JPS62253619A - Heat-resistant resin and production thereof - Google Patents
Heat-resistant resin and production thereofInfo
- Publication number
- JPS62253619A JPS62253619A JP9669986A JP9669986A JPS62253619A JP S62253619 A JPS62253619 A JP S62253619A JP 9669986 A JP9669986 A JP 9669986A JP 9669986 A JP9669986 A JP 9669986A JP S62253619 A JPS62253619 A JP S62253619A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- diphenyl
- substituted aromatic
- polymer
- alkali
- 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 4
- 229920006015 heat resistant resin Polymers 0.000 title description 2
- 125000003118 aryl group Chemical class 0.000 claims abstract description 21
- 229920001643 poly(ether ketone) Polymers 0.000 claims abstract description 19
- 239000003513 alkali Substances 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims abstract description 8
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 5
- -1 alkali metal salt Chemical class 0.000 claims description 11
- 229910052783 alkali metal Inorganic materials 0.000 claims description 10
- 150000001340 alkali metals Chemical class 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 3
- 230000009477 glass transition Effects 0.000 abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 8
- 239000002994 raw material Substances 0.000 abstract description 5
- 238000010521 absorption reaction Methods 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 abstract description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract description 2
- 150000003839 salts Chemical class 0.000 abstract description 2
- RBYDBPDZUIJOHN-UHFFFAOYSA-N (4-fluorophenyl)-(4-hydroxy-3,5-diphenylphenyl)methanone Chemical compound OC1=C(C=2C=CC=CC=2)C=C(C(=O)C=2C=CC(F)=CC=2)C=C1C1=CC=CC=C1 RBYDBPDZUIJOHN-UHFFFAOYSA-N 0.000 abstract 1
- ATGFTMUSEPZNJD-UHFFFAOYSA-N 2,6-diphenylphenol Chemical compound OC1=C(C=2C=CC=CC=2)C=CC=C1C1=CC=CC=C1 ATGFTMUSEPZNJD-UHFFFAOYSA-N 0.000 abstract 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 abstract 1
- 238000005727 Friedel-Crafts reaction Methods 0.000 abstract 1
- 229910052736 halogen Inorganic materials 0.000 abstract 1
- 150000002367 halogens Chemical group 0.000 abstract 1
- 239000011347 resin Substances 0.000 abstract 1
- 229920005989 resin Polymers 0.000 abstract 1
- 229920000642 polymer Polymers 0.000 description 34
- 238000006116 polymerization reaction Methods 0.000 description 17
- 239000000178 monomer Substances 0.000 description 11
- 239000002904 solvent Substances 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 8
- 125000000468 ketone group Chemical group 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- 238000002844 melting Methods 0.000 description 7
- 230000008018 melting Effects 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 6
- 125000001033 ether group Chemical group 0.000 description 5
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical group [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 238000000921 elemental analysis Methods 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 229920006158 high molecular weight polymer Polymers 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 description 3
- 235000011181 potassium carbonates Nutrition 0.000 description 3
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 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
- 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
- 229930194542 Keto Natural products 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000032683 aging Effects 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
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 150000001491 aromatic compounds Chemical class 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 2
- 239000012776 electronic material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000012778 molding material Substances 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920000570 polyether Polymers 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
- 239000011541 reaction mixture Substances 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 235000017550 sodium carbonate Nutrition 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001256 steam distillation Methods 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
- SQLQDWKOQMCACP-UHFFFAOYSA-N (4-hydroxyphenyl)-(2-phenylphenyl)methanone Chemical compound C1=CC(O)=CC=C1C(=O)C1=CC=CC=C1C1=CC=CC=C1 SQLQDWKOQMCACP-UHFFFAOYSA-N 0.000 description 1
- HLRVUOFDBXRZBI-UHFFFAOYSA-N 4-fluoro-4'-hydroxybenzophenone Chemical compound C1=CC(O)=CC=C1C(=O)C1=CC=C(F)C=C1 HLRVUOFDBXRZBI-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 238000005618 Fries rearrangement reaction Methods 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- HGTYEBNTDPDGIC-UHFFFAOYSA-N [N].[Au] Chemical group [N].[Au] HGTYEBNTDPDGIC-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 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
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012777 electrically insulating material Substances 0.000 description 1
- 229920006351 engineering plastic Polymers 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
- KEDRKJFXBSLXSI-UHFFFAOYSA-M hydron;rubidium(1+);carbonate Chemical compound [Rb+].OC([O-])=O KEDRKJFXBSLXSI-UHFFFAOYSA-M 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229940050176 methyl chloride Drugs 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000001953 recrystallisation Methods 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
- 238000007086 side reaction Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Landscapes
- Polyethers (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ケト／及びその製造
法に関するものである。さらに詳しくいえば、本発明は
、エーテル基及びケトン基金弁してフェニレン基が連結
され、かつフェニレン基の一部が２個のフェニル基で置
換されている化学構造？有し、耐熱性、耐溶剤性、低吸
湿性、低誘電率、難燃性、機械的性質などの物性に優れ
た新規な重合体及びそれ？工業的に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 ketone and its production method. More specifically, the present invention relates to a chemical structure in which a phenylene group is connected to an ether group and a ketone group, and a part of the phenylene group is substituted with two phenyl groups. A novel polymer with excellent physical properties such as heat resistance, solvent resistance, low moisture absorption, low dielectric constant, flame retardance, and mechanical properties. It relates to a method for industrial production.
従来の技術
これまで、エーテル基及びケトン基金弁してフェニレン
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
、例えば式
で示される繰り返し単位金もつ重合体が知られており、
これらは優れた耐熱性、耐溶剤性、難燃性、機械的強度
含有するために、成形材料として注目されている。BACKGROUND ART Hitherto, as a polymer compound having a structure in which phenylene groups are linked through an ether group and a ketone group, for example, a polymer having a gold repeating unit represented by the formula is known.
These materials are attracting attention as molding materials because they have excellent heat resistance, solvent resistance, flame retardancy, and mechanical strength.
しかしながら、これらのポリエーテルケト／は、そのガ
ラス転移温度及び融点が低いために利用範囲が制限され
る上に、ガラス転移温度以上の温度において剛性の低下
が著しいという欠点を有している。However, these polyether ketones have the disadvantage that their range of use is limited due to their low glass transition temperature and melting point, and that their rigidity decreases significantly at temperatures above the glass transition temperature.
このため、ガラス転移温度を上げる目的で、芳香族環に
アルキル基金導入することが試みられたが、アルキル基
金導入するとガラス転移温度は高くなるものの、重合体
自体の耐熱老化性の低下を免れない。また、ケトン基含
有量？多くしたポリエーテルケトンも知られているが、
このものは融点は十分に高くなるとしても、ガラス転移
温度はそれほど高くならないため、必ずしも満足しうる
ものとはいえない。For this reason, attempts have been made to introduce an alkyl group into the aromatic ring in order to raise the glass transition temperature, but although introducing an alkyl group increases the glass transition temperature, it inevitably reduces the heat aging resistance of the polymer itself. . Also, the ketone group content? Polyetherketone with a large amount is also known,
Although this material has a sufficiently high melting point, the glass transition temperature does not become very high, so it cannot be said to be necessarily satisfactory.
発明が解決しようとする問題点
本発明の目的はこのような事情のもとで、芳香族ポリエ
ーテルケトンが本来有する特性？損うことなく、ガラス
転移温度及び融点を大幅に高めて、より耐熱性に優れた
芳香族ポリエーテルケト／全提供することにある。Problems to be Solved by the Invention Under these circumstances, the purpose of the present invention is to solve the problems inherent in aromatic polyetherketones. The object of the present invention is to provide an aromatic polyether ketone/alloy with superior heat resistance by significantly increasing the glass transition temperature and melting point without any damage.
問題点全解決するための手段
本発明者らは鋭意研究２重ねた結果、原料として特定の
構造を有するジフェニル置換へロフェノール又はそのア
ルカリ金属塩？用い、重合して得られた特定構造の結晶
性芳香族ポリエーテルケトンが、前記目的に適合し、し
かも誘電率及び吸湿率が低いことを見出し、この知見に
基づいて本発明全完成するに至った。Means to Solve All Problems As a result of two intensive studies, the present inventors found that diphenyl-substituted herophenol or its alkali metal salt having a specific structure was used as a raw material. It was discovered that a crystalline aromatic polyetherketone having a specific structure obtained by polymerization and polymerization is suitable for the above purpose and has a low dielectric constant and moisture absorption rate, and based on this knowledge, the present invention was completed. Ta.
すなわち、本発明は、式
で表わされる繰り返し単位から成シ、かつ０，１５以゛
上の極限粘度？有するジフェニル置換芳香族ポリエー
テルケトンを提供するものであり、このものは、一般式
（式中のＸはハロゲン原子である）
で表わされるジフェニル置換芳香族へロフェノールをア
ルカリの存在下に重合するか、又は前記一般式動で表わ
されるジフェニル置換芳香族へロフェノールのアルカリ
金属塩を重合することによって製造することができる。That is, the present invention is composed of repeating units represented by the formula and has an intrinsic viscosity of 0.15 or more. The present invention provides a diphenyl-substituted aromatic polyetherketone having a diphenyl-substituted aromatic polyetherketone having the general formula (wherein Alternatively, it can be produced by polymerizing an alkali metal salt of a diphenyl-substituted aromatic herophenol represented by the above general formula.
本発明において、原料単量体としそ用いられる前記一般
式蜀で泰わされるジフェニル置換芳香族・・ロフェノー
ルは新規化合物であり、例えばｐ−ハロゲノベンゾイル
クロリドと２，６−ジフェニルフェノールとを塩化アル
ミニウムなどの触媒全周いて７リ一デルクラフト反応さ
せることによって製造することができるし、また２、６
−シフエニルフエニルー４′−ハロゲノベンゾエートの
フリース転位によっても製造することができる。In the present invention, the diphenyl-substituted aromatic compound phenol having the general formula: It can be produced by a 7-Lidell-Crafts reaction using a catalyst such as aluminum chloride, and 2,6
It can also be produced by Fries rearrangement of -siphenylphenyl-4'-halogenobenzoate.
また、本発明において用いられるもう−りの原料単量体
である、一般式
（式中のＸはハロゲン原子、Ｍはアルカリ金属である）
で表わされるジ７工二ル置換芳香族へロフェノールのア
ルカリ金属塩は、例えば前記一般式■で衆わされるジフ
ェニル置換芳香族へロフェノールトアルカリ金属の水酸
化物とを反応させることによって製造することができる
。Further, another raw material monomer used in the present invention, a di-7-enyl-substituted aromatic helophenol represented by the general formula (in the formula, X is a halogen atom and M is an alkali metal) The alkali metal salt can be produced, for example, by reacting a diphenyl-substituted aromatic helophenol represented by the general formula (1) with an alkali metal hydroxide.
前記一般式動で表わされる原料単量体としては、４−フ
ルオロ−３？ ｓ／−ジフェニル−４′−ヒドロキシベ
ンゾフェノ／や４−クロロ−３τダージフエ二ル−４′
−ヒドロキシベンゾフェノンなどがある。The raw material monomer represented by the above general formula is 4-fluoro-3? s/-diphenyl-4'-hydroxybenzopheno/ or 4-chloro-3τdiphenyl-4'
-Hydroxybenzophenone, etc.
本発明のポリエーテルケト／の製造に際しては、これら
の単量体をそれぞれ単独で用いてもよいし１２種以上組
み合わせて用いてもよい。また、前記一般式（至）で表
わされる原料単量体としては、４−フルオロ−３？５’
−ジフェニル−４／−ヒ）’ ｏ キシベンゾフェノン
のナトリウム塩やカリウム塩、４−クロロ−３？ ５’
−ジフェニル−４′−ヒドロキシベンゾフェノンのナ
トリウム塩やカリウム塩などがある。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。In producing the polyether keto/ of the present invention, these monomers may be used alone or in combination of 12 or more. In addition, as the raw material monomer represented by the general formula (to), 4-fluoro-3?5'
-diphenyl-4/-hi)' o Sodium salt or potassium salt of xybenzophenone, 4-chloro-3? 5'
Examples include sodium salt and potassium salt of -diphenyl-4'-hydroxybenzophenone. These may be used alone or in combination of two or more.
また、これらの単量体の中で、４−フルオロ−３？ ５
’ −ジフェニル−４′−ヒドロキシベンゾフェノン及
びそのアルカリ金属塩は反応性に富み、かつ熱安定性の
良好な重合体が得られるので好適でおる。さらに、本発
明においては、得られる重合体の特性を損わない範囲で
、少量の４−フルオロ−４′−ヒドロキシベンゾフェノ
ン又はそのアルカリ金ＦＡ塩？、前記４−フルオロ−３
？ ｓ／−ジフェニル−４′−ヒドロキシベンゾフェノ
ン又はそのアルカリ金属塩にそれぞれ組み合わせて用い
てもよい０本発明においては、重合反応は溶媒の存在下
又は不存在下に行うことができるが、一般に溶媒の存在
下に行つことが望ましい。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／、スルホラン
などのスルホン化合物などが好ましく、特に芳香族系化
合物が好適である。Also, among these monomers, 4-fluoro-3? 5
'-Diphenyl-4'-hydroxybenzophenone and its alkali metal salts are preferred because they are highly reactive and provide polymers with good thermal stability. Furthermore, in the present invention, a small amount of 4-fluoro-4'-hydroxybenzophenone or its alkali gold FA salt is used within a range that does not impair the properties of the resulting polymer. , the 4-fluoro-3
? May be used in combination with s/-diphenyl-4'-hydroxybenzophenone or its alkali metal salt. In the present invention, the polymerization reaction can be carried out in the presence or absence of a solvent, but generally the It is desirable to go in the presence. The solvent used in this case is preferably, for example, a ketone compound such as xanthone, benzophenone, phenoxybenzophenone, or dibenzoylbenzene, or a sulfone compound such as diphenylsulfone, ditolylsulfo/sulfolane, or sulfolane, and aromatic compounds are particularly preferred.
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、特に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る。このような化合物とし
ては、例えば炭酸ナトリウム、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。ま九、
これらの中で、特に好適なのは炭酸ナトリウム、炭酸カ
リウム、炭酸水素ナトリウム、炭酸水素カリウムである
。Examples of the alkali used in the present invention include alkali metal carbonates, alkali metal bicarbonates, and alkali metal hydroxides, with alkali metal carbonates and alkali metal bicarbonates being particularly preferred. Examples of such compounds include sodium carbonate, 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. Maku,
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、前記一般式頭で表わされる単量体
１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ＩＪ ？過剰に使用す
ると、反応が激しくなシすぎて、有害な副反応の原因と
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０．３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 used in proportions such that the amount of alkali metal atoms is 0.3 to 2 gram atoms, preferably 0.5 to 1.2 gram atoms, per mol of the monomer represented by the above general formula. used in The Arca IJ? If used in excess, the reaction will be too vigorous, causing harmful side reactions and also being 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 0.3 gram atoms, the reaction rate is slow and it becomes difficult to obtain a polymer with a desired high molecular weight.
次に、本発明における重合について、好ましい実施態様
の例？示すと、所定の溶媒中に前記一般式ωで表わされ
る単量体とアルカリの所定量？添加し九混合物、又は所
望の溶媒中に前記一般式（Ｖ）で表わされる単量体の所
定量？添加した混合物？、例えば窒素、アルゴンなどの
不活性ガス雰囲気下で加熱し、好ましくは２００〜４０
０℃、さらに好ましくは２５０〜３５０℃の範囲の温度
において重合反応を行う。反応温度が２００℃未満では
高分子量の重合体が得られに＜（、一方４００℃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, what are some examples of preferred embodiments of polymerization in the present invention? If the amount of the monomer represented by the general formula ω and the alkali in the given solvent is ? Adding a predetermined amount of the monomer represented by the general formula (V) to a mixture or a desired solvent? Added mixture? , for example, under an inert gas atmosphere such as nitrogen or argon, preferably at a temperature of 200 to 40
The polymerization reaction is carried out at a temperature in the range of 0°C, more preferably 250-350°C. If the reaction temperature is less than 200° C., a high molecular weight polymer cannot be obtained. On the other hand, if the reaction temperature exceeds 400° C., the resulting polymer will be undesirably colored due to deterioration.
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？得るためには、重合温度は最
終的には２００℃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。Also, a high molecular weight polymer? In order to obtain this, it is necessary to ultimately set the polymerization temperature to 200° C. or higher, but prepolymerization at a temperature lower than that is also an advantageous method.
一般式潤で表わされる単量体？アルカリの存在下で重合
する場合、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い。除去する方法どしては、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。A monomer expressed by the general formula Jun? When polymerizing in the presence of an alkali, water is generated during the polymerization, but it is desirable to remove this water from the system. Methods for removal include introducing a dry inert gas into the polymerization system or replacing the gas phase with the inert gas, or adding a solvent that is azeotropic with water to the polymerization system and distilling it out of the system together with the solvent. Methods such as removing the material 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、具体的にはジクロ口ジ７二二ルスルホン
、ジフルオロベンゾフェノン１モノフルオロベンゾフエ
ノン、塩化メチルなト金反応系に添加、反応させること
により停止させることができ、ま念これによってポリマ
ー鎖の末端全安定化できる。The polymerization reaction is carried out by adding a suitable terminal capping agent, such as a monofunctional or polyfunctional halide, specifically, dichloro-di722lsulfone, difluorobenzophenone, monofluorobenzophenone, or methyl chloride to the gold reaction system. The polymer chain can be terminated by this, and the entire terminal end of the polymer chain can be stabilized by this.
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結晶性の高分子量重合体であ
る。The thus obtained polymer of the present invention is a crystalline 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０３１５以上のものであり
、フィルム？得るためには０．３以上のものが、特に強
靭なフィルム全必要とする場合は０．６以上のものが好
ましい。この極限粘度が０．１５未満のものは重合体と
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 0315 or more, and has a film? A value of 0.3 or more is preferable in order to obtain a film, and a value of 0.6 or more is preferable when a particularly strong film is required. A polymer having an intrinsic viscosity of less than 0.15 exhibits no properties as a polymer and is unsuitable.
発明の効果
本発明の芳香族ポリエーテルケト／は、エーテル基及び
ケト／基を介してフェニレン基が連結され、かつフェニ
レン基の一部が２個のフェニル基で置換されている化学
構造？有する新規な重合体であり、従来のポリエーテル
ケトンに比べて融点及びガラス転移温度がはるかに高い
上に、分子中にベンゼン環が多く含まれ、極性基である
ケトン基やエーテル基の含有量が少ないため、吸湿性及
び誘電率が低く、特に電子材料として好適である。Effects of the Invention The aromatic polyether keto/ of the present invention has a chemical structure in which phenylene groups are connected via an ether group and a keto/ group, and a part of the phenylene group is substituted with two phenyl groups. It is a new polymer with a much higher melting point and glass transition temperature than conventional polyetherketones, and it also contains many benzene rings in the molecule and has a high content of polar groups such as ketone groups and ether groups. Because of its low hygroscopicity and dielectric constant, it is particularly suitable as an electronic material.
また、重合体の耐熱老化性については、ベンゼン環とケ
トン基とエーテル基しか含まないため、従来のポリエー
テルケトンと同程度に優れている。In addition, the heat aging resistance of the polymer is as good as that of conventional polyetherketone because it contains only benzene rings, ketone groups, and ether groups.
したがって、本発明のジフェニル置換芳香族ポリエーテ
ルケトンは高温下で厳しい条件で使用される成形材料と
して好適である。この重合体は圧意の所望の形状、例え
ば成形品、被覆、フィルム、繊維などにして用いること
ができ、さらに各種のエンジニアリングプラスチック、
ポリエーテルケトン、ポリエーテルスルホン、ポリフェ
ニレンスルフイドなどの耐熱性樹脂、ガラス繊維、炭素
繊維、無機質などと混合し、アロイ化やコンポジット化
して使用することができる。Therefore, the diphenyl-substituted aromatic polyetherketone of the present invention is suitable as a molding material used under severe conditions at high temperatures. This polymer can be used in any desired shape, such as molded products, coatings, films, fibers, etc., and can also be used in various engineering plastics,
It can be mixed with heat-resistant resins such as polyetherketone, polyethersulfone, and polyphenylene sulfide, glass fibers, carbon fibers, inorganic materials, etc., and used as an alloy or composite.
実施例
次に実施例により本発明をさらに詳細に説明子し
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。EXAMPLES Next, the present invention will be explained in more detail by examples, but the present invention is not limited to these examples in any way.
なお、本発明の重合体は、わずかに濃硫酸にとけるのみ
で、一般の有機溶媒には不溶であるので、平均分子量を
求めることが困難である。したがって、極限粘度をもっ
て分子量の尺度とする。The polymer of the present invention is only slightly soluble in concentrated sulfuric acid and is insoluble in general organic solvents, so it is difficult to determine its average molecular weight. Therefore, the intrinsic viscosity is used as a measure of molecular weight.
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
密度１．８４Ｐ／ｉの濃硫酸全使用し、溶液ＩＱＯｉ当
シ重合体０．１ｆｋ含む溶液と溶液１００ｉ当９重合体
０．５ｆｔ−含む溶液を調製し、その粘度を２５℃で測
定し、式
％式％
〔ただし、？７ ｒｅ！は相対粘度、Ｃは濃度（ｒ／１
００−）であり、Ｃ→０は（＋７ｒｅ！−１）／Ｃの値
を濃度ＣがＯの点に外挿したこと？意味する〕を用いて
求めた。(1) Using concentrated sulfuric acid with an intrinsic viscosity density of 1.84 P/i, prepare a solution containing 0.1 fk of polymer per solution IQOi and a solution containing 0.5 ft of 9 polymer per 100 i of solution, and reduce the viscosity to 25 Measured in °C, formula % formula % [However? 7 re! is the relative viscosity, C is the concentration (r/1
00-), and C→0 means extrapolating the value of (+7re!-1)/C to the point where the concentration C is O? [meaning]] was used.
（２）結晶融点（Ｔｍ） 、ガラス転移温度（１ｇ）ｎ
ｓｃ（示差走査熱量計）により昇温速度１０’Ｃ／ｍｉ
ｎで測定した。(2) Crystal melting point (Tm), glass transition temperature (1g) n
Temperature increase rate 10'C/mi by sc (differential scanning calorimeter)
Measured at n.
１ｔの三つロフラスコに、ニトロペンゼ／４００ｍ、ｐ
−フルオロベンゾイルクロリド３ｕ、７ｒ（２００ミリ
モル）及び塩化アルミニウム２９．４ Ｆ （２２０ミ
リモル）を投入し、系内金窒素置換したのち、これに２
．６−ジフェニルフェノール４９．２ Ｆ （２００ミ
リモル）を徐々に添加し、８０℃で反応させた。Nitropense/400m, p in a 1t three-necked flask
- Fluorobenzoyl chloride 3u, 7r (200 mmol) and aluminum chloride 29.4 F (220 mmol) were introduced, the system was replaced with gold nitrogen, and then 2
．． 6-diphenylphenol 49.2 F (200 mmol) was gradually added and reacted at 80°C.
反応終了後、塩酸を加え反応混合物？水蒸気蒸留してニ
トロベンゼンを留去した。次いで、水蒸気蒸留残液よシ
固形物をろ別し、再結晶して精製した。このものは、融
点が１６２．５〜１６３．５℃であシ、元素分析、工Ｒ
スペクトル（第１図）及びＮＭＲスペクトルより、４−
フルオｏ−３ｊダージフェニル−４′−ヒドロキシベン
ゾフェノンであることを確認した。After the reaction is complete, add hydrochloric acid to form a reaction mixture. Nitrobenzene was removed by steam distillation. Next, solid matter was filtered from the steam distillation residue and purified by recrystallization. This material has a melting point of 162.5-163.5°C, elemental analysis, and engineering R.
From the spectrum (Fig. 1) and NMR spectrum, 4-
It was confirmed that it was fluoro-3jdiphenyl-4'-hydroxybenzophenone.
元素分析結果
ＣＥ（ＯＦ
実測値（チ） ８１．３ ４．８ ８．９ ５．
０計算値（チ） ８１．５ ４．７ ８．７ ５
．２（Ｃ，Ｈｌ、０２Ｆとして）
４−フルオロ−３？５′−ジフェニル−４′−ヒドロキ
シベンゾフェノンを等モルの水酸化カリウムを含む１規
定のＫＯＨ水溶液に溶解したのち、二ノくボレーターで
水分を留去し、次いで９０℃で１０時間真空乾燥して、
４−フルオロ−３でゲージフェニル−４′−ヒドロキシ
ベンゾフエノンのカリウム塩を得た。Elemental analysis result CE (OF Actual value (CH) 81.3 4.8 8.9 5.
0 calculated value (ch) 81.5 4.7 8.7 5
．． 2 (as C, Hl, 02F) 4-fluoro-3?5'-diphenyl-4'-hydroxybenzophenone was dissolved in a 1N KOH aqueous solution containing equimolar potassium hydroxide, and then water was removed using a Ninoku borator. evaporated and then vacuum dried at 90°C for 10 hours.
The potassium salt of gauge phenyl-4'-hydroxybenzophenone was obtained with 4-fluoro-3.
実施例１
かきまぜ機、窒素導入管及び冷却器を備えたセパラブル
フラスコに、４−フルオロ−３τ５′−ジフェニル−４
′−ヒドロキシベンゾフェノン２２．０ｆ（０，０６モ
ル）、無水炭酸カリウム４．４ ｆ （０，０３モル）
及びベンゾフェノ７４０ Ｐｉ投入し、窒素雰囲気下に
加熱？開始し、系中の水分を窒素ガスによシ系外へ除去
しながら３２０℃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′−ジフルオロベ
ンシフエノン２ ｔ ｆ 添加して、３０分間反応させ
た。Example 1 4-Fluoro-3τ5'-diphenyl-4 was placed in a separable flask equipped with a stirrer, a nitrogen inlet tube, and a condenser.
'-Hydroxybenzophenone 22.0 f (0.06 mol), anhydrous potassium carbonate 4.4 f (0.03 mol)
and benzopheno 740 Pi and heated under nitrogen atmosphere? The temperature was raised to 320°C while water in the system was removed from the system using nitrogen gas, and polymerization was carried out at that temperature for 6 hours. t f was added and allowed to react for 30 minutes.
反応終了後、冷却して得られた固形換金粉砕し、温アセ
トンで２回、温湯で２回、さらに温アセトンで１回洗浄
して重合体粉末？得た。After the reaction is completed, the solid obtained by cooling is pulverized and washed twice with warm acetone, twice with hot water, and once with warm acetone to obtain a polymer powder. Obtained.
得られた重合体の極限粘度は０．９５であシ、融点（Ｔ
ｍ）は４０２℃、ガラス転移温度（Ｔｇ）は２１８℃で
あった。また、重合体はゲルを含まず濃硫酸に完全に溶
解した。The intrinsic viscosity of the obtained polymer was 0.95, and the melting point (T
m) was 402°C, and the glass transition temperature (Tg) was 218°C. Furthermore, the polymer did not contain any gel and was completely dissolved in concentrated sulfuric acid.
さらに、塩化メチノン、クロロホルム、Ｎ、Ｎ−ジメチ
ルホルムアミド、スルホラン、ジメチルスルホキシド、
ヘキサン、トルエンなどの溶媒に室温では溶解しなかつ
次。Furthermore, methinone chloride, chloroform, N,N-dimethylformamide, sulfolane, dimethyl sulfoxide,
It does not dissolve in solvents such as hexane and toluene at room temperature.
この重合体のＸ線回折チャート、工Ｒ分析チャート全そ
れぞれ第２図、第３図に示す。The entire X-ray diffraction chart and engineering R analysis chart of this polymer are shown in FIGS. 2 and 3, respectively.
重合体の元素分析の結果は、
ＣＨＯ
実測値（チ） ８６．３ ４．４ ９．３計
算値（％） ８６．２ ４．６ ９．２（−
Ｈｌ、Ｏ，として）
であシ、この重合体は、
の構造金もつものであることが確かめられた。The results of elemental analysis of the polymer are as follows: CHO Actual value (CH) 86.3 4.4 9.3 Calculated value (%) 86.2 4.6 9.2 (-
It was confirmed that this polymer had the following structure: (Hl, O,).
この重合体？４３０℃で４分間プレスして得られたフィ
ルムは繰り返し折シ曲げに対して極めて丈夫なものであ
シ、このフィルムの引張シ強度は７ｃｉｏＫｐ／ｃｒ１
１破断時伸びは１２０チであった（測定法ＡＳＴＭ ｐ
ｓｓｚ ）。This polymer? The film obtained by pressing at 430°C for 4 minutes is extremely durable against repeated bending, and the tensile strength of this film is 7cioKp/cr1.
The elongation at break was 120 inches (measurement method ASTM p
ssz).
この重合体のＩ ＫＨｚにおける誘電率は２．８であり
、置換基金倉まないポリエーテルケトン４ｃ４ｏ六の誘
電率３．３よりも低く、低誘電率電子材料として好適で
ある。測定はＡＳＴＭ Ｄ １５０に従って行った。The dielectric constant of this polymer at I KHz is 2.8, which is lower than the dielectric constant of polyetherketone 4c4o6, which does not have a substitution fund, of 3.3, and is suitable as a low dielectric constant electronic material. Measurements were performed according to ASTM D 150.
また、この重合体の吸水率（４０＄Ｒ）Ｘ、２４時間）
は０．１３チでおり、置換基を含まない前記ポリエーテ
ルケト／の０．１５１よシも低く、電気絶縁材料として
好適である。Also, the water absorption rate of this polymer (40$R)X, 24 hours)
is 0.13, which is lower than 0.151 of the polyether ketone containing no substituents, and is suitable as an electrically insulating material.
さらに、この重合体について、ＴＧＡ’ｉ用いて熱減量
を測定したところ５００″Ｃ″！ｆ：では減量金示さず
、５重量％熱減量温度は５５０’Ｃでおった（第４図）
。Furthermore, when the thermal loss of this polymer was measured using TGA'i, it was 500''C''! f: No gold loss was shown, and the 5% heat loss temperature was 550'C (Figure 4)
.
実施例２〜５
単量体、アルカリ、重合溶媒、重合温度及び重合時間に
ついては次表に示す条件で重合７行い、その他の条件は
実施例１と同様な方法で重合７行った。得られた重合体
の極限粘度を次表に示す。Examples 2 to 5 Polymerization 7 was conducted under the conditions shown in the following table regarding the monomer, alkali, polymerization solvent, polymerization temperature, and polymerization time, and the other conditions were the same as in Example 1. The intrinsic viscosity of the obtained polymer is shown in the following table.
実施例６
４−フルオロ−３τ５′−ジフェニル−４′−ヒドロキ
シベンゾフェノンのカリウム塩２４．４ ｆ （０，０
６モル）トジフェニルスルホン４０ｆ’ｆｌ−かきます
機、窒素導入管及び冷却器を備え九セパラブルフラスコ
に仕込み、窒素雰囲気下、３２０℃で６時間反応させた
。次いで、反応混合物を実施例１と同様な処理を行い、
極限粘度０．７８のフェニル置換芳香族ポリエーテルケ
トンを得た。Example 6 Potassium salt of 4-fluoro-3τ5'-diphenyl-4'-hydroxybenzophenone 24.4 f (0,0
6 mol) Todiphenylsulfone (40 f'fl) was charged into a nine separable flask equipped with a stirrer, a nitrogen inlet tube and a condenser, and reacted at 320° C. for 6 hours under a nitrogen atmosphere. The reaction mixture was then treated in the same manner as in Example 1,
A phenyl-substituted aromatic polyetherketone with an intrinsic viscosity of 0.78 was obtained.
第１図は本発明に用いられる単量体４−フルオロ−３？
ｓ／−ジフェニル−４′−ヒドロキシベンゾフェノン
の工Ｒスペクトルチャート、第２図、第３図及び第４図
は、それぞれ本発明重合体の実施例のＸ線回折スペクト
ルチャート、工Ｒスペクトルチャート及び熱減量チャー
トである。Figure 1 shows the monomer 4-fluoro-3? used in the present invention.
s/-diphenyl-4'-hydroxybenzophenone, Fig. 2, Fig. 3, and Fig. 4 are the X-ray diffraction spectrum chart, the Fig. 4 R spectrum chart, and the thermal R spectrum chart of Examples of the polymer of the present invention, respectively. This is a weight loss chart.
Claims (1)
の極限粘度を有するジフェニル置換芳香族ポリエーテル
ケトン。 ２ アルカリの存在下、一般式 ▲数式、化学式、表等があります▼ （式中のＸはハロゲン原子である） で表わされるジフェニル置換芳香族ハロフェノールを重
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ジフェニル置換芳香族ポリエーテル
ケトンの製造法。 ３ 一般式 ▲数式、化学式、表等があります▼ （式中のＸはハロゲン原子、Ｍはアルカリ金属である） で表わされるジフェニル置換芳香族ハロフェノールのア
ルカリ金属塩を重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ジフェニル置換芳香族ポリエーテル
ケトンの製造法。[Claims] 1. A diphenyl-substituted aromatic polyether ketone 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 Formula ▲Mathematical formula characterized by polymerizing diphenyl-substituted aromatic halophenol represented by the general formula ▲Mathematical formula, chemical formula, table, etc.▼ (X in the formula is a halogen atom) in the presence of an alkali. , chemical formula, table, etc. ▼ A method for producing a diphenyl-substituted aromatic polyetherketone that is composed of repeating units represented by and has an intrinsic viscosity of 0.15 or more. 3. It is characterized by polymerizing an alkali metal salt of diphenyl-substituted aromatic halophenol represented by the general formula ▲ Numerical formula, chemical formula, table, etc. ▼ (X in the formula is a halogen atom, M is an alkali metal) , a method for producing a diphenyl-substituted aromatic polyether ketone consisting of repeating units represented by the formula ▲ Numerical formula, chemical formula, table, etc.▼ and having an intrinsic viscosity of 0.15 or more.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9669986A JPH0676487B2 (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 |
|---|---|---|---|
| JP9669986A JPH0676487B2 (en) | 1986-04-28 | 1986-04-28 | Heat resistant resin and its manufacturing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62253619A true JPS62253619A (en) | 1987-11-05 |
| JPH0676487B2 JPH0676487B2 (en) | 1994-09-28 |
Family
ID=14172010
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9669986A Expired - Lifetime JPH0676487B2 (en) | 1986-04-28 | 1986-04-28 | Heat resistant resin and its manufacturing method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0676487B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104262127A (en) * | 2014-09-28 | 2015-01-07 | 陕西师范大学 | Brush-type difluoro monomer and synthetic method thereof |
-
1986
- 1986-04-28 JP JP9669986A patent/JPH0676487B2/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104262127A (en) * | 2014-09-28 | 2015-01-07 | 陕西师范大学 | Brush-type difluoro monomer and synthetic method thereof |
| CN104262127B (en) * | 2014-09-28 | 2015-12-30 | 陕西师范大学 | Brush-type two fluorine monomer and synthetic method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0676487B2 (en) | 1994-09-28 |
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