JPH02235842A - Alicyclic tetracarboxylic acid and derivative thereof - Google Patents
Alicyclic tetracarboxylic acid and derivative thereofInfo
- Publication number
- JPH02235842A JPH02235842A JP1057368A JP5736889A JPH02235842A JP H02235842 A JPH02235842 A JP H02235842A JP 1057368 A JP1057368 A JP 1057368A JP 5736889 A JP5736889 A JP 5736889A JP H02235842 A JPH02235842 A JP H02235842A
- Authority
- JP
- Japan
- Prior art keywords
- acid
- reaction
- compound
- group
- tetracarboxylic
- 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
- -1 Alicyclic tetracarboxylic acid Chemical class 0.000 title claims abstract description 37
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 37
- 229920001721 polyimide Polymers 0.000 abstract description 27
- 150000001875 compounds Chemical class 0.000 abstract description 26
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 abstract description 23
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 21
- 239000004642 Polyimide Substances 0.000 abstract description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 13
- 229910052763 palladium Inorganic materials 0.000 abstract description 11
- 239000003054 catalyst Substances 0.000 abstract description 10
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract description 8
- 229910002091 carbon monoxide Inorganic materials 0.000 abstract description 8
- 239000003795 chemical substances by application Substances 0.000 abstract description 7
- 150000002430 hydrocarbons Chemical group 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 6
- 150000002506 iron compounds Chemical class 0.000 abstract description 3
- 239000003822 epoxy resin Substances 0.000 abstract description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 abstract description 2
- 229930195733 hydrocarbon Natural products 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- 239000004014 plasticizer Substances 0.000 abstract description 2
- 229920000647 polyepoxide Polymers 0.000 abstract description 2
- 229920000728 polyester Polymers 0.000 abstract description 2
- 229920000915 polyvinyl chloride Polymers 0.000 abstract description 2
- 239000004800 polyvinyl chloride Substances 0.000 abstract description 2
- 239000004215 Carbon black (E152) Substances 0.000 abstract 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract 1
- 229910052802 copper Inorganic materials 0.000 abstract 1
- 239000010949 copper Substances 0.000 abstract 1
- 150000000000 tetracarboxylic acids Chemical class 0.000 description 25
- 229920005575 poly(amic acid) Polymers 0.000 description 24
- 239000003960 organic solvent Substances 0.000 description 21
- 239000000243 solution Substances 0.000 description 17
- 239000002904 solvent Substances 0.000 description 16
- 235000019441 ethanol Nutrition 0.000 description 13
- 150000004985 diamines Chemical class 0.000 description 12
- 238000000034 method Methods 0.000 description 10
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 9
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 8
- 150000003512 tertiary amines Chemical class 0.000 description 8
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 7
- 239000002798 polar solvent Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000000862 absorption spectrum Methods 0.000 description 6
- 239000009719 polyimide resin Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 150000008065 acid anhydrides Chemical class 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000005749 Copper compound Substances 0.000 description 3
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000003377 acid catalyst Substances 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 150000001880 copper compounds Chemical class 0.000 description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 238000005979 thermal decomposition reaction Methods 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- OOCCDEMITAIZTP-QPJJXVBHSA-N (E)-cinnamyl alcohol Chemical compound OC\C=C\C1=CC=CC=C1 OOCCDEMITAIZTP-QPJJXVBHSA-N 0.000 description 2
- KVNYFPKFSJIPBJ-UHFFFAOYSA-N 1,2-diethylbenzene Chemical compound CCC1=CC=CC=C1CC KVNYFPKFSJIPBJ-UHFFFAOYSA-N 0.000 description 2
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 2
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- KMKWGXGSGPYISJ-UHFFFAOYSA-N 4-[4-[2-[4-(4-aminophenoxy)phenyl]propan-2-yl]phenoxy]aniline Chemical compound C=1C=C(OC=2C=CC(N)=CC=2)C=CC=1C(C)(C)C(C=C1)=CC=C1OC1=CC=C(N)C=C1 KMKWGXGSGPYISJ-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 208000005156 Dehydration Diseases 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-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
- 125000002723 alicyclic group Chemical group 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 2
- 229960003280 cupric chloride Drugs 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 150000008282 halocarbons Chemical class 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- GGAUUQHSCNMCAU-ZXZARUISSA-N (2s,3r)-butane-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C[C@H](C(O)=O)[C@H](C(O)=O)CC(O)=O GGAUUQHSCNMCAU-ZXZARUISSA-N 0.000 description 1
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- KJDRSWPQXHESDQ-UHFFFAOYSA-N 1,4-dichlorobutane Chemical compound ClCCCCCl KJDRSWPQXHESDQ-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- PWGJDPKCLMLPJW-UHFFFAOYSA-N 1,8-diaminooctane Chemical compound NCCCCCCCCN PWGJDPKCLMLPJW-UHFFFAOYSA-N 0.000 description 1
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 1
- LTMRRSWNXVJMBA-UHFFFAOYSA-L 2,2-diethylpropanedioate Chemical compound CCC(CC)(C([O-])=O)C([O-])=O LTMRRSWNXVJMBA-UHFFFAOYSA-L 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 1
- AKCRQHGQIJBRMN-UHFFFAOYSA-N 2-chloroaniline Chemical compound NC1=CC=CC=C1Cl AKCRQHGQIJBRMN-UHFFFAOYSA-N 0.000 description 1
- QHTJSSMHBLGUHV-UHFFFAOYSA-N 2-methylbutan-2-ylbenzene Chemical compound CCC(C)(C)C1=CC=CC=C1 QHTJSSMHBLGUHV-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 0.000 description 1
- ZBMISJGHVWNWTE-UHFFFAOYSA-N 3-(4-aminophenoxy)aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=CC(N)=C1 ZBMISJGHVWNWTE-UHFFFAOYSA-N 0.000 description 1
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 1
- ZSPTYLOMNJNZNG-UHFFFAOYSA-N 3-Buten-1-ol Chemical compound OCCC=C ZSPTYLOMNJNZNG-UHFFFAOYSA-N 0.000 description 1
- DKKYOQYISDAQER-UHFFFAOYSA-N 3-[3-(3-aminophenoxy)phenoxy]aniline Chemical compound NC1=CC=CC(OC=2C=C(OC=3C=C(N)C=CC=3)C=CC=2)=C1 DKKYOQYISDAQER-UHFFFAOYSA-N 0.000 description 1
- UDKYPBUWOIPGDY-UHFFFAOYSA-N 3-amino-n-(4-aminophenyl)benzamide Chemical compound C1=CC(N)=CC=C1NC(=O)C1=CC=CC(N)=C1 UDKYPBUWOIPGDY-UHFFFAOYSA-N 0.000 description 1
- ICNFHJVPAJKPHW-UHFFFAOYSA-N 4,4'-Thiodianiline Chemical compound C1=CC(N)=CC=C1SC1=CC=C(N)C=C1 ICNFHJVPAJKPHW-UHFFFAOYSA-N 0.000 description 1
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- HSBOCPVKJMBWTF-UHFFFAOYSA-N 4-[1-(4-aminophenyl)ethyl]aniline Chemical compound C=1C=C(N)C=CC=1C(C)C1=CC=C(N)C=C1 HSBOCPVKJMBWTF-UHFFFAOYSA-N 0.000 description 1
- JCRRFJIVUPSNTA-UHFFFAOYSA-N 4-[4-(4-aminophenoxy)phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC(C=C1)=CC=C1OC1=CC=C(N)C=C1 JCRRFJIVUPSNTA-UHFFFAOYSA-N 0.000 description 1
- UTDAGHZGKXPRQI-UHFFFAOYSA-N 4-[4-[4-(4-aminophenoxy)phenyl]sulfonylphenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=C(S(=O)(=O)C=2C=CC(OC=3C=CC(N)=CC=3)=CC=2)C=C1 UTDAGHZGKXPRQI-UHFFFAOYSA-N 0.000 description 1
- KIFDSGGWDIVQGN-UHFFFAOYSA-N 4-[9-(4-aminophenyl)fluoren-9-yl]aniline Chemical compound C1=CC(N)=CC=C1C1(C=2C=CC(N)=CC=2)C2=CC=CC=C2C2=CC=CC=C21 KIFDSGGWDIVQGN-UHFFFAOYSA-N 0.000 description 1
- HOOIIRHGHALACD-UHFFFAOYSA-N 5-(2,5-dioxooxolan-3-yl)-3-methylcyclohex-3-ene-1,2-dicarboxylic acid Chemical compound C1C(C(O)=O)C(C(O)=O)C(C)=CC1C1C(=O)OC(=O)C1 HOOIIRHGHALACD-UHFFFAOYSA-N 0.000 description 1
- LNJNDNSXTZQOOP-UHFFFAOYSA-N 5-chloro-4-(2-chloro-5-methoxyphenyl)-2-methoxycyclohexa-2,4-diene-1,1-diamine Chemical group C1C(N)(N)C(OC)=CC(C=2C(=CC=C(OC)C=2)Cl)=C1Cl LNJNDNSXTZQOOP-UHFFFAOYSA-N 0.000 description 1
- JVERADGGGBYHNP-UHFFFAOYSA-N 5-phenylbenzene-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(=O)O)=CC(C=2C=CC=CC=2)=C1C(O)=O JVERADGGGBYHNP-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229920004482 WACKER® Polymers 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- OOCCDEMITAIZTP-UHFFFAOYSA-N allylic benzylic alcohol Natural products OCC=CC1=CC=CC=C1 OOCCDEMITAIZTP-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000004984 aromatic diamines Chemical class 0.000 description 1
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- YHASWHZGWUONAO-UHFFFAOYSA-N butanoyl butanoate Chemical compound CCCC(=O)OC(=O)CCC YHASWHZGWUONAO-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 125000000490 cinnamyl group Chemical group C(C=CC1=CC=CC=C1)* 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 1
- 229940076286 cupric acetate Drugs 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 description 1
- XCIXKGXIYUWCLL-UHFFFAOYSA-N cyclopentanol Chemical compound OC1CCCC1 XCIXKGXIYUWCLL-UHFFFAOYSA-N 0.000 description 1
- 125000002433 cyclopentenyl group Chemical group C1(=CCCC1)* 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- WYACBZDAHNBPPB-UHFFFAOYSA-N diethyl oxalate Chemical compound CCOC(=O)C(=O)OCC WYACBZDAHNBPPB-UHFFFAOYSA-N 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- LSACYLWPPQLVSM-UHFFFAOYSA-N isobutyric acid anhydride Chemical compound CC(C)C(=O)OC(=O)C(C)C LSACYLWPPQLVSM-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 229940100630 metacresol Drugs 0.000 description 1
- RTWNYYOXLSILQN-UHFFFAOYSA-N methanediamine Chemical compound NCN RTWNYYOXLSILQN-UHFFFAOYSA-N 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- KQSABULTKYLFEV-UHFFFAOYSA-N naphthalene-1,5-diamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1N KQSABULTKYLFEV-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- SXJVFQLYZSNZBT-UHFFFAOYSA-N nonane-1,9-diamine Chemical compound NCCCCCCCCCN SXJVFQLYZSNZBT-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 150000002940 palladium Chemical class 0.000 description 1
- ZVSLRJWQDNRUDU-UHFFFAOYSA-L palladium(2+);propanoate Chemical compound [Pd+2].CCC([O-])=O.CCC([O-])=O ZVSLRJWQDNRUDU-UHFFFAOYSA-L 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 1
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
- DUCKXCGALKOSJF-UHFFFAOYSA-N pentanoyl pentanoate Chemical compound CCCCC(=O)OC(=O)CCCC DUCKXCGALKOSJF-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- TVDSBUOJIPERQY-UHFFFAOYSA-N prop-2-yn-1-ol Chemical compound OCC#C TVDSBUOJIPERQY-UHFFFAOYSA-N 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- ORXDFZVXVSSTPU-UHFFFAOYSA-J tetrapotassium tetrachloride Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[K+].[K+].[K+].[K+] ORXDFZVXVSSTPU-UHFFFAOYSA-J 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は、ポリイミド、水溶性ポリエステルなどの原料
、ポリ塩化ビニルの可塑剤、エポキシ樹脂の硬化剤、そ
の他として広汎な分野で利用され得る新規な脂環式テト
ラカルボン酸およびその誘導体に関する。Detailed Description of the Invention [Field of Industrial Application] The present invention is a novel material that can be used in a wide range of fields as raw materials for polyimides, water-soluble polyesters, plasticizers for polyvinyl chloride, curing agents for epoxy resins, etc. The present invention relates to alicyclic tetracarboxylic acids and derivatives thereof.
［従来の技術〕
一般にテトラカルボン酸はポリイミド原料として有用で
あり、従来より汎用されているテトラカルボン酸の主な
ものとしては、ピロメリット酸、ペンゾフエノンテトラ
カルボン酸、ビフエニルテトラカルボン酸などの芳香族
テトラカルボン酸類が知られており、また、脂肪族テト
ラカルボン酸としては、ブタンテトラカルボン酸、５−
（２．５−ジオキソテトラヒド口−３−フラニル）−
３−メチル−３−シクロヘキセン−１，２−ジカルボン
酸などが知られている。[Prior art] Tetracarboxylic acids are generally useful as polyimide raw materials, and the main tetracarboxylic acids that have been widely used include pyromellitic acid, penzophenonetetracarboxylic acid, biphenyltetracarboxylic acid, etc. Aromatic tetracarboxylic acids are known, and aliphatic tetracarboxylic acids include butanetetracarboxylic acid, 5-
(2,5-dioxotetrahydro-3-furanyl)-
3-methyl-3-cyclohexene-1,2-dicarboxylic acid and the like are known.
［発明が解決しようとする問題点］
しかるに、芳香族テトラカルボン酸類を原料として得ら
れるポリイミド樹脂は耐熱性には優れているものの、溶
剤に対して全く不溶であったり、分解温度以下では溶融
しないなど、作業性が著しく悪いという問題点を有し、
一方、脂肪族テトラカルボン酸類を原料とするポリイミ
ド樹脂は、溶剤に対する溶解性には優れているものの、
芳香族テトラカルボン酸類によるポリイミド樹脂に比し
て耐熱性が劣るという問題点を有している。[Problems to be solved by the invention] However, although polyimide resins obtained using aromatic tetracarboxylic acids as raw materials have excellent heat resistance, they are completely insoluble in solvents or do not melt below the decomposition temperature. It has the problem of extremely poor workability, such as
On the other hand, polyimide resins made from aliphatic tetracarboxylic acids have excellent solubility in solvents, but
It has a problem of inferior heat resistance compared to polyimide resins made of aromatic tetracarboxylic acids.
このような背景から、溶剤可溶性に優れていて、しかも
耐熱性の優れたポリイミド樹脂を与えるテトラカルボン
酸類の開発が要請されており、現在までに、メチルジク
ロ口オクテンテトラカルボン酸類（特開昭６０−６１５
７９号公報、特開昭６０−６１５８２号公報）、３，
５． ６−トリ力ルボキシ−２−カルボキシメチルノ
ルボルナン類（特開昭６０−１０４０９１号公報）、ビ
シクロ［２． ２． １）ヘブタン−２． ３，
５． ６−テトラカルボン酸類（特開昭６３−５
７５５７号公報、特開昭６３−５７５８９号公報）など
が提案されている。これらは、剛直な構造を有する脂環
式テトラカルボン酸類である。Against this background, there has been a demand for the development of tetracarboxylic acids that provide polyimide resins with excellent solvent solubility and excellent heat resistance. 615
No. 79, JP-A No. 60-61582), 3.
5. 6-tricarboxy-2-carboxymethylnorbornanes (JP-A-60-104091), bicyclo[2. 2. 1) Hebutane-2. 3,
5. 6-tetracarboxylic acids (JP-A-63-5
7557, Japanese Unexamined Patent Publication No. 63-57589), etc. have been proposed. These are alicyclic tetracarboxylic acids with a rigid structure.
しかしながら、従来の脂環式テトラカルボン酸類は、可
溶性、可融性、゛吸水性、耐熱性などの諸特性において
、なお十分な物性を有するポリイミド樹脂を与えるもの
ではない。However, conventional alicyclic tetracarboxylic acids do not provide polyimide resins that still have sufficient physical properties in terms of solubility, fusibility, water absorption, heat resistance, and other properties.
［問題点を解決するための手段］
本発明は、以上のような事情に基づいてなされたもので
あって、例えば、好適な特性を有するポリイミド樹脂を
得るための原料、またはその中間体として有用な新規な
脂環式テトラカルボン酸およびその誘導体を提供するも
のである。[Means for Solving the Problems] The present invention has been made based on the above circumstances, and is useful as a raw material for obtaining a polyimide resin having suitable characteristics, or an intermediate thereof, for example. The present invention provides novel alicyclic tetracarboxylic acids and derivatives thereof.
すなわち、本発明は、下記一般式（Ｉ）または一般式（
ＩＩ）で表わされる脂環式テトラカルボン酸およびその
誘導体（以下、これらを総称して［テトラカルボン酸類
」という）を提供するものである。That is, the present invention provides the following general formula (I) or general formula (
The present invention provides alicyclic tetracarboxylic acids represented by II) and derivatives thereof (hereinafter collectively referred to as "tetracarboxylic acids").
（式中、Ｒ１〜Ｒ４はそれぞれ同一でも異なってもよく
、水素原子または炭化水素基を示す。）り
Ｃ
前記一般式（Ｉ）におけるＲ１〜Ｒ４において、炭化水
素基としては、メチル基、エチル基、プロビル基、イソ
プロビル基、ブチル基、シクロペンチル基、シクロヘキ
シル基、アリル基、ポモアリル基、シクロペンテニル基
、シクロへキセニル基、シンナミル基、プロパルギル基
などの炭素数１〜２５の脂肪族炭化水素基、フエニル基
、トリル基、キシリル基、ナフチル基などの炭素数６〜
２５の芳香族炭化水素基を挙げることができる。(In the formula, R1 to R4 may be the same or different, and represent a hydrogen atom or a hydrocarbon group.)
C In R1 to R4 in the general formula (I), the hydrocarbon group includes a methyl group, an ethyl group, a probyl group, an isopropyl group, a butyl group, a cyclopentyl group, a cyclohexyl group, an allyl group, a pomoallyl group, and a cyclopentenyl group. , aliphatic hydrocarbon groups having 1 to 25 carbon atoms such as cyclohexenyl group, cinnamyl group, and propargyl group; and aliphatic hydrocarbon groups having 6 to 25 carbon atoms such as phenyl group, tolyl group, xylyl group, and naphthyl group.
25 aromatic hydrocarbon groups may be mentioned.
本発明のテト．ラカルボン酸類のうち、一般式（１）に
おけるＲ１〜Ｒ４が炭化水素基である脂環式テトラカル
ボン酸の誘導体（以下、単に「誘導体」という）は、下
記一般式（ｍ）で表わされる化合物（以下、「化合物（
■）」という）に、パラジウム触媒の存在下、一酸化炭
素およびアルコールを反応させることにより、製造する
ことができる。Tet of the present invention. Among the lacarboxylic acids, derivatives of alicyclic tetracarboxylic acids in which R1 to R4 in general formula (1) are hydrocarbon groups (hereinafter simply referred to as "derivatives") are compounds represented by the following general formula (m) ( Hereinafter, "compound (
It can be produced by reacting carbon monoxide and alcohol in the presence of a palladium catalyst.
ここで用いることのできるパラジウム触媒としては、塩
化パラジウム、硝酸パラジウム、カリウムテトラク口口
バラデート、硫酸パラジウムなどのパラジウム無機酸塩
、酢酸パラジウム、プロピオン酸パラジウムなどのパラ
ジウム有機酸塩、およびパラジウム炭素、パラジウムシ
リカ、パラジウムアルミナなどの担体に担持させた金属
パラジウムが挙げられる。このパラジウム触媒は、化合
物（■）１モルに対して、通常、０．０００１〜０．
１モルの範囲で用いられる。Palladium catalysts that can be used here include palladium chloride, palladium nitrate, potassium tetrachloride, palladium inorganic acid salts such as palladium sulfate, palladium organic acid salts such as palladium acetate and palladium propionate, and palladium on carbon. Examples include metal palladium supported on a carrier such as palladium silica and palladium alumina. This palladium catalyst is usually 0.0001 to 0.00% per mole of compound (■).
It is used in a range of 1 mol.
この反応の遂行においては、通常、パラジウム触媒の再
酸化剤を併用することが好ましい。この再酸化剤として
は、銅化合物、鉄化合物などが使用され、例えば、塩化
第２銅、硝酸第２銅、硫酸第２銅、酢酸第２銅、塩化第
２鉄、硝酸第２鉄などを挙げることができる。また、再
酸化剤として酸素ガスと前記銅化合物を用い、ワッカー
反応を利用することも可能である。これらの銅化合物ま
たは鉄化合物の使用量は、化合物（■）１モルに対して
、通常、０．１〜１２モルの範囲で用いられる。In carrying out this reaction, it is usually preferable to use a palladium-catalyzed reoxidizing agent in combination. Copper compounds, iron compounds, and the like are used as the reoxidizing agent, such as cupric chloride, cupric nitrate, cupric sulfate, cupric acetate, ferric chloride, and ferric nitrate. can be mentioned. It is also possible to utilize Wacker reaction using oxygen gas and the copper compound as a reoxidizing agent. The amount of these copper compounds or iron compounds to be used is usually in the range of 0.1 to 12 mol per 1 mol of compound (■).
この反応に用いられるアルコールとしては、例えば、メ
タノール、エタノール、プロパノール、ブタノール、シ
クロペンタノール、シクロヘキサノール、アリルアルコ
ール、ホモアリルアルコール、シクロペンテニルアルコ
ール、シクロへキセニルアルコール、シンナミルアルコ
ール、プロパルギルアルコールなどの脂肪族アルコール
、ベンジルアルコール、ナフチルアルコールなどを単独
で、あるいは２種以上混合して用いることができ、上記
のうちでは脂肪族アルコール、特にメタノールが好まし
い。これらのアルコールの使用量は、化合物（■）１モ
ルに対して、通常、４モル以上、好ましくは４〜４００
モルである。Examples of alcohols used in this reaction include methanol, ethanol, propanol, butanol, cyclopentanol, cyclohexanol, allyl alcohol, homoallyl alcohol, cyclopentenyl alcohol, cyclohexenyl alcohol, cinnamyl alcohol, propargyl alcohol, etc. These aliphatic alcohols, benzyl alcohol, naphthyl alcohol, etc. can be used alone or in combination of two or more kinds, and among the above aliphatic alcohols, methanol is particularly preferred. The amount of these alcohols used is usually 4 mol or more, preferably 4 to 400 mol, per 1 mol of compound (■).
It is a mole.
この反応に用いられる一酸化炭素は、純粋な一酸化炭素
のみではなく、例えば、１０体積％以上の濃度となる割
合で一酸化炭素を含有するアルゴン、窒素などの不活性
ガスでもよい。なお、反応系への一酸化炭素の供給方法
としては、反応液中に加圧により導入する方法、反応液
中に常圧でパブリングさせながら導入する方法、単に反
応液表面に常圧で接触させる方法などが挙げられる。The carbon monoxide used in this reaction is not only pure carbon monoxide, but may also be an inert gas such as argon or nitrogen containing carbon monoxide at a concentration of 10% by volume or more. In addition, methods for supplying carbon monoxide to the reaction system include introducing it into the reaction solution under pressure, introducing it into the reaction solution while bubbling at normal pressure, and simply bringing it into contact with the surface of the reaction solution at normal pressure. Examples include methods.
この反応は、通常、溶媒の存在下で行なうが、溶媒とし
ては、ｎ−ヘキサン、シクロヘキサンなどの炭化水素化
合物、テトラヒドロフラン、ジメトキシエタンなどのエ
ーテル化合物、塩化メチレン、クロロホルムなどのハロ
ゲン化炭化水素などを用いることができ、化合物（ｍ）
と反応させるアルコール自体を溶媒として用いることも
できる。This reaction is usually carried out in the presence of a solvent, such as hydrocarbon compounds such as n-hexane and cyclohexane, ether compounds such as tetrahydrofuran and dimethoxyethane, and halogenated hydrocarbons such as methylene chloride and chloroform. Compound (m) can be used
The alcohol itself to be reacted with can also be used as a solvent.
この反応の反応温度は−８０〜１００℃、反応圧力は常
圧〜５０ｋｇ／ｃｊ，反応時間は１〜７２時間が適当で
ある。The appropriate reaction temperature for this reaction is -80 to 100°C, the reaction pressure is normal pressure to 50 kg/cj, and the reaction time is 1 to 72 hours.
本発明のテトラカルボン酸類のうち、一般式（Ｉ）にお
けるＲ１〜Ｒ４が水素原子である脂環式テトラカルボン
酸（以下、単に「テトラカルボン酸」という）は、前記
のようにして得られる誘導体を加水分解することにより
、製造することができる。Among the tetracarboxylic acids of the present invention, alicyclic tetracarboxylic acids in which R1 to R4 in general formula (I) are hydrogen atoms (hereinafter simply referred to as "tetracarboxylic acids") are derivatives obtained as described above. It can be produced by hydrolyzing.
この加水分解は、例えば、酸触媒または塩基触媒を用い
る方法によって高い効率で行なうことができる。ここで
、酸触媒としては、塩酸、硝酸、硫酸などの無機酸、ｐ
−トルエンスルホン酸、ギ酸、トリフルオロ酢酸などの
有機酸を用いることができ、また、塩基触媒としては、
水酸化ナトリウム、水酸化カリウムなどのアルカリ化合
物が用いられる。この加水分解は、一般的には溶媒の存
在下で行なわれ、溶媒としては水、または水とメタノー
ル、アセトン、テトラヒド口フランなどの親水性有機溶
媒との混合溶媒が用いられる。この加水分解における酸
触媒または塩基触媒の使用量は、誘導体１モルに対して
、通常、０．０００１〜０．４モルであり、反応温度は
室温〜１２０℃が適当である。This hydrolysis can be carried out with high efficiency, for example, by a method using an acid catalyst or a base catalyst. Here, as the acid catalyst, inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid, p
- Organic acids such as toluenesulfonic acid, formic acid, and trifluoroacetic acid can be used, and as base catalysts,
Alkaline compounds such as sodium hydroxide and potassium hydroxide are used. This hydrolysis is generally carried out in the presence of a solvent, and the solvent used is water or a mixed solvent of water and a hydrophilic organic solvent such as methanol, acetone, or tetrahydrofuran. The amount of the acid catalyst or base catalyst used in this hydrolysis is usually 0.0001 to 0.4 mol per 1 mol of the derivative, and the reaction temperature is suitably from room temperature to 120°C.
本発明の脂環式テトラカルボン酸類のうち、前記一般式
（ＩＩ）で表わされる脂環式テトラカルボン酸無水物（
以下、「テトラカルボン酸無水物」という）は、前記テ
トラカルボン酸を加熱処理、または脱水処理することに
より得られる。Among the alicyclic tetracarboxylic acids of the present invention, the alicyclic tetracarboxylic anhydride (
The tetracarboxylic acid anhydride (hereinafter referred to as "tetracarboxylic anhydride") can be obtained by subjecting the tetracarboxylic acid to heat treatment or dehydration treatment.
この加熱処理は、減圧下または不活性ガス下において、
テトラカルボン酸を、例えば１２０〜２５０℃の温度で
加熱する方法が利用される。この加熱処理は、テトラカ
ルボン酸に対して不活性な溶媒、例えばジエチルベンゼ
ン、ｔｅｒｔ−アミルベンゼンなどの中で行なうことが
できる。This heat treatment is performed under reduced pressure or inert gas.
A method is used in which tetracarboxylic acid is heated, for example, at a temperature of 120 to 250°C. This heat treatment can be carried out in a solvent inert to the tetracarboxylic acid, such as diethylbenzene or tert-amylbenzene.
また、脱水処理としては、無水酢酸などの脱水用酸無水
物を作用させる方法が代表的であり、テトラカルボン酸
１モルに対して、脱水用酸無水物を通常２モル以上、好
ましくは１０モル以上用い、例えば、ベンゼン、トルエ
ンなどの芳香族炭化水素化合物よりなる溶媒中、あるい
は無溶媒で行なう方法が挙げられる。In addition, a typical dehydration treatment is a method in which a dehydrating acid anhydride such as acetic anhydride is applied, and the dehydrating acid anhydride is usually 2 moles or more, preferably 10 moles or more, per 1 mole of tetracarboxylic acid. Examples of the above methods include methods in which the reaction is carried out in a solvent consisting of an aromatic hydrocarbon compound such as benzene and toluene, or in the absence of a solvent.
本発明のテトラカルボン酸類は、再結晶などにより精製
することもできる。The tetracarboxylic acids of the present invention can also be purified by recrystallization or the like.
本発明のテトラカルボン酸またはテトラカルボン酸無水
物は、ジアミンと反応させることによりポリ．アミド酸
（以下、単に「ボリアミド酸」という）とした後、該ポ
リアミド酸を脱水することにより、下記一般式（ＩＶ）
で表わされる繰り返し構造単位を有するポリイミド（以
下、単に「ポリイミド」という）にすることもできる。The tetracarboxylic acid or tetracarboxylic anhydride of the present invention can be reacted with a diamine to produce a polyurethane. After making the polyamic acid (hereinafter simply referred to as "boriamic acid"), by dehydrating the polyamic acid, the following general formula (IV) is obtained.
Polyimide having a repeating structural unit represented by (hereinafter simply referred to as "polyimide") can also be used.
（式中、Ｒ５は二価の有機基を示す。）上記一般式（Ｉ
Ｖ）におけるＲ５としては、例えば、
Ｘ１
ｎは０または１を示す）で示される芳香族基、（ＣＨ２
） （ｎ＝２ 〜２０）、ｎ
ＣＨ３
ζ
− （ＣＨ２）３ −Ｃ 一 （ＣＨ２）３ −ＣＨ
３
（式中、ｘ，、ｘ２、Ｘ３およびＸ４は同一でも異なっ
てもよく、−Ｈ，−ＣＨ３または−ＯＣＨ３、Ｙは−Ｃ
Ｈ２、−Ｃ２Ｈ４− 一〇一−Ｓ−
ＣＨ３
Ｉ
ＣＦ３
で示される炭素数２〜２０の脂肪族基または脂環族基な
どが挙げられる。(In the formula, R5 represents a divalent organic group.) The above general formula (I
R5 in V) is, for example, an aromatic group represented by (X1 n represents 0 or 1), (CH2
) (n=2 to 20), n CH3 ζ − (CH2)3 −C one (CH2)3 −CH
3 (where x, x2, X3 and X4 may be the same or different, -H, -CH3 or -OCH3, Y is -C
Examples include aliphatic groups or alicyclic groups having 2 to 20 carbon atoms represented by H2, -C2H4- 101-S- CH3 I CF3 .
ここで用いられるジアミンとしては、パラフエニレンジ
アミン、メタフエニレンジアミン、４，４′−ジアミノ
ジフエニルメタン、４，４′−ジアミノジフエニルエタ
ン、ベンジジン、４．４’−ジアミノジフエニルスルフ
ィド、４．４’ −ジアミノジフエニルスルホン、４．
４’ −ジアミノジフエニルエーテル、１，５−ジアミ
ノナフタレン、３，３′−ジチメル−４．４′ −ジア
ミノビフエニル、３．４’ −ジアミノベンズアニリド
、３，４′−ジアミノジフエニルエーテル、３．３′−
ジアミノベンゾフエノン、３．４’ −ジアミノベンゾ
フエノン、４．４’ −ジアミノベンゾフエノン、２
，２−ビス（４−（４−アミノフエノキシ）フエニル〕
プロパン、ビス（４−（４一アミノフエノキシ）フエニ
ル〕スルホン、１，４一ビス（４−アミノフエノキシ）
ベンゼン、ｌ，３−ビス（４−アミノフエノキシ）ベン
ゼン、１，３−ビス（３−アミノフエノキシ）ベンゼン
、９，９−ビス（４−アミノフエニル）−１０−ヒドロ
ーアンスラセン、９，９−ビス（４−アミノフエニル）
フルオレン、４．４′ −メチレンービス（２−クロロ
アニリン）、２．２’ ，５．５’テトラクロ口−４．
４′−ジアミノビフエニル、２，２′−ジクロロー４，
４−ジアミノ−５，５′−ジメトキシビフエニル、３．
３’ −ジメトキシ−４，４′−ジアミノビフエニルな
どの芳香族ジアミン、１．１’ −メタキシリレンジア
ミン、１．３−ブロバンジアミン、テトラメチレンジア
ミン、ペンタメチレンジアミン、ヘキサメチレンジアミ
ン、ヘブタメチレンジアミン、オクタメチレンジアミン
、ノナメチレンジアミン、４．４’一ジメチルへブタメ
チレンジアミン、１，４−ジアミノシク口ヘキサン、イ
ソホロンジアミン、テトラヒド口ジシク口ペンタジエニ
レンジアミン、ヘキサヒド口−４．７−メタノインダニ
レンジメチレンジアミン、トリシクロ（６．２．１．０
２゜７）一ウンデシレンジメチルジアミンなどの脂肪族
または脂環族ジアミン、および
（式中、Ｒは炭素数１〜１２のメチル基、エチル基、プ
ロビル基などのアルキル基、シクロヘキシル基などの脂
環族基、またはフエニル基などの芳香族基、ｍは１〜３
整数、ｎは１〜２０の整数を示す。）
などで示されるジアミノオルガノシロキサンを挙げるこ
とができる。The diamines used here include paraphenylene diamine, metaphenylene diamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ethane, benzidine, 4,4'-diaminodiphenyl sulfide, 4.4'-diaminodiphenylsulfone, 4.
4'-diaminodiphenyl ether, 1,5-diaminonaphthalene, 3,3'-dithymel-4,4'-diaminobiphenyl, 3,4'-diaminobenzanilide, 3,4'-diaminodiphenyl ether, 3.3'-
Diaminobenzophenone, 3.4'-diaminobenzophenone, 4.4'-diaminobenzophenone, 2
,2-bis(4-(4-aminophenoxy)phenyl)
Propane, bis(4-(4-aminophenoxy)phenyl)sulfone, 1,4-bis(4-aminophenoxy)
Benzene, l,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 9,9-bis(4-aminophenyl)-10-hydroanthracene, 9,9-bis( 4-aminophenyl)
Fluorene, 4.4'-methylenebis(2-chloroaniline), 2.2',5.5'tetrachloro-4.
4'-diaminobiphenyl, 2,2'-dichloro 4,
4-diamino-5,5'-dimethoxybiphenyl, 3.
Aromatic diamines such as 3'-dimethoxy-4,4'-diaminobiphenyl, 1,1'-methaxylylene diamine, 1,3-brobanediamine, tetramethylene diamine, pentamethylene diamine, hexamethylene diamine, hebutylene diamine, etc. Methylene diamine, octamethylene diamine, nonamethylene diamine, 4.4'-dimethylbutamethylene diamine, 1,4-diaminoxyhexane, isophorone diamine, tetrahydride pentadienyl diamine, hexahydride-4.7- Methanoindani dimethylenediamine, tricyclo(6.2.1.0
2.7) Aliphatic or alicyclic diamines such as undecylendimethyldiamine, and (wherein R is an alkyl group having 1 to 12 carbon atoms such as a methyl group, an ethyl group, or a probyl group, or an alicyclic group such as a cyclohexyl group) group group or aromatic group such as phenyl group, m is 1 to 3
An integer, n represents an integer of 1 to 20. ) and the like are diaminoorganosiloxanes.
また、これらのジアミンは２種以上併用することもでき
る。Moreover, two or more types of these diamines can also be used in combination.
前記一般式（ＩＶ）におけるＲ５は、これらのジアミン
の残基である。R5 in the general formula (IV) is a residue of these diamines.
ポリイミドを得るには、まずテトラカルボン酸またはテ
トラカルボン酸無水物とジアミンとを、通常、有機溶媒
中で反応させてポリアミック酸の有機溶媒溶液を得る。To obtain polyimide, first, a tetracarboxylic acid or tetracarboxylic acid anhydride and a diamine are reacted, usually in an organic solvent, to obtain an organic solvent solution of polyamic acid.
得られたポリアミック酸の有機溶媒溶液は、そのまま、
または有機溶媒溶液から常法によりポリアミック酸を回
収し、必要に応じて精製した後、再度有機溶媒に溶解し
、有機カルボン酸無水物の存在下に、所望により３級ア
ミンを添加してイミド化反応を行なう。The obtained organic solvent solution of polyamic acid was used as it was.
Alternatively, polyamic acid is recovered from an organic solvent solution by a conventional method, purified if necessary, then dissolved in an organic solvent again, and imidized by adding a tertiary amine if desired in the presence of an organic carboxylic acid anhydride. Carry out the reaction.
本発明に、おけるイミド化反応時の有機溶媒としては、
例えば、Ｎ−メチルピロリドン、Ｎ， Ｎージメチル
アセトアミド、Ｎ，Ｎ−ジメチルホルムアミド、ジメチ
ルスルホキシド、テトラメチル尿素、ヘキサメチルホス
ホルトリアミドなどの極性溶媒が使用される。In the present invention, as the organic solvent during the imidization reaction,
For example, polar solvents such as N-methylpyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethylsulfoxide, tetramethylurea, hexamethylphosphortriamide, etc. are used.
テトラカルボン酸またはテトラカルボン酸無水物とジア
ミンとの反応割合は、当モルで行なうのが好ましいが、
目的とするポリアミック酸が得られる限り、これらのモ
ノマーの比率を若干変動させてもよい。例えば、高分子
量のポリアミック酸を得るためには、テトラカルボン酸
またはテトラカルボン酸無水物４モルに対して、ジアミ
ン０．７〜１．３モル程度使用することが好ましい。ま
た、モノアミンやジカルボン酸無水物を添加してポリア
ミック酸の分子量を調整することもできる。The reaction ratio of tetracarboxylic acid or tetracarboxylic acid anhydride and diamine is preferably carried out in equimolar terms;
The ratio of these monomers may be slightly varied as long as the desired polyamic acid is obtained. For example, in order to obtain a high molecular weight polyamic acid, it is preferable to use about 0.7 to 1.3 moles of diamine per 4 moles of tetracarboxylic acid or tetracarboxylic acid anhydride. Moreover, the molecular weight of the polyamic acid can also be adjusted by adding a monoamine or a dicarboxylic acid anhydride.
ポリアミック酸を製造する際の反応温度は、通常、テト
ラカルボン酸を用いるときは５０〜３００℃、好ましく
は１００〜２５０℃、テトラカルボン酸無水物を用いる
ときは０〜１００℃である。一般的にテトラカルボン酸
とテトラカルボン酸無水物とでは、テトラカルボン酸無
水物を用いることが好ましく、有機溶媒に可溶なポリア
ミック酸の製造が容易になる。The reaction temperature when producing polyamic acid is usually 50 to 300°C when using a tetracarboxylic acid, preferably 100 to 250°C, and 0 to 100°C when using a tetracarboxylic anhydride. In general, it is preferable to use a tetracarboxylic acid anhydride as the tetracarboxylic acid and the tetracarboxylic anhydride, which facilitates the production of a polyamic acid that is soluble in an organic solvent.
なお、テトラカルボン酸またはテトラカルボン酸無水物
とジアミンとを反応させる際の有機溶媒としでは、前記
極性溶媒以外に一般的有機溶媒であるアルコール類、フ
ェノール類、ケトン類、エステル類、ラクトン類、エー
テル類、ハロゲン化炭化水素類、炭化水素類、例えばメ
チルアルコール、エチルアルコール、イソプロビルアル
コール、エチレングリコール、ブロビレングリコール、
１，４−ブタンジオール、トリエチレングリコール、エ
チレングリコールモノメチルエーテル、フェノール、ｍ
−クレゾール、アセトン、メチルエチルケトン、メチル
イソブチルケトン、シクロヘキサノン、酢酸メチル、酢
酸エチル、酢酸ブチル、シュウ酸ジエチル、マロン酸ジ
エチル、γ−プチロラクトン、ジエチルエーテル、エチ
レングリコールジメチルエーテル、ジエチレングリコー
ルジメチルエーテル、テトラヒド口フラン、ジクロルメ
タン、１，２−ジクロルエタン、１，４−ジクロルブタ
ン、トリクロルエタン、クロルベンゼン、０−ジクロル
ベンゼン、ヘキサン、ヘブタン、オクタン、ベンゼン、
トルエン、キシレンなども使用することができる。In addition, in addition to the polar solvents mentioned above, general organic solvents such as alcohols, phenols, ketones, esters, lactones, Ethers, halogenated hydrocarbons, hydrocarbons such as methyl alcohol, ethyl alcohol, isopropyl alcohol, ethylene glycol, brobylene glycol,
1,4-butanediol, triethylene glycol, ethylene glycol monomethyl ether, phenol, m
-Cresol, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, diethyl malonate, γ-butyrolactone, diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene, 0-dichlorobenzene, hexane, hebutane, octane, benzene,
Toluene, xylene, etc. can also be used.
特に、上記極性溶媒と一般的な有機溶媒とを混合して用
いると高分子量のポリアミック酸を得やすくなる。例え
ば、アセトン／ジメチルホルムアミド＝７／３ （容量
比）程度の溶媒を用いてテトラカルボン酸無水物とジア
ミンとを反応させると反応系が均一となり、特に高分子
量のポアミック酸が得やすくなる。In particular, when the above polar solvent and a general organic solvent are mixed and used, it becomes easier to obtain a high molecular weight polyamic acid. For example, when a tetracarboxylic acid anhydride and a diamine are reacted using a solvent of acetone/dimethylformamide=7/3 (volume ratio), the reaction system becomes homogeneous, and a poamic acid having a particularly high molecular weight is easily obtained.
これらの一般的有機溶媒を用いてテトラカルボン酸また
はテトラカルボン酸無水物とジアミンとを反応させた場
合は、一般的には生成したポリアミック酸を回収し、再
度上記極性溶媒溶液としてイミド化させる。When a tetracarboxylic acid or a tetracarboxylic anhydride is reacted with a diamine using these general organic solvents, the produced polyamic acid is generally recovered and imidized again as a solution in the above polar solvent.
このようにして得られるポリアミック酸の極限粘度（０
．５ｇ：／Ｊ，極性溶媒中、３０℃）は、好ましくは０
．２〜１０濯／ｇである。The intrinsic viscosity of the polyamic acid obtained in this way (0
．． 5g:/J, in a polar solvent at 30°C) is preferably 0
．． The amount is 2 to 10 rinsings/g.
本発明で使用されるポリアミック酸の有機溶媒溶液の濃
度は、好ましくは１〜５０重量％、特に好ましくは１〜
３０重量％である。The concentration of the organic solvent solution of polyamic acid used in the present invention is preferably 1 to 50% by weight, particularly preferably 1 to 50% by weight.
It is 30% by weight.
本発明で使用される有機カルボン酸無水物の沸点は、２
５０°Ｃ以下であることが好ましい。有機カルボン酸無
水物の沸点が２５０℃を超えると、フィルム化時に加熱
により溶媒を除去する工程で、有機カルボン酸無水物が
同時に除去されず、フィルム中に残留することになり、
物性などに悪影響を与える。The boiling point of the organic carboxylic acid anhydride used in the present invention is 2
Preferably, the temperature is 50°C or less. If the boiling point of the organic carboxylic acid anhydride exceeds 250°C, the organic carboxylic acid anhydride will not be removed at the same time in the process of removing the solvent by heating during film formation, and will remain in the film.
Adversely affects physical properties, etc.
このような有機カルボン酸無水物としては、例えば、無
水酢酸、無水プロビオン酸、無水酪酸、無水イソ酪酸、
無水吉草酸などが使用される。これらの有機カルボン酸
の混合酸無水物、例えば、酢酸とブロビオン酸から得ら
れる酸無水物なども使用可能である。Examples of such organic carboxylic acid anhydrides include acetic anhydride, probionic anhydride, butyric anhydride, isobutyric anhydride,
Valeric anhydride and the like are used. Mixed acid anhydrides of these organic carboxylic acids, such as acid anhydrides obtained from acetic acid and brobionic acid, can also be used.
有機カルボン酸無水物の添加量は、ポリアミック酸の繰
り返し構造単位１モル当り０．２〜２０倍モルが好まし
い。０．２倍モル未満の場合はイミド化反応の進行が遅
くなり、また２０倍モルを超えるとポリアミック酸の有
機溶媒に対する溶解度が低下する。The amount of organic carboxylic acid anhydride added is preferably 0.2 to 20 moles per mole of repeating structural unit of polyamic acid. When the amount is less than 0.2 times the mole, the imidization reaction progresses slowly, and when it exceeds 20 times the mole, the solubility of the polyamic acid in the organic solvent decreases.
本発明において、イミド化反応を促進させるために、所
望により触媒として３級アミンを添加することができる
。３級アミンは、イミド化反応の促進のほかに、得られ
るポリイミド化合物の溶液粘度の低下を抑制する効果も
生ずる。In the present invention, in order to promote the imidization reaction, a tertiary amine can be added as a catalyst if desired. In addition to promoting the imidization reaction, the tertiary amine also has the effect of suppressing a decrease in the solution viscosity of the resulting polyimide compound.
本発明に使用される３級アミンは、有機カルボン酸無水
物の場合と同様な理由で沸点２５０℃以下のものが好ま
しく、例えば、トリエチルアミン、トリブロビルアミン
、トリブチルアミンなどの脂肪族３級アミン、Ｎ，Ｎ−
ジメチルアニリンなどの芳香族３級アミン、ビリジン、
２−メチルビリジン、Ｎ−メチルイミダゾール、キノリ
ンなどの複素環化合物が挙げられる。The tertiary amine used in the present invention preferably has a boiling point of 250°C or lower for the same reason as the organic carboxylic acid anhydride. For example, aliphatic tertiary amines such as triethylamine, tribubylamine, and tributylamine , N, N-
Aromatic tertiary amines such as dimethylaniline, pyridine,
Examples include heterocyclic compounds such as 2-methylpyridine, N-methylimidazole, and quinoline.
３級アミンの添加量は、ポリアミック酸の繰り返し構造
単位１モルあたりの２０倍モル以下が好ましい。２０倍
モルを超えるとポリアミック酸の有機溶媒に対する溶解
性が低下する傾向にある。The amount of the tertiary amine added is preferably 20 times or less in mole per mole of repeating structural units of the polyamic acid. When the amount exceeds 20 times the mole, the solubility of polyamic acid in organic solvents tends to decrease.
本発明においてイミド化反応は、前記反応で得られたポ
リアミック酸の有機溶媒溶液をそのまま加熱処理するか
、生成したポリアミック酸を回収した後、必要に応じて
精製し、ポリアミド酸の製造に用いた溶媒と同一または
異なる有機溶媒に再溶解させたものを加熱処理して行な
われる。イミド化反応の反応温度は、好ましくは６０〜
２００℃、特に好ましくは１００〜１７０℃である。６
０℃未満ではイミド化反応の進行が遅れ、また２００℃
を超えるとポリイミド化合物の分子量が大きく低下する
。In the present invention, the imidization reaction is carried out by heat-treating the organic solvent solution of polyamic acid obtained in the reaction as it is, or by collecting the produced polyamic acid, and then purifying it as necessary and using it for producing polyamic acid. This is carried out by redissolving the solvent in the same or different organic solvent and heat-treating it. The reaction temperature of the imidization reaction is preferably 60~
The temperature is 200°C, particularly preferably 100-170°C. 6
At temperatures below 0°C, the progress of the imidization reaction is delayed, and at temperatures below 200°C,
If it exceeds this, the molecular weight of the polyimide compound will decrease significantly.
有機カルボン酸無水物および３級アミンの添加順序は、
いずれが先でもよく、また両者を混合してから添加して
もよい。The order of addition of organic carboxylic acid anhydride and tertiary amine is:
Either one may be added first, or the two may be mixed and then added.
このようにして得られるポリイミドの極限粘度（０．
５ｇ／ｄｆ！、極性溶媒中、３０℃）は、通常０．１
５〜８ｄｆ！／ｇ，好ましくは０． ３〜４ｄｌ／ｇ
である。The intrinsic viscosity of the polyimide thus obtained (0.
5g/df! , in a polar solvent at 30°C) is usually 0.1
5~8df! /g, preferably 0. 3~4dl/g
It is.
このようにして得られたポリイミドは、ガラス板、金属
板などの基材の上に、反応後のポリイミドの有機溶媒溶
液を流延した後、加熱などの方法により有機溶媒、有機
カルボン酸無水物および３級アミンを除去することによ
りフィルム化することができる。また、反応後のポリイ
ミドの有機溶媒溶液から、ポリイミドを回収した後、有
機溶媒に再溶解させ、次いで上記方法によりフィルム化
することもできる。この再溶解に用いられる有機溶媒と
しては、前記の極性溶媒のほか、ポリイミドを溶解する
溶媒、例えばメタクレゾールなどのフェノール系溶媒な
どが挙げられる。The polyimide thus obtained is produced by casting a solution of the reacted polyimide in an organic solvent onto a substrate such as a glass plate or a metal plate, and then applying the organic solvent, organic carboxylic acid anhydride, etc. by heating or other methods. A film can be formed by removing the tertiary amine and the tertiary amine. Alternatively, after the polyimide is recovered from the organic solvent solution of the polyimide after the reaction, it can be redissolved in the organic solvent and then formed into a film by the above method. Examples of the organic solvent used for this redissolution include, in addition to the above-mentioned polar solvents, solvents that dissolve polyimide, such as phenolic solvents such as metacresol.
本発明のテトラカルボン酸類を用いて得られるポリイミ
ドは、耐熱性、機械的特性、電気特性、耐薬品特性など
に優れ、しかもフィルム製造時の作業性に優れ、フィル
ム化時の収縮が少な《、高温下で使用するフィルム、接
着剤、塗料などに有用であり、具体的にはプリント配線
基板、フレキシブルプリント配線基板、半導体集積回路
素子の表面保護膜、エナメル電線用被覆剤、各種積層板
などの電気絶縁材料などとして広範囲の用途に使用する
ことができる。The polyimide obtained using the tetracarboxylic acids of the present invention has excellent heat resistance, mechanical properties, electrical properties, chemical resistance properties, etc., and also has excellent workability during film production and has little shrinkage during film formation. It is useful for films, adhesives, paints, etc. that are used under high temperatures.Specifically, it is useful for printed wiring boards, flexible printed wiring boards, surface protection films for semiconductor integrated circuit elements, coatings for enameled electric wires, various laminates, etc. It can be used in a wide range of applications, including as an electrical insulating material.
［実 施 例］
以下、実施例を挙げ本発明をさらに具体的に説明するが
、本発明はこれらの実施例に制限されるものではない。[Examples] Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.
実施例１
化合物（ＩＩＩ） １６． ２ｇ （０． １０ｍｏ
ｌ ） 、塩化第２銅１１０． ４ｇ （０． ８２
ｍｏｌ ） 、５重量パラジウム炭素３． １ｇ （
０． ０００２９ｍｏｌ ）、およびメタノール３０
０ｍｌを反応容器に仕込み、一酸化炭素を導入しながら
室温にて激しく撹拌し、４時間反応させた後、系内から
一酸化炭素を除き、反応液をＰ過し、Ｐ液を濃縮後、ク
ロロホルム１００ｍｌを加え、水１００ｍｌで洗浄した
。さらに、このクロロホルム層を飽和炭素水素ナトリウ
ム水溶液で洗浄した後、クロロホルム層を濃縮し、残留
固形分をエタノールから再結晶することにより、下記の
構造を有する分子量３９４、融点１４６〜１４７℃の化
合物を２２．９ｇ得た。得られた化合物の赤外吸収スペ
クトルおよび核磁気共鳴スペクトルを測定した。チャー
トをそれぞれ第１図および第２図に示す。Example 1 Compound (III) 16. 2g (0.10mo
l), cupric chloride 110. 4g (0.82
mol), 5 weight palladium on carbon 3. 1g (
0. 00029 mol), and methanol 30
Pour 0ml into a reaction container, stir vigorously at room temperature while introducing carbon monoxide, react for 4 hours, remove carbon monoxide from the system, filter the reaction solution with P, concentrate the P solution, 100 ml of chloroform was added and washed with 100 ml of water. Furthermore, after washing this chloroform layer with a saturated sodium bicarbonate aqueous solution, the chloroform layer was concentrated and the remaining solid content was recrystallized from ethanol to obtain a compound having the following structure with a molecular weight of 394 and a melting point of 146-147°C. 22.9g was obtained. The infrared absorption spectrum and nuclear magnetic resonance spectrum of the obtained compound were measured. The charts are shown in FIGS. 1 and 2, respectively.
実施例２
実施例１で得られた化合物１０ｇ （０．０２５ｍｏｌ
）を反応容器に入れ、メタノール３０ｍｌに懸濁させ
た後、塩酸（４０ｍｌ）および水（３０ｍｌ）を加え、
５０℃で４８時間反応させた。その後、溶媒を留去して
濃縮し、下記の構造を有する融点１９８℃の化合物８．
１２ｇを得、得られた化合物の赤外吸収スペクトルを測
定した。チャートを第３図に示す。Example 2 10 g (0.025 mol) of the compound obtained in Example 1
) was placed in a reaction vessel and suspended in 30 ml of methanol, then hydrochloric acid (40 ml) and water (30 ml) were added.
The reaction was carried out at 50°C for 48 hours. Thereafter, the solvent was distilled off and concentrated, and a compound 8. having the following structure and a melting point of 198°C was obtained.
12 g was obtained, and the infrared absorption spectrum of the obtained compound was measured. The chart is shown in Figure 3.
実施例３
（１）実施例２で得られた化合物１０ｇ （０． ０
３ｍｏｌ ）を１００ｍｌ無水酢酸に溶解し、還流下、
６時間反応させた。放冷後、析出した白色固体を無水エ
ーテルで洗浄することにより、下記の構造を有する分子
量３０３ （Ｍ” １．） 、融点３０５〜３０６゜Ｃ
の化合物７．８ｇを得た。得られた化合物の赤外吸収ス
ペクトル測定した。チャートを第４図に示す。Example 3 (1) 10 g of the compound obtained in Example 2 (0.0
3 mol) was dissolved in 100 ml acetic anhydride, and under reflux,
The reaction was allowed to proceed for 6 hours. After cooling, the precipitated white solid was washed with anhydrous ether to obtain the following structure with a molecular weight of 303 (M" 1.) and a melting point of 305-306°C.
7.8 g of the compound was obtained. The infrared absorption spectrum of the obtained compound was measured. The chart is shown in Figure 4.
試験例１
４，４′−ジアミノジフエニルエーテル１０．０１ｇ
（０．０５ｍｏｌ ）を無水Ｎ−メチルビロリドン１０
０．！５２ｇに溶解せしめ、この溶液中に実施例３で得
られた化合物１５．１２ｇ （０．０５ｍｏｌ）を添加
し、室温で４時間、窒素雰囲気下で撹拌し、粘調なポリ
アミド酸のＮ−メチルビロリドン溶液を得た。このボリ
アミド酸の極限粘度〔η〕 （３０℃、Ｎ−メチルピロ
リドン中）は０．８０ｃｌｆ／ｇであった。このポリア
ミド酸溶液をガラス板上に流延し、１２０℃で１時間、
２００°Ｃで３時間加熱することにより、下記の繰り返
し構造単位を有し、極限粘度〔η〕 （３０℃、Ｎ−メ
チルビ口ドン中）が０．５８ｄ１／ｇであるポリイミド
を得た。Test Example 1 4,4'-diaminodiphenyl ether 10.01g
(0.05 mol) of anhydrous N-methylpyrrolidone 10
0. ! 15.12 g (0.05 mol) of the compound obtained in Example 3 was added to this solution, and the mixture was stirred at room temperature for 4 hours under a nitrogen atmosphere. A solution was obtained. The intrinsic viscosity [η] (30° C., in N-methylpyrrolidone) of this polyamic acid was 0.80 clf/g. This polyamic acid solution was cast onto a glass plate and heated at 120°C for 1 hour.
By heating at 200°C for 3 hours, a polyimide having the following repeating structural unit and having an intrinsic viscosity [η] (30°C, in N-methylbibutene) of 0.58 d1/g was obtained.
イミド結合の確認は、赤外吸収スペクトルにおいて、ポ
リアミド酸が有する１５４０ｃｍ”付近のＮＨの吸収の
消失、および新たなイミドカルボニル基に由来する１７
５０〜１７８０付近の吸収により確認した。第１表に得
られたポリイミドの５％加熱減量温度および熱分解温度
を示す。The imide bond was confirmed by the disappearance of the NH absorption of polyamic acid near 1540 cm in the infrared absorption spectrum and the 17
Confirmed by absorption around 50 to 1780. Table 1 shows the 5% heating loss temperature and thermal decomposition temperature of the polyimide obtained.
ＩＩ ＩＩＯ
ｏ
試験例２
試験例１において、４．４’ −ジアミノジフエニルエ
ーテルのかわりに、４．４’ −ジアミノジフエニルメ
タン９． ９１ｇ （０． ０５ｍｏｌ ）を用い
、無水Ｎ−メチルピロリドンの使用量を１００．１２ｇ
とした以外は、試験例１と同様に反応を行ない、下記の
繰り返し構造単位を有し、極限粘度〔η〕 （３０℃、
Ｎ−メチルビロリドン中）が０．４２瀬／ｇであるポリ
アミドを得た。第１表に得られたポリイミドの５％加熱
減量温度および熱分解温度を示す。II IIO
o Test Example 2 In Test Example 1, 4.4'-diaminodiphenyl methane 9. was used instead of 4.4'-diaminodiphenyl ether. Using 91 g (0.05 mol), the amount of anhydrous N-methylpyrrolidone used was 100.12 g.
The reaction was carried out in the same manner as in Test Example 1, except that the following repeating structural units were used, and the intrinsic viscosity [η] (30℃
A polyamide containing 0.42 N-methylpyrrolidone/g was obtained. Table 1 shows the 5% heating loss temperature and thermal decomposition temperature of the polyimide obtained.
試験例３
試験例１において、４，４′−ジアミノジフエニルエー
テルのかわりに、２，２−ビス〔４一（４−アミノフエ
ノキシ）フエニル〕プロパン２０． ５２ｇ （０．
０５ｍｏｌ ）を用い、無水Ｎ−メチルピロリドン
の使用毒を１４２、５６ｇとした以外は、試験例１と同
様に反応を行ない、下記の繰り返し構造単位を有し、極
限粘度〔η〕３０℃、Ｎ−メチルビロリドン中）が０．
９１ｃｌｅ／ｇであるポリイミドを得た。第１表に得ら
れたポリイミドの５％加熱減量温度および熱分解温度を
示す。Test Example 3 In Test Example 1, 2,2-bis[4-(4-aminophenoxy)phenyl]propane was used instead of 4,4'-diaminodiphenyl ether. 52g (0.
The reaction was carried out in the same manner as in Test Example 1, except that the amount of anhydrous N-methylpyrrolidone used was 142.56 g. - in methylpyrrolidone) is 0.
A polyimide having a concentration of 91 cle/g was obtained. Table 1 shows the 5% heating loss temperature and thermal decomposition temperature of the polyimide obtained.
以下余白
第１表
［発明の効果］
本発明の脂環式テトラカルボン酸類は、可溶性、低吸水
性、耐熱性などに優れたポリイミドを与える原料として
有用である。Below is Table 1 in the margin [Effects of the Invention] The alicyclic tetracarboxylic acids of the present invention are useful as raw materials for producing polyimides with excellent solubility, low water absorption, heat resistance, and the like.
第１図は、実施例１で得られた化合物の赤外吸収スペク
トルを、第２図は、実施例１で得られた化合物の核磁気
共鳴スペクトルを、第３図は、実施例２で得られた化合
物の赤外吸収スペクトルを、第４図は、実施例３で得ら
れた化合物の赤外吸収スペクトルを示す図である。
特許出願人 日本合成ゴム株式会社
透過率（％）
透過率
（％）
透過率
（％）Figure 1 shows the infrared absorption spectrum of the compound obtained in Example 1, Figure 2 shows the nuclear magnetic resonance spectrum of the compound obtained in Example 1, and Figure 3 shows the nuclear magnetic resonance spectrum of the compound obtained in Example 2. FIG. 4 shows an infrared absorption spectrum of the compound obtained in Example 3. Patent applicant: Japan Synthetic Rubber Co., Ltd. Transmittance (%) Transmittance (%) Transmittance (%)
Claims (1)
される脂環式テトラカルボン酸およびその誘導体。 ▲数式、化学式、表等があります▼・・・・・・・・・
（ I ） （式中、Ｒ＾１〜Ｒ＾４はそれぞれ同一でも異なっても
よく、水素原子または炭化水素基を示す。） ▲数式、化学式、表等があります▼・・・・・・・・・
・・・・（II）(1) Alicyclic tetracarboxylic acids represented by the following general formula (I) or general formula (II) and derivatives thereof. ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・・・・
(I) (In the formula, R^1 to R^4 may be the same or different, and represent a hydrogen atom or a hydrocarbon group.) ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・・・・・・・
...(II)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1057368A JP2666457B2 (en) | 1989-03-09 | 1989-03-09 | Alicyclic tetracarboxylic acids and derivatives thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1057368A JP2666457B2 (en) | 1989-03-09 | 1989-03-09 | Alicyclic tetracarboxylic acids and derivatives thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02235842A true JPH02235842A (en) | 1990-09-18 |
| JP2666457B2 JP2666457B2 (en) | 1997-10-22 |
Family
ID=13053647
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1057368A Expired - Lifetime JP2666457B2 (en) | 1989-03-09 | 1989-03-09 | Alicyclic tetracarboxylic acids and derivatives thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2666457B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008007629A1 (en) * | 2006-07-10 | 2008-01-17 | Nissan Chemical Industries, Ltd. | Polyamic acid and polyimide |
| JP5345709B2 (en) * | 2010-02-09 | 2013-11-20 | Ｊｘ日鉱日石エネルギー株式会社 | Norbornane-2-spiro-α-cycloalkanone-α′-spiro-2 ″ -norbornane-5,5 ″, 6,6 ″ -tetracarboxylic dianhydrides, norbornane-2-spiro-α -Cycloalkanone-α'-spiro-2 ''-norbornane-5,5 '', 6,6 ''-tetracarboxylic acid and its esters, norbornane-2-spiro-α-cycloalkanone-α ′ -Spiro-2 "-norbornane-5,5", 6,6 "-tetracarboxylic dianhydride production method, polyimide obtained using the same, and polyimide production method |
| WO2014050788A1 (en) * | 2012-09-28 | 2014-04-03 | Ｊｘ日鉱日石エネルギー株式会社 | Method for producing carboxylic acid anhydride |
| WO2017209199A1 (en) * | 2016-05-31 | 2017-12-07 | 宇部興産株式会社 | Method for producing alicyclic tetracarboxylic acid dianhydride |
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1989
- 1989-03-09 JP JP1057368A patent/JP2666457B2/en not_active Expired - Lifetime
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008007629A1 (en) * | 2006-07-10 | 2008-01-17 | Nissan Chemical Industries, Ltd. | Polyamic acid and polyimide |
| US8067527B2 (en) | 2006-07-10 | 2011-11-29 | Nissan Chemical Industries, Ltd. | Polyamic acid and polyimide |
| JP5345709B2 (en) * | 2010-02-09 | 2013-11-20 | Ｊｘ日鉱日石エネルギー株式会社 | Norbornane-2-spiro-α-cycloalkanone-α′-spiro-2 ″ -norbornane-5,5 ″, 6,6 ″ -tetracarboxylic dianhydrides, norbornane-2-spiro-α -Cycloalkanone-α'-spiro-2 ''-norbornane-5,5 '', 6,6 ''-tetracarboxylic acid and its esters, norbornane-2-spiro-α-cycloalkanone-α ′ -Spiro-2 "-norbornane-5,5", 6,6 "-tetracarboxylic dianhydride production method, polyimide obtained using the same, and polyimide production method |
| WO2014050788A1 (en) * | 2012-09-28 | 2014-04-03 | Ｊｘ日鉱日石エネルギー株式会社 | Method for producing carboxylic acid anhydride |
| WO2017209199A1 (en) * | 2016-05-31 | 2017-12-07 | 宇部興産株式会社 | Method for producing alicyclic tetracarboxylic acid dianhydride |
| CN109415379A (en) * | 2016-05-31 | 2019-03-01 | 宇部兴产株式会社 | The method for generating Alicyclic tetracarboxylic acid dianhydride |
| JPWO2017209199A1 (en) * | 2016-05-31 | 2019-04-04 | 宇部興産株式会社 | Method for producing alicyclic tetracarboxylic dianhydride |
| JP2021138952A (en) * | 2016-05-31 | 2021-09-16 | 宇部興産株式会社 | Polyimide precursor, polyimide, polyimide film, substrate, and tetracarboxylic acid dianhydride used for producing polyimide |
| CN111961061A (en) * | 2019-05-20 | 2020-11-20 | 北京八亿时空液晶科技股份有限公司 | Novel dianhydride compound and preparation method and application thereof |
| CN111961061B (en) * | 2019-05-20 | 2023-06-02 | 北京八亿时空液晶科技股份有限公司 | Dianhydride compound and preparation method and application thereof |
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| Publication number | Publication date |
|---|---|
| JP2666457B2 (en) | 1997-10-22 |
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