JP2023005590A - Polyarylene ether ketone resin and method for producing the same, and molding - Google Patents
Polyarylene ether ketone resin and method for producing the same, and molding Download PDFInfo
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- 229920005989 resin Polymers 0.000 title claims abstract description 95
- 239000011347 resin Substances 0.000 title claims abstract description 95
- -1 ether ketone Chemical class 0.000 title claims abstract description 31
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 229920000412 polyarylene Polymers 0.000 title claims abstract description 21
- 238000004519 manufacturing process Methods 0.000 title claims description 18
- 238000000465 moulding Methods 0.000 title description 7
- 239000000178 monomer Substances 0.000 claims description 53
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims description 21
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 12
- 238000002844 melting Methods 0.000 abstract description 18
- 230000008018 melting Effects 0.000 abstract description 18
- 230000009477 glass transition Effects 0.000 abstract description 13
- 229920001643 poly(ether ketone) Polymers 0.000 abstract description 7
- 229920001955 polyphenylene ether Polymers 0.000 abstract 1
- 229920000642 polymer Polymers 0.000 description 66
- 229920006260 polyaryletherketone Polymers 0.000 description 57
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 45
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 39
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 38
- 239000000203 mixture Substances 0.000 description 36
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 30
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 28
- 238000009835 boiling Methods 0.000 description 24
- WVDRSXGPQWNUBN-UHFFFAOYSA-N 4-(4-carboxyphenoxy)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1OC1=CC=C(C(O)=O)C=C1 WVDRSXGPQWNUBN-UHFFFAOYSA-N 0.000 description 22
- 238000002425 crystallisation Methods 0.000 description 18
- 230000008025 crystallization Effects 0.000 description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 16
- 229940098779 methanesulfonic acid Drugs 0.000 description 15
- 229910052757 nitrogen Inorganic materials 0.000 description 14
- UVGPELGZPWDPFP-UHFFFAOYSA-N 1,4-diphenoxybenzene Chemical compound C=1C=C(OC=2C=CC=CC=2)C=CC=1OC1=CC=CC=C1 UVGPELGZPWDPFP-UHFFFAOYSA-N 0.000 description 11
- 238000010992 reflux Methods 0.000 description 11
- 239000000243 solution Substances 0.000 description 10
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 238000001914 filtration Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 239000012046 mixed solvent Substances 0.000 description 8
- 125000003118 aryl group Chemical group 0.000 description 7
- 238000010792 warming Methods 0.000 description 7
- 238000001816 cooling Methods 0.000 description 6
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 6
- 238000006068 polycondensation reaction Methods 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- 238000007336 electrophilic substitution reaction Methods 0.000 description 4
- 229920001652 poly(etherketoneketone) Polymers 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 230000004580 weight loss Effects 0.000 description 4
- LSQARZALBDFYQZ-UHFFFAOYSA-N 4,4'-difluorobenzophenone Chemical compound C1=CC(F)=CC=C1C(=O)C1=CC=C(F)C=C1 LSQARZALBDFYQZ-UHFFFAOYSA-N 0.000 description 3
- 239000004696 Poly ether ether ketone Substances 0.000 description 3
- 125000001033 ether group Chemical group 0.000 description 3
- 239000012765 fibrous filler Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 125000000468 ketone group Chemical group 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 229920002530 polyetherether ketone Polymers 0.000 description 3
- 239000011342 resin composition Substances 0.000 description 3
- NXTDJHZGHOFSQG-UHFFFAOYSA-N 3-phenoxybenzoic acid Chemical compound OC(=O)C1=CC=CC(OC=2C=CC=CC=2)=C1 NXTDJHZGHOFSQG-UHFFFAOYSA-N 0.000 description 2
- RYAQFHLUEMJOMF-UHFFFAOYSA-N 4-phenoxybenzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1OC1=CC=CC=C1 RYAQFHLUEMJOMF-UHFFFAOYSA-N 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- 229920004695 VICTREX™ PEEK Polymers 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- JUPQTSLXMOCDHR-UHFFFAOYSA-N benzene-1,4-diol;bis(4-fluorophenyl)methanone Chemical compound OC1=CC=C(O)C=C1.C1=CC(F)=CC=C1C(=O)C1=CC=C(F)C=C1 JUPQTSLXMOCDHR-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 150000001875 compounds Chemical class 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
- 229920006351 engineering plastic Polymers 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000010534 nucleophilic substitution 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
- 238000000926 separation method Methods 0.000 description 2
- 238000004904 shortening Methods 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- GQGTXJRZSBTHOB-UHFFFAOYSA-N 1-phenoxy-4-(4-phenoxyphenoxy)benzene Chemical compound C=1C=C(OC=2C=CC(OC=3C=CC=CC=3)=CC=2)C=CC=1OC1=CC=CC=C1 GQGTXJRZSBTHOB-UHFFFAOYSA-N 0.000 description 1
- CULWHZJWAKFHMK-UHFFFAOYSA-N 3-(4-carboxyphenoxy)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1OC1=CC=CC(C(O)=O)=C1 CULWHZJWAKFHMK-UHFFFAOYSA-N 0.000 description 1
- RXNYJUSEXLAVNQ-UHFFFAOYSA-N 4,4'-Dihydroxybenzophenone Chemical compound C1=CC(O)=CC=C1C(=O)C1=CC=C(O)C=C1 RXNYJUSEXLAVNQ-UHFFFAOYSA-N 0.000 description 1
- WBPQEFPQYPXLSK-UHFFFAOYSA-N 4-(4-phenoxyphenoxy)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1OC(C=C1)=CC=C1OC1=CC=CC=C1 WBPQEFPQYPXLSK-UHFFFAOYSA-N 0.000 description 1
- QVLMBWTVLGOLHI-UHFFFAOYSA-N 4-[4-(4-carboxyphenoxy)phenoxy]benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1OC(C=C1)=CC=C1OC1=CC=C(C(O)=O)C=C1 QVLMBWTVLGOLHI-UHFFFAOYSA-N 0.000 description 1
- BNNMDMGPZUOOOE-UHFFFAOYSA-N 4-methylbenzenesulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1.CC1=CC=C(S(O)(=O)=O)C=C1 BNNMDMGPZUOOOE-UHFFFAOYSA-N 0.000 description 1
- AOOZVQGGMFGGEE-UHFFFAOYSA-N 4-phenoxybenzoyl chloride Chemical compound C1=CC(C(=O)Cl)=CC=C1OC1=CC=CC=C1 AOOZVQGGMFGGEE-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 102100021202 Desmocollin-1 Human genes 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 101000968043 Homo sapiens Desmocollin-1 Proteins 0.000 description 1
- 101000880960 Homo sapiens Desmocollin-3 Proteins 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- CCIVGXIOQKPBKL-UHFFFAOYSA-M ethanesulfonate Chemical compound CCS([O-])(=O)=O CCIVGXIOQKPBKL-UHFFFAOYSA-M 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000007943 implant Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- LEMQFBIYMVUIIG-UHFFFAOYSA-N trifluoroborane;hydrofluoride Chemical compound F.FB(F)F LEMQFBIYMVUIIG-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- Polyethers (AREA)
Abstract
Description
本発明は、ポリアリーレンエーテルケトン樹脂及びその製造方法、並びに成形体に関する。 TECHNICAL FIELD The present invention relates to a polyarylene ether ketone resin, a method for producing the same, and a molded article.
ポリアリーレンエーテルケトン樹脂（以下「ＰＡＥＫ樹脂」と略すことがある。）は、耐熱性、耐薬品性、強靭性等に優れ、高温で連続使用可能な結晶性スーパーエンプラとして、電気電子部品、自動車部品、医療用部品、繊維、フィルム用途等に幅広く利用されている。 Polyarylene ether ketone resin (hereinafter sometimes abbreviated as "PAEK resin") is excellent in heat resistance, chemical resistance, toughness, etc., and is a crystalline super engineering plastic that can be used continuously at high temperatures. Widely used for parts, medical parts, fibers, films, etc.
従来、ＰＡＥＫ樹脂としては、４，４’－ジフルオロベンゾフェノンとハイドロキノンの２つのモノマーを、ジフェニルスルホン中で炭酸カリウムを用いた芳香族求核置換型溶液重縮合反応（例えば、特許文献１参照）により製造される、１つの繰り返し単位中に２つのエーテル基と１つのケトン基を持つポリエーテルエーテルケトン樹脂（以下「ＰＥＥＫ樹脂」と略すことがある。）がよく知られている。
また、ハイドロキノンの代わりに、４，４’－ジヒドロキシベンゾフェノンを使用することで製造される、１つの繰り返し単位中にエーテル基、ケトン基を１つずつ持つポリエーテルケトン樹脂（以下「ＰＥＫ樹脂」と略すことがある。）や、１つの繰り返し単位中に１つのエーテル基、２つのケトン基を有するポリエーテルケトンケトン樹脂（以下「ＰＥＫＫ樹脂」と略すことがある。）もある。
Conventionally, as a PAEK resin, two monomers, 4,4'-difluorobenzophenone and hydroquinone, are subjected to an aromatic nucleophilic substitution type solution polycondensation reaction using potassium carbonate in diphenylsulfone (see, for example, Patent Document 1). Polyether ether ketone resins having two ether groups and one ketone group in one repeating unit (hereinafter sometimes abbreviated as "PEEK resin") are well known.
In addition, instead of hydroquinone, a polyether ketone resin having one ether group and one ketone group in one repeating unit (hereinafter referred to as "PEK resin") is produced by using 4,4'-dihydroxybenzophenone. ) and polyether ketone ketone resin (hereinafter sometimes abbreviated as "PEKK resin") having one ether group and two ketone groups in one repeating unit.
しかしながら、これらのＰＡＥＫ樹脂の製造に用いられている芳香族求核置換型溶液重縮合反応は、モノマーに高価な４，４’－ジフルオロベンゾフェノンを使用するため原料費が高く、かつ、反応温度が３００℃以上で製造工程費も高いという欠点があり、樹脂の価格が高くなる傾向にある。 However, the aromatic nucleophilic substitution type solution polycondensation reaction used in the production of these PAEK resins uses expensive 4,4'-difluorobenzophenone as a monomer, so the raw material cost is high and the reaction temperature is high. There is a drawback that the manufacturing process cost is high at 300° C. or higher, and the price of the resin tends to be high.
そこで、モノマーに４，４’－ジフルオロベンゾフェノンを用いることなく、かつ、温和な重合条件で、ＰＡＥＫ樹脂を製造する芳香族求電子置換型溶液重縮合反応が知られている。
芳香族求電子置換型溶液重縮合反応を用いた例として、４－フェノキシ安息香酸クロリドをフッ化水素－三フッ化ホウ素の存在下で反応させる方法によるＰＥＫ樹脂（例えば、特許文献２参照）、テレフタル酸クロリドとジフェニルエーテルをルイス酸の存在下で反応させる方法によるＰＥＫＫ樹脂（例えば、特許文献３参照）、４－フェノキシ安息香酸をメタンスルホン酸と五酸化二リンの混合物存在下で反応させる方法によるＰＥＫ樹脂（例えば、特許文献４参照）等がある。
Therefore, an aromatic electrophilic substitution solution polycondensation reaction is known that produces a PAEK resin under mild polymerization conditions without using 4,4'-difluorobenzophenone as a monomer.
As an example using an aromatic electrophilic substitution type solution polycondensation reaction, a PEK resin obtained by a method of reacting 4-phenoxybenzoic acid chloride in the presence of hydrogen fluoride-boron trifluoride (see, for example, Patent Document 2), By a method of reacting terephthalic acid chloride and diphenyl ether in the presence of a Lewis acid PEKK resin (see, for example, Patent Document 3), by a method of reacting 4-phenoxybenzoic acid in the presence of a mixture of methanesulfonic acid and diphosphorus pentoxide PEK resin (see, for example, Patent Document 4) and the like.
上述した従来のＰＥＥＫ樹脂、ＰＥＫ樹脂、ＰＥＫＫ樹脂等のＰＡＥＫ樹脂は、部分結晶性のポリマーであり、そのガラス転移温度は高く耐熱性に優れるものの、結晶融点も高く、成形加工に高い温度や圧力を要して成形加工性が劣るという欠点がある。 PAEK resins such as the above-mentioned conventional PEEK resin, PEK resin, and PEKK resin are partially crystalline polymers, and although they have a high glass transition temperature and excellent heat resistance, they also have a high crystalline melting point, and are not suitable for molding at high temperatures and pressures. There is a drawback that the moldability is inferior due to the need for
そこで、本発明は、耐熱性に優れ高いガラス転移温度を有し、低融点化が可能で、良好な成形加工性を有するポリアリーレンエーテルケトン樹脂を提供することを目的とする。また、本発明は、このポリアリーレンエーテルケトン樹脂の製造に好適な製造方法を提供することを目的とする。 Accordingly, an object of the present invention is to provide a polyarylene ether ketone resin that has excellent heat resistance, a high glass transition temperature, a low melting point, and good moldability. Another object of the present invention is to provide a production method suitable for producing this polyarylene ether ketone resin.
ＰＡＥＫ樹脂などのスーパーエンプラは、高い耐熱性を実現するため、できるだけ不純物のない均一構造のポリマーが望ましいものとされていた。したがって、従来、ＰＡＥＫ樹脂としては単一の繰り返し単位を有するポリマーの開発が中心であった。しかし単一の繰り返し単位構造では結晶融点などの熱物性の調整が難しく、成形加工性の改良が困難であった。 For super engineering plastics such as PAEK resin, it has been considered desirable to use a polymer having a uniform structure with as little impurities as possible in order to achieve high heat resistance. Therefore, conventionally, the development of polymers having a single repeating unit has focused on PAEK resins. However, with a single repeating unit structure, it is difficult to control thermophysical properties such as the crystal melting point, and it is difficult to improve moldability.
本発明者は、上記課題を解決するために鋭意研究を重ねた結果、剛直かつ靭性成分である下記繰り返し単位（１－１）及び下記繰り返し単位（３－１）と、柔軟成分である下記繰り返し単位（２－１）とを共重合させたＰＡＥＫ樹脂は、結晶融点を低下させることが可能で、良好な耐熱性及び成形加工性を発現できることを見出し、本発明を完成するに至った。 As a result of intensive research to solve the above problems, the present inventors have found that the following repeating unit (1-1) and repeating unit (3-1), which are rigid and tough components, and the following repeating unit, which is a flexible component The inventors have found that the PAEK resin copolymerized with the unit (2-1) can lower the crystalline melting point and exhibit good heat resistance and moldability, and have completed the present invention.
すなわち、本発明は、以下の態様を包含するものである。
[１]下記一般式（１－１）、（２－１）及び（３－１）で表される繰り返し単位を有するポリアリーレンエーテルケトン樹脂。
That is, the present invention includes the following aspects.
[1] A polyarylene ether ketone resin having repeating units represented by the following general formulas (1-1), (2-1) and (3-1).
[２]前記繰り返し単位（１－１）と（３－１）の合計モル量と、前記繰り返し単位（２－１）のモル量との割合が、モル比で、（１－１）＋（３－１）：（２－１）＝９５：５～４０：６０の範囲である、前記［１］に記載のポリアリーレンエーテルケトン樹脂。
[３]下記一般式（１－２）で表されるモノマー（１－２）と、下記一般式（２－２）で表されるモノマー（２－２）と、下記一般式（３－２）で表されるモノマー（３－２）とを、有機スルホン酸及び五酸化二リンの存在下で反応させる、前記［１］または［２］に記載のポリアリーレンエーテルケトン樹脂の製造方法。
[2] The molar ratio of the total molar amount of the repeating units (1-1) and (3-1) to the molar amount of the repeating unit (2-1) is (1-1) + ( 3-1): The polyarylene ether ketone resin according to the above [1], wherein (2-1) is in the range of 95:5 to 40:60.
[3] a monomer (1-2) represented by the following general formula (1-2), a monomer (2-2) represented by the following general formula (2-2), and the following general formula (3-2) ) and the monomer (3-2) represented by ) in the presence of an organic sulfonic acid and diphosphorus pentoxide.
[４]前記モノマー（１－２）が下記モノマー（１－２－Ａ）であり、前記モノマー（２－２）が下記モノマー（２－２－Ａ）であり、前記モノマー（３－２）が下記モノマー（３－２－Ａ）である、前記［３］に記載のポリアリーレンエーテルケトン樹脂の製造方法。
[4] The monomer (1-2) is the monomer (1-2-A) below, the monomer (2-2) is the monomer (2-2-A) below, and the monomer (3-2) is the following monomer (3-2-A), the method for producing a polyarylene ether ketone resin according to [3] above.
本発明は、耐熱性に優れ高いガラス転移温度を有するとともに、低融点化が可能で、良好な成形加工性を有するポリアリーレンエーテルケトン樹脂を提供することができる。また、本発明は、このポリアリーレンエーテルケトン樹脂の製造に好適な製造方法を提供することができる。 INDUSTRIAL APPLICABILITY The present invention can provide a polyarylene ether ketone resin that has excellent heat resistance, a high glass transition temperature, a low melting point, and good moldability. Moreover, the present invention can provide a production method suitable for producing this polyarylene ether ketone resin.
以下、本発明のＰＡＥＫ樹脂、及び該ＰＡＥＫ樹脂の製造方法について詳細に説明するが、以下に記載する構成要件の説明は、本発明の一実施態様としての一例であり、これらの内容に特定されるものではない。 The PAEK resin of the present invention and the method for producing the PAEK resin will be described in detail below. not something.
（ポリアリーレンエーテルケトン樹脂（ＰＡＥＫ樹脂））
本発明のＰＡＥＫ樹脂は、下記一般式（１－１）、（２－１）及び（３－１）で表される繰り返し単位を有する。
(Polyarylene ether ketone resin (PAEK resin))
The PAEK resin of the present invention has repeating units represented by the following general formulas (1-1), (2-1) and (3-1).
本発明のＰＡＥＫ樹脂は、剛直かつ靭性成分である、繰り返し単位（１－１）及び（３－１）と、柔軟成分である、繰り返し単位（２－１）を有するので、繰り返し単位（１－１）及び（３－１）と繰り返し単位（２－１）との割合を調整することにより、結晶融点を制御することができる。本発明のＰＡＥＫ樹脂は、結晶融点を低くすることができる。
また、上記繰り返し単位（１－１）、（２－１）、及び（３－１）は、全て置換基がパラ位に配置されている構造となっており、このような繰り返し単位（１－１）、（２－１）、及び（３－１）を有する本発明のＰＡＥＫ樹脂は、下記実施例でも示す通り、結晶化する時間（結晶化時間）を短くすることができる。
ところで、一般に、結晶性熱可塑性樹脂の場合、ガラス転移温度まで冷却しなくても、樹脂が結晶化して固化すれば脱型できる。したがって、溶融状態から結晶状態にする結晶化速度が生産性を左右する。例えば、結晶化速度が遅い（＝固化までに時間がかかる）場合には、金型からの離型性が悪化することに加え、長い成形時間サイクルを要することから生産性が悪化する。このため、熱可塑性樹脂の成形（特に射出成形）において、結晶化速度の向上（結晶化時間を短くすること）による成形サイクルの短縮要求は大きい。
本発明によれば、ＰＡＥＫ樹脂の結晶化時間を短くすることができる。結晶化時間が早くなれば、冷却時間が短縮され成形加工性が向上する。したがって、本発明によれば、成形加工性の向上が図れるＰＡＥＫ樹脂の提供が可能となる。
尚、結晶化時間は、例えば、示差走査熱量計（Ｆｌａｓｈ ＤＳＣ）による等温結晶化時間を測定することにより求めることができる。具体的には、例えば、樹脂を溶融した後、所定の温度まで急冷（数１０００Ｋ／ｓ）して、その温度で等温保持した際の結晶化にかかる時間を測定する。
Since the PAEK resin of the present invention has the repeating units (1-1) and (3-1), which are rigid and tough components, and the repeating unit (2-1), which is a flexible component, the repeating unit (1- The crystal melting point can be controlled by adjusting the ratio of 1) and (3-1) to the repeating unit (2-1). The PAEK resin of the present invention can have a low crystalline melting point.
Further, the above repeating units (1-1), (2-1), and (3-1) all have a structure in which a substituent is arranged at the para position, and such a repeating unit (1- The PAEK resin of the present invention having 1), (2-1), and (3-1) can shorten the crystallization time (crystallization time), as shown in the examples below.
By the way, in general, in the case of a crystalline thermoplastic resin, it can be removed from the mold if the resin is crystallized and solidified without being cooled to the glass transition temperature. Therefore, the rate of crystallization from the molten state to the crystalline state determines the productivity. For example, when the crystallization speed is slow (=it takes a long time to solidify), the releasability from the mold deteriorates, and a long molding time cycle is required, resulting in deterioration of productivity. Therefore, in the molding of thermoplastic resins (injection molding in particular), there is a great demand for shortening the molding cycle by improving the crystallization speed (shortening the crystallization time).
According to the present invention, the crystallization time of PAEK resin can be shortened. If the crystallization time is shortened, the cooling time is shortened and the moldability is improved. Therefore, according to the present invention, it is possible to provide a PAEK resin capable of improving moldability.
The crystallization time can be obtained by measuring the isothermal crystallization time with a differential scanning calorimeter (Flash DSC), for example. Specifically, for example, after the resin is melted, it is rapidly cooled to a predetermined temperature (several thousand K/s), and the time required for crystallization when isothermally maintained at that temperature is measured.
本発明のＰＡＥＫ樹脂において、繰り返し単位（１－１）と（３－１）の合計モル量と、上記繰り返し単位（２－１）のモル量との割合が、モル比〔（繰り返し単位（１－１）のモル量＋繰り返し単位（３－１）のモル量）：繰り返し単位（２－１）のモル量〕で、９５：５～４０：６０の範囲であることが好ましく、９０：１０～６０：４０の範囲であることがより好ましい。この割合の範囲で、繰り返し単位（２－１）のモル量に対する、繰り返し単位（１－１）及び繰り返し単位（３－１）の合計モル量の比の値を大きくすることで、ガラス転移温度（Ｔｇ）を高く調整することができ、結晶化度及び結晶融点（Ｔｍ）を高くすることができて、耐熱性に優れたＰＡＥＫ樹脂とすることができる。また、この割合の範囲で、繰り返し単位（２－１）のモル量に対する、繰り返し単位（１－１）及び繰り返し単位（３－１）の合計モル量の比の値を小さくすることで、結晶融点（Ｔｍ）を比較的低くすることができ、成形加工性に優れたＰＡＥＫ樹脂とすることができる。
この割合を調整することで、本発明のＰＡＥＫ樹脂のガラス転移温度（Ｔｇ）を１２０℃以上、より好ましくは１４０℃以上に調整することができる。より具体的には、１２０～１６５℃、好ましくは１２５～１６０℃、より好ましくは１４０～１５５℃に調整することができる。
また、本発明のＰＡＥＫ樹脂の結晶融点（Ｔｍ）を３５０℃以下に調整することができる。より具体的には、２８０～３５０℃、好ましくは３００～３５０℃、より好ましくは３１０～３４９℃に調整することができる。
繰り返し単位（１－１）及び（３－１）と繰り返し単位（２－１）との割合を最適化することで、耐熱性、及び成形加工性に優れるＰＡＥＫ樹脂とすることができる。
In the PAEK resin of the present invention, the molar ratio [(repeating unit (1 -1) molar amount + molar amount of repeating unit (3-1)):molar amount of repeating unit (2-1)], preferably in the range of 95:5 to 40:60, 90:10 It is more preferably in the range of ~60:40. Within this ratio range, by increasing the ratio of the total molar amount of the repeating unit (1-1) and the repeating unit (3-1) to the molar amount of the repeating unit (2-1), the glass transition temperature (Tg) can be adjusted to be high, the degree of crystallinity and crystal melting point (Tm) can be increased, and a PAEK resin having excellent heat resistance can be obtained. In addition, within this ratio range, by reducing the ratio of the total molar amount of the repeating unit (1-1) and the repeating unit (3-1) to the molar amount of the repeating unit (2-1), the crystal The melting point (Tm) can be made relatively low, and a PAEK resin having excellent moldability can be obtained.
By adjusting this ratio, the glass transition temperature (Tg) of the PAEK resin of the present invention can be adjusted to 120°C or higher, more preferably 140°C or higher. More specifically, it can be adjusted to 120 to 165°C, preferably 125 to 160°C, more preferably 140 to 155°C.
Also, the crystalline melting point (Tm) of the PAEK resin of the present invention can be adjusted to 350° C. or less. More specifically, it can be adjusted to 280 to 350°C, preferably 300 to 350°C, more preferably 310 to 349°C.
By optimizing the ratio of the repeating units (1-1) and (3-1) to the repeating unit (2-1), a PAEK resin having excellent heat resistance and moldability can be obtained.
（ポリアリーレンエーテルケトン樹脂（ＰＡＥＫ樹脂）の製造方法）
本発明のＰＡＥＫ樹脂の製造方法の一の態様は、下記一般式（１－２）で表されるモノマー（１－２）と、下記一般式（２－２）で表されるモノマー（２－２）と、下記一般式（３－２）で表されるモノマー（３－２）とを、有機スルホン酸及び五酸化二リンの存在下で反応させる、ＰＡＥＫ樹脂の製造方法である。
(Method for producing polyarylene ether ketone resin (PAEK resin))
One aspect of the method for producing a PAEK resin of the present invention is a monomer (1-2) represented by the following general formula (1-2) and a monomer (2-) represented by the following general formula (2-2) 2) and a monomer (3-2) represented by the following general formula (3-2) are reacted in the presence of an organic sulfonic acid and diphosphorus pentoxide to produce a PAEK resin.
上記モノマー（１－２）としては、４、４’－オキシビス安息香酸（ｋ＝１）、１，４－ビス（４－カルボキシフェノキシ）ベンゼン（ｋ＝２）、４，４’－ビス（ｐ－カルボキシフェノキシ）ジフェニルエーテル（ｋ＝３）が挙げられる。
上記モノマー（２－２）としては、例えば４－フェノキシ安息香酸（ｍａ＝０）、４－（４－フェノキシフェノキシ）安息香酸（ｍａ＝１）、４－（４－（４－フェノキシフェノキシ）フェノキシ）安息香酸（ｍａ＝２）等が挙げられる。
上記モノマー（３－２）としては、ジフェニルエーテル（ｎ＝０）、１、４－ジフェノキシベンゼン（ｎ＝１）、４，４’－オキシビス（フェノキシベンゼン）（ｎ＝２）が挙げられる。
Examples of the monomer (1-2) include 4,4′-oxybisbenzoic acid (k=1), 1,4-bis(4-carboxyphenoxy)benzene (k=2), 4,4′-bis(p -carboxyphenoxy)diphenyl ether (k=3).
Examples of the monomer (2-2) include 4-phenoxybenzoic acid (ma=0), 4-(4-phenoxyphenoxy)benzoic acid (ma=1), 4-(4-(4-phenoxyphenoxy)phenoxy ) and benzoic acid (ma=2).
Examples of the monomer (3-2) include diphenyl ether (n=0), 1,4-diphenoxybenzene (n=1), and 4,4′-oxybis(phenoxybenzene) (n=2).
本発明のＰＡＥＫ樹脂の製造方法の好ましい実施態様としては、上記モノマー（１－２）が、ｋ＝１の場合の下記モノマー（１－２－Ａ）であり、上記モノマー（２－２）が、ｍａ＝２の場合の下記モノマー（２－２－Ａ）であり、上記モノマー（３－２）が、ｎ＝１の場合の下記モノマー（３－２－Ａ）である、ＰＡＥＫ樹脂の製造方法が挙げられる。 In a preferred embodiment of the method for producing a PAEK resin of the present invention, the above monomer (1-2) is the following monomer (1-2-A) when k = 1, and the above monomer (2-2) is , the monomer (2-2-A) below when ma = 2, and the monomer (3-2) is the monomer (3-2-A) below when n = 1. method.
本発明のＰＡＥＫ樹脂の製造方法は、芳香族求電子置換型溶液重縮合反応であるので、温和な重合条件で反応させることができ、具体的には、有機スルホン酸及び五酸化二リンを２０～１００℃で１～４０時間で混合してから、この混合液に、上記モノマー（１－２）、上記モノマー（２－２）及び上記モノマー（３－２）を添加する。 Since the method for producing the PAEK resin of the present invention is an aromatic electrophilic substitution type solution polycondensation reaction, the reaction can be carried out under mild polymerization conditions. After mixing at ~100°C for 1 to 40 hours, the above monomer (1-2), the above monomer (2-2) and the above monomer (3-2) are added to the mixture.
本発明のＰＡＥＫ樹脂の製造方法の一実施態様として、有機スルホン酸及び五酸化二リンの混合液に、上記モノマー（１－２）、上記モノマー（２－２）及び上記モノマー（３－２）を添加し、混合し、これらモノマーを一括で反応させる製造方法が挙げられる。
この場合、例えば、有機スルホン酸及び五酸化二リンの混合液に、上記モノマー（１－２）、上記モノマー（２－２）及び上記モノマー（３－２）を添加し、混合し、昇温させてから、例えば、４０～１００℃、より好ましくは６０～９０℃、さらに好ましくは６０～８０℃で１～１００時間、一括して反応させることで、ＰＡＥＫ樹脂を製造することができる。
As one embodiment of the method for producing a PAEK resin of the present invention, the above monomer (1-2), the above monomer (2-2) and the above monomer (3-2) are added to a mixed solution of an organic sulfonic acid and diphosphorus pentoxide. are added, mixed, and these monomers are reacted all at once.
In this case, for example, the above monomer (1-2), the above monomer (2-2), and the above monomer (3-2) are added to a mixed solution of an organic sulfonic acid and diphosphorus pentoxide, mixed, and heated. Then, the PAEK resin can be produced by collectively reacting at 40 to 100° C., more preferably 60 to 90° C., still more preferably 60 to 80° C. for 1 to 100 hours.
本発明のＰＡＥＫ樹脂の製造方法は、下記実施例でも示す通り、重合工程が１００℃以下という温和な条件で実施可能である。また副生成物が環境への負担のない水のみである。本発明のＰＡＥＫ樹脂の製造方法は、反応モノマーや溶媒にフッ素を含有しない。例えば、反応工程において、トリフルオロメタンスルホン酸を使用しなくてはいけないとすると、廃棄処理において、フッ素イオンを含むガスが発生し、環境負荷が大きい。しかし、例えば、反応工程において、メタンスルホン酸を使用する限りにおいては、かような環境負荷の問題は発生しない。 As shown in the examples below, the method for producing the PAEK resin of the present invention can be carried out under mild conditions in which the polymerization step is carried out at 100° C. or less. Moreover, the only by-product is water, which is not harmful to the environment. The method for producing the PAEK resin of the present invention does not contain fluorine in the reaction monomers or solvents. For example, if trifluoromethanesulfonic acid must be used in the reaction process, a gas containing fluorine ions is generated during waste disposal, which has a large environmental impact. However, as long as methanesulfonic acid is used, for example, in the reaction step, the problem of environmental load does not arise.
有機スルホン酸としては、特に制限はなく、目的に応じて適宜選択できるが、例えば、脂肪族スルホン酸、芳香族スルホン酸等が挙げられる。中でも、脂肪族スルホン酸が好ましい。より具体的には、有機スルホン酸として、例えば、メタンスルホン酸、エタンスルホン酸、ベンゼンスルホン酸、ｐ－トルエンスルホン酸（トシル酸）等が挙げられる。 The organic sulfonic acid is not particularly limited and can be appropriately selected depending on the intended purpose. Examples thereof include aliphatic sulfonic acid and aromatic sulfonic acid. Among them, aliphatic sulfonic acids are preferred. More specifically, examples of organic sulfonic acids include methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid (tosylic acid), and the like.
有機スルホン酸の添加量と、五酸化二リンの添加量との割合は、質量比で、１００：３５～１００：１の範囲であることが好ましく、１００：３０～１００：５の範囲であることがより好ましく、１００：２５～１００：５の範囲であることがさらに好ましい。 The ratio of the amount of organic sulfonic acid added to the amount of diphosphorus pentoxide added is preferably in the range of 100:35 to 100:1, more preferably in the range of 100:30 to 100:5. is more preferred, and a range of 100:25 to 100:5 is even more preferred.
上記モノマー（１－２）、上記モノマー（２－２）及び上記モノマー（３－２）の合計の添加量と、有機スルホン酸及び五酸化二リンの合計の添加量との割合は、質量比で、１：１００～４０：１００の範囲であることが好ましく、２：１００～３０：１００の範囲であることがより好ましく、５：１００～２５：１００の範囲であることがさらに好ましい。
本発明のＰＡＥＫ樹脂の製造において、有機スルホン酸（例えば、特にメタンスルホン酸）及び五酸化二リンを用いることにより、良好な特性を示すＰＡＥＫ樹脂を製造することができる。例えば、有機スルホン酸と五酸化二リンを用いる代わりに、無水塩化アルミニウムを用いてＰＡＥＫ樹脂を製造しようとすると、重合速度が速すぎて、ポリマーシーケンスの制御が困難になる。
The ratio of the total amount of the monomer (1-2), the monomer (2-2) and the monomer (3-2) added to the total amount of the organic sulfonic acid and diphosphorus pentoxide is the mass ratio. , preferably in the range of 1:100 to 40:100, more preferably in the range of 2:100 to 30:100, even more preferably in the range of 5:100 to 25:100.
By using an organic sulfonic acid (e.g., especially methanesulfonic acid) and diphosphorus pentoxide in the production of the PAEK resin of the present invention, a PAEK resin exhibiting good properties can be produced. For example, if anhydrous aluminum chloride is used to produce PAEK resin instead of organic sulfonic acid and diphosphorus pentoxide, the polymerization rate is too fast and the polymer sequence is difficult to control.
上記反応工程における上記モノマー（１－２）の添加量と、上記モノマー（３－２）の添加量との割合は、本反応が芳香族求電子置換型重縮合反応であることから、実質的に当モルになることが望ましい。具体的には、モル比で、９０：１００～１１０：１００の範囲であることが好ましく、９２：１００～１０８：１００の範囲であることがより好ましく、９２：１０２～１０８：１００の範囲であることが特に好ましい。 Since this reaction is an aromatic electrophilic substitution polycondensation reaction, the ratio between the amount of the monomer (1-2) added and the amount of the monomer (3-2) added in the reaction step is substantially It is desirable to be equimolar to . Specifically, the molar ratio is preferably in the range of 90:100 to 110:100, more preferably in the range of 92:100 to 108:100, and in the range of 92:102 to 108:100. It is particularly preferred to have
上記モノマー（１－２）及び上記モノマー（３－２）の合計の添加量と、上記モノマー（２－２）の添加量との割合は、モル比で、９５：５～４０：６０の範囲であることが好ましく、９０：１０～６０：４０の範囲であることがより好ましい。 The molar ratio of the total addition amount of the monomer (1-2) and the monomer (3-2) to the addition amount of the monomer (2-2) is in the range of 95:5 to 40:60. and more preferably in the range of 90:10 to 60:40.
＜ポリアリーレンエーテルケトン樹脂（ＰＡＥＫ樹脂）を含有する樹脂組成物＞
本発明に係るＰＡＥＫ樹脂は、他の配合物と合わせて樹脂組成物を作製することができる。
他の配合物としては、特に制限はなく、目的に応じて適宜選択できるが、例えば、無機フィラー、有機フィラー等が挙げられる。
フィラーの形状としては、特に限定はなく、例えば、粒子状、板状、繊維状等のフィラーが挙げられる。
ＰＡＥＫ樹脂を含有する樹脂組成物は、フィラーとしては繊維状フィラーを含有することがより好ましい。繊維状フィラーの中でも、カーボン繊維とガラス繊維は、産業上利用範囲が広いため、好ましい。
<Resin composition containing polyarylene ether ketone resin (PAEK resin)>
The PAEK resins of the present invention can be combined with other formulations to form resin compositions.
Other compounds are not particularly limited and can be appropriately selected depending on the intended purpose. Examples thereof include inorganic fillers and organic fillers.
The shape of the filler is not particularly limited, and examples thereof include particulate, plate-like and fibrous fillers.
A resin composition containing a PAEK resin more preferably contains a fibrous filler as a filler. Among fibrous fillers, carbon fiber and glass fiber are preferable because of their wide industrial application.
＜ポリアリーレンエーテルケトン樹脂（ＰＡＥＫ樹脂）を含む成形体＞
本発明に係るＰＡＥＫ樹脂は、耐熱性に優れ高いガラス転移温度（Ｔｇ）を有するとともに、低融点化が可能で、良好な成形加工性を有する。そのため、ニートレジンとしての使用や、ガラス繊維、炭素繊維、フッ素樹脂等のコンパウンドとしての使用が可能である。そして、本発明に係るＰＡＥＫ樹脂を成形することで、ロッド、ボード、フィルム、フィラメント等の一次加工品や、各種射出加工品、各種切削加工品、ギア、軸受、コンポジット、インプラント、３Ｄ成形品等の二次加工品を製造することができ、これらの本発明に係るＰＡＥＫ樹脂を成形してなる成形品は、自動車、航空機、電気電子、医療用部材等の利用が可能である。
<Molded body containing polyarylene ether ketone resin (PAEK resin)>
The PAEK resin according to the present invention has excellent heat resistance, a high glass transition temperature (Tg), a low melting point, and good moldability. Therefore, it can be used as a neat resin or as a compound of glass fiber, carbon fiber, fluororesin, or the like. By molding the PAEK resin according to the present invention, primary processed products such as rods, boards, films, and filaments, various injection processed products, various cut products, gears, bearings, composites, implants, 3D molded products, etc. can be produced, and the molded products obtained by molding these PAEK resins according to the present invention can be used for automobiles, aircraft, electric and electronic parts, medical parts, and the like.
（ガラス転移点（Ｔｇ）及び結晶融点（Ｔｍ））
パーキンエルマー製ＤＳＣ装置（Ｐｙｒｉｓ Ｄｉａｍｏｎｄ）を用いて、５０ｍＬ／ｍｉｎの窒素流下、２０℃／ｍｉｎの昇温条件で４０～４００℃まで測定を行い、ガラス転移点（Ｔｇ）及び結晶融点（Ｔｍ）を求めた。
(Glass transition point (Tg) and crystalline melting point (Tm))
Using a Perkin Elmer DSC device (Pyris Diamond), under a nitrogen flow of 50 mL / min, measurement was performed from 40 to 400 ° C. at a temperature increase of 20 ° C. / min, and the glass transition point (Tg) and crystalline melting point (Tm). asked for
（５％重量減少温度（Ｔｄ５（℃）））
ＴＧ－ＤＴＡ装置（株式会社リガク ＴＧ－８１２０）を用いて、２０ｍＬ／ｍｉｎの窒素流下、２０℃／ｍｉｎの昇温速度で測定を行い、５％重量減少温度を測定した。
(5% weight loss temperature (Td5 (°C)))
Using a TG-DTA device (Rigaku TG-8120), measurement was performed under a nitrogen flow of 20 mL/min at a heating rate of 20° C./min to measure the 5% weight loss temperature.
（還元粘度（ＰＡＥＫ樹脂の分子量相当）ｄＬ／ｇ）
キャノンフェンスケ粘度計（柴田科学株式会社製）を用いて、２５℃において、溶媒、及び、溶媒１００ｍＬ中にポリマー０．３ｇを溶解したポリマー溶液の流出時間を測定し、次式で還元粘度を算出した。なお溶媒には、クロロホルムとトリフルオロ酢酸を４：１の質量比で混合した溶液を用いた。
還元粘度（ｄＬ／ｇ）＝（ｔ－ｔ０）／（ｃ×ｔ０）
ここで、ｔ０は溶媒の流出時間、ｔはポリマー溶液の流出時間、ｃはポリマー溶液中のポリマー濃度（ｇ／ｄＬ）を示す。
(Reduced viscosity (equivalent to molecular weight of PAEK resin) dL/g)
Using a Canon Fenske viscometer (manufactured by Shibata Scientific Co., Ltd.), at 25 ° C., measure the outflow time of the solvent and the polymer solution in which 0.3 g of polymer is dissolved in 100 mL of the solvent, and calculate the reduced viscosity with the following formula. Calculated. As a solvent, a mixed solution of chloroform and trifluoroacetic acid at a mass ratio of 4:1 was used.
Reduced viscosity (dL/g) = (t−t0)/(c×t0)
Here, t0 is the outflow time of the solvent, t is the outflow time of the polymer solution, and c is the polymer concentration (g/dL) in the polymer solution.
（結晶化時間）
メトラートレード社製の示差走査熱量計（Ｆｌａｓｈ ＤＳＣ１）を用いて、４０ｍＬ／ｍｉｎの窒素流下、下記の２種類のいずれかの方法により２００℃における結晶化する時間を測定した。
１）３０℃から１００Ｋ／ｓで３６０℃まで昇温した後、３６０℃で1秒保持して、サンプルを溶融後、６０００Ｋ／ｓで２００℃まで急冷し、その温度で等温保持を行った際の結晶化による発熱ピークを求めた。
２）３０℃から１００Ｋ／ｓで３６０℃まで昇温した後、３６０℃で1秒保持して、サンプルを溶融後、６０００Ｋ／ｓで２００℃まで急冷し、その温度で様々な時間において等温保持をした融解熱量を測定し、時間に対してどの程度結晶化が進行しているかにより求めた。
(crystallization time)
A differential scanning calorimeter (Flash DSC1) manufactured by Mettler Trade was used to measure the crystallization time at 200° C. under nitrogen flow of 40 mL/min by either of the following two methods.
1) After heating from 30 ° C. to 360 ° C. at 100 K / s, holding at 360 ° C. for 1 second, melting the sample, quenching at 6000 K / s to 200 ° C., and isothermally holding at that temperature. An exothermic peak due to crystallization of was determined.
2) After heating from 30° C. to 360° C. at 100 K/s, held at 360° C. for 1 second, the sample was melted, then quenched at 6000 K/s to 200° C., and held isothermally at that temperature for various times. The amount of heat of fusion was measured, and it was obtained from how much crystallization progressed with respect to time.
（実施例１）
窒素導入管、温度計、還流冷却器、及び撹拌装置を備えた４つ口のセパラブルフラスコに、メタンスルホン酸１９．２４ｇに五酸化二リン１．９３ｇを徐々に添加した後、４０℃に昇温し、２時間撹拌した。その後４，４’－オキシビス安息香酸０．７６２ｇ、４－（４－（４－フェノキシフェノキシ）フェノキシ）安息香酸０．２９４ｇと１，４－ジフェノキシベンゼン０．８３７ｇとを仕込み、６０℃まで昇温後、２２時間反応させた。
その後、４－クロロフェノールを加えた後、６５℃まで冷却し、水を添加した。析出したポリマーを濾別し、メタノールとイオン交換水で洗浄した。得られたポリマーを別容器に移送し、Ｎ－メチルー２－ピロリドン（以下、ＮＭＰ）を加えて１５０℃で１５分間撹拌した後、濾過を行った。濾別したポリマーに対してＮＭＰと沸騰水の混合溶媒による洗浄を２回繰り返した。得られたポリマーをさらに別容器に移送し、沸騰水及び３Ｎ塩酸を加え１０分間撹拌した後、濾過を行った。濾別したポリマーに対して沸騰水による洗浄を２回繰り返した。その後、ポリマーを真空下の１２０℃で４時間乾燥させた。これによりＰＡＥＫ樹脂：収量１．２２ｇ、収率７２％で得た。
(Example 1)
19.24 g of methanesulfonic acid and 1.93 g of diphosphorus pentoxide were gradually added to a four-necked separable flask equipped with a nitrogen inlet tube, a thermometer, a reflux condenser, and a stirrer, and the temperature was raised to 40°C. Warmed and stirred for 2 hours. After that, 0.762 g of 4,4'-oxybisbenzoic acid, 0.294 g of 4-(4-(4-phenoxyphenoxy)phenoxy)benzoic acid and 0.837 g of 1,4-diphenoxybenzene were added, and the temperature was raised to 60°C. After warming, the mixture was allowed to react for 22 hours.
Then, after adding 4-chlorophenol, the mixture was cooled to 65° C. and water was added. The precipitated polymer was separated by filtration and washed with methanol and deionized water. The obtained polymer was transferred to another container, N-methyl-2-pyrrolidone (hereinafter referred to as NMP) was added, and the mixture was stirred at 150° C. for 15 minutes and then filtered. The filtered polymer was washed twice with a mixed solvent of NMP and boiling water. The obtained polymer was further transferred to another container, boiling water and 3N hydrochloric acid were added, and the mixture was stirred for 10 minutes and then filtered. The filtered polymer was washed twice with boiling water. The polymer was then dried at 120° C. under vacuum for 4 hours. This gave PAEK resin: Yield 1.22 g, 72% yield.
（実施例２）
窒素導入管、温度計、還流冷却器、および撹拌装置を備えた４つ口のセパラブルフラスコに、メタンスルホン酸１９．２４ｇに五酸化二リン１．９３ｇを徐々に添加した後、４０℃に昇温し、２時間撹拌した。その後４，４’－オキシビス安息香酸０．７６２ｇ、４－（４－（４－フェノキシフェノキシ）フェノキシ）安息香酸０．２９４ｇと１，４－ジフェノキシベンゼン０．８３７ｇとを仕込み、８０℃まで昇温後、２２時間反応させた。
その後、４－クロロフェノールを加えた後、６５℃まで冷却し、水を添加した。析出したポリマーを濾別し、メタノールとイオン交換水で洗浄した。得られたポリマーを別容器に移送し、ＮＭＰを加えて１５０℃で１５分間撹拌した後、濾過を行った。濾別したポリマーに対してＮＭＰと沸騰水の混合溶媒による洗浄を２回繰り返した。得られたポリマーをさらに別容器に移送し、沸騰水及び３Ｎ塩酸を加え１０分間撹拌した後、濾過を行った。濾別したポリマーに対して沸騰水による洗浄を２回繰り返した。その後、ポリマーを真空下の１２０℃で４時間乾燥させた。これによりＰＡＥＫ樹脂：収量１．３１ｇ、収率７７％で得た。
(Example 2)
19.24 g of methanesulfonic acid was slowly added with 1.93 g of diphosphorus pentoxide in a four-necked separable flask equipped with a nitrogen inlet tube, a thermometer, a reflux condenser, and a stirrer, and then heated to 40°C. Warmed and stirred for 2 hours. After that, 0.762 g of 4,4'-oxybisbenzoic acid, 0.294 g of 4-(4-(4-phenoxyphenoxy)phenoxy)benzoic acid and 0.837 g of 1,4-diphenoxybenzene were charged, and the temperature was raised to 80°C. After warming, the mixture was allowed to react for 22 hours.
Then, after adding 4-chlorophenol, the mixture was cooled to 65° C. and water was added. The precipitated polymer was separated by filtration and washed with methanol and deionized water. The obtained polymer was transferred to another container, NMP was added, and the mixture was stirred at 150° C. for 15 minutes, and then filtered. The filtered polymer was washed twice with a mixed solvent of NMP and boiling water. The obtained polymer was further transferred to another container, boiling water and 3N hydrochloric acid were added, and the mixture was stirred for 10 minutes and then filtered. The filtered polymer was washed twice with boiling water. The polymer was then dried at 120° C. under vacuum for 4 hours. This gave PAEK resin: Yield 1.31 g, 77% yield.
（実施例３）
窒素導入管、温度計、還流冷却器、および撹拌装置を備えた４つ口のセパラブルフラスコに、メタンスルホン酸１９．２４ｇに五酸化二リン１．９３ｇを徐々に添加した後、４０℃に昇温し、２時間撹拌した。その後４，４’－オキシビス安息香酸０．７６２ｇ、４－（４－（４－フェノキシフェノキシ）フェノキシ）安息香酸０．２９４ｇと１，４－ジフェノキシベンゼン０．８３７ｇとを仕込み、９０℃まで昇温後、２２時間反応させた。
その後、４－クロロフェノールを加えた後、６５℃まで冷却し、水を添加した。析出したポリマーを濾別し、メタノールとイオン交換水で洗浄した。得られたポリマーを別容器に移送し、Ｎ－メチル２－ピロリドン（以下、ＮＭＰ）を加えて１５０℃で１５分間撹拌した後、濾過を行った。濾別したポリマーに対してＮＭＰと沸騰水の混合溶媒による洗浄を２回繰り返した。得られたポリマーをさらに別容器に移送し、沸騰水及び３Ｎ塩酸を加え１０分間撹拌した後、濾過を行った。濾別したポリマーに対して沸騰水による洗浄を２回繰り返した。その後、ポリマーを真空下の１２０℃で４時間乾燥させた。これによりＰＡＥＫ樹脂：収量１．２８ｇ、収率７５％で得た。
(Example 3)
19.24 g of methanesulfonic acid was slowly added with 1.93 g of diphosphorus pentoxide in a four-necked separable flask equipped with a nitrogen inlet tube, a thermometer, a reflux condenser, and a stirrer, and then heated to 40°C. Warmed and stirred for 2 hours. After that, 0.762 g of 4,4'-oxybisbenzoic acid, 0.294 g of 4-(4-(4-phenoxyphenoxy)phenoxy)benzoic acid and 0.837 g of 1,4-diphenoxybenzene were charged, and the temperature was raised to 90°C. After warming, the mixture was allowed to react for 22 hours.
Then, after adding 4-chlorophenol, the mixture was cooled to 65° C. and water was added. The precipitated polymer was separated by filtration and washed with methanol and deionized water. The obtained polymer was transferred to another container, N-methyl 2-pyrrolidone (hereinafter referred to as NMP) was added, and the mixture was stirred at 150° C. for 15 minutes and then filtered. The filtered polymer was washed twice with a mixed solvent of NMP and boiling water. The obtained polymer was further transferred to another container, boiling water and 3N hydrochloric acid were added, and the mixture was stirred for 10 minutes and then filtered. The filtered polymer was washed twice with boiling water. The polymer was then dried at 120° C. under vacuum for 4 hours. This gave PAEK resin: Yield 1.28 g, 75% yield.
（実施例４）
窒素導入管、温度計、還流冷却器、および撹拌装置を備えた４つ口のセパラブルフラスコに、メタンスルホン酸１８．５０ｇに五酸化二リン１．８５ｇを徐々に添加した後、４０℃に昇温し、２時間撹拌した。その後４，４’－オキシビス安息香酸０．６８２ｇ、４－（４－（４－フェノキシフェノキシ）フェノキシ）安息香酸０．４５ｇと１，４－ジフェノキシベンゼン０．７４８ｇとを仕込み、８０℃まで昇温後、２２時間反応させた。その後、４－クロロフェノールを加えた後、６５℃まで冷却し、水を添加した。析出したポリマーを濾別し、メタノールとイオン交換水で洗浄した。得られたポリマーを別容器に移送し、ＮＭＰを加えて１５０℃で１５分間撹拌した後、濾過を行った。濾別したポリマーに対してＮＭＰと沸騰水の混合溶媒による洗浄を２回繰り返した。得られたポリマーをさらに別容器に移送し、沸騰水及び３Ｎ塩酸を加え１０分間撹拌した後、濾過を行った。濾別したポリマーに対して沸騰水による洗浄を２回繰り返した。その後、ポリマーを真空下の１２０℃で４時間乾燥させた。これによりＰＡＥＫ樹脂：収量１．３１ｇ、収率７７％で得た。
(Example 4)
18.50 g of methanesulfonic acid and 1.85 g of diphosphorus pentoxide were gradually added to a four-necked separable flask equipped with a nitrogen inlet tube, a thermometer, a reflux condenser, and a stirrer, and the temperature was raised to 40°C. Warmed and stirred for 2 hours. After that, 0.682 g of 4,4'-oxybisbenzoic acid, 0.45 g of 4-(4-(4-phenoxyphenoxy)phenoxy)benzoic acid and 0.748 g of 1,4-diphenoxybenzene were charged, and the temperature was raised to 80°C. After warming, the mixture was allowed to react for 22 hours. Then, after adding 4-chlorophenol, the mixture was cooled to 65° C. and water was added. The precipitated polymer was separated by filtration and washed with methanol and deionized water. The obtained polymer was transferred to another container, NMP was added, and the mixture was stirred at 150° C. for 15 minutes, and then filtered. The filtered polymer was washed twice with a mixed solvent of NMP and boiling water. The obtained polymer was further transferred to another container, boiling water and 3N hydrochloric acid were added, and the mixture was stirred for 10 minutes and then filtered. The filtered polymer was washed twice with boiling water. The polymer was then dried at 120° C. under vacuum for 4 hours. This gave PAEK resin: Yield 1.31 g, 77% yield.
（実施例５）
窒素導入管、温度計、還流冷却器、および撹拌装置を備えた４つ口のセパラブルフラスコに、メタンスルホン酸１７．７６ｇに五酸化二リン１．７８ｇを徐々に添加した後、４０℃に昇温し、２時間撹拌した。その後４，４’－オキシビス安息香酸０．５９９ｇ、４－（４－（４－フェノキシフェノキシ）フェノキシ）安息香酸０．６１８ｇと１，４－ジフェノキシベンゼン０．６５８ｇとを仕込み、８０℃まで昇温後、２２時間反応させた。
その後、４－クロロフェノールを加えた後、６５℃まで冷却し、水を添加した。析出したポリマーを濾別し、メタノールとイオン交換水で洗浄した。得られたポリマーを別容器に移送し、ＮＭＰを加えて１５０℃で１５分間撹拌した後、濾過を行った。濾別したポリマーに対してＮＭＰと沸騰水の混合溶媒による洗浄を２回繰り返した。得られたポリマーをさらに別容器に移送し、沸騰水及び３Ｎ塩酸を加え１０分間撹拌した後、濾過を行った。濾別したポリマーに対して沸騰水による洗浄を２回繰り返した。その後、ポリマーを真空下の１２０℃で４時間乾燥させた。これによりＰＡＥＫ樹脂：収量１．１７ｇ、収率６８％で得た。
(Example 5)
17.76 g of methanesulfonic acid was slowly added with 1.78 g of diphosphorus pentoxide in a four-necked separable flask equipped with a nitrogen inlet tube, a thermometer, a reflux condenser, and a stirrer, and then heated to 40°C. Warmed and stirred for 2 hours. After that, 0.599 g of 4,4'-oxybisbenzoic acid, 0.618 g of 4-(4-(4-phenoxyphenoxy)phenoxy)benzoic acid and 0.658 g of 1,4-diphenoxybenzene were added, and the temperature was raised to 80°C. After warming, the mixture was allowed to react for 22 hours.
Then, after adding 4-chlorophenol, the mixture was cooled to 65° C. and water was added. The precipitated polymer was separated by filtration and washed with methanol and deionized water. The obtained polymer was transferred to another container, NMP was added, and the mixture was stirred at 150° C. for 15 minutes, and then filtered. The filtered polymer was washed twice with a mixed solvent of NMP and boiling water. The obtained polymer was further transferred to another container, boiling water and 3N hydrochloric acid were added, and the mixture was stirred for 10 minutes and then filtered. The filtered polymer was washed twice with boiling water. The polymer was then dried at 120° C. under vacuum for 4 hours. This gave PAEK resin: Yield 1.17 g, 68% yield.
（実施例６）
窒素導入管、温度計、還流冷却器、および撹拌装置を備えた４つ口のセパラブルフラスコに、メタンスルホン酸１７．０２ｇに五酸化二リン１．７１ｇを徐々に添加した後、４０℃に昇温し、２時間撹拌した。その後４，４’－オキシビス安息香酸０．５１１ｇ、４－（４－（４－フェノキシフェノキシ）フェノキシ）安息香酸０．７８９ｇと１，４－ジフェノキシベンゼン０．５６１ｇとを仕込み、８０℃まで昇温後、２２時間反応させた。
その後、４－クロロフェノールを加えた後、６５℃まで冷却し、水を添加した。析出したポリマーを濾別し、メタノールとイオン交換水で洗浄した。得られたポリマーを別容器に移送し、ＮＭＰを加えて１５０℃で１５分間撹拌した後、濾過を行った。濾別したポリマーに対してＮＭＰと沸騰水の混合溶媒による洗浄を２回繰り返した。得られたポリマーをさらに別容器に移送し、沸騰水及び３Ｎ塩酸を加え１０分間撹拌した後、濾過を行った。濾別したポリマーに対して沸騰水による洗浄を２回繰り返した。その後、ポリマーを真空下の１２０℃で４時間乾燥させた。これによりＰＡＥＫ樹脂：収量１．０８ｇ、収率６３％で得た。
(Example 6)
17.02 g of methanesulfonic acid was slowly added with 1.71 g of diphosphorus pentoxide in a four-necked separable flask equipped with a nitrogen inlet tube, a thermometer, a reflux condenser, and a stirrer, and then heated to 40°C. Warmed and stirred for 2 hours. After that, 0.511 g of 4,4'-oxybisbenzoic acid, 0.789 g of 4-(4-(4-phenoxyphenoxy)phenoxy)benzoic acid and 0.561 g of 1,4-diphenoxybenzene were charged, and the temperature was raised to 80°C. After warming, the mixture was allowed to react for 22 hours.
Then, after adding 4-chlorophenol, the mixture was cooled to 65° C. and water was added. The precipitated polymer was separated by filtration and washed with methanol and deionized water. The obtained polymer was transferred to another container, NMP was added, and the mixture was stirred at 150° C. for 15 minutes, and then filtered. The filtered polymer was washed twice with a mixed solvent of NMP and boiling water. The obtained polymer was further transferred to another container, boiling water and 3N hydrochloric acid were added, and the mixture was stirred for 10 minutes and then filtered. The filtered polymer was washed twice with boiling water. The polymer was then dried at 120° C. under vacuum for 4 hours. This gave PAEK resin: Yield 1.08 g, 63% yield.
（実施例７）
窒素導入管、温度計、還流冷却器、および撹拌装置を備えた４つ口のセパラブルフラスコに、メタンスルホン酸１９．２４ｇに五酸化二リン１．９３ｇを徐々に添加した後、４０℃に昇温し、２時間撹拌した。その後４，４’－オキシビス安息香酸０．７６２ｇ、４－（４－（４－フェノキシフェノキシ）フェノキシ）安息香酸０．２９４ｇと１，４－ジフェノキシベンゼン０．８３７ｇとを仕込み、１００℃まで昇温後、２２時間反応させた。
その後、４－クロロフェノールを加えた後、６５℃まで冷却し、水を添加した。析出したポリマーを濾別し、メタノールとイオン交換水で洗浄した。得られたポリマーを別容器に移送し、ＮＭＰを加えて１５０℃で１５分間撹拌した後、濾過を行った。濾別したポリマーに対してＮＭＰと沸騰水の混合溶媒による洗浄を２回繰り返した。得られたポリマーをさらに別容器に移送し、沸騰水及び３Ｎ塩酸を加え１０分間撹拌した後、濾過を行った。濾別したポリマーに対して沸騰水による洗浄を２回繰り返した。その後、ポリマーを真空下の１２０℃で４時間乾燥させた。これによりＰＡＥＫ樹脂：収量１．３３ｇ、収率７８％で得た。
(Example 7)
19.24 g of methanesulfonic acid was slowly added with 1.93 g of diphosphorus pentoxide in a four-necked separable flask equipped with a nitrogen inlet tube, a thermometer, a reflux condenser, and a stirrer, and then heated to 40°C. Warmed and stirred for 2 hours. After that, 0.762 g of 4,4'-oxybisbenzoic acid, 0.294 g of 4-(4-(4-phenoxyphenoxy)phenoxy)benzoic acid and 0.837 g of 1,4-diphenoxybenzene were charged, and the temperature was raised to 100°C. After warming, the mixture was allowed to react for 22 hours.
Then, after adding 4-chlorophenol, the mixture was cooled to 65° C. and water was added. The precipitated polymer was separated by filtration and washed with methanol and deionized water. The obtained polymer was transferred to another container, NMP was added, and the mixture was stirred at 150° C. for 15 minutes, and then filtered. The filtered polymer was washed twice with a mixed solvent of NMP and boiling water. The obtained polymer was further transferred to another container, boiling water and 3N hydrochloric acid were added, and the mixture was stirred for 10 minutes and then filtered. The filtered polymer was washed twice with boiling water. The polymer was then dried at 120° C. under vacuum for 4 hours. This gave PAEK resin: Yield 1.33 g, 78% yield.
実施例１～７に係るＰＡＥＫ樹脂のガラス転移温度（Ｔｇ）、結晶融点（Ｔｍ）、５％重量減少温度（Ｔｄ５（℃））、還元粘度（ｄＬ／ｇ）、及び結晶化時間（秒）を測定し、結果を表１に示した。 Glass transition temperature (Tg), crystalline melting point (Tm), 5% weight loss temperature (Td5 (° C.)), reduced viscosity (dL/g), and crystallization time (seconds) of PAEK resins according to Examples 1 to 7 was measured and the results are shown in Table 1.
（比較例１）
窒素導入管、温度計、還流冷却器、および撹拌装置を備えた４つ口のセパラブルフラスコに、メタンスルホン酸１２．５８ｇに五酸化二リン１．２６ｇを徐々に添加した後、４０℃に昇温し、２時間撹拌した。その後４－（４－（４－フェノキシフェノキシ）フェノキシ）安息香酸１．７９ｇを仕込み、８０℃まで昇温後、２２時間反応させた。
その後、４－クロロフェノールを加えた後、６５℃まで冷却し、水を添加した。析出したポリマーを濾別し、メタノールとイオン交換水で洗浄した。得られたポリマーを別容器に移送し、ＮＭＰを加えて１５０℃で１５分間撹拌した後、生成物はＮＭＰに完溶し、目的物を得ることはできなかった。
したがって、比較例１では、各種測定が行えなかった（下記表２参照）。
(Comparative example 1)
12.58 g of methanesulfonic acid was slowly added with 1.26 g of diphosphorus pentoxide in a four-necked separable flask equipped with a nitrogen inlet tube, a thermometer, a reflux condenser, and a stirrer, and then heated to 40°C. Warmed and stirred for 2 hours. After that, 1.79 g of 4-(4-(4-phenoxyphenoxy)phenoxy)benzoic acid was charged, heated to 80° C., and reacted for 22 hours.
Then, after adding 4-chlorophenol, the mixture was cooled to 65° C. and water was added. The precipitated polymer was separated by filtration and washed with methanol and deionized water. The resulting polymer was transferred to another container, NMP was added, and the mixture was stirred at 150° C. for 15 minutes.
Therefore, in Comparative Example 1, various measurements could not be performed (see Table 2 below).
（比較例２）
窒素導入管、温度計、還流冷却器、及び撹拌装置を備えた４つ口のセパラブルフラスコに、メタンスルホン酸１２．２９ｇと五酸化二リン２．９５ｇを仕込み、１００℃に昇温し、４時間撹拌した。その後８０℃まで冷却後、４，４’－オキシビス安息香酸１．１７ｇ、３－フェノキシ安息香酸０．５８１ｇと１，４－ジフェノキシベンゼン１．２０ｇとを仕込み、２４時間反応させた。
その後、室温まで冷却し、反応溶液を強撹拌したメタノール中に注ぎ込み、ポリマーを析出させた。そして、析出したポリマーを濾過した。
更に析出したポリマーをメタノールで２回洗浄した。次に、イオン交換水で２回洗浄した。その後、固液分離し、濾過した洗浄ケーキを真空下の１８０℃で１０時間乾燥させることにより、ＰＡＥＫ樹脂：収量２．５６ｇを収率９２％で得た。
(Comparative example 2)
12.29 g of methanesulfonic acid and 2.95 g of diphosphorus pentoxide were charged into a four-necked separable flask equipped with a nitrogen inlet tube, a thermometer, a reflux condenser, and a stirrer, and the temperature was raised to 100°C. Stirred for 4 hours. After cooling to 80° C., 1.17 g of 4,4′-oxybisbenzoic acid, 0.581 g of 3-phenoxybenzoic acid and 1.20 g of 1,4-diphenoxybenzene were charged and reacted for 24 hours.
After cooling to room temperature, the reaction solution was poured into strongly stirred methanol to precipitate a polymer. Then, the precipitated polymer was filtered.
Furthermore, the precipitated polymer was washed twice with methanol. Next, it was washed twice with ion-exchanged water. Thereafter, solid-liquid separation was performed, and the filtered washed cake was dried under vacuum at 180° C. for 10 hours to obtain PAEK resin: 2.56 g with a yield of 92%.
（比較例３）
窒素導入管、温度計、還流冷却器、及び撹拌装置を備えた４つ口のセパラブルフラスコに、メタンスルホン酸１２．２９ｇと五酸化二リン２．９５ｇを仕込み、１００℃に昇温し、４時間撹拌した。その後８０℃まで冷却後、４，４’－オキシビス安息香酸１．１７ｇ、３－フェノキシ安息香酸０．５８１ｇと１，４－ジフェノキシベンゼン１．２０ｇとを仕込み、２４時間反応させた。
その後、４－クロロフェノールを加えた後、６５℃まで冷却し、水を添加した。析出したポリマーを濾別し、メタノールとイオン交換水で洗浄した。得られたポリマーを別容器に移送し、ＮＭＰを加えて１５０℃で１５分間撹拌した後、濾過を行った。濾別したポリマーに対してＮＭＰと沸騰水の混合溶媒による洗浄を２回繰り返した。得られたポリマーをさらに別容器に移送し、沸騰水及び３Ｎ塩酸を加え１０分間撹拌した後、濾過を行った。濾別したポリマーに対して沸騰水による洗浄を２回繰り返した。その後、ポリマーを真空下の１２０℃で４時間乾燥させた。これによりＰＡＥＫ樹脂：収量２．２０ｇ、収率７９％で得た。
(Comparative Example 3)
12.29 g of methanesulfonic acid and 2.95 g of diphosphorus pentoxide were charged into a four-necked separable flask equipped with a nitrogen inlet tube, a thermometer, a reflux condenser, and a stirrer, and the temperature was raised to 100°C. Stirred for 4 hours. After cooling to 80° C., 1.17 g of 4,4′-oxybisbenzoic acid, 0.581 g of 3-phenoxybenzoic acid and 1.20 g of 1,4-diphenoxybenzene were charged and reacted for 24 hours.
Then, after adding 4-chlorophenol, the mixture was cooled to 65° C. and water was added. The precipitated polymer was separated by filtration and washed with methanol and deionized water. The obtained polymer was transferred to another container, NMP was added, and the mixture was stirred at 150° C. for 15 minutes, and then filtered. The filtered polymer was washed twice with a mixed solvent of NMP and boiling water. The obtained polymer was further transferred to another container, boiling water and 3N hydrochloric acid were added, and the mixture was stirred for 10 minutes and then filtered. The filtered polymer was washed twice with boiling water. The polymer was then dried at 120° C. under vacuum for 4 hours. This gave PAEK resin: Yield 2.20 g, 79% yield.
（比較例４）
窒素導入管、温度計、還流冷却器、および撹拌装置を備えた４つ口のセパラブルフラスコに、メタンスルホン酸２０．４ｇと五酸化二リン２．０４ｇを仕込み、４０℃に昇温し、２時間撹拌した。その後、１，４－ジフェノキシベンゼン１．００ｇ、４，４’－オキシビス安息香酸０．５４６ｇと３，４’－オキシビス安息香酸０．３６４ｇとを仕込み、６０℃まで昇温後、２２時間反応させた。室温まで冷却後、反応溶液を強撹拌したメタノール中に注ぎ込み、ポリマーを析出させた。そして、析出したポリマーを濾過した。
更に析出したポリマーをメタノールで２回洗浄した。次に、イオン交換水で２回洗浄した。その後、固液分離し、濾過した洗浄ケーキを真空下の１８０℃で１０時間乾燥させることにより、ポリマーを得た。
(Comparative Example 4)
20.4 g of methanesulfonic acid and 2.04 g of diphosphorus pentoxide were charged into a four-necked separable flask equipped with a nitrogen inlet tube, a thermometer, a reflux condenser, and a stirrer, and the temperature was raised to 40°C. Stirred for 2 hours. Then, 1.00 g of 1,4-diphenoxybenzene, 0.546 g of 4,4'-oxybisbenzoic acid and 0.364 g of 3,4'-oxybisbenzoic acid were charged, heated to 60°C, and reacted for 22 hours. let me After cooling to room temperature, the reaction solution was poured into strongly stirred methanol to precipitate a polymer. Then, the precipitated polymer was filtered.
Furthermore, the precipitated polymer was washed twice with methanol. Next, it was washed twice with ion-exchanged water. Thereafter, solid-liquid separation was performed, and the filtered washed cake was dried under vacuum at 180° C. for 10 hours to obtain a polymer.
（比較例５）
比較用のＰＥＫ樹脂として、市販品のＶＩＣＴＲＥＸ ＨＴ（ビクトレックス社製）を比較例５として用いた。
(Comparative Example 5)
As a PEK resin for comparison, a commercially available VICTREX HT (manufactured by Victrex) was used as Comparative Example 5.
比較例２～５に係るＰＡＥＫ樹脂のガラス転移温度（Ｔｇ）、結晶融点（Ｔｍ）、５％重量減少温度（Ｔｄ５（℃））、還元粘度（ｄＬ／ｇ）、及び結晶化時間（秒）を測定し、結果を表２に示した。 Glass transition temperature (Tg), crystalline melting point (Tm), 5% weight loss temperature (Td5 (° C.)), reduced viscosity (dL/g), and crystallization time (seconds) of PAEK resins according to Comparative Examples 2-5 was measured and the results are shown in Table 2.
表１に示されるように、実施例のＰＡＥＫ樹脂は、ガラス転移温度（Ｔｇ）を１４０℃以上に調整することができる。また、実施例のＰＡＥＫ樹脂は、このように優れた耐熱性を保持したまま、３４６℃以下の結晶融点（Ｔｍ）に制御することが可能であり、良好な成形加工性を有する。また、実施例のＰＡＥＫ樹脂は、結晶化時間が短いため、冷却時間が短縮され成形加工性の向上が実現できる。
As shown in Table 1, the PAEK resins of Examples can be adjusted to have a glass transition temperature (Tg) of 140° C. or higher. Moreover, the PAEK resins of Examples can be controlled to have a crystal melting point (Tm) of 346° C. or lower while maintaining such excellent heat resistance, and have good moldability. Moreover, since the PAEK resin of the example has a short crystallization time, the cooling time is shortened, and the improvement of moldability can be realized.
Claims (5)
A molded article containing the polyarylene ether ketone resin according to claim 1 or 2.
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