JP2019500468A - フタロニトリル樹脂 - Google Patents
フタロニトリル樹脂 Download PDFInfo
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- 229920006391 phthalonitrile polymer Polymers 0.000 title claims abstract description 46
- XQZYPMVTSDWCCE-UHFFFAOYSA-N phthalonitrile Chemical compound N#CC1=CC=CC=C1C#N XQZYPMVTSDWCCE-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 239000011347 resin Substances 0.000 title claims abstract description 37
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- 239000003795 chemical substances by application Substances 0.000 claims description 34
- 125000002947 alkylene group Chemical group 0.000 claims description 25
- 125000001118 alkylidene group Chemical group 0.000 claims description 25
- 238000006243 chemical reaction Methods 0.000 claims description 24
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- 229920000642 polymer Polymers 0.000 claims description 22
- 125000000217 alkyl group Chemical group 0.000 claims description 20
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- 239000001257 hydrogen Substances 0.000 claims description 15
- -1 aromatic amine compound Chemical class 0.000 claims description 11
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- 229910052717 sulfur Inorganic materials 0.000 claims description 10
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- 238000000034 method Methods 0.000 abstract description 30
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- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 1
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- PLKGXLAOFVILEL-UHFFFAOYSA-N OC1=CC=C(C=C1)C(C(F)(F)F)(C(F)(F)F)C1=CC=C(C=C1)O.FC(CC(F)(F)F)(F)F.OC1=CC=C(C=C1)C1=CC=CC=C1 Chemical compound OC1=CC=C(C=C1)C(C(F)(F)F)(C(F)(F)F)C1=CC=C(C=C1)O.FC(CC(F)(F)F)(F)F.OC1=CC=C(C=C1)C1=CC=CC=C1 PLKGXLAOFVILEL-UHFFFAOYSA-N 0.000 description 1
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- 229920006231 aramid fiber Polymers 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
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- 239000004305 biphenyl Substances 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical group C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
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- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
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- 229910052801 chlorine Inorganic materials 0.000 description 1
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- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
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- 125000005417 glycidoxyalkyl group Chemical group 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 125000005647 linker group Chemical group 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
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- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000002121 nanofiber Substances 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 125000002560 nitrile group Chemical group 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- VYMDGNCVAMGZFE-UHFFFAOYSA-N phenylbutazonum Chemical compound O=C1C(CCCC)C(=O)N(C=2C=CC=CC=2)N1C1=CC=CC=C1 VYMDGNCVAMGZFE-UHFFFAOYSA-N 0.000 description 1
- 238000011417 postcuring Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/0683—Polycondensates containing six-membered rings, condensed with other rings, with nitrogen atoms as the only ring hetero atoms
- C08G73/0688—Polycondensates containing six-membered rings, condensed with other rings, with nitrogen atoms as the only ring hetero atoms with only one nitrogen atom in the ring, e.g. polyquinolines
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/0622—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
- C08G73/0638—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with at least three nitrogen atoms in the ring
- C08G73/065—Preparatory processes
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- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
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- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/38—Polyamides prepared from aldehydes and polynitriles
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- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
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Abstract
Description
NMR分析は、Agilent社の500MHzのNMR装備を使用して製造社のマニュアルによって行った。NMRの測定のためのサンプルは、化合物をDMSO(dimethylsulfoxide)−d6に溶解させて製造した。
DSC分析は、TA instrument社のQ20システムを使用して35℃から450℃まで10℃/分の昇温速度で昇温しつつ、N2flow雰囲気で行った。
TGA分析は、Mettler−Toledo社のTGAe850装備を使用して行った。製造例で製造された化合物の場合、25℃から800℃まで10℃/分の昇温速度で昇温しつつ、N2flow雰囲気で分析し、実施例または比較例で製造された組成物の場合は、375℃の温度でポスト硬化させた後、25℃から900℃まで10℃/分の昇温速度で昇温しつつ、N2flow雰囲気で分析した。
下記化学式Aの化合物は、次の方式で合成した。まず、4,4’−ビス(ヒドロキシフェニルメタン)28gと150mLのDMF(dimethyl formamide)を500mLの3ネックRBF(3 neck round−bottom flast)に投入し、常温で撹拌し、溶解させた。前記に4−ニトロフタロニトリル48.5gを追加し、DMF50gを追加した後、撹拌し、溶解させた。次いで、炭酸カリウム58.1gおよびDMF50gを共に投入した後、撹拌し、温度を85℃まで昇温した。5時間程度反応させた後、常温まで冷却させる。冷却された反応溶液を0.2N塩酸水溶液に注いで中和沈殿した。フィルタリングした後、水で洗浄した。その後、フィルタリングされた反応物を100℃の真空オーブンで一日間乾燥させた。水と残留溶媒を除去した後、目的化合物を85重量%の収率で収得した。
前記化学式Aの化合物、下記化学式Bの化合物および下記化学式Cの化合物の混合物は、次の方式で合成した。まず、4,4’−ビス(ヒドロキシフェニルメタン)、2,4’−ビス(ヒドロキシフェニルメタン)および2,2’−ビス(ヒドロキシフェニルメタン)の混合物28gと150mLのDMF(dimethyl formamide)を500mLの3ネックRBF(3 neck round−bottom flast)に投入し、常温で撹拌し、溶解させた。前記混合物において4,4’−ビス(ヒドロキシフェニルメタン)、2,4’−ビス(ヒドロキシフェニルメタン)および2,2’−ビス(ヒドロキシフェニルメタン)の重量比は、60:35:5(4,4’−ビス(ヒドロキシフェニルメタン):2,4’−ビス(ヒドロキシフェニルメタン):2,2’−ビス(ヒドロキシフェニルメタン))であった。前記に4−ニトロフタロニトリル48.5gを追加し、DMF50gを追加した後、撹拌し、溶解させた。次いで、炭酸カリウム58.1gおよびDMF50gを共に投入した後、撹拌し、温度を85℃まで昇温した。5時間程度反応させた後、常温まで冷却させる。冷却された反応溶液を0.2N塩酸水溶液に注いで中和沈殿した。フィルタリングした後、水で洗浄した。その後、フィルタリングされた反応物を100℃の真空オーブンで一日間乾燥させた。水と残留溶媒を除去した後、目的混合物を80重量%の収率で収得した。
4,4’−ジヒドロキシビフェニルエーテル25.3gおよび100mLのDMF(dimethyl formamide)を3ネックRBF(3 neck round−bottom flast)に投入し、常温で撹拌し、溶解させた。前記に4ニトロフタロニトリル43.3gを追加し、DMF70gを追加した後、撹拌し、溶解させた。次いで、炭酸カリウム51.8gおよびDMF50gを共に投入した後、撹拌し、温度を85℃まで昇温した。5時間程度反応させた後、常温まで冷却させる。冷却された反応溶液を0.2N塩酸水溶液に注いで中和沈殿した。フィルタリングした後、水で洗浄した。その後、フィルタリングされた反応物を100℃の真空オーブンで一日間乾燥させた。水と残留溶媒を除去した後、下記化学式Dの化合物(PN3)を88重量%の収率で収得した。
4,4’−ジヒドロキシビフェニル27.9gおよび100mLのDMF(dimethyl formamide)を3ネックRBF(3 neck round−bottom flast)に投入し、常温で撹拌し、溶解させた。前記に4ニトロフタロニトリル51.9gを追加し、DMF50gを追加した後、撹拌し、溶解させた。次いで、炭酸カリウム62.2gおよびDMF50gを共に投入し後、撹拌し、温度を85℃まで昇温した。5時間程度反応させた後、常温まで冷却させる。冷却された反応溶液を0.2N塩酸水溶液に注いで中和沈殿した。フィルタリングした後、水で洗浄した。その後、フィルタリングされた反応物を100℃の真空オーブンで一日間乾燥させた。水と残留溶媒を除去した後、下記化学式Eの化合物(PN4)を83重量%の収率で収得した。前記化合物に対するNMR結果は、図4に記載し、DSCおよびTGA分析結果は、表1に整理した。
4,4’−ビス(4−ヒドロキシビフェニル)ヘキサフルオロプロパン(2,2−bis(4−hydroxyphenyl)hexafluoropropane)50.4gおよび150mLのDMF(dimethyl formamide)を3ネックRBF(3 neckround−bottom flast)に投入し、常温で撹拌し、溶解させた。前記に4ニトロフタロニトリル51.9gを追加し、DMF50gを追加した後、撹拌し、溶解させた。次いで、炭酸カリウム62.2gおよびDMF50gを共に投入した後、撹拌し、温度を85℃まで昇温した。5時間程度反応させた後、常温まで冷却させる。冷却された反応溶液を0.2N塩酸水溶液に注いで中和沈殿した。フィルタリングした後、水で洗浄した。その後、フィルタリングされた反応物を100℃の真空オーブンで一日間乾燥させた。水と残留溶媒を除去した後、下記化学式Fの化合物(PN5)を87重量%の収率で収得した。前記化合物に対するNMR結果は、図5に記載し、DSCおよびTGA分析結果は、表1に整理した。
硬化剤として使用した下記化学式Gの化合物は、TCI(Tokyo Chemical Industry Co.、Ltd.)社の市販製品を入手し、追加精製することなく使用した。
製造例1の化合物(PN1)に前記硬化剤(CA1、1,3−bis(3−aminophenoxy)benzene)を前記化合物(PN1)1モル当たり約0.15モルが存在するように配合し、重合性組成物を製造した。前記組成物に対してDSCとTGA分析を行った結果は、下記表2に記載されている。
製造例2の混合物(PN2)を製造例1の化合物(PN1)の代わりに使用したことを除いて、実施例1と同一に重合性組成物を製造した。前記組成物に対してDSCとTGA分析を行った結果は、下記表2に記載されている。
製造例3の化合物(PN3)を製造例1の化合物(PN1)の代わりに使用したことを除いて、実施例1と同一に重合性組成物を製造した。前記組成物に対してDSCとTGA分析を行った結果は、下記表2に記載されている。
製造例4の化合物(PN4)を製造例1の化合物(PN1)の代わりに使用したことを除いて、実施例1と同一に重合性組成物を製造した。前記組成物に対してDSCとTGA分析を行った結果は、下記表2に記載されている。
製造例5の化合物(PN5)を製造例1の化合物(PN1)の代わりに使用したことを除いて、実施例1と同一に重合性組成物を製造した。前記組成物に対してDSCとTGA分析を行った結果は、下記表2に記載されている。
Claims (17)
- 化学式1の化合物由来の重合単位は、化学式3の化合物由来の重合単位および化学式4または5の化合物の重合単位を含む、請求項2に記載のフタロニトリル樹脂。
- 化学式1の化合物由来の重合単位は、化学式3の化合物由来の重合単位、化学式4の化合物由来の重合単位および化学式5の化合物の重合単位を含む、請求項2に記載のフタロニトリル樹脂。
- 化学式1の化合物由来の重合単位は、化学式3の化合物由来の重合単位100重量部に対して化学式4または5の化合物由来の重合単位1〜200重量部を含む、請求項2に記載のフタロニトリル樹脂。
- 芳香族アミン化合物の重合単位をさらに含む、請求項1に記載のフタロニトリル樹脂。
- 化学式3の化合物;化学式4または5の化合物;および硬化剤を含む、請求項8に記載の重合性組成物。
- 化学式3の化合物、化学式4の化合物、化学式5の化合物および硬化剤を含む、請求項8に記載の重合性組成物。
- 硬化剤は、芳香族アミン化合物、フェノール化合物、無機酸、有機酸、金属または金属塩である、請求項7に記載の重合性組成物。
- 加工温度が50℃〜200℃の範囲内にある、請求項7に記載の重合性組成物。
- 加工温度と硬化反応開始温度との差の絶対値が50℃以上である、請求項12に記載の重合性組成物。
- 請求項7に記載の重合性組成物の反応物であるプレポリマー。
- 請求項1に記載のフタロニトリル樹脂を含む複合体。
- 充填剤をさらに含む、請求項15に記載の複合体。
- 請求項7に記載の重合性組成物または請求項14に記載のプレポリマーを含む前駆体を硬化させる段階を含む複合体の製造方法。
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