conducted on this polyvinylene sulfide, no yellow liquid was observed to be generated due to thermal decomposition up to 210°C.
実施例 5
容量50mlのオートクレーブ内をアルゴンガスで
置換し、セレン化ナトリウムNa2Se8gと、塩化
第一銅0.8gとを入れ、シス−1,2−ジクロル
エチレン2gとジメチルスルホキシド30mlの混合
液を滴下し、室温で12時間激しく攪拌した。反応
液を600mlのメタノール中に注いだところ、黄
褐色沈殿が0.65g生じた。IRスペクトル測定によ
り、ポリビニレンセレニド構造であることを確認
した。Example 5 The inside of an autoclave with a capacity of 50 ml was replaced with argon gas, 8 g of sodium selenide Na 2 Se and 0.8 g of cuprous chloride were added, and a mixed solution of 2 g of cis-1,2-dichloroethylene and 30 ml of dimethyl sulfoxide was added. was added dropwise, and the mixture was vigorously stirred at room temperature for 12 hours. When the reaction solution was poured into 600 ml of methanol, 0.65 g of a yellow brown precipitate was produced. IR spectrum measurement confirmed that it had a polyvinylene selenide structure.
このポリビニレンセレニドについて加熱実験を
行つたところ、230℃まで熱分解が起こらなかつ
た。 When a heating experiment was conducted on this polyvinylene selenide, no thermal decomposition occurred up to 230°C.
実施例 6
容量50mlのオートクレーブ内をアルゴンガスで
置換し、セレン化ナトリウムNa2Se8gと、ベン
ジルトリブチルアンモニウムブロマイド0.45gと
を入れ、1,2−ジブロムエチレンのシス、トラ
ンス混合体12gとジメチルスルホキシド30mlの混
合液を滴下し、室温で24時間激しく攪拌した。反
応液を600mlのメタノールに注いだところ、褐
色のポリビニレンセレニドの沈殿物が0.8g得ら
れた。Example 6 The inside of an autoclave with a capacity of 50 ml was replaced with argon gas, 8 g of sodium selenide Na 2 Se and 0.45 g of benzyltributylammonium bromide were added, and 12 g of a cis-trans mixture of 1,2-dibromoethylene and dimethyl sulfoxide were added. 30 ml of the mixture was added dropwise and stirred vigorously at room temperature for 24 hours. When the reaction solution was poured into 600 ml of methanol, 0.8 g of brown polyvinylene selenide precipitate was obtained.
このポリビニレンセレニドについて加熱実験を
行つたところ、215℃まで熱分解が起こらなかつ
た。 When a heating experiment was conducted on this polyvinylene selenide, no thermal decomposition occurred up to 215°C.
Claims (1)
属硫化物又はアルカリ金属セレン化物との反応系
中に第B族金属の塩化物又は第4級アンモニウ
ム塩、第4級ホスホニウム塩、環状ポリエーテ
ル、多環性環状化合物、環状ポリエーテルアミン
及び環状ポリエーテルスルフイドのうちの1種を
添加することを特徴とするポリビニレンスルフイ
ドまたはポリビニレンセレニドの製造方法。1 In the reaction system of 1,2-dihalogenated ethylene and alkali metal sulfide or alkali metal selenide, Group B metal chloride or quaternary ammonium salt, quaternary phosphonium salt, cyclic polyether, polycyclic 1. A method for producing polyvinylene sulfide or polyvinylene selenide, which comprises adding one of a polycyclic compound, a cyclic polyether amine, and a cyclic polyether sulfide.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP26966284A JPS61148235A (en) | 1984-12-22 | 1984-12-22 | Production of polyvinylene chalcogenide |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP26966284A JPS61148235A (en) | 1984-12-22 | 1984-12-22 | Production of polyvinylene chalcogenide |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS61148235A JPS61148235A (en) | 1986-07-05 |
JPH038655B2 true JPH038655B2 (en) | 1991-02-06 |
Family
ID=17475466
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP26966284A Granted JPS61148235A (en) | 1984-12-22 | 1984-12-22 | Production of polyvinylene chalcogenide |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS61148235A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20130038266A (en) * | 2010-05-07 | 2013-04-17 | 퀄컴 인코포레이티드 | Transmission power dependent imbalance compensation for multi-antenna systems |
-
1984
- 1984-12-22 JP JP26966284A patent/JPS61148235A/en active Granted
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20130038266A (en) * | 2010-05-07 | 2013-04-17 | 퀄컴 인코포레이티드 | Transmission power dependent imbalance compensation for multi-antenna systems |
Also Published As
Publication number | Publication date |
---|---|
JPS61148235A (en) | 1986-07-05 |
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