JPS6362530B2 - - Google Patents
Info
- Publication number
- JPS6362530B2 JPS6362530B2 JP7173384A JP7173384A JPS6362530B2 JP S6362530 B2 JPS6362530 B2 JP S6362530B2 JP 7173384 A JP7173384 A JP 7173384A JP 7173384 A JP7173384 A JP 7173384A JP S6362530 B2 JPS6362530 B2 JP S6362530B2
- Authority
- JP
- Japan
- Prior art keywords
- formula
- polymer
- solvent
- same meanings
- reduced viscosity
- 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
- 229920000642 polymer Polymers 0.000 claims description 43
- 239000002904 solvent Substances 0.000 claims description 20
- FDQSRULYDNDXQB-UHFFFAOYSA-N benzene-1,3-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(C(Cl)=O)=C1 FDQSRULYDNDXQB-UHFFFAOYSA-N 0.000 claims description 12
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 claims description 8
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 229910052783 alkali metal Inorganic materials 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 150000001340 alkali metals Chemical class 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 2
- 239000003513 alkali Substances 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 claims 1
- 239000002184 metal Substances 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- 238000010521 absorption reaction Methods 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 7
- 238000002076 thermal analysis method Methods 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- -1 alkali metal salt Chemical class 0.000 description 3
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical compound C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 150000002430 hydrocarbons Chemical group 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 2
- BNBRIFIJRKJGEI-UHFFFAOYSA-N 2,6-difluorobenzonitrile Chemical compound FC1=CC=CC(F)=C1C#N BNBRIFIJRKJGEI-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- ZYDGHQSJZAFMLU-UHFFFAOYSA-N 2,6-dinitrobenzonitrile Chemical compound [O-][N+](=O)C1=CC=CC([N+]([O-])=O)=C1C#N ZYDGHQSJZAFMLU-UHFFFAOYSA-N 0.000 description 1
- VWGKEVWFBOUAND-UHFFFAOYSA-N 4,4'-thiodiphenol Chemical compound C1=CC(O)=CC=C1SC1=CC=C(O)C=C1 VWGKEVWFBOUAND-UHFFFAOYSA-N 0.000 description 1
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- ZYUVGYBAPZYKSA-UHFFFAOYSA-N 5-(3-hydroxybutan-2-yl)-4-methylbenzene-1,3-diol Chemical compound CC(O)C(C)C1=CC(O)=CC(O)=C1C ZYUVGYBAPZYKSA-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- NHADDZMCASKINP-HTRCEHHLSA-N decarboxydihydrocitrinin Natural products C1=C(O)C(C)=C2[C@H](C)[C@@H](C)OCC2=C1O NHADDZMCASKINP-HTRCEHHLSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
Landscapes
- Polyethers (AREA)
Description
〔発明の技術分野〕
本発明は新規重合体およびその製造方法に関
し、更に詳しくは、耐熱性、難燃性、耐溶剤性に
優れた新規なシアンアリールオキシ重合体とその
製造方法に関する。
〔発明の技術的背景とその問題点〕
ジニトロベンゾニトリルと二価フエノールとか
ら合成された種々のシアンアリールオキシ重合体
が特開昭47−14270号に開示されている。これら
の重合体は耐熱性を備えているものの、その熱分
解開始温度（Td）は400℃前後であり、必ずしも
実用上充分な耐熱性を備えているとは言い難い。
また、上記公報で開示されているように、二価
フエノールとしてビスフエノールＡを用いて製造
した重合体は、そのガラス転移温度（Tg）が173
℃と一定でありこれを変化させることができな
い。すなわち、上記公報記載の方法ではシアンア
リールオキシ重合体の耐熱性を調節することがで
きない。したがつて、得られた重合体も各種の耐
熱性が要求される用途分野に柔軟に対応できない
ことになる。
〔発明の目的〕
本発明は、上記した重合体よりも耐熱性が優れ
ていると同時に、難燃性、耐溶剤性にも優れ、更
には共重合組成を変化させればその耐熱性も適宜
に変えることが可能な新規重合体およびその製造
方法を提供することを目的とする。
〔発明の概要〕
本発明の新規重合体は、
次式：
（式中、Arは
[Technical Field of the Invention] The present invention relates to a novel polymer and a method for producing the same, and more particularly to a novel cyanaryloxy polymer having excellent heat resistance, flame retardance, and solvent resistance, and a method for producing the same. [Technical background of the invention and its problems] Various cyanaryloxy polymers synthesized from dinitrobenzonitrile and dihydric phenol are disclosed in JP-A-47-14270. Although these polymers have heat resistance, their thermal decomposition initiation temperature (Td) is around 400°C, and it cannot be said that they necessarily have sufficient heat resistance for practical use. Furthermore, as disclosed in the above publication, a polymer produced using bisphenol A as a dihydric phenol has a glass transition temperature (Tg) of 173
It is constant at °C and cannot be changed. That is, the heat resistance of the cyanaryloxy polymer cannot be adjusted by the method described in the above publication. Therefore, the obtained polymer cannot be flexibly applied to various fields of application requiring heat resistance. [Object of the invention] The present invention has better heat resistance than the above-mentioned polymers, as well as excellent flame retardancy and solvent resistance, and furthermore, by changing the copolymer composition, the heat resistance can be adjusted as appropriate. The purpose of the present invention is to provide a new polymer that can be changed into a new polymer and a method for producing the same. [Summary of the invention] The novel polymer of the present invention has the following formula: (In the formula, Ar is
【式】【formula】
【式】【formula】
【式】【formula】
【式】【formula】
【式】【formula】
【式】（ただし、Ｒは炭素
数１〜13の二価の炭化水素基を表わす）のいずれ
かを表わし、ｎは１〜50の整数を表わす）で示さ
れる繰り返し単位を有し、
末端基が―OH又は
[Formula] (wherein R represents a divalent hydrocarbon group having 1 to 13 carbon atoms), and n represents an integer of 1 to 50), and has a terminal group Ga-OH or
【式】（式中、Ar
及びｎは上と同じ意味を有する）であり、かつ、
Ｎ―メチルピロリドンを溶媒とする0.2ｇ/dl濃度
の溶液の30℃における還元粘度が0.3dl/ｇ以上で
あることを特徴とし、その製造方法は、
次式：
（式中、Ｘはハロゲン原子を表わす）
で示されるジハロゲノベンゾニトリルと、
次式：
MO―Ar―OM ……（）
（式中、Arは[Formula] (wherein Ar and n have the same meanings as above), and
The reduced viscosity at 30°C of a solution with a concentration of 0.2 g/dl using N-methylpyrrolidone as a solvent is 0.3 dl/g or more, and its production method is as follows: (In the formula, X represents a halogen atom) Dihalogenobenzonitrile represented by
【式】【formula】
【式】【formula】
【式】【formula】
【式】【formula】
【式】【formula】
【式】（ただし、Ｒは炭素
数１〜13の二価の炭化水素基を表わす）のいずれ
かを表わし、Ｍはアルカリ金属を表わす）
で示される二価フエノールのアルカリ金属塩と
を、溶媒の存在下で反応させることにより得られ
た、
次式：
（式中、Ar、Ｍは上と同じ意味を有し、ｎは１
〜50の整数を表わす）
で示されるオリゴマーと、イソフタロイルクロラ
イド及び／又はテレフタロイルクロライドとを、
溶媒の存在下で反応させ、ついで、得られた反応
生成物を水又はアルコールで処理することを特徴
とする。
本発明の新規重合体は、式（）のオリゴマー
とイソフタロイルクロライド又はテレフタロイル
クロライドとが縮合して成る式（）の繰り返し
単位が複数個直鎖状に連結して成る骨格を有し、
全体の末端は―OH又は
[Formula] (wherein R represents a divalent hydrocarbon group having 1 to 13 carbon atoms) and M represents an alkali metal), and an alkali metal salt of a divalent phenol represented by The following formula was obtained by reacting in the presence of: (In the formula, Ar and M have the same meanings as above, and n is 1
(representing an integer of ~50) and isophthaloyl chloride and/or terephthaloyl chloride,
It is characterized in that the reaction is carried out in the presence of a solvent, and then the obtained reaction product is treated with water or alcohol. The novel polymer of the present invention has a skeleton in which a plurality of repeating units of formula (), which are formed by condensing an oligomer of formula () and isophthaloyl chloride or terephthaloyl chloride, are connected in a linear chain. ,
The whole terminal is -OH or
【式】でブロツク
されている。式（）の繰返し単位における構造
単位：It is blocked by [expression]. Structural unit in the repeating unit of formula ():
【式】及び末端基[Formula] and terminal group
【式】において、 ArはIn [formula], Ar is
【式】【formula】
【式】【formula】
【式】【formula】
【式】【formula】
【式】【formula】
【式】
（ただし、Ｒは炭素数１〜13の二価の炭化水素基
を表わす）のいずれかであり、ｎは１〜50の整数
である。
本発明の重合体は、この重合体をＮ―メチルピ
ロリドンに溶解してその濃度を0.2ｇ/dlにしたと
き、この樹脂溶液の30℃における還元粘度
（ηsp／ｃ）が0.3dl/ｇ以上であるような分子量を
有する重合体である。このηsp／ｃが0.3dl/ｇ未
満であるような重合度の場合には、重合体は低分
子量であるため耐熱性が低減する。
本発明の重合体は次のようにして製造される。
すなわち、式（）で示されるジハロゲノベン
ゾニトリルと式（）で示される二価フエノール
のアルカリ金属塩とを後述する溶媒及び条件下で
反応させることにより式（）で示されるオリゴ
マーを得るオリゴマー生成反応と、このオリゴマ
ーとイソフタロイルクロライド及び／又はテレフ
タロイルクロライドとを後述する溶媒及び条件下
で反応させて目的とする重合体を得る縮重合反応
とから製造される。この時、イソフタロイルクロ
ライド及び／又はテレフタロイルクロライドは縮
合剤として機能する。
式（）の化合物で、ハロゲンＸとしては、
Ｆ、Clが好ましい。式（）の化合物でＭはアル
カリ金属であれば何であつてもよいが、特にＫ、
Naは好ましいものである。また、Arとしては上
に列挙したものであれば何であつてもよいが、と
くに、[Formula] (wherein R represents a divalent hydrocarbon group having 1 to 13 carbon atoms), and n is an integer of 1 to 50. The polymer of the present invention has a reduced viscosity (ηsp/c) of 0.3 dl/g or more at 30°C of the resin solution when the polymer is dissolved in N-methylpyrrolidone to a concentration of 0.2 g/dl. It is a polymer having a molecular weight such that When the degree of polymerization is such that ηsp/c is less than 0.3 dl/g, the polymer has a low molecular weight and therefore has low heat resistance. The polymer of the present invention is produced as follows. That is, oligomer production in which an oligomer represented by formula () is obtained by reacting a dihalogenobenzonitrile represented by formula () with an alkali metal salt of a divalent phenol represented by formula () in the solvent and under the conditions described below. reaction, and a polycondensation reaction in which this oligomer is reacted with isophthaloyl chloride and/or terephthaloyl chloride under the solvent and conditions described below to obtain the desired polymer. At this time, isophthaloyl chloride and/or terephthaloyl chloride function as a condensing agent. In the compound of formula (), as halogen X,
F and Cl are preferred. In the compound of formula (), M may be any alkali metal, but especially K,
Na is preferred. In addition, Ar may be anything listed above, but in particular,
【式】【formula】
【式】などは好ましいもの
である。更に、Ｒとしては上に列挙したものであ
れば何であつてもよいが、とくに―CH2―、
[Formula] etc. are preferable. Furthermore, R may be any of those listed above, especially -CH 2 -,
実施例 １
アルゴンガス吹込管、精留装置ならびに撹拌装
置を備えた300mlのセパラブルフラスコに２，６
―ジフルオロベンゾニトリル6.259ｇ（0.045モ
ル）、４，4′―ビフエノール9.3ｇ（0.05モル）、炭
酸カリウム6.91ｇ、Ｎ―メチルピロリドン100ml
およびトルエン40mlを仕込みアルゴンガスを吹込
みながら撹拌して150〜160℃で２時間、180〜190
℃において１時間反応させることにより、重合度
約10〜30のオリゴマーを得た。ついで、反応器を
室温に冷却して、これにイソフタロイルジクロラ
イド1.015ｇ（0.005モル）を添加し20℃において
１時間重縮合反応をおこなつた。つぎに得られた
生成物をメタノール中に投入して重合体を析出さ
せこれを回収して、ワーニング社製ブレンダーに
より粉砕し、水１、メタノール１でそれぞれ
洗浄し、120℃で８時間真空乾燥した。
この結果、重合体14.3ｇが得られた（収率100
％）。この重合体の0.2ｇ/dl濃度のＮ―メチルピ
ロリドン溶液の30℃における還元粘度〔ηsp／
ｃ〕は1.20dl/ｇであつた。また、この重合体を
赤外吸収スペクトル（IR）分析にかけたところ、
3030cm-1と830cm-1にベンゼン環のＣ―Ｈ結合に
よる吸収、1590cm-1にベンゼン環のＣ―Ｃ結合に
よる吸収、2220cm-1に芳香族ニトリルによる吸
収、1735cm-1にエステル結合のカルボニル基によ
る吸収、1240cm-1に芳香族エーテル結合による吸
収が認められた。また、この重合体の熱分析の結
果、ガラス転移温度（Tg）は208℃、融点
（Tm）は333℃、熱分解開始温度（Td）は542℃
であつた。
さらに、この重合体のフイルムを用いて各種溶
剤に対する溶解性を調べるという耐溶剤性試験を
行なつたところ、アセトン、クロロホルム、塩化
メチレンに対して不溶であつた。またこの重合体
のフイルムにライターの炎を10秒間あてた後、炎
を遠ざけるという難燃性試験を行なつたところ火
は直ちに消え、溶融滴下は見られなかつた。
実施例 ２
縮合剤としてイソフタロイルジクロライドに代
えて、テレフタロイルジクロライド1.015ｇ
（0.005モル）を用いたほかは、実施例１と同様に
して重合体を得た。重合体の収量は14.3ｇ（収率
100％）。還元粘度〔ηsp／ｃ〕は1.32dl/ｇ。熱分
析の結果、Tgは確認できず、Tmは350℃、Tdは
527℃であつた。IR分析、耐溶剤性ならびに難燃
性の試験結果はいずれも実施例１と同様であつ
た。
実施例 ３
２，６―ジフルオロベンゾニトリルの使用量を
4.868ｇ（0.035モル）とし、かつイソフタロイル
ジクロライドの使用量を3.045ｇ（0.015モル）と
したほかは、実施例１と同様にして重合体を得
た。重合体の収量は14.61ｇ（収率100％）。還元
粘度〔ηsp／ｃ〕は0.63dl/ｇ。熱分析の結果、
Tgは186℃、Tmは247℃、Tdは497℃であつた。
IR分析、耐溶剤性ならびに難燃性の試験結果は
いずれも実施例１と同様であつた。
実施例 ４
二価フエノールとして４，4′―ビフエノールに
代え、４，4′―チオビスフエノール10.913ｇ
（0.05モル）を用いたほかは実施例１と同様にし
て重合体を得た。重合体の収量は15.9ｇ（収率
100％）。還元粘度〔ηsp／ｃ〕は0.34dl/ｇ。熱分
析の結果、Tgは170℃、Tdは455℃であつた。IR
分析、耐溶剤性、難燃性の試験結果はいずれも実
施例１と同様であつた。
実施例 ５
二価フエノールとして４，4′―ビフエノールに
代え、２，２―ビス（４―ヒドロキシフエニル）
プロパン11.4ｇ（0.05モル）を用いた他は実施例
１と同様にして重合体を得た。重合体の収量16.4
ｇ（収率100％）。還元粘度〔ηsp／ｃ〕は0.41dl/
ｇ。熱分析の結果、Tgは150℃、Tdは471℃であ
つた。IR分析の結果、実施例１の各吸収のほか
2950cm-1にイソプロピル基による吸収があつた。
耐溶剤性、難燃性の試験結果はいずれも実施例１
と同様であつた。
実施例 ６
縮合剤としてイソフタロイルジクロライドに代
えて、テレフタロイルジクロライド0.508ｇ
（0.0025モル）とイソフタロイルジクロライド
0.508ｇ（0.0025モル）との混合物を用いたほか
は実施例１と同様にして重合体を得た。重合体の
収量は14.3ｇ（収率100％）。還元粘度〔ηsp／ｃ〕
は1.26dl/ｇ。熱分析の結果、Tgは観測されず、
Tmは340℃、Tdは473℃であつた。IR分析、耐
溶剤性、難燃性の試験結果はいずれも実施例１と
同様であつた。
実施例 ７
縮合剤としてイソフタロイルジクロライドに代
えて、テレフタロイルジクロライド1.523ｇ
（0.0075モル）とイソフタロイルジクロライド
1.523ｇ（0.0075モル）の混合物を用いたほかは
実施例３と同様にして重合体を得た。重合体の収
量は14.6ｇ（収率100％）。還元粘度〔ηsp／ｃ〕
は0.89dl/ｇ。熱分析の結果、Tgは183℃、Tdは
511℃であつた。IR分析、耐溶剤性、難燃性の試
験結果はいずれも実施例１と同様であつた。
〔発明の効果〕
以上の説明で明らかなように、本発明の重合体
は、従来のシアンアリールオキシ重合体に比べて
耐熱性に優れているとともに難燃性、耐溶剤性に
も優れている。しかも本発明の重合体はその組
成、具体的にはオリゴマーの重合度すなわちオリ
ゴマーの生成に使用される２種の化合物のモル比
を変化させると、Tg、Tdともに変化するため、
多様な耐熱性の要求に対応することができる。
本発明の重合体は耐熱性、耐溶剤性、難燃性な
どが要求される各種の電気・電子機器、機械部分
の素材として有用である。
Example 1 2,6
-Difluorobenzonitrile 6.259g (0.045mol), 4,4'-biphenol 9.3g (0.05mol), potassium carbonate 6.91g, N-methylpyrrolidone 100ml
Add 40 ml of toluene and stir at 150-160℃ for 2 hours at 180-190℃ while blowing argon gas.
By reacting at ℃ for 1 hour, an oligomer having a degree of polymerization of about 10 to 30 was obtained. Then, the reactor was cooled to room temperature, 1.015 g (0.005 mol) of isophthaloyl dichloride was added thereto, and a polycondensation reaction was carried out at 20° C. for 1 hour. Next, the obtained product was poured into methanol to precipitate a polymer, which was collected, pulverized using a Warning blender, washed with 1 part of water and 1 part of methanol, and dried under vacuum at 120°C for 8 hours. did. As a result, 14.3 g of polymer was obtained (yield: 100
%). Reduced viscosity of this polymer in N-methylpyrrolidone solution with a concentration of 0.2 g/dl at 30°C [ηsp/
c] was 1.20 dl/g. In addition, when this polymer was subjected to infrared absorption spectrum (IR) analysis, it was found that
Absorption due to the C-H bond of the benzene ring at 3030 cm -1 and 830 cm -1 , absorption due to the C-C bond of the benzene ring at 1590 cm -1 , absorption due to the aromatic nitrile at 2220 cm -1 , and carbonyl of the ester bond at 1735 cm -1 Absorption due to groups and absorption due to aromatic ether bonds at 1240 cm -1 were observed. Additionally, as a result of thermal analysis of this polymer, the glass transition temperature (Tg) is 208℃, the melting point (Tm) is 333℃, and the thermal decomposition onset temperature (Td) is 542℃.
It was hot. Furthermore, when a solvent resistance test was conducted using a film of this polymer to examine its solubility in various solvents, it was found to be insoluble in acetone, chloroform, and methylene chloride. In addition, a flame retardant test was conducted in which the flame of a lighter was applied to the film of this polymer for 10 seconds and then the flame was moved away.The flame was immediately extinguished and no melting and dripping was observed. Example 2 1.015 g of terephthaloyl dichloride instead of isophthaloyl dichloride as a condensing agent
A polymer was obtained in the same manner as in Example 1 except that (0.005 mol) was used. The yield of polymer was 14.3g (yield
100%). Reduced viscosity [ηsp/c] is 1.32 dl/g. As a result of thermal analysis, Tg could not be confirmed, Tm was 350℃, and Td was
It was 527℃. The IR analysis, solvent resistance, and flame retardancy test results were all the same as in Example 1. Example 3 The amount of 2,6-difluorobenzonitrile used
A polymer was obtained in the same manner as in Example 1, except that the amount of isophthaloyl dichloride used was 4.868 g (0.035 mol) and 3.045 g (0.015 mol). The yield of polymer was 14.61 g (yield 100%). Reduced viscosity [ηsp/c] is 0.63 dl/g. As a result of thermal analysis,
Tg was 186°C, Tm was 247°C, and Td was 497°C.
The IR analysis, solvent resistance, and flame retardancy test results were all the same as in Example 1. Example 4 10.913 g of 4,4'-thiobisphenol instead of 4,4'-biphenol as divalent phenol
A polymer was obtained in the same manner as in Example 1 except that (0.05 mol) was used. The yield of polymer was 15.9g (yield
100%). Reduced viscosity [ηsp/c] is 0.34 dl/g. As a result of thermal analysis, Tg was 170°C and Td was 455°C. IR
The analysis, solvent resistance, and flame retardancy test results were all the same as in Example 1. Example 5 2,2-bis(4-hydroxyphenyl) was used instead of 4,4'-biphenol as the divalent phenol.
A polymer was obtained in the same manner as in Example 1, except that 11.4 g (0.05 mol) of propane was used. Polymer yield 16.4
g (100% yield). Reduced viscosity [ηsp/c] is 0.41dl/
g. As a result of thermal analysis, Tg was 150°C and Td was 471°C. As a result of IR analysis, in addition to each absorption of Example 1
Absorption by isopropyl group occurred at 2950 cm -1 .
Both solvent resistance and flame retardant test results are from Example 1.
It was the same. Example 6 0.508 g of terephthaloyl dichloride instead of isophthaloyl dichloride as a condensing agent
(0.0025 mol) and isophthaloyl dichloride
A polymer was obtained in the same manner as in Example 1, except that a mixture with 0.508 g (0.0025 mol) was used. The yield of polymer was 14.3g (yield 100%). Reduced viscosity [ηsp/c]
is 1.26dl/g. As a result of thermal analysis, Tg was not observed.
Tm was 340°C and Td was 473°C. The IR analysis, solvent resistance, and flame retardancy test results were all the same as in Example 1. Example 7 1.523 g of terephthaloyl dichloride instead of isophthaloyl dichloride as a condensing agent
(0.0075 mol) and isophthaloyl dichloride
A polymer was obtained in the same manner as in Example 3 except that 1.523 g (0.0075 mol) of the mixture was used. The yield of polymer was 14.6g (yield 100%). Reduced viscosity [ηsp/c]
is 0.89dl/g. As a result of thermal analysis, Tg is 183℃ and Td is
It was 511℃. The IR analysis, solvent resistance, and flame retardancy test results were all the same as in Example 1. [Effects of the Invention] As is clear from the above explanation, the polymer of the present invention has superior heat resistance as well as flame retardancy and solvent resistance compared to conventional cyanaryloxy polymers. . Moreover, when the composition of the polymer of the present invention is changed, specifically, the degree of polymerization of the oligomer, that is, the molar ratio of the two types of compounds used to generate the oligomer, both Tg and Td change.
It can meet various heat resistance requirements. The polymer of the present invention is useful as a material for various electrical/electronic devices and mechanical parts that require heat resistance, solvent resistance, flame retardance, etc.
Claims (1)
かを表わし、ｎは１〜50の整数を表わす）で示さ
れる繰り返し単位を有し、末端基が―OH又は （式中、Ar及びｎは上と同じ意味を有する）で
あり、かつ、Ｎ―メチルピロリドンを溶媒とする
0.2ｇ/dl濃度の溶液の30℃における還元粘度が
0.3dl/ｇ以上である新規重合体。 ２ 次式： （式中、Ｘはハロゲン原子を表わす） で示されるジハロゲノベンゾニトリルと、 次式： MO―Ar―OM ……（） （式中、Arは【式】【式】 【式】 【式】 【式】 【式】 【式】（ただし、Ｒは炭素 数１〜13の二価の炭化水素基を表わす）のいずれ
かを表わし、Ｍはアルカリ金属を表わす） で示される二価フエノールのアルカリ金属塩と
を、溶媒の存在下で反応させることにより得られ
た、 次式： （式中、Ar、Ｍは上と同じ意味を有し、ｎは１
〜50の整数を表わす） で示されるオリゴマーと、イソフタロイルクロラ
イド及び／又はテレフタロイルクロライドとを、
溶媒の存在下で反応させ、ついで、得られた反応
生成物を水又はアルコールで処理することを特徴
とする： 次式： （式中、Ar及びｎは上と同じ意味を有する） で示される繰返し単位を有し、末端基が―OH又
は【式】（式中、 Ar及びｎは上と同じ意味を有する）であり、か
つ、Ｎ―メチルピロリドンを溶媒とする0.2ｇ/dl
濃度の溶液の30℃における還元粘度が0.3dl/ｇ以
上である新規重合体の製造方法。[Claims] Primary formula: (wherein, Ar is either [formula] [formula] [formula] [formula] [formula] [formula] [formula] (wherein R represents a divalent hydrocarbon group having 1 to 13 carbon atoms) , n is an integer from 1 to 50), and the terminal group is -OH or (wherein Ar and n have the same meanings as above), and N-methylpyrrolidone is used as a solvent.
The reduced viscosity at 30℃ of a solution with a concentration of 0.2g/dl is
A new polymer with a concentration of 0.3 dl/g or more. Quadratic formula: (In the formula, X represents a halogen atom) Dihalogenobenzonitrile represented by the following formula: MO-Ar-OM ...... () (In the formula, Ar is [Formula] [Formula] [Formula] [Formula] [Formula] [Formula] [Formula] (wherein R represents a divalent hydrocarbon group having 1 to 13 carbon atoms, M represents an alkali metal) an alkali of divalent phenol represented by The following formula obtained by reacting metal salt in the presence of a solvent: (In the formula, Ar and M have the same meanings as above, and n is 1
(representing an integer of ~50) and isophthaloyl chloride and/or terephthaloyl chloride,
It is characterized by reacting in the presence of a solvent and then treating the resulting reaction product with water or alcohol: (In the formula, Ar and n have the same meanings as above) and the terminal group is -OH or [Formula] (In the formula, Ar and n have the same meanings as above) , and 0.2g/dl using N-methylpyrrolidone as a solvent.
A method for producing a novel polymer having a reduced viscosity of 0.3 dl/g or more at 30°C in a concentrated solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7173384A JPS60217236A (en) | 1984-04-12 | 1984-04-12 | Novel polymer and its production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7173384A JPS60217236A (en) | 1984-04-12 | 1984-04-12 | Novel polymer and its production |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60217236A JPS60217236A (en) | 1985-10-30 |
| JPS6362530B2 true JPS6362530B2 (en) | 1988-12-02 |
Family
ID=13469015
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7173384A Granted JPS60217236A (en) | 1984-04-12 | 1984-04-12 | Novel polymer and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60217236A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62275124A (en) * | 1986-05-23 | 1987-11-30 | Idemitsu Kosan Co Ltd | Production of modified polycyanoaryl ether |
-
1984
- 1984-04-12 JP JP7173384A patent/JPS60217236A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60217236A (en) | 1985-10-30 |
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