JPS63256604A - Sulfur-containing di-substituted acetylene polymer and manufacture thereof - Google Patents
Sulfur-containing di-substituted acetylene polymer and manufacture thereofInfo
- Publication number
- JPS63256604A JPS63256604A JP9258687A JP9258687A JPS63256604A JP S63256604 A JPS63256604 A JP S63256604A JP 9258687 A JP9258687 A JP 9258687A JP 9258687 A JP9258687 A JP 9258687A JP S63256604 A JPS63256604 A JP S63256604A
- Authority
- JP
- Japan
- Prior art keywords
- polymer
- polymerization
- formula
- monomer
- group
- 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.)
- Granted
Links
- 229920000642 polymer Polymers 0.000 title claims abstract description 44
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 7
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 7
- 239000011593 sulfur Substances 0.000 title claims abstract description 7
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- -1 di-substituted acetylene Chemical group 0.000 title abstract description 4
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 20
- 239000000178 monomer Substances 0.000 claims abstract description 14
- 150000003623 transition metal compounds Chemical class 0.000 claims abstract description 7
- 150000001875 compounds Chemical class 0.000 claims abstract 2
- 239000000126 substance Substances 0.000 claims description 5
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 2
- 239000003054 catalyst Substances 0.000 abstract description 8
- 239000012528 membrane Substances 0.000 abstract description 4
- 229920001940 conductive polymer Polymers 0.000 abstract description 3
- 150000002430 hydrocarbons Chemical group 0.000 abstract description 3
- GICWIDZXWJGTCI-UHFFFAOYSA-I molybdenum pentachloride Chemical compound Cl[Mo](Cl)(Cl)(Cl)Cl GICWIDZXWJGTCI-UHFFFAOYSA-I 0.000 abstract description 3
- 239000002798 polar solvent Substances 0.000 abstract description 3
- 229920006254 polymer film Polymers 0.000 abstract description 3
- 229910004537 TaCl5 Inorganic materials 0.000 abstract description 2
- 150000000475 acetylene derivatives Chemical class 0.000 abstract description 2
- 238000005266 casting Methods 0.000 abstract description 2
- 229930195733 hydrocarbon Natural products 0.000 abstract description 2
- OEIMLTQPLAGXMX-UHFFFAOYSA-I tantalum(v) chloride Chemical compound Cl[Ta](Cl)(Cl)(Cl)Cl OEIMLTQPLAGXMX-UHFFFAOYSA-I 0.000 abstract description 2
- CZZVBNLIUBAYTA-UHFFFAOYSA-N 4-hept-2-yn-4-ylsulfanylhept-2-yne Chemical compound C(#CC)C(CCC)SC(CCC)C#CC CZZVBNLIUBAYTA-UHFFFAOYSA-N 0.000 abstract 1
- 239000004215 Carbon black (E152) Substances 0.000 abstract 1
- 229910015221 MoCl5 Inorganic materials 0.000 abstract 1
- 229910052751 metal Inorganic materials 0.000 abstract 1
- 239000002184 metal Substances 0.000 abstract 1
- 230000000379 polymerizing effect Effects 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 238000000862 absorption spectrum Methods 0.000 description 8
- 238000010586 diagram Methods 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- LWISLHRIEATKTM-UHFFFAOYSA-N 2-Ethynylthiophene Chemical compound C#CC1=CC=CS1 LWISLHRIEATKTM-UHFFFAOYSA-N 0.000 description 2
- 239000003426 co-catalyst Substances 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 150000002902 organometallic compounds Chemical class 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- KPGXUAIFQMJJFB-UHFFFAOYSA-H tungsten hexachloride Chemical compound Cl[W](Cl)(Cl)(Cl)(Cl)Cl KPGXUAIFQMJJFB-UHFFFAOYSA-H 0.000 description 2
- SITAOHYNYVWWQZ-UHFFFAOYSA-N 5-prop-1-ynyl-5-(1-prop-1-ynylcyclohexa-2,4-dien-1-yl)sulfanylcyclohexa-1,3-diene Chemical compound C(#CC)C1(CC=CC=C1)SC1(CC=CC=C1)C#CC SITAOHYNYVWWQZ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- CUDSBWGCGSUXDB-UHFFFAOYSA-N Dibutyl disulfide Chemical compound CCCCSSCCCC CUDSBWGCGSUXDB-UHFFFAOYSA-N 0.000 description 1
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 1
- 229910003091 WCl6 Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 239000005078 molybdenum compound Substances 0.000 description 1
- 150000002752 molybdenum compounds Chemical class 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920001197 polyacetylene Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- MWWATHDPGQKSAR-UHFFFAOYSA-N propyne Chemical group CC#C MWWATHDPGQKSAR-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は２例えば、ガス分離膜、導電性ポリマー、耐熱
性ポリマーとして有用であり、新規な物質である、イオ
ウを含有し二置換アセチレンの高重合度ポリマーとその
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 is directed to the production of sulfur-containing disubstituted acetylene, which is a novel substance useful as, for example, gas separation membranes, conductive polymers, and heat-resistant polymers. The present invention relates to high polymerization degree polymers and methods for producing the same.
本発明者らは、種々のアセチレン誘導体からポリマーを
製造する方法として六塩化タングステンなどの■族遷移
金属化合物を主体とする触媒を用いる方法を発明し、そ
れらの方法は、特公昭５１−３７３１２号、特公昭５２
−２０５１１号、特公昭５５−２３５８５号、特公昭５
４−４３０３７号、特公昭５５−３０７２２号、特開昭
５７−３１９１１号、特開昭５７−３８１０８号、特開
昭５８−３２６０８号、特開昭５８−２０６６１１号、
特開昭５ト８３７０５号、特開昭８１−２４７７１４号
、特開昭８１−２５４８１４号の各公報に開示されてい
る。ヘテロ原子としてイオウを含有するポリアセチレン
として、２−エチニルチオフェンのポリマーが知られて
いる。The present inventors have invented a method of producing polymers from various acetylene derivatives using a catalyst mainly composed of a Group I transition metal compound such as tungsten hexachloride, and these methods are disclosed in Japanese Patent Publication No. 51-37312. , special public service 1972
-20511, Special Publication No. 55-23585, Special Publication No. 55
4-43037, JP 55-30722, JP 57-31911, JP 57-38108, JP 58-32608, JP 58-206611,
It is disclosed in Japanese Patent Application Laid-Open No. 83705, No. 81-247714, and Japanese Patent Application Laid-Open No. 81-254814. A polymer of 2-ethynylthiophene is known as a polyacetylene containing sulfur as a heteroatom.
しかし、上記の２−エチニルチオフェンのポリマーは、
重合度が小さいため、膜形成能を有しない、そこで本発
明は、膜形成能が良好で新規な物質である、イオウを含
有し高重合度な二置換アセチレンのポリマーを提供する
ことを目的とする。However, the above polymer of 2-ethynylthiophene is
Due to its low degree of polymerization, it does not have film-forming ability. Therefore, the object of the present invention is to provide a sulfur-containing disubstituted acetylene polymer with a high degree of polymerization, which is a novel substance with good film-forming ability. do.
前記の目的を達成する新規物質は、一般式％式％
この物質を製造する方法は、一般式
Ｒ１−Ｃ＝Ｃ−３−Ｒ２
で表わされる単量体化合物を、第Ｖ族または第■族遷移
金属化合物の存在下で重合させる。The new substance that achieves the above object has the general formula: Polymerize in the presence of a transition metal compound.
式中のＲ１、Ｒ２は炭素数１〜４の炭化水素基、ｎは繰
り返し単位数である。In the formula, R1 and R2 are hydrocarbon groups having 1 to 4 carbon atoms, and n is the number of repeating units.
Ｒ１とＲ２の炭素数の和は５以下であることが好ましい
、５より大きい場合は高重合度のポリマーが得られにく
く、ｆｆｉ合されたポリマーは、良好な膜形成能を有さ
ない。The sum of the carbon numbers of R1 and R2 is preferably 5 or less; if it is larger than 5, it is difficult to obtain a polymer with a high degree of polymerization, and the ffi-combined polymer does not have good film-forming ability.
第Ｖ族または第■族遷移金属化合物は、例えばＭｏＣｌ
５．ＷＣｌ６．ＴａＣｌ５．ＮｂＣ１ｂ、Ｎｏ（ＧＯ）
６．Ｗ（ＧＯ）６が挙げられる。好ましくは第■族遷移
金属化合物であり、特にモリブデン化合物が好ましい、
これらの触媒はモノマー１００モルに対し０．２〜１０
モルの範囲で使用するのが適当である。Group V or Group II transition metal compounds are, for example, MoCl
5. WCl6. TaCl5. NbC1b, No (GO)
6. W(GO)6 is mentioned. Group Ⅰ transition metal compounds are preferred, and molybdenum compounds are particularly preferred.
These catalysts are used in amounts of 0.2 to 10 per 100 moles of monomer.
It is appropriate to use it in a molar range.
さらに共触媒を併用すれば、前記触媒の作用を助長し、
より重合度の高いポリマーを得るのに有利である。共触
媒としては有機金属化合物、例えば、ＰｈａＳｉＨ，Ｅ
ｔ３ＳｉＨ，Ｐｈ４Ｓｎ、ｎＢｕ４ｓｎ、Ｐｈ３Ｓｂ、
Ｐｈ５Ｂｉ、ｎＢｕＬｉである。 （ｐｈは７．ニル
、Ｅｔはエチル、 ｎＢｕはｎ−ブチルを示す、）この
共触媒の使用量は前記第Ｖ族または第■族遷移金属化合
物１モルに対し０．３〜３モルの範囲が好ましい。Furthermore, if a co-catalyst is used, the action of the catalyst will be promoted,
This is advantageous in obtaining a polymer with a higher degree of polymerization. Cocatalysts include organometallic compounds such as PhaSiH, E
t3SiH, Ph4Sn, nBu4sn, Ph3Sb,
Ph5Bi, nBuLi. (ph is 7.nyl, Et is ethyl, nBu is n-butyl) The amount of this cocatalyst used is in the range of 0.3 to 3 mol per 1 mol of the Group V or Group II transition metal compound. is preferred.
重合反応は有機溶媒中で行われる。有機溶媒としては炭
化水素、ハロゲン化炭化水素を用いることが好ましい、
特にベンゼン、トルエン、シクロヘキサンを用いると、
収率が良く、重合度の高いポリマーを得られる等の点で
好適である０重合反応におけるモノマー濃度は０．１〜
５モル／ＪＬの範囲が好ましい６反応温度は０〜１００
℃で１反応時間は数十分〜数十時間である０以上の重合
反応により、目的とする重合体を含む反応混合物が得ら
れる。この反応混合物から目的の生成重合体を単離する
には、反応混合物をアセトン、メタノール等に投入する
ことにより、生成重合体を沈殿させ、ｉ１！別して回収
すれば良い。The polymerization reaction is carried out in an organic solvent. It is preferable to use hydrocarbons and halogenated hydrocarbons as the organic solvent.
Especially when using benzene, toluene, and cyclohexane,
The monomer concentration in the zero polymerization reaction, which is suitable for obtaining a polymer with a good yield and a high degree of polymerization, is 0.1 to 0.
6 Reaction temperature is preferably in the range of 5 mol/JL from 0 to 100
A reaction mixture containing the desired polymer is obtained through 0 or more polymerization reactions at a temperature of 0.degree. C. and a reaction time of several tens of minutes to several tens of hours. To isolate the desired polymer produced from this reaction mixture, the reaction mixture is poured into acetone, methanol, etc. to precipitate the produced polymer, i1! It should be collected separately.
実施例１
先ずプロピンの１位をリチウム化し、続いて１位をジ−
ｎ−ブチルジスルフィドと反応させてｌ−プロピニル−
ｎ−ブチルスルフィドモノマー（ＣＨｑＣ＝ ｎ−５−
１’Ｊｂ ｎＨｑｌ’！ｌＪっｒ！ｕウ ）４ Δ
ｄｒ −４−１乾燥窒素雰囲気下で充分精製したトルエ
ン２００履ｌ中に五塩化モリブデン４ミリモルを加え溶
解し、次に前記により得たｌ−プロピニル−ｎ−ブチル
−スルフィドモノマー ０．１モル（１２，８ｇ）を添
加し、８０℃で２４時間重合反応させる０反応終了後、
反応混合物を大量のアセトン中に投入して生成ポリマー
を沈殿させ、ｍ別、乾燥を行う、このようにして分離さ
れたアセトンに不溶なポリマーの収率はモノマーの仕込
み量を基準として４０％であった。Example 1 First, the 1st position of propyne is lithiated, and then the 1st position is di-lithiated.
By reacting with n-butyl disulfide, l-propynyl-
n-Butyl sulfide monomer (CHqC= n-5-
1'Jb nHql'! lJr! uu )4 Δ
dr-4-1 4 mmol of molybdenum pentachloride was added and dissolved in 200 l of toluene sufficiently purified under a dry nitrogen atmosphere, and then 0.1 mol of the l-propynyl-n-butyl-sulfide monomer obtained above was added ( 12.8 g) was added and polymerized at 80°C for 24 hours.
The reaction mixture is poured into a large amount of acetone to precipitate the produced polymer, separated by m, and dried.The yield of the acetone-insoluble polymer separated in this way is 40% based on the amount of monomer charged. there were.
生成重合体のトルエン可溶部の重量平均分子量Ｍｗは１
２万であった。生成ポリマーは淡褐色の粉末で、トルエ
ン、ヘキサン、四塩化炭素等の低極性溶媒に可溶である
が、極性の高い溶媒に不溶であった。さらに、生成ポリ
マーの溶液を平滑な平面上にキャストしたところ、丈夫
なポリマーフィルムを作成することが出来た。The weight average molecular weight Mw of the toluene soluble portion of the produced polymer is 1
It was 20,000. The resulting polymer was a light brown powder that was soluble in low polar solvents such as toluene, hexane, and carbon tetrachloride, but insoluble in highly polar solvents. Furthermore, when a solution of the resulting polymer was cast onto a smooth flat surface, a durable polymer film could be created.
ｌ−プロピニル−ｎ−ブチルスルフィドモノマーの赤外
吸収スペクトルを第１図に、 ＩＨＮＭＲを第２図、
１３ＯＮＮＲヲ第３図ニ示ス。The infrared absorption spectrum of l-propynyl-n-butyl sulfide monomer is shown in Figure 1, the IHNMR is shown in Figure 2,
13ONNR shown in Figure 3.
また、実施例１で得られたポリマーの赤外吸収スペクト
ルを第４図に、 ＩＨＮＭＲを第５図、ｌ’ｌＣｌ訂を
第６図に示す。これらの図から生成したポリマーの構造
が
であることが確認できた。Further, the infrared absorption spectrum of the polymer obtained in Example 1 is shown in FIG. 4, the IHNMR is shown in FIG. 5, and the l'lCl correction is shown in FIG. From these figures, it was confirmed that the structure of the produced polymer was as follows.
実施例２〜１１
実施例１の五塩化モリブデンのかわりに、第１表に示す
触媒（主触媒４ミリモル、共触媒８ミリモル）を用いる
。その他は実施例１と同様にして重合を行った。（実施
例９のみ、主触媒量が２ミリモル、共触媒なしで光照射
を行う、）得られたポリマーの収率と重量平均分子量ｉ
を第１表に示す。Examples 2 to 11 In place of molybdenum pentachloride in Example 1, catalysts shown in Table 1 (4 mmol of main catalyst, 8 mmol of co-catalyst) are used. Other than that, polymerization was carried out in the same manner as in Example 1. (Example 9 only, the main catalyst amount was 2 mmol, and the light irradiation was performed without a cocatalyst) Yield and weight average molecular weight i of the obtained polymer
are shown in Table 1.
実施例１２
モノマーとしてｌ−プロピニル−ｎ−メチルスルフィド
の代わりに、ｌ−へキシニル−メチルスルフィドを用い
る以外は実施例４と同様にして重合を行った。得られた
ポリマーの収率および重量平均分子量を第１表に、赤外
吸収スペクトルを第７図に示す、また、得られたポリマ
ーの溶液を、平滑な平面上にキャストしたところ、良好
な膜形成能を有していた。Example 12 Polymerization was carried out in the same manner as in Example 4 except that l-hexynyl-methyl sulfide was used as the monomer instead of l-propynyl-n-methyl sulfide. The yield and weight average molecular weight of the obtained polymer are shown in Table 1, and the infrared absorption spectrum is shown in Fig. 7. When the obtained polymer solution was cast on a smooth flat surface, a good film was obtained. It had the ability to form.
比較例１
モノマーとして１−プロピニル−フェニルスルフィドを
用いる以外は実施例４と同様にして重合を行った。得ら
れたポリマーの収率は３２％であったが、溶媒不溶性で
膜形成能を有しないものであった。Comparative Example 1 Polymerization was carried out in the same manner as in Example 4 except that 1-propynyl-phenyl sulfide was used as the monomer. The yield of the obtained polymer was 32%, but it was insoluble in solvents and did not have film-forming ability.
（以下余白）
第１表
（表中のｐｈはフェニル、Ｅｔはエチル、 ｎＢｕはｎ
−ブチルを示す、）
〔発明の効果〕
以上詳細に説明したように１本発明のポリマーは重合度
が大きく熱安定性が良好である。また、低極性の溶媒に
可溶なため、溶液を平滑な平面上にキャストすることに
より丈夫なポリマーフィルムを容易に作成出来、膜形成
能に優れている。このポリマーはガス分離膜、導電性付
与ポリマー等へも応用出来る。(Left below) Table 1 (In the table, ph is phenyl, Et is ethyl, nBu is n
-butyl) [Effects of the Invention] As explained above in detail, the polymer of the present invention has a high degree of polymerization and good thermal stability. In addition, since it is soluble in low polarity solvents, it is possible to easily create a strong polymer film by casting the solution onto a smooth flat surface, and it has excellent film-forming ability. This polymer can also be applied to gas separation membranes, conductive polymers, etc.
また、本発明の製造方法では重合触媒として第Ｖ族また
は第■族の遷移金属を用いることにより重合度の高いポ
リマーを得ることが出来る。なお共触媒として有機金属
化合物を併用することにより、触媒の作用を助長するこ
とができる。Furthermore, in the production method of the present invention, a polymer with a high degree of polymerization can be obtained by using a Group V or Group (I) transition metal as a polymerization catalyst. Note that the action of the catalyst can be promoted by using an organometallic compound as a cocatalyst.
第１図は重合原料の１例の七ツマ−の赤外吸収スペクト
ル図、第２図は同じく重合原料の１例のモノマーのｌ
）ＩＮＭＲ図、第３図は同じく重合原料の１例の七ツマ
−の１３ ＣＮＭＲ図、第４図は本発明のポリマーの１
例の赤外吸収スペクトル図、第５図は同じくポリマーの
１例のｌ ）ＩＮＭＲ図、第６図は同じくポリマーの１
例の１３ ＣＮＭＲ図、第７図は本発明のポリマーの別
な例の赤外吸収スペクトル図である。
特許出願人 東 村 敏 延
代 理 人 弁理士 小 宮 良雄
第１ 図 ＩＲ咀収スペクトル
モノマー ＣＨ３ＣＥ Ｃ−Ｓ −ＣＨ２ＣＨ２Ｃ
１−１２ＣＨ３（ｐｐｍ）
（ｐｐｍ）
第４ 図 ＩＲ吸伏スタクトル
ｐｐｍ
ｐｐｍ
第７図 ＩＲ咀収ズ■２トル
ＣＨ２ＣＨ２ＣＨ２ＣＨ３Figure 1 is an infrared absorption spectrum of a monomer of an example of a polymerization raw material, and Figure 2 is a monomer infrared absorption spectrum of an example of a polymerization raw material.
) INMR diagram, Figure 3 is a 13 CNMR diagram of a seven-layer polymer, which is an example of a polymerization raw material, and Figure 4 is a 13 CNMR diagram of a polymer of the present invention.
Figure 5 is an infrared absorption spectrum diagram of an example of the same polymer. Figure 6 is an INMR diagram of an example of the same polymer.
Example 13 CNMR diagram and FIG. 7 are infrared absorption spectrum diagrams of another example of the polymer of the present invention. Patent applicant Satoshi Higashimura Nobuyo Patent attorney Yoshio Komiya Figure 1 IR absorption spectrum monomer CH3CE C-S -CH2CH2C
1-12CH3 (ppm) (ppm) Fig. 4 IR adsorption stractor ppm ppm Fig. 7 IR absorption ■ 2 torr CH2CH2CH2CH3
Claims (1)
繰り返し単位数） で表わされるイオウを含有する二置換アセチレンポリマ
ー。 ２、一般式 Ｒ１−Ｃ≡Ｃ−Ｓ−Ｒ２ （式中のＲ１、Ｒ２は炭素数１〜４の炭化水素基）で表
わされる単量体化合物を、第Ｖ族または第VI族遷移金属
化合物の存在下で重合させて一般式▲数式、化学式、表
等があります▼ で表わされるイオウを含有する二置換アセチレンポリマ
ーを製造する方法。[Claims] 1. Contains sulfur represented by the general formula ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (In the formula, R1 and R2 are hydrocarbon groups having 1 to 4 carbon atoms, and n is the number of repeating units) disubstituted acetylene polymer. 2. A monomer compound represented by the general formula R1-C≡C-S-R2 (R1 and R2 in the formula are hydrocarbon groups having 1 to 4 carbon atoms) is a Group V or Group VI transition metal compound. A method for producing a sulfur-containing disubstituted acetylene polymer by polymerization in the presence of the general formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9258687A JPH0649734B2 (en) | 1987-04-14 | 1987-04-14 | Disubstituted acetylene polymer containing sulfur and process for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9258687A JPH0649734B2 (en) | 1987-04-14 | 1987-04-14 | Disubstituted acetylene polymer containing sulfur and process for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63256604A true JPS63256604A (en) | 1988-10-24 |
| JPH0649734B2 JPH0649734B2 (en) | 1994-06-29 |
Family
ID=14058545
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9258687A Expired - Fee Related JPH0649734B2 (en) | 1987-04-14 | 1987-04-14 | Disubstituted acetylene polymer containing sulfur and process for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0649734B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998040422A1 (en) * | 1997-03-07 | 1998-09-17 | Commonwealth Scientific And Industrial Research Organisation | Reduced temperature curing of acetylenic polymers |
| AU721200B2 (en) * | 1997-03-07 | 2000-06-29 | Boeing Company, The | Reduced temperature curing of acetylenic polymers |
-
1987
- 1987-04-14 JP JP9258687A patent/JPH0649734B2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998040422A1 (en) * | 1997-03-07 | 1998-09-17 | Commonwealth Scientific And Industrial Research Organisation | Reduced temperature curing of acetylenic polymers |
| AU721200B2 (en) * | 1997-03-07 | 2000-06-29 | Boeing Company, The | Reduced temperature curing of acetylenic polymers |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0649734B2 (en) | 1994-06-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Deeter et al. | A new polymerization reaction for the synthesis of aromatic polyketones | |
| JPS63256604A (en) | Sulfur-containing di-substituted acetylene polymer and manufacture thereof | |
| Gal et al. | Polymerization of Phosphorus-Containing Acetylenes. 3. Polymerization of Triethyl. alpha.-Propargylphosphonoacetate by Transition Metal Catalysts | |
| JPH0617414B2 (en) | Phenylacetylene polymer having a substituent at the ortho position | |
| Gal et al. | Polymerization of bis (3-trimethylsilyl-2-propynyl) ether and its copolymerization with diethyl dipropargylmalonate | |
| JPH0225369B2 (en) | ||
| JPS58206611A (en) | Polymerization of trialkylsilylacetylene | |
| US5216083A (en) | Polymerization of cis-5,6-bis(trimethylsiloxy)-1,3-cyclohexadiene and other substituted cyclohexadienes | |
| JPH0142964B2 (en) | ||
| JPS62260804A (en) | Production of fluorine-containing polyphenylacetylene | |
| JPH0610216B2 (en) | 0- (trialkylsilyl) phenylacetylene polymer and process for producing the same | |
| JP3379590B2 (en) | Method for producing diphenylacetylene copolymer | |
| Yoshida et al. | Polymerization and polymer properties of (p‐tert‐butyl‐o, o‐dimethylphenyl) acetylene | |
| JPH0225370B2 (en) | ||
| US4812520A (en) | Method for the preparation of novel polyacetylene-type polymers | |
| JP2974369B2 (en) | Diphenylacetylene polymer having a substituent on the aromatic ring | |
| JPS61247714A (en) | Silyl group-containing polymer and its production | |
| JPH0582403B2 (en) | ||
| JP2575958B2 (en) | Method for producing polyhydroxystyrene | |
| JPH0142965B2 (en) | ||
| JPS61118412A (en) | Silylarylacetylene copolymer and its production | |
| JP2900042B2 (en) | Copolymers of substituted acetylenes and norbornene | |
| US5191025A (en) | Polymerization of cis-5,6-bis(trimethylsiloxy)-1,3-cyclohexadiene and other substituted cyclohexadienes | |
| JPH0224285B2 (en) | ||
| JPS5978218A (en) | Production of 1-chloro-2-phenylacetylene polymer |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |