JPS62253627A - Heat-resistant resin and production thereof - Google Patents
Heat-resistant resin and production thereofInfo
- Publication number
- JPS62253627A JPS62253627A JP9670086A JP9670086A JPS62253627A JP S62253627 A JPS62253627 A JP S62253627A JP 9670086 A JP9670086 A JP 9670086A JP 9670086 A JP9670086 A JP 9670086A JP S62253627 A JPS62253627 A JP S62253627A
- Authority
- JP
- Japan
- Prior art keywords
- diphenyl
- sulfone
- polymer
- dihydroxy
- formula
- 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
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 229920006015 heat resistant resin Polymers 0.000 title 1
- 229920006393 polyether sulfone Polymers 0.000 claims abstract description 19
- 239000004695 Polyether sulfone Substances 0.000 claims abstract description 16
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 9
- 239000003513 alkali Substances 0.000 claims abstract description 8
- 125000003118 aryl group Chemical class 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims abstract description 6
- -1 aromatic aromatic compound Chemical class 0.000 claims description 13
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 claims description 11
- 238000006068 polycondensation reaction Methods 0.000 claims description 3
- 150000001340 alkali metals Chemical class 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- 150000003457 sulfones Chemical class 0.000 abstract description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 abstract description 2
- LLEMOWNGBBNAJR-UHFFFAOYSA-N biphenyl-2-ol Chemical compound OC1=CC=CC=C1C1=CC=CC=C1 LLEMOWNGBBNAJR-UHFFFAOYSA-N 0.000 abstract 2
- GPAPPPVRLPGFEQ-UHFFFAOYSA-N 4,4'-dichlorodiphenyl sulfone Chemical compound C1=CC(Cl)=CC=C1S(=O)(=O)C1=CC=C(Cl)C=C1 GPAPPPVRLPGFEQ-UHFFFAOYSA-N 0.000 abstract 1
- 235000010292 orthophenyl phenol Nutrition 0.000 abstract 1
- 239000011347 resin Substances 0.000 abstract 1
- 229920005989 resin Polymers 0.000 abstract 1
- 229920000642 polymer Polymers 0.000 description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- 238000006116 polymerization reaction Methods 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 10
- 238000010521 absorption reaction Methods 0.000 description 8
- 229920002492 poly(sulfone) Polymers 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 6
- 239000000178 monomer Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 230000009477 glass transition Effects 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 125000001174 sulfone group Chemical group 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229920006158 high molecular weight polymer Polymers 0.000 description 3
- 238000000691 measurement method Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 description 3
- 235000011181 potassium carbonates Nutrition 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 241000283690 Bos taurus Species 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 2
- 150000008041 alkali metal carbonates Chemical class 0.000 description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- KCIDZIIHRGYJAE-YGFYJFDDSA-L dipotassium;[(2r,3r,4s,5r,6r)-3,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl] phosphate Chemical class [K+].[K+].OC[C@H]1O[C@H](OP([O-])([O-])=O)[C@H](O)[C@@H](O)[C@H]1O KCIDZIIHRGYJAE-YGFYJFDDSA-L 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 125000001033 ether group Chemical group 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000012778 molding material Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000011736 potassium bicarbonate Substances 0.000 description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 2
- 235000015497 potassium bicarbonate Nutrition 0.000 description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 2
- 229940086066 potassium hydrogencarbonate Drugs 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- JNELGWHKGNBSMD-UHFFFAOYSA-N xanthone Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3OC2=C1 JNELGWHKGNBSMD-UHFFFAOYSA-N 0.000 description 2
- BWQOPMJTQPWHOZ-UHFFFAOYSA-N (2,3-difluorophenyl)-phenylmethanone Chemical compound FC1=CC=CC(C(=O)C=2C=CC=CC=2)=C1F BWQOPMJTQPWHOZ-UHFFFAOYSA-N 0.000 description 1
- OJLABXSUFRIXFL-UHFFFAOYSA-N (2-benzoylphenyl)-phenylmethanone Chemical compound C=1C=CC=C(C(=O)C=2C=CC=CC=2)C=1C(=O)C1=CC=CC=C1 OJLABXSUFRIXFL-UHFFFAOYSA-N 0.000 description 1
- LERREUOVCXYKGR-UHFFFAOYSA-N (2-phenoxyphenyl)-phenylmethanone Chemical compound C=1C=CC=C(OC=2C=CC=CC=2)C=1C(=O)C1=CC=CC=C1 LERREUOVCXYKGR-UHFFFAOYSA-N 0.000 description 1
- OGTSHGYHILFRHD-UHFFFAOYSA-N (4-fluorophenyl)-phenylmethanone Chemical compound C1=CC(F)=CC=C1C(=O)C1=CC=CC=C1 OGTSHGYHILFRHD-UHFFFAOYSA-N 0.000 description 1
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 1
- IBRQUKZZBXZOBA-UHFFFAOYSA-N 1-chloro-3-(3-chlorophenyl)sulfonylbenzene Chemical compound ClC1=CC=CC(S(=O)(=O)C=2C=C(Cl)C=CC=2)=C1 IBRQUKZZBXZOBA-UHFFFAOYSA-N 0.000 description 1
- PZDAAZQDQJGXSW-UHFFFAOYSA-N 1-fluoro-4-(4-fluorophenyl)benzene Chemical group C1=CC(F)=CC=C1C1=CC=C(F)C=C1 PZDAAZQDQJGXSW-UHFFFAOYSA-N 0.000 description 1
- KZCDMIJHGSSDFO-UHFFFAOYSA-N 1-methyl-2-(2-methylphenyl)sulfonylbenzene Chemical compound CC1=CC=CC=C1S(=O)(=O)C1=CC=CC=C1C KZCDMIJHGSSDFO-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 101100145155 Escherichia phage lambda cIII gene Proteins 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- ZMCUDHNSHCRDBT-UHFFFAOYSA-M caesium bicarbonate Chemical compound [Cs+].OC([O-])=O ZMCUDHNSHCRDBT-UHFFFAOYSA-M 0.000 description 1
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 1
- 229910000024 caesium carbonate Inorganic materials 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
- KEDRKJFXBSLXSI-UHFFFAOYSA-M hydron;rubidium(1+);carbonate Chemical compound [Rb+].OC([O-])=O KEDRKJFXBSLXSI-UHFFFAOYSA-M 0.000 description 1
- 125000005647 linker group Chemical group 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920001643 poly(ether ketone) Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- WPFGFHJALYCVMO-UHFFFAOYSA-L rubidium carbonate Chemical compound [Rb+].[Rb+].[O-]C([O-])=O WPFGFHJALYCVMO-UHFFFAOYSA-L 0.000 description 1
- 229910000026 rubidium carbonate Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Polyethers (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明は新規な芳香族ポリエーテルスルホン及びその製
法に関するものである。さらに詳しくいえば、本発明は
エーテル基及びスルホン基を介しイ1〒i1ノンtP−
IIIZ ’*壮(h−九りづエニレン其の一部がフェ
ニル基で置換されている化学構造を有する、耐熱性、吸
水性、誘電特性、機械的性質などに優れた新規重合体及
びそれを製造するための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 novel aromatic polyether sulfone and a method for producing the same. More specifically, the present invention provides 1-1 non-tP-
IIIZ' * So (h-9Ryzu) A new polymer with a chemical structure in which a part of enylene is substituted with a phenyl group and has excellent heat resistance, water absorption, dielectric properties, mechanical properties, etc., and its use. It relates to a method for manufacturing.
従来の技術
これまで、エーテル基及びスルホン基を介してフェニレ
ン基が連結されている構造を有する高分子化合物として
は、一般にポリスルホンと呼ばれる、構造式
で表わされるものや、一般にポリエーテルスルホンと呼
ばれる、構造式
で表わされるものが知られており、これらは優れた耐熱
性、成形性、機械的強度を有するために、成形材料とし
て注目されでいる。BACKGROUND ART Until now, polymer compounds having a structure in which phenylene groups are linked via an ether group and a sulfone group include those generally called polysulfones, represented by the structural formula, and those generally called polyethersulfones. Those represented by the structural formula are known, and these have attracted attention as molding materials because they have excellent heat resistance, moldability, and mechanical strength.
しかしながら、前記式(I)で表わされるポリスルホン
は、脂肪族基をもつため吸水性が低く、かつ誘電率も低
くて電気材料として適しているが、逆に脂肪族基をもつ
ことから、熱変形温度が低い上に、長期の耐熱老化性に
劣るという欠点を有している。However, since the polysulfone represented by the formula (I) has an aliphatic group, it has low water absorption and a low dielectric constant, making it suitable as an electrical material. It has the drawbacks of low temperature and poor long-term heat aging resistance.
一方、前記式(II)で表わされるポリエーテルスルボ
ンは、脂肪族基を含まず、結合基以外はすべてフェニレ
ン基で構成されているため、長期の耐熱老化性に優れ、
かつ熱変形温度もポリスルホンよりも優れているが、ポ
リスルホンに比べ極性基テあるスルホン基の含有率が高
いため吸水率や誘電率が高いという欠点を有している。On the other hand, the polyether sulfone represented by the above formula (II) does not contain aliphatic groups and is composed of all phenylene groups except for bonding groups, so it has excellent long-term heat aging resistance,
Although it has a higher heat distortion temperature than polysulfone, it has a higher content of sulfone groups, which are polar groups, than polysulfone, so it has a drawback of high water absorption and dielectric constant.
発明が解決しようとする問題点
本発明の目的は、ポリエーテルスルホンのもつ優れた熱
変形温度特性と熱安定性を損わず、しかも誘電特性と吸
水性を改良したフェニル置換芳香族ポリエーテルスルホ
/を提供することにある。Problems to be Solved by the Invention The object of the present invention is to provide a phenyl-substituted aromatic polyether sulfone which does not impair the excellent thermal deformation temperature characteristics and thermal stability of polyether sulfone, and which has improved dielectric properties and water absorption. The goal is to provide /.
問題点を解決するための手段
本発明者らは鋭意研究を重ねた結果、原料としテ4.4
’−ジハロジフェニルスルホンと4.4′−ジヒドロキ
シ−3,3′−ジフェニル−ジフェニルスルホン又はそ
のアルカリ金属塩とを用い、これらを重縮合させること
により、特定構造を有する非品性重合体が得られ、前記
目的を達成しうろことを見出し、この知児に基づいて本
発明を完成するに至った。Means for Solving the Problems As a result of intensive research, the inventors found that the raw material was Te 4.4.
By polycondensing '-dihalodiphenylsulfone and 4,4'-dihydroxy-3,3'-diphenyl-diphenylsulfone or its alkali metal salt, a non-quality polymer having a specific structure can be produced. The inventors have found that the above object can be achieved, and have completed the present invention based on this knowledge.
すなわち、本発明は、式
で表わされる繰り返し単位から成り、かつ0.15以上
の極限粘度を有するフェニル置換芳香族ポリエーテルス
ルホンを提供するものであり、この重合体は、実質上等
モルの4,4′−ジノ・ロジフェニルスルホンと4,4
′−ジヒドロキシ−5,5’−ジフェニル−ジフェニル
スルホンとをアルカリの存在下に4叔5人 、、h 1
L+P L 77Ijdブ千キ^h+!htr
−t−1,/r% J A/ −、zへ
ロジフェニルスルホンと4.4′−ジヒドロキシ−3、
!!−ジフェニルージフェニルスルホンのアルカリ金属
塩とを重縮合させることによって製造することができる
。That is, the present invention provides a phenyl-substituted aromatic polyether sulfone that is composed of repeating units represented by the formula and has an intrinsic viscosity of 0.15 or more, and this polymer has substantially equimolar amounts of 4 ,4'-dino-rodiphenylsulfone and 4,4
'-dihydroxy-5,5'-diphenyl-diphenylsulfone in the presence of an alkali, 4 hours and 5 hours, h 1
L+P L 77Ijd bu thousand ki^h+! htr
-t-1,/r% J A/ -, zherodiphenylsulfone and 4,4'-dihydroxy-3,
! ! - Diphenylsulfone can be produced by polycondensation with an alkali metal salt of diphenylsulfone.
本発明において、一方の原料単量体として用いられる4
、4′−ジヒドロキン−3,3′−ジフェニル−ジフェ
ニルスルホン及びそのアルカリ金属塩は新規化合物であ
って、前者は、例えば0−フェニルフェノールと濃硫酸
の縮合により容易に製造することができるし、また後者
はこのものにアルカリ金属の水酸化物を反応させること
により容易に製造することができる。In the present invention, 4 used as one raw material monomer
, 4'-dihydroquine-3,3'-diphenyl-diphenylsulfone and its alkali metal salts are new compounds, and the former can be easily produced, for example, by condensation of 0-phenylphenol and concentrated sulfuric acid; Moreover, the latter can be easily produced by reacting this material with an alkali metal hydroxide.
本発明で用いられるもう一方の原料単量体は4゜4′−
ジハロジフェニルスルホンであり、このものの具体例と
しては、A、、4’−ジクロロジフェニルスルホン、4
.4’−ジフルオロジフェニルスルホン、4−フルオロ
−4′−クロロジフェニルスルホンなどが好ましく挙げ
られる。これらはそれぞれ単独で用いてもよいし、2種
以上組み合わせて用いてもよい、
本発明における4、4′−ジヒドロキシ−3,5−ジフ
ェニル−ジフェニルスルホン又はそのアルカリ金属塩と
4.4′−ジハロジフェニルスルホンとの使用割合につ
いては、実質的に等モルである牛とが、必要で、通常前
者1モル当り、後者は0.95〜1.05モルの範囲で
用いられる。The other raw material monomer used in the present invention is 4゜4'-
It is a dihalodiphenylsulfone, and specific examples thereof include A, 4'-dichlorodiphenylsulfone, 4
.. Preferred examples include 4'-difluorodiphenylsulfone and 4-fluoro-4'-chlorodiphenylsulfone. Each of these may be used alone or in combination of two or more. 4,4'-dihydroxy-3,5-diphenyl-diphenylsulfone or its alkali metal salt and 4,4'- Regarding the ratio of dihalodiphenylsulfone used, it is necessary to use substantially equimolar amounts of bovine and bovine, and the latter is usually used in a range of 0.95 to 1.05 mol per 1 mol of the former.
また、得られる重合体の特性を損わない範囲で、所望に
応じ少量のジヒドロキシジフェニルスルホンを4.4′
−ジヒドロキシ−3,3′−ジフェニル−ジフェニルス
ルホンと組み合わせて用いてもよい。Additionally, if desired, a small amount of dihydroxydiphenyl sulfone may be added to 4.4' without impairing the properties of the resulting polymer.
It may be used in combination with -dihydroxy-3,3'-diphenyl-diphenylsulfone.
本発明において用いるアルカリとしては、アルカリ金属
炭酸塩、アルカリ金属重炭酸塩、アルカリ金属水酸化物
などが挙げられるが、アルカリ金属炭酸塩及びアルカリ
金属重炭酸塩が好適であり、具体的には炭酸ナトリウム
、炭酸カリウム、炭酸ルビジウム、炭酸セシウム、炭酸
水素ナトリウム、炭酸水素カリウム、炭酸水素ルビジウ
ム、炭酸水素セシウムなどを挙げることができる。これ
らはそれぞれ単独で用いてもよいし、2種以上組み合わ
せて用いてもよい。また、これらの中で、特に炭酸ナト
リウム、炭酸カリウム、炭酸水素ナトリウム、炭酸水素
カリウムが好適である。Examples of the alkali used in the present invention include alkali metal carbonates, alkali metal bicarbonates, alkali metal hydroxides, etc., but alkali metal carbonates and alkali metal bicarbonates are preferable, and specifically carbonate Examples include sodium, potassium carbonate, rubidium carbonate, cesium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, rubidium hydrogen carbonate, and cesium hydrogen carbonate. These may be used alone or in combination of two or more. Among these, particularly preferred are sodium carbonate, potassium carbonate, sodium hydrogen carbonate, and potassium hydrogen carbonate.
これらのアルカリは、4.4′ニジヒドロキシ−3゜5
′−ジフェニル−ジフェニルスルホン0.5モルに対し
、アルカリ金属原子の量が0.3〜2グラム原子、好ま
しくは0.5〜1.2グラム原子になるような割合で用
いられる。該アルカリを過剰に使用すると、反応が激し
くなりすぎて、有害な副反応を起す原因となる上に、コ
スト面でも不利になるからできるだけ少ない量の使用が
望ましい。しかし、アルカリ金属原子の量が0.5グラ
ム原子未満になると、反応速度が遅くて所望の高分子量
の重合体が得られにくくなる。These alkalis are 4.4′ dihydroxy-3°5
The alkali metal atoms are used in proportions such that the amount of alkali metal atoms is from 0.3 to 2 gram atoms, preferably from 0.5 to 1.2 gram atoms, per 0.5 mole of '-diphenyl-diphenylsulfone. If the alkali is used in excess, the reaction becomes too vigorous, causing harmful side reactions, and is also disadvantageous in terms of cost, so it is desirable to use as little amount as possible. However, when the amount of alkali metal atoms is less than 0.5 gram atom, the reaction rate is slow and it becomes difficult to obtain a desired high molecular weight polymer.
本発明においては、重合反応は溶媒の存在下又は不在下
に行うことができるが、一般に溶媒の存在下に行うこと
が望ましい。この際使用する溶媒としては、例えばキサ
ントン、ベンゾフェノン、フェノキシベンゾフェノン、
ジベンゾイルベンゼンなどのケトン化合物、ジフェニル
スルホン、ジトリルスルホン、スルホランなどのスルホ
ン化合物、ジメチルスルホキシド、N−メチル−2−ピ
ロリドン、ヘキサメチルホスホルアミドなどの極性溶媒
などが挙げられるが、高温で重合する場合には、アルキ
ル基を含まない芳香族系化合物が好適である。In the present invention, the polymerization reaction can be carried out in the presence or absence of a solvent, but it is generally desirable to carry out it in the presence of a solvent. Examples of solvents used at this time include xanthone, benzophenone, phenoxybenzophenone,
Examples include ketone compounds such as dibenzoylbenzene, sulfone compounds such as diphenylsulfone, ditolylsulfone, and sulfolane, and polar solvents such as dimethylsulfoxide, N-methyl-2-pyrrolidone, and hexamethylphosphoramide. In this case, aromatic compounds containing no alkyl group are suitable.
次に、本発明における重合について、好ましい実施態様
の1例を示すと、所望の溶媒中K、4.4’−ジハロジ
フェニルスルホンと4.4′−ジヒドロキシ−3,5′
−ジフェニル−ジフェニルスルホンとを実質的に等モル
の割合で添加し、さらに所半量のアルカリを添加した混
合物、又は所望の溶媒中に、4141−ジハロジフェニ
ルスルポンと4,4′−ジヒドロキン−5+3′−ジフ
ェニル−ジフェニルスルホンのアルカリ金属塩とを実質
的に等モルの割合で添加した混合物を、例えば窒素、ア
ルゴンなどの不活性ガス雰囲気下、200〜400℃、
好ましくは250〜350℃の範囲の温度に加熱して重
合反応を行う。反応温度が200°C未満では高分子量
の重合体が得られに<<、一方400°Cを超えると生
成した重合体の劣化による着色が著しくなるので好まし
くない。Next, to show one example of a preferred embodiment of the polymerization in the present invention, K, 4,4'-dihalodiphenylsulfone and 4,4'-dihydroxy-3,5'
4141-dihalodiphenylsulfone and 4,4'-dihydroquin- A mixture of 5+3'-diphenyl-diphenylsulfone and an alkali metal salt added in substantially equimolar proportions is heated at 200 to 400°C under an inert gas atmosphere such as nitrogen or argon.
Preferably, the polymerization reaction is carried out by heating to a temperature in the range of 250 to 350°C. If the reaction temperature is less than 200°C, a polymer with a high molecular weight will not be obtained. On the other hand, if the reaction temperature exceeds 400°C, the resulting polymer will become significantly colored due to deterioration, which is not preferable.
重合時の昇温は徐々に行い、また重合系が均一な温度に
保たれるように工夫することが、ゲルや着色のない良好
な重合体を得るために重要である。It is important to gradually raise the temperature during polymerization and to keep the polymerization system at a uniform temperature in order to obtain a good polymer that is free from gel and coloration.
また、高分子量の重合体を得るためには、重合温度は最
終的には200’Q以上にすることが必要であるが、そ
れ以下の温度で予備重合することも有利な方法である。Further, in order to obtain a high molecular weight polymer, it is necessary to ultimately set the polymerization temperature to 200'Q or more, but it is also an advantageous method to prepolymerize at a temperature lower than that.
アルカリの存在下、該単量体を重合させる場合、重合中
に水分が発生するが、この水分は系外に除去することが
望ましく、除去する方法としては、重合系に乾燥した不
活性ガスを導入又はガス相を該不活性ガスで置換する方
法、水と共沸する溶媒を重合系に加えて、これと共に系
外へ留去する方法などが用いられる。When the monomer is polymerized in the presence of an alkali, water is generated during the polymerization, but it is desirable to remove this water from the system. A method of introducing or replacing the gas phase with the inert gas, a method of adding a solvent azeotropic with water to the polymerization system and distilling it out of the system together, etc. are used.
重合反応は適当な末端停止剤、例えば単官能又は多官能
ハロゲン化物、具体的にはジクロロジフェニルスルホン
、ジフルオロベンゾフェノン、モノフルオロベンゾフェ
ノン、塩化メチルなどを反応系に添加、反応させること
により停止させることができ、またこれによってポリマ
ー鎖の末端な安定化できる。The polymerization reaction can be stopped by adding a suitable terminal capping agent, such as a monofunctional or polyfunctional halide, specifically dichlorodiphenylsulfone, difluorobenzophenone, monofluorobenzophenone, methyl chloride, etc. to the reaction system and causing the reaction. This can also stabilize the ends of the polymer chain.
このようにして得られた本発明の重合体は、式で表わさ
れる繰り返し単位から成る非品性の高分子量重合体であ
る。The polymer of the present invention thus obtained is a non-quality high molecular weight polymer consisting of repeating units represented by the formula.
本発明の重合体は極限粘度が0.15以上のものであり
、特にフィルムを得るためには0.5以上であることが
好ましい。この極限粘度が0.15未満のものは1重合
体としての特性を示さず不適当である。The polymer of the present invention has an intrinsic viscosity of 0.15 or more, particularly preferably 0.5 or more in order to obtain a film. A polymer having an intrinsic viscosity of less than 0.15 does not exhibit the characteristics of a monopolymer and is therefore unsuitable.
発明の効果
本発明の芳香族ポリエーテルスルホンは、エーテル基及
びスルホン基を介してフェニレン基が結合され、かつフ
ェニレン基の一部がフェニル基で置換されている化学構
造を有する新規な重合体で4って、従来のポリエーテル
スルホンに比べ優れた吸水性、誘電率を有するとともに
公知のポリスルホンに比べ優れた耐熱性を有するので、
これまで知られていない耐熱性と吸水性と誘電率のバラ
ンスのとれたポリマーとして有望であり、高温下、か酷
な条件で使用する成形材料として好適である。Effects of the Invention The aromatic polyether sulfone of the present invention is a novel polymer having a chemical structure in which phenylene groups are bonded via an ether group and a sulfone group, and a portion of the phenylene groups are substituted with phenyl groups. 4. It has superior water absorption and dielectric constant compared to conventional polyether sulfone, as well as superior heat resistance compared to known polysulfone.
It is promising as a polymer with a hitherto unknown balance of heat resistance, water absorption, and dielectric constant, and is suitable as a molding material used under harsh conditions at high temperatures.
したがって、各種形状の成形品、被覆、フィルム、繊維
などに成形し、あるいは他のポリマー例えばポリエーテ
ルケトン、ポリエーテルスルホンなどや補強材料例えば
ガラス繊維、炭素繊維などと複合して、各分野に利用す
ることができる。 ′実施例
次に実施例により本発明をさらに詳細に説明するが、本
発明はこれらの例によってなんら限定されるものではな
い。Therefore, it can be used in various fields by being molded into various shapes of molded products, coatings, films, fibers, etc., or composited with other polymers such as polyetherketone, polyethersulfone, etc. or reinforcing materials such as glass fiber, carbon fiber, etc. can do. 'Examples Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples in any way.
また、重合体の物性は次のようにして測定した。Further, the physical properties of the polymer were measured as follows.
(1)極限粘度
N−メチルピロリドン(NMP )を使用し、溶液to
ocM3当り重合体0.1gを含む溶液と溶液100i
当り重合体0.5gを含む溶液を調製し、その粘度を2
5°Cで測定し、式
%式%
〔ただし、ηre!!は相対粘度、Cは濃度(、!il
/100m1 )であり、C→0は(rlrel−1)
/cの値を濃度Cが0の点に外挿したことを意味する
)を用いて求めた。(1) Using intrinsic viscosity N-methylpyrrolidone (NMP), the solution to
Solution containing 0.1 g of polymer per ocM3 and solution 100i
A solution containing 0.5 g of polymer per bottle was prepared, and its viscosity was adjusted to 2.
Measured at 5°C, formula % formula % [However, ηre! ! is the relative viscosity, C is the concentration (,!il
/100m1), and C→0 is (rlrel-1)
(meaning that the value of /c is extrapolated to the point where the concentration C is 0).
(2)ガラス転移温度(Tg)
DSO(示差走査熱量計)により昇温速度10°ンmi
nで測定した。(2) Glass transition temperature (Tg) Temperature increase rate of 10°m by DSO (differential scanning calorimeter)
Measured at n.
5ootxtの三つロフラスコに0−フェニルフェノー
ル519 (300ミリモル)及び98%濃硫酸j5,
2 iを仕込み、室温より160°Cまで1時間を要し
て昇温し、その後170℃で7.5時間反応させた。な
お、反応中には系内に窒素ガスを流した。0-phenylphenol 519 (300 mmol) and 98% concentrated sulfuric acid j5,
2i was charged, the temperature was raised from room temperature to 160°C over 1 hour, and then the reaction was carried out at 170°C for 7.5 hours. Note that nitrogen gas was flowed into the system during the reaction.
次に、反応生成物を熱水でよく洗浄したのち、固体部分
を分離し乾燥した。これを加熱したトルエン300m1
でよく洗浄してろ過し、さらに加熱したヘキサンsoo
g/でよく洗浄したのち、ろ過した。Next, the reaction product was thoroughly washed with hot water, and then the solid portion was separated and dried. 300ml of toluene heated
Wash thoroughly with water, filter, and heat the hexane soo.
After washing thoroughly with 100 g/g/g/g/g/g of water, the mixture was filtered.
その後水酸化ナトリウム10重量%水溶液に溶解したの
ち、塩酸を加えて固形物を析出させ、次いでこの固形物
を0−ジクロロベンゼンで再結晶した。Thereafter, it was dissolved in a 10% by weight aqueous solution of sodium hydroxide, and then hydrochloric acid was added to precipitate a solid, which was then recrystallized from 0-dichlorobenzene.
再結晶して得られた生成物の融点は249〜250℃で
あり、元素分析、工Rスペクトル(第1図)、NMRス
ペクトル(第2図)により、次の構造を有する4、4′
−ジヒドロキン−5,5’−ジフェニル−ジフェニルス
ルホンであると固定した。The melting point of the product obtained by recrystallization is 249-250°C, and elemental analysis, engineering R spectrum (Fig. 1), and NMR spectrum (Fig. 2) show that it has the following structure: 4,4'
-dihydroquine-5,5'-diphenyl-diphenylsulfone.
理論値鈍) 71,6 4.5 8,0 15
.9(C24Hl 8604として)
塩の製造
4.4′−ジヒドロキシ、−5,3’−ジフェニル−ジ
フェニルスルポンとその2倍モルの水酸化カリウムを含
む1規定のKQE水溶液とを混合したのち、工バポレー
ターで水分を留去し、次いで90℃で10時間真空乾燥
して、 4.4’−ジヒドロキシ−3゜3′−ジフェニ
ル−ジフェニルスルホンのジカリウム塩を得た。Theoretical value dull) 71,6 4.5 8,0 15
.. 9 (as C24Hl 8604) Preparation of salt 4. After mixing 4'-dihydroxy, -5,3'-diphenyl-diphenyl sulfone and a 1N aqueous solution of KQE containing twice the molar amount of potassium hydroxide, Water was distilled off using a vaporator, and then vacuum-dried at 90°C for 10 hours to obtain the dipotassium salt of 4,4'-dihydroxy-3°3'-diphenyl-diphenylsulfone.
実施例1
かきまぜ機、窒素導入管及び冷却管を備えたセパラブル
フラスコに、4.4’−ジヒドロキシ−3,3′−ジフ
ェニル−ジフェニルスルホン12j li (50ミリ
モル)、4.4’−ジフルオロジフェニルスルホン7.
6.9 (30ミリモル)、無水炭酸カリウム2.11
I(15ミリモル)、無水炭酸ナトリウム1.69 (
15ミリモル)及びジフェニルスルホン20.9を入れ
、窒素雰囲気下に加熱を開始し、系中の水分を窒素ガス
により系外へ除去しながら310℃まで昇温し、その温
度で6時間重合を行ったのち、この温度において4.4
′−ジフルオロジフェニルスルホン2gを添加して、3
0分間反応させた。Example 1 4,4'-dihydroxy-3,3'-diphenyl-diphenylsulfone 12j li (50 mmol) and 4,4'-difluorodiphenyl were placed in a separable flask equipped with a stirrer, a nitrogen inlet tube, and a cooling tube. Sulfone7.
6.9 (30 mmol), anhydrous potassium carbonate 2.11
I (15 mmol), anhydrous sodium carbonate 1.69 (
15 mmol) and 20.9 g of diphenyl sulfone were added, heating was started under a nitrogen atmosphere, and the temperature was raised to 310°C while removing water in the system from the system with nitrogen gas, and polymerization was carried out at that temperature for 6 hours. Later, at this temperature, 4.4
'-Difluorodiphenylsulfone 2g was added, and 3
The reaction was allowed to proceed for 0 minutes.
反応終了後、冷却して得られた固形物を粉砕し、温メタ
ノールで2回、温湯で2回、さらに温メタノールで1回
洗浄して重合体粉末を得た。収率は97%であった。After the reaction was completed, the solid material obtained by cooling was pulverized and washed twice with warm methanol, twice with hot water, and once with warm methanol to obtain a polymer powder. The yield was 97%.
得られた重合体はNMPに完全に溶解し、NMPでの極
限粘度は0.83であり、またD8Cの測定によるガラ
ス転移温度(Tg)は210℃であった。重合体の元素
分析の結果、このものは、式
の構造を有することが確認された。The obtained polymer was completely dissolved in NMP, had an intrinsic viscosity of 0.83 in NMP, and had a glass transition temperature (Tg) of 210° C. as measured by D8C. As a result of elemental analysis of the polymer, it was confirmed that it had the structure of the formula.
計算値鏝) 71,6 4,5 15,9 8.
0(036馬4 o、 82として)
この重合体の工Rスペクトルを第5図に示す。Calculated value) 71,6 4,5 15,9 8.
0 (as 036 horse 4 o, 82) The R spectrum of this polymer is shown in FIG.
この重合体を340°Cで4分間プレスして得られたフ
ィルムは、透明で繰り返し折り曲げに対して極めて丈夫
なものであり、このフィルムの引張り強度は910 k
g/cIII” 、破断時伸びは105%であった(測
定法ASTM D882 )。この重合体の熱安定性を
熱天秤で測定したところ、512℃で5重量%の重量減
であった。なお、5重量%減量の温度はポリスルホンで
490℃、ポリエーテルスルホンで510℃である。The film obtained by pressing this polymer at 340°C for 4 minutes is transparent and extremely durable against repeated bending, with a tensile strength of 910 k.
g/cIII", and the elongation at break was 105% (measurement method ASTM D882). When the thermal stability of this polymer was measured using a thermobalance, it was found that the weight loss was 5% by weight at 512°C. , the temperature for 5% weight loss is 490°C for polysulfone and 510°C for polyethersulfone.
この重合体のj KHzにおける誘電率は3.0であり
、ポリエーテルスルホンの3.5よす優れ、ポリスルホ
ンの3.1と同等であった(測定法はASTMD150
)。The dielectric constant of this polymer at j KHz was 3.0, which was better than polyethersulfone's 3.5 and equivalent to polysulfone's 3.1 (the measurement method was ASTM D150).
).
また、この重合体の吸水率は0.25でありポリエーテ
ルスルホンの0.43より優れ、ポリスルホンの0.3
0よりも若干優れていた(測定法A8TMD570 )
。In addition, the water absorption rate of this polymer is 0.25, which is superior to polyethersulfone's 0.43, and polysulfone's 0.3.
Slightly better than 0 (Measurement method A8TMD570)
.
これらの結果から、本発明重合体はポリエーテルスルホ
ン基の耐熱安定性を有し、しかも誘電率、吸水性の点で
ポリエーテルスルホンより優れており、電気・電子材料
として好適である。From these results, the polymer of the present invention has the heat resistance stability of a polyether sulfone group, and is superior to polyether sulfone in terms of dielectric constant and water absorption, and is suitable as an electrical/electronic material.
なおポリエーテルスルホンとしては工C工の1ctre
x Pm8200F、ポリスルホンとしてはUCC(7
)Udel F−3500を使用した。In addition, as polyether sulfone, 1ctre of Kogyo C Kogyo
x Pm8200F, UCC (7
) Udel F-3500 was used.
単量体、アルカリ、重合溶媒、重合温度、時間について
は次表に示す条件で重合を行い、それ以外は実施例1と
同様な方法で重合を行った。Polymerization was carried out under the conditions shown in the following table regarding the monomer, alkali, polymerization solvent, polymerization temperature, and time, and the polymerization was carried out in the same manner as in Example 1 except for the following conditions.
得られた重合体の極限粘度とガラス転移温度な該表に示
す。The intrinsic viscosity and glass transition temperature of the obtained polymer are shown in the table.
実施例7
4.41−ジヒドロキシ−3,3′−ジフェニル−ジフ
ェニルスルホンのジカリウム塩14.39 (50ミ、
!J モル) s 44’−ジフルオロジフェニルスル
ホン7.6.9 (50ミリモル)及びジフェニルスル
ホン25:!を混合し、実施例1と同様な方法で重合し
て、極限粘度0,56.ガラス転移温度198°Cの重
合体をほぼ定量的に得た。Example 7 Dipotassium salt of 4.41-dihydroxy-3,3'-diphenyl-diphenylsulfone 14.39 (50 mi,
! J mol) s 44'-difluorodiphenylsulfone 7.6.9 (50 mmol) and diphenylsulfone 25:! were mixed and polymerized in the same manner as in Example 1 to obtain an intrinsic viscosity of 0.56. A polymer having a glass transition temperature of 198°C was obtained almost quantitatively.
第1図及び第2図はそれぞれ、本発明で用いる単量体4
.4′−ジヒドロキシ−6,6′−ジフェニル−ジフェ
ニルスルホンの工Rスペクトルチャート及びNMRスペ
クトルチャートであり、第3図は本発明重合体の工Rス
ペクトルチャートである。Figures 1 and 2 respectively show the monomer 4 used in the present invention.
.. These are the R spectrum chart and the NMR spectrum chart of 4'-dihydroxy-6,6'-diphenyl-diphenylsulfone, and FIG. 3 is the R spectrum chart of the polymer of the present invention.
Claims (1)
の極限粘度を有するフェニル置換芳香族ポリエーテルス
ルホン。 2 アルカリの存在下、実質上等モルの4,4′−ジハ
ロジフェニルスルホンと4,4′−ジヒドロキシ−3,
3′−ジフェニル−ジフェニルスルホンとを重縮合させ
ることを特徴とする、式 ▲数式、化学式、表等があります▼ で表わされる繰り返し単位から成り、かつ0.15以上
の極限粘度を有するフェニル置換芳香族ポリエーテルス
ルホンの製法。 3 実質上等モルの4,4′−ジハロジフェニルスルホ
ンと4,4′−ジヒドロキシ−3、3′−ジフェニル−
ジフェニルスルホンのアルカリ金属塩とを重縮合させる
ことを特徴とする、式 ▲数式、化学式、表等があります▼ で表わされる繰り返し単位を有し、かつ0.15以上の
極限粘度を有するフェニル置換芳香族ポリエーテルスル
ホンの製法。[Claims] 1. A phenyl-substituted aromatic polyether sulfone consisting of a repeating unit represented by the formula ▲ Numerical formula, chemical formula, table, etc. ▼ and having an intrinsic viscosity of 0.15 or more. 2 In the presence of an alkali, substantially equimolar amounts of 4,4'-dihalodiphenylsulfone and 4,4'-dihydroxy-3,
A phenyl-substituted aromatic aromatic compound characterized by polycondensation of 3'-diphenyl-diphenylsulfone, consisting of a repeating unit represented by the formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼, and having an intrinsic viscosity of 0.15 or more. Method for producing polyether sulfones. 3 Substantially equimolar amounts of 4,4'-dihalodiphenylsulfone and 4,4'-dihydroxy-3,3'-diphenyl-
A phenyl-substituted aromatic aromatic compound characterized by polycondensation of diphenyl sulfone with an alkali metal salt, which has a repeating unit represented by the formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼ and has an intrinsic viscosity of 0.15 or more. Method for producing polyether sulfones.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP9670086A JPH0686519B2 (en) | 1986-04-28 | 1986-04-28 | Heat resistant resin and its manufacturing method |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP9670086A JPH0686519B2 (en) | 1986-04-28 | 1986-04-28 | Heat resistant resin and its manufacturing method |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS62253627A true JPS62253627A (en) | 1987-11-05 |
JPH0686519B2 JPH0686519B2 (en) | 1994-11-02 |
Family
ID=14172037
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP9670086A Expired - Lifetime JPH0686519B2 (en) | 1986-04-28 | 1986-04-28 | Heat resistant resin and its manufacturing method |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH0686519B2 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0198629A (en) * | 1987-10-13 | 1989-04-17 | Idemitsu Kosan Co Ltd | Novel polysulfone resin and its production |
EP0388358A2 (en) * | 1989-03-17 | 1990-09-19 | Sumitomo Chemical Company, Limited | Polyarylene ether |
-
1986
- 1986-04-28 JP JP9670086A patent/JPH0686519B2/en not_active Expired - Lifetime
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0198629A (en) * | 1987-10-13 | 1989-04-17 | Idemitsu Kosan Co Ltd | Novel polysulfone resin and its production |
EP0388358A2 (en) * | 1989-03-17 | 1990-09-19 | Sumitomo Chemical Company, Limited | Polyarylene ether |
Also Published As
Publication number | Publication date |
---|---|
JPH0686519B2 (en) | 1994-11-02 |
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