JPH0218422A - Aromatic polyamide-imide resin and production hereof - Google Patents
Aromatic polyamide-imide resin and production hereofInfo
- Publication number
- JPH0218422A JPH0218422A JP16925388A JP16925388A JPH0218422A JP H0218422 A JPH0218422 A JP H0218422A JP 16925388 A JP16925388 A JP 16925388A JP 16925388 A JP16925388 A JP 16925388A JP H0218422 A JPH0218422 A JP H0218422A
- Authority
- JP
- Japan
- Prior art keywords
- fluorine
- aromatic
- formula
- aromatic polyamide
- carboxylic acid
- 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.)
- Pending
Links
- 239000011347 resin Substances 0.000 title claims abstract description 31
- 229920005989 resin Polymers 0.000 title claims abstract description 31
- 239000004962 Polyamide-imide Substances 0.000 title claims description 31
- 229920002312 polyamide-imide Polymers 0.000 title claims description 31
- 125000003118 aryl group Chemical group 0.000 title claims description 30
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 29
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000011737 fluorine Substances 0.000 claims abstract description 28
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 18
- -1 aromatic tricarboxylic acid Chemical class 0.000 claims abstract description 17
- 150000004985 diamines Chemical class 0.000 claims abstract description 9
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 7
- 239000002798 polar solvent Substances 0.000 claims abstract description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 5
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 7
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 125000000524 functional group Chemical group 0.000 claims description 5
- 150000008065 acid anhydrides Chemical class 0.000 claims description 4
- 125000001153 fluoro group Chemical group F* 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 abstract description 12
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 abstract description 2
- 229920000642 polymer Polymers 0.000 description 22
- 238000006798 ring closing metathesis reaction Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 239000000047 product Substances 0.000 description 9
- 239000002253 acid Substances 0.000 description 8
- 239000000843 powder Substances 0.000 description 7
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 239000004952 Polyamide Substances 0.000 description 6
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 229920002647 polyamide Polymers 0.000 description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000000835 fiber Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 238000005299 abrasion Methods 0.000 description 4
- 239000010425 asbestos Substances 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 239000008188 pellet Substances 0.000 description 4
- 229910052895 riebeckite Inorganic materials 0.000 description 4
- MHSKRLJMQQNJNC-UHFFFAOYSA-N terephthalamide Chemical compound NC(=O)C1=CC=C(C(N)=O)C=C1 MHSKRLJMQQNJNC-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 3
- 238000000921 elemental analysis Methods 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 239000002516 radical scavenger Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-dimethylpyridine Chemical compound CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-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
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000003949 imides Chemical class 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000010445 mica Substances 0.000 description 2
- 229910052618 mica group Inorganic materials 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- NJMOHBDCGXJLNJ-UHFFFAOYSA-N trimellitic anhydride chloride Chemical compound ClC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 NJMOHBDCGXJLNJ-UHFFFAOYSA-N 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- LJGHYPLBDBRCRZ-UHFFFAOYSA-N 3-(3-aminophenyl)sulfonylaniline Chemical group NC1=CC=CC(S(=O)(=O)C=2C=C(N)C=CC=2)=C1 LJGHYPLBDBRCRZ-UHFFFAOYSA-N 0.000 description 1
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 1
- ZSEYIZWTJQYCRJ-UHFFFAOYSA-N 4-N,4-N-bis(3-aminophenyl)benzene-1,4-dicarboxamide Chemical compound C(C1=CC=C(C(=O)N)C=C1)(=O)N(C1=CC(=CC=C1)N)C1=CC(=CC=C1)N ZSEYIZWTJQYCRJ-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000004129 EU approved improving agent Substances 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N Tetrahydrothiophene-1,1-dioxide, Natural products O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- HOPRXXXSABQWAV-UHFFFAOYSA-N anhydrous collidine Natural products CC1=CC=NC(C)=C1C HOPRXXXSABQWAV-UHFFFAOYSA-N 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- 235000012241 calcium silicate Nutrition 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- UTBIMNXEDGNJFE-UHFFFAOYSA-N collidine Natural products CC1=CC=C(C)C(C)=N1 UTBIMNXEDGNJFE-UHFFFAOYSA-N 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 239000012024 dehydrating agents Substances 0.000 description 1
- HPYNZHMRTTWQTB-UHFFFAOYSA-N dimethylpyridine Natural products CC1=CC=CN=C1C HPYNZHMRTTWQTB-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 238000009775 high-speed stirring Methods 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229940018564 m-phenylenediamine Drugs 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000010137 moulding (plastic) Methods 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- UZUFPBIDKMEQEQ-UHFFFAOYSA-N perfluorononanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F UZUFPBIDKMEQEQ-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- WYVAMUWZEOHJOQ-UHFFFAOYSA-N propionic anhydride Chemical compound CCC(=O)OC(=O)CC WYVAMUWZEOHJOQ-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 102200082816 rs34868397 Human genes 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- GFYHSKONPJXCDE-UHFFFAOYSA-N sym-collidine Natural products CC1=CN=C(C)C(C)=C1 GFYHSKONPJXCDE-UHFFFAOYSA-N 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003739 xylenols Chemical class 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Landscapes
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
Abstract
Description
【発明の詳細な説明】
〈産業上の利用分野〉
本発明は耐熱性、摺動特性に優れた芳香族ポリアミドイ
ミド樹脂およびその製造方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to an aromatic polyamideimide resin having excellent heat resistance and sliding properties, and a method for producing the same.
〈従来の技術〉
芳香族ポリアミドイミド樹脂は、優れた耐熱性、機械特
性、摺動特性などを有しているために、近年、電気・電
子機器産業、自動車産業、航空・宇宙産業などにおいて
、急速に需要が高まってきている一０中でも、耐熱摺動
材料としての期待は大きく、機器の高速化、高性能化が
進むにつれて必要不可欠な素材になりつつある。<Conventional technology> Aromatic polyamide-imide resin has excellent heat resistance, mechanical properties, sliding properties, etc., so in recent years, it has been used in the electrical and electronic equipment industry, the automobile industry, the aerospace industry, etc. Demand for it is increasing rapidly, and there are great expectations for it as a heat-resistant sliding material, and it is becoming an indispensable material as equipment becomes faster and more sophisticated.
芳香族ポリアミドイミド樹脂はそのままでも優れた摺動
特性を有しているが、さらに耐摩耗性を向上させるため
にフッ素樹脂の添加が有効であることがよく知られてい
る。Although aromatic polyamide-imide resins have excellent sliding properties as they are, it is well known that addition of fluororesin is effective in further improving wear resistance.
例えばポリテトラフロロエチレンを配合した芳香族ポリ
アミドイミド樹脂が「工業材料ＪＶＯＩ２７、ＮＯ３，
ｐ、５１（１９７９）に記載されている。For example, aromatic polyamideimide resin blended with polytetrafluoroethylene is ``industrial materials JVOI27, NO3,
p. 51 (1979).
〈発明が解決しようとする課題〉
しかしながら、市場においてはより苛酷な条件に耐える
摺動材料が要求されており、従来のフッ素樹脂配合芳香
族ポリアミドイミド樹脂では耐摩擦摩耗特性が依然とし
て不十分であり、さらに改善が望まれている。また、一
般に、フッ素樹脂と、芳香族ポリアミドイミド樹脂は、
相溶性に乏しいため、フッ素樹脂の配合量を増すと、成
形品表面の剥離、顕著な機械強度の低下がみちれ、この
点の改善も望まれる。<Problem to be solved by the invention> However, the market demands sliding materials that can withstand even more severe conditions, and the conventional aromatic polyamide-imide resins containing fluororesin still have insufficient friction and wear resistance. , further improvements are desired. In addition, in general, fluororesins and aromatic polyamide-imide resins are
Due to poor compatibility, increasing the amount of fluororesin blended results in peeling of the surface of the molded product and a significant decrease in mechanical strength, and improvements in this point are desired.
そこで本発明は、耐摩擦、摩耗特性が改善された芳香族
ポリアミドイミド樹脂およびその製造方法を開発するこ
とを課題とする。Therefore, an object of the present invention is to develop an aromatic polyamide-imide resin with improved friction resistance and wear characteristics and a method for producing the same.
く課題を解決するための手段〉
本発明者らは上記課題を解決すべく説意検討した結果、
芳香族ポリアミドイミド樹脂にパーフロロ炭化水素基を
共有結余させることが有効であることを見出し、本発明
に到達した。Means for Solving the Problems> As a result of the present inventors' discussion and study to solve the above problems,
The inventors have discovered that it is effective to covalently bond a perfluorohydrocarbon group to an aromatic polyamide-imide resin, and have arrived at the present invention.
すなわち本発明は、分子鎖末端に下記一般式（Ｉ）およ
び／または（Ｉｆ）で表わされるフッ素含有官能基を持
ち、かつ、Ｎ−メチルピロリドン中、濃度０．５ｇ／ｄ
ｊ、温度３０℃の条件で測定した対数粘度が０．２〜３
．０ｄｊ／ｒの範囲である芳香族ポリアミドイミド樹脂
および、Ｒｔ−ｃｏ−（Ｉ）
トイミド樹脂の製造方法である。That is, the present invention has a fluorine-containing functional group represented by the following general formula (I) and/or (If) at the end of the molecular chain, and has a concentration of 0.5 g/d in N-methylpyrrolidone.
j, the logarithmic viscosity measured at a temperature of 30°C is 0.2 to 3
．． This is a method for producing an aromatic polyamideimide resin and an Rt-co-(I) toimide resin in the range of 0dj/r.
ｒｔｔ−ｃｏ−ＣＩ）
Ｒｔ −ＣＯＯＨ（ＩＮ）
（式中Ｒｔは、水素原子の半数以上がフッ素原子に置き
換った炭素数１〜１ｏの１価の脂肪族残基を示す、）
（２）芳香族トリカルボン酸とジアミンおよび／または
ジイソシアネートとを、有機極性溶媒中で反応させ、芳
香族ポリアミドイミド樹脂を製造する工程において、下
記一般式（ＩＩＩ）および／または（ＩＶ）で表わされ
るフッ素含有カルボン酸またはそれから誘導される酸塩
化物、酸無水物、エステルを添加し、分子鎖末端に、下
記一般式（Ｉ）および／または（ＩＦ）で表わされるフ
ッ素含有官能基を導入することを特徴とする芳香族ポリ
アミ（式中Ｒｆは、水素原子の半数以上がフッ素原子に
置き換った炭素数１〜１ｏの１価の脂肪族残基を示す、
）
本発明で用いる芳香族ポリアミドイミド樹脂は、一般式
（Ｖ）
１００＼
（−ＮＨＣＯ−Ａｒ Ｎ−
Ｒ） （Ｖ）＼ＣＯ／
で表わされる繰返し単位を主要構造単位として有する芳
香族共重合体である。(2 ) In the step of producing an aromatic polyamideimide resin by reacting an aromatic tricarboxylic acid with a diamine and/or diisocyanate in an organic polar solvent, a fluorine-containing compound represented by the following general formula (III) and/or (IV) is used. It is characterized by adding a carboxylic acid or an acid chloride, an acid anhydride, or an ester derived therefrom, and introducing a fluorine-containing functional group represented by the following general formula (I) and/or (IF) at the molecular chain end. aromatic polyamide (in the formula, Rf represents a monovalent aliphatic residue having 1 to 1 o carbon atoms in which more than half of the hydrogen atoms are replaced with fluorine atoms,
) The aromatic polyamideimide resin used in the present invention has the general formula (V) 100\ (-NHCO-Ar N-
R) (V) It is an aromatic copolymer having a repeating unit represented by \CO/ as a main structural unit.
ここでＡｒは少なくとも１つの炭素６員環を含む３価の
芳香族残基であり、そのうちの２価は、２個のカルボニ
ル基がＡｒ基のベンゼン環内の隣接する炭素原子に結合
していることによって特徴づけられ、例えば
ＣＦ。Here, Ar is a trivalent aromatic residue containing at least one carbon 6-membered ring, of which the divalent one is formed by bonding two carbonyl groups to adjacent carbon atoms in the benzene ring of the Ar group. For example, CF.
Ｆ ｓ ＯＨ。Fs Oh.
ＣＨ。CH.
等の楕遺を具体的に列挙することができる。It is possible to specifically enumerate the ellipses such as
Ｒは２価の芳香族および／または脂肪族残基であり、具
体例としては、
ＣＨ。R is a divalent aromatic and/or aliphatic residue, specific examples being CH.
Ｊ ＣＨ。J CH.
ＣＨ３
Ｃ，ｌＩ
Ｈｉ
（ＣＨ２
（ＣＨ２
）１□−
また、（Ｖ）は単独のポリマであってもよいし、あるい
は共重合体であっても構わない、さらに（Ｖ）の構造の
中のイミド結合の一部が、その閉環前駆体としてのアミ
ド結合
ＯＯＨ
の状態でとどまっているものも含まれる。CH3 C,lI Hi (CH2 (CH2)1□- In addition, (V) may be a single polymer or a copolymer, and furthermore, imide in the structure of (V) It also includes a bond in which a portion of the bond remains in the form of an amide bond OOH as its ring-closing precursor.
このような芳香族ポリアミドイミド樹脂は、有機極性溶
媒中で、芳香族トリカルボン酸類（例えば、カルボン酸
、酸無水物、酸塩化物、ニスデル）とジアミン、・およ
び／またはジイソシアネートを例えば、式（Ｖｌ）、（
Ｖｌｌ）、（■）のような組合わせで反応させることに
より製造され、特公昭４４−１９２７４号公報、同４５
−２３９７号公報、同４９−４０７７号公報等に記載さ
れた製造方法で製造される。Such an aromatic polyamide-imide resin is prepared by combining aromatic tricarboxylic acids (e.g., carboxylic acid, acid anhydride, acid chloride, Nisdel), diamine, and/or diisocyanate in an organic polar solvent, for example, with the formula (Vl ), (
It is produced by reacting combinations such as Vll) and (■), and is produced by
It is manufactured by the manufacturing method described in JP-A-2397, JP-A-49-4077, and the like.
Ｏ１１
１１／Ｃ＼
ＨＯＣＡｒ Ｏ／Ｈ２Ｎ ＲＮＨｉ＼。／
０ （■）
Ｊ
＋＋ Ｃ
／ ＼
ＣＡｒ Ｏ／Ｈ２Ｎ ＲＮＨ４Ｎ。／
＋＋ （Ｖｌｌ ）１１ ／
Ｃ＼
ＨＯ−Ｃ−八ｒ Ｏ／ ＯＣＮ −Ｒ−Ｎ
ＣＯ＼。／
０ （■）
本発明でいう分子鎖末端とは、分子銀の片末端および／
または両末端であり、側鎖も含まれる。O11 11/C\HOCAr O/H2N RNHi\. / 0 (■) J ++ C / \ CAr O/H2N RNH4N. / ++ (Vll)11 /
C\ HO-C-8r O/ OCN -R-N
CO\. / 0 (■) In the present invention, the terminus of the molecular chain refers to one end of molecular silver and /
or both ends, including side chains.
本発明でいうフッ素含有官能基は一般式（Ｉ）または（
ｎ）で表わされるものである。The fluorine-containing functional group referred to in the present invention is represented by the general formula (I) or (
n).
Ｒｆ−ＣＯ−
（Ｉ）
フッ素含有カルボン酸またはそれから誘導されるここで
Ｒｆは水素原子の半数以上、好ましくは全てがフッ素原
子に置き換った炭素数１〜１０の１価の脂肪族残基であ
る。具体的には
ＣＦ、−１Ｃ２Ｆｓ−５Ｃｘ Ｆ ｔ
Ｃ４ＦｓＨ−１Ｃ＊Ｆｒ＋−１ＣｔＨｔｓＣ−Ｆｒ＊−
Ｆ
Ｒｆ−ＣＯＯＨ（ＩＩＩ）
ここでＲｆは前記一般式（Ｉ）、（Ｉｔ）のＲｆと同様
である。中でも好ましいフッ素含有カルボ１パ・
本発明の要点は、芳香族ポリアミドイミド樹脂の分子鎖
末端にパーフロロ炭化水素基を導入する点にあるが、そ
のために、本発明では芳香族ポリアミドイミド樹脂を製
造する工程において、下記一般式（１）および／または
（ＩＶ）で表わされるで表わされるものが挙げられ、（
株）ネオス社よりＰＦＮＡ”の商品名で市販されている
ものを用いることができる。Rf-CO- (I) A fluorine-containing carboxylic acid or a fluorine-containing carboxylic acid derived therefrom, where Rf is a monovalent aliphatic residue having 1 to 10 carbon atoms in which half or more of the hydrogen atoms, preferably all, are replaced with fluorine atoms. It is. Specifically, CF, -1C2Fs-5Cx F t C4FsH-1C*Fr+-1CtHtsC-Fr*- F Rf-COOH (III) Here, Rf is the same as Rf in the general formulas (I) and (It) above. . Among these, preferable fluorine-containing carboxylic acid is preferred.The main point of the present invention is to introduce a perfluorohydrocarbon group to the molecular chain end of an aromatic polyamide-imide resin, and for this purpose, the aromatic polyamide-imide resin is manufactured in the present invention In the step, those represented by the following general formulas (1) and/or (IV) may be mentioned;
A product commercially available from Neos Co., Ltd. under the trade name ``PFNA'' can be used.
また、フッ素含有カルボン酸類は、重合末期に重合溶液
中に添加することが好ましいが、重合中に、他のモノマ
と同時に添加することもできる。Moreover, although it is preferable to add fluorine-containing carboxylic acids to the polymerization solution at the end of polymerization, they can also be added simultaneously with other monomers during polymerization.
本発明の芳香族ポリアミドイミド樹脂を製造するにあた
っては、前述したような通常の製造方法のうち、酸塩化
物とジアミンを用いる方法（式（■））が最も好ましく
推奨され、これを用いた本発明の製造方法を具体的に説
明すると次の通りである。In producing the aromatic polyamide-imide resin of the present invention, the method using an acid chloride and a diamine (formula (■)) is most preferably recommended among the usual production methods described above. The manufacturing method of the invention will be specifically explained as follows.
すなわち、芳香族トリカルボン酸無水物モノクロライト
１モルおよびジアミン０．８〜１．２モルを有機極性溶
媒中に溶解する。That is, 1 mol of aromatic tricarboxylic acid anhydride monochlorite and 0.8 to 1.2 mol of diamine are dissolved in an organic polar solvent.
次にこれを一２０〜８０℃の温度条件下、約０゜５〜１
時間時間上た後、式（ＩＩ［）および／または（ＩＶ）
で表わされるフッ素含有カルボン酸またはそれより誘導
される酸塩化物、酸無水物、エステル、好ましくは酸塩
化物を添加し、さらに０．５〜３時間反応させる。必要
に応じて塩加水素スカベンジャーを０．９〜１．２モル
程度添加して重合反応を促進させると、常温付近、反応
時間０゜５〜１０時間で生成する重合体は、本発明のポ
リアミドイミド重合体の大部分（例えば５０〜１００％
）を閉環前駆体のアミドアミド酸単位／Ｃ０ＮＨ−Ｒ→
一＋Ｎ Ｈ−ＣＯ−Ａ ｒ
＼ＣＯＯＨ
に変換した構造、いわゆるポリアミド・アミド酸になっ
ている。この第一工程に用いられる有機極性溶媒中
ジアルキルカルボン酸アミド類、Ｎ−メチルピロリドン
、テトラヒドロチオフェン−１，１−ジオキシドなどの
複素環式化合物類、クレゾール、キシレノールなどのフ
ェノール類などであり、特に、Ｎ−メチルピロリドンお
よびＮ−Ｎ−ジメチルアセトアミドが好ましい、また上
記第１工程に必要に応じて添加される塩加水素スカベン
ジャーは、トリメチルアミン、トリエチルアミン、トリ
プロピルアミン、トリブチルアミンのような脂肪族第３
級アミン類、ピリジン、ルチジン、コリジン、キノリン
のような環状有機塩基、エチレンオキシド、プロピレン
オキシドのような有機オキシド類などである。Next, this is heated at a temperature of -20 to 80 degrees Celsius to approximately 0.5 to 1
After increasing the time, formula (II[) and/or (IV)
A fluorine-containing carboxylic acid represented by the following formula or an acid chloride, an acid anhydride, or an ester derived therefrom, preferably an acid chloride, is added thereto, and the mixture is further reacted for 0.5 to 3 hours. If necessary, about 0.9 to 1.2 moles of a salt hydrogenated scavenger are added to accelerate the polymerization reaction, and the polymer produced at room temperature and reaction time of 0° for 5 to 10 hours is the polyamide of the present invention. Most of the imide polymer (e.g. 50-100%
) is converted into the ring-closing precursor amide amic acid unit/C0NH-R→1+NH-CO-A r \COOH, resulting in a so-called polyamide amic acid. The organic polar solvent used in this first step includes dialkylcarboxylic acid amides, N-methylpyrrolidone, heterocyclic compounds such as tetrahydrothiophene-1,1-dioxide, and phenols such as cresol and xylenol. , N-methylpyrrolidone and N-N-dimethylacetamide are preferred, and the salt hydrogen scavenger optionally added to the first step is an aliphatic scavenger such as trimethylamine, triethylamine, tripropylamine, tributylamine. 3
cyclic organic bases such as pyridine, lutidine, collidine, and quinoline, and organic oxides such as ethylene oxide and propylene oxide.
上記の第一工程で得られたポリアミドアミド酸は、続い
て第２の脱水閉環工程にかけられ、本発明のポリアミド
イミド重合体に変換される。脱水閉環操作は、溶液中に
おける液相熱閉環または固体で加熱する固相熱閉環のい
ずれかで行われる。The polyamideamic acid obtained in the first step above is subsequently subjected to a second dehydration ring closure step and converted into the polyamideimide polymer of the present invention. The dehydration ring closure operation is carried out either by liquid phase thermal ring closure in solution or solid phase thermal ring closure by heating in a solid.
液相閉環には化学的脱水剤を用いる液相化学閉環と、単
純な液相化閉環法の２通りがある。There are two types of liquid phase ring closure: liquid phase chemical ring closure using a chemical dehydrating agent and simple liquid phase ring closure.
化学閉環は、無水酢酸、無水プロピオン酸のような脂肪
族酸無水物、ＰＯＣＪ！ 、 、５ＯＣＪ！□のような
ハロゲン化合物、Ｐ２Ｏ５等の化学的脱水剤を添加し、
５０〜４００°Ｃ１好ましくは１００〜２５０℃に加熱
することによって行われる。その際、水の除去に役立つ
共沸溶媒、例えばベンゼン、トルエン、キシレン、クロ
ルベンゼンなどを併用するとより効果的である。同相熱
閉環は、まず、第一工程で得られたポリアミドアミド酸
溶液からポリアミドアミド酸重合体を単離し、これを固
相状態で熱処理することによって行われる。ポリアミド
アミド酸重合体単離用の沈澱剤としては、反応混合溶媒
とは混和性であるが、その中にポリアミド・アミド酸自
体が不溶である液体例えば水、メタノールなどが採用さ
れる。熱閉環は、通常１５０〜３５０°Ｃ１０，５〜５
０時間の条件から目的の閉環率および溶融時流動性を確
保するように設定される。Chemical ring closure involves aliphatic acid anhydrides such as acetic anhydride, propionic anhydride, POCJ! , ,5OCJ! Add halogen compounds such as □, chemical dehydrating agents such as P2O5,
It is carried out by heating to 50-400°C, preferably 100-250°C. At this time, it is more effective to use an azeotropic solvent useful for water removal, such as benzene, toluene, xylene, chlorobenzene, etc. in combination. In-phase thermal ring closure is performed by first isolating a polyamide amic acid polymer from the polyamide amic acid solution obtained in the first step and heat-treating it in a solid phase state. As the precipitant for isolating the polyamide/amic acid polymer, a liquid that is miscible with the reaction mixture solvent but in which the polyamide/amic acid itself is insoluble, such as water or methanol, is employed. Thermal ring closure is usually performed at 150-350°C10.5-5
The conditions are set to ensure the desired ring closure rate and melting fluidity from the 0 hour condition.
２５０〜３５０°Ｃの領域で長時間酸処理しすぎると、
重合体そのものが３次元架橋構造を形成して、溶融時の
流動性を著しく低下させる傾向を示すので注意する必要
がある。If acid treatment is carried out for too long in the range of 250-350°C,
Care must be taken because the polymer itself tends to form a three-dimensional crosslinked structure and significantly reduce fluidity when melted.
以上に詳述した’ＪＡ遣方法によって、本発明の目的と
するポリアミドイミド重合体が得られるが、さらに反応
系に他の共重合成分を併用し、共重合することは可能で
ある。Although the polyamide-imide polymer targeted by the present invention can be obtained by the JA method described in detail above, it is possible to further copolymerize by using other copolymerization components in the reaction system.
追加成分の具体例としては例えば、芳香族テトラカルボ
ン酸、芳香族ジカルボン酸、芳香族アミノカルボン酸お
よびそれらの誘導体などが挙げられる。これらの追加成
り１の共重合により本発明のポリアミドイミド重合体を
種々改質することができる６例えば場合により、引張強
度、伸度、耐屈曲性、溶解性、加工性、接着性等を改善
することができる。Specific examples of additional components include aromatic tetracarboxylic acids, aromatic dicarboxylic acids, aromatic aminocarboxylic acids, and derivatives thereof. By copolymerizing these additional components, the polyamide-imide polymer of the present invention can be modified in various ways.6 For example, in some cases, tensile strength, elongation, bending resistance, solubility, processability, adhesion, etc. can be improved. can do.
また、本発明の芳香族ポリアミドイミド樹脂の対数粘度
はＮ−メチルピロリドン中、濃度０゜５ｇ／ｄＪ、温度
３０℃の条件で測定して０．２〜３．０ｄｌ／ｇの範囲
である。Further, the logarithmic viscosity of the aromatic polyamide-imide resin of the present invention is in the range of 0.2 to 3.0 dl/g when measured in N-methylpyrrolidone at a concentration of 0.5 g/dJ and a temperature of 30°C.
対数粘度が０．２以下では、力学強度が低く、実用的で
ない、また、対数粘度が３．０以上では、成形加工が困
難であり、好ましくない。If the logarithmic viscosity is 0.2 or less, the mechanical strength is low and it is not practical, and if the logarithmic viscosity is 3.0 or more, molding is difficult, which is not preferable.
また、本発明の芳香族ポリアミドイミド樹脂には必要に
応じて０″−７０重量％の範囲で次のような充填剤類を
含有させることができる。（ａ）耐阜耗性向上剤；グラ
ファイト、カーボランダム、ゲイ石粉、二硫化モリブデ
ン、フッ素樹脂など、（ｂ）補強材ニガラス繊維、カー
ボン繊維、ボロン繊維、炭化ケイ素繊維、カーボンウィ
スカーアスベスト繊維、石綿、金属繊維など、（ｃ）難
燃性向上剤二三酸化アンチモン、炭酸マグネシウム、炭
酸カルシウムなど、（ａ）ｆｆｉ気特性向上剖：クレー
、マイカなど、（ｅ）ｉｉｉｔ）ラッキング向上荊二石
綿、シリカ、グラファイトなと、（ｆ）耐酸性向上剤：
硫酸バリウム、シリカ、メタケイ酸カルシウムなど、（
ｇ）熱伝導度向上剤二鉄、亜鉛、アルミニウム、銅など
の金属粉末、（ｈ）その他ニガラスビーズ、ガラス球、
炭酸カルシウム、・アルミナ、タルク、ケイソウ土、水
和アルミナ、マイカ、シラスバルーン、石綿、各種金属
酸化物、無機質顔料など３００℃以上で安定な合成およ
び天然の化合物類が含まれる。Further, the aromatic polyamide-imide resin of the present invention may contain the following fillers in the range of 0'' to 70% by weight as necessary. (a) Abrasion resistance improver; graphite , carborundum, gay stone powder, molybdenum disulfide, fluororesin, etc. (b) Reinforcement materials Niglass fiber, carbon fiber, boron fiber, silicon carbide fiber, carbon whisker asbestos fiber, asbestos, metal fiber, etc. (c) Flame retardant Improving agents such as antimony ditrioxide, magnesium carbonate, calcium carbonate, etc. (a) Improving ffi properties: clay, mica, etc., (e) iii) Improving racking, such as asbestos, silica, graphite, etc., (f) Acid resistance Improver:
Barium sulfate, silica, calcium metasilicate, etc.
g) Thermal conductivity improvers Metal powders such as diferon, zinc, aluminum, copper, etc. (h) Other glass beads, glass balls,
Contains synthetic and natural compounds that are stable at temperatures above 300°C, such as calcium carbonate, alumina, talc, diatomaceous earth, hydrated alumina, mica, shirasu balloons, asbestos, various metal oxides, and inorganic pigments.
また、本発明の芳香族ポリアミドイミド樹脂は、通常の
プラスチックを成形する手法、すなわち、射出成形、押
出成形、圧縮成形、焼結成形などに適用することが可能
であり、それにより、望ましい形状の成形品とすること
ができる。In addition, the aromatic polyamide-imide resin of the present invention can be applied to ordinary plastic molding methods, such as injection molding, extrusion molding, compression molding, and sintering molding, thereby making it possible to form desired shapes. It can be made into a molded product.
〈実施例〉 以下、実施例を挙げて本発明をさらに詳述する。<Example> Hereinafter, the present invention will be further explained in detail by giving examples.
なお、実施例において芳香族ポリアミドイミド樹脂の対
数粘度（ηｉｎｈ ）はＮ−メチルピロリドン（ＮＭＰ
）中、濃度０．５ｇ／ｄｊ、温度３０℃で測定したもの
である。In addition, in the examples, the logarithmic viscosity (ηinh) of the aromatic polyamideimide resin is N-methylpyrrolidone (NMP
) at a concentration of 0.5 g/dj and a temperature of 30°C.
さらに摩耗試験はスラスト摩耗試験８！ｌ（銘木式摩耗
試験機）を用いて行ない、相手剤は鋼（Ｓ４５Ｃ）を用
いた。Furthermore, the wear test is thrust wear test 8! The test was conducted using a precious wood type abrasion tester, and steel (S45C) was used as the partner material.
合成例１
くフッ素含有カルボン酸クロライドの合成〉撹拌機、温
度計およびコンデンサーを供えた１１の丸底フラスコに
また、塩素含呈は６．０１％で理論値の６．０４同様に
して下記のフッ素含有カルボン酸クロライド（Ｂ）およ
び（Ｃ）を合成した。Synthesis Example 1 Synthesis of fluorine-containing carboxylic acid chloride> In 11 round bottom flasks equipped with a stirrer, a thermometer and a condenser, the following reaction was carried out with a chlorine content of 6.01% and a theoretical value of 6.04. Fluorine-containing carboxylic acid chlorides (B) and (C) were synthesized.
（ネオス社製、商品名“ＰＦＮＡ“）３９７．７ｇ （
０，７モル）および５ＯＣｊ２１２４．９ｇ（１，０５
モル）を仕込み、撹拌した。フラスコな油浴内に入れ、
内温を７０℃から８５℃まで、５時間かけて昇温しなが
ら撹拌した０次にコンデンサーをはずし、真空ポンプを
用いて１０ｗＨｇ下、１３５℃で２時間濃縮を行ない、
過剰分の５ＯＣｊ窃を取り除いた。フラスコを冷却した
ところ１、反応物３２８ｇを得な。(Manufactured by Neos, product name “PFNA”) 397.7g (
0,7 mol) and 5OCj2124.9 g (1,05
mol) and stirred. Place it in a flask oil bath,
The internal temperature was raised from 70 °C to 85 °C over 5 hours while stirring, then the condenser was removed, and concentration was performed at 135 °C for 2 hours under 10 wHg using a vacuum pump.
Removed excess 5OCj theft. When the flask was cooled, 328 g of reactant was obtained.
得られた反応物のＩ）１スペクトルから、反応物は下記
（Ａ）の構造をしていることが示された。The I)1 spectrum of the obtained reaction product showed that the reaction product had the following structure (A).
Ｃ，Ｐ、Ｈ−ＣＯＣｊ （Ｃ）合
成例２
くフッ素含有カルボン酸無水物の合成〉合成例１におい
て、５ＯＣｊ２のかわりに無水酢酸を用い、５時間還流
することにより、下記構造式（Ｄ）を有するフッ素含有
カルボン酸無水物実施例１
撹拌機、温度計および窒素導入管を備えた５１の丸底フ
ラスコに４．４−一ジアミノジフェニルエーテル１６８
．３ｇ （０，８４モル）、ｍ−フェニレンジアミン３
８．９ｇ （０，３６モル）およびＮ、Ｎ−ジメチルア
セトアミド２，０ＯＯｓｒを仕込み、撹拌し、均一溶液
を得た。次にこのフラスコを氷／水浴で１０°Ｃ以下に
冷却した後、４（クロロホルミル）無水フタル酸２２７
ｇ（１゜０８モル）を、重合系の温度を１０〜３０℃に
保持するような速度で少量ずつ分割添加した。１時間撹
拌した後、フッ素含有カルボン酸クロライド（Ａ）７０
．４ｓｒ （０，１２モル）を加えた。C,P,H-COCj (C) Synthesis Example 2 Synthesis of fluorine-containing carboxylic acid anhydride> In Synthesis Example 1, by using acetic anhydride instead of 5OCj2 and refluxing for 5 hours, the following structural formula (D) Fluorine-Containing Carboxylic Anhydride Example 1 4.4-1 diaminodiphenyl ether 168 in a 51 round bottom flask equipped with a stirrer, thermometer and nitrogen inlet
．． 3g (0.84 mol), m-phenylenediamine 3
8.9 g (0.36 mol) and 2,000 sr of N,N-dimethylacetamide were charged and stirred to obtain a homogeneous solution. The flask was then cooled to below 10°C in an ice/water bath, and then 4(chloroformyl)phthalic anhydride 227
g (1.08 mol) was added in small portions at a rate such that the temperature of the polymerization system was maintained at 10 to 30°C. After stirring for 1 hour, fluorine-containing carboxylic acid chloride (A) 70
．． 4sr (0.12 mol) was added.
添加終了後、さらに３０℃で１時間撹拌を続行して重合
反応を終了し、高速撹拌下の大証の水中に、得られた重
合液を徐々に投入して重合体を粒状に析出させた。続い
て析出重合体を水洗／脱水した後、熱風乾燥機中で１５
０℃で５時間、次いで２００°Ｃで３時間乾燥したとこ
ろ対数粘度が０゜６５の重合体粉末が約４２０ｇ得られ
た。After the addition was completed, stirring was further continued at 30° C. for 1 hour to complete the polymerization reaction, and the obtained polymerization solution was gradually poured into OSE water under high speed stirring to precipitate the polymer in granular form. Subsequently, the precipitated polymer was washed with water/dehydrated, and then dried in a hot air dryer for 15 minutes.
After drying at 0° C. for 5 hours and then at 200° C. for 3 hours, about 420 g of a polymer powder having a logarithmic viscosity of 0°65 was obtained.
ここで得られた重合体の理論的構造単位式およびそれに
対応する分子式は次の通りである。また、重合体の元素
分析の結果は下記の通り、理論値とよい一致を示した。The theoretical structural unit formula and the corresponding molecular formula of the polymer obtained here are as follows. Furthermore, the results of elemental analysis of the polymer showed good agreement with the theoretical values, as shown below.
ａ ／ ｂ ／ ｃ ／ ｄ ＝ １０８ ／ １２
／ ８４ ／ ３６（モル比）
一方、ソックスレー抽出機を用いて、上記の重合体１ｇ
にアセトン２００ｇを加え、アセトンリフラックス下で
８時間抽出を行なった。その結果、アセトン抽出液に原
料であるフッ素含有カルボン酸クロライド（Ａ）は抽出
されず、分子鎖末端に固定されていた。a / b / c / d = 108 / 12
/ 84 / 36 (molar ratio) On the other hand, using a Soxhlet extractor, 1 g of the above polymer
200 g of acetone was added to the solution, and extraction was performed for 8 hours under acetone reflux. As a result, the raw material fluorine-containing carboxylic acid chloride (A) was not extracted into the acetone extract, but was fixed at the ends of the molecular chains.
次に得られた重合体粉末をブラベンダーエクストルーダ
−（シリンダー温度３４０〜３６０℃）に供給して溶融
混練しながら押出し、ベレットを得た。Next, the obtained polymer powder was supplied to a Brabender extruder (cylinder temperature: 340 to 360°C) and extruded while melt-kneading to obtain pellets.
続いて得られたベレットの射出成形を行ない、試験片を
作成した。この試験片を用いて摩擦・摩耗試験を行なっ
た。結果を表１に示したが、耐摩擦・摩耗特性が優れて
おり、成形品の外観は良好であった。Subsequently, the obtained pellet was injection molded to prepare a test piece. Friction and wear tests were conducted using this test piece. The results are shown in Table 1, and the friction and wear resistance was excellent, and the molded product had a good appearance.
比較例１〜３
４−（クロロホルミル）無水フタル酸の添加量を２５３
＋ｒ （１，２モル）にして、フッ素含有カルボン酸ク
ロライド（Ａ）の添加をしなかった以外は実施例１と同
様の操作を行ない、重合体粉末を得た（比較例１）、続
いてこの重合体粉末にポリテトラフルオロエチレン樹脂
（ＰＴＦＥ）を３重量％（比較例２）および１０ｆｆｉ
量％（比較例３）配合した後、グラベンダーエクス１−
ルーダ−で溶融混練しながら押出してベレットを得た。Comparative Examples 1 to 3 The amount of 4-(chloroformyl)phthalic anhydride added was 253
+r (1.2 mol) and the same operation as in Example 1 was performed except that fluorine-containing carboxylic acid chloride (A) was not added to obtain a polymer powder (Comparative Example 1). 3% by weight of polytetrafluoroethylene resin (PTFE) (Comparative Example 2) and 10ffi were added to this polymer powder.
Amount % (Comparative Example 3) After blending, Gravender Ex 1-
A pellet was obtained by extrusion while melt-kneading with a Ruder.
続いてこのベレットを用いて射出成形を行ない、摺動用
の試験片を作成した。Subsequently, injection molding was performed using this pellet to create a sliding test piece.
試験片の摩擦・摩耗特性を測定し、表１に示した。フッ
素含有カルボン酸クロライドを用いない比較例１ではフ
ッ素がないために摩擦・摩耗特性が悪い、また比較例１
にＰＴＦＥを３重置％配合した比較例２は摺動特性が未
だ悪く、不満足であった。一方、ＰＴＦＥを１０重量％
配合した比校例３は、摺動特性はかなり改善されたもの
の、成形品の表面にＰＴＦＥが浮き出て外観不良であっ
た。The friction and wear characteristics of the test pieces were measured and shown in Table 1. Comparative Example 1, which does not use fluorine-containing carboxylic acid chloride, has poor friction and wear characteristics due to the lack of fluorine;
In Comparative Example 2, in which PTFE was added in a 3-fold ratio, the sliding properties were still poor and unsatisfactory. On the other hand, 10% by weight of PTFE
In Compounding Example 3, although the sliding properties were considerably improved, PTFE stood out on the surface of the molded product and the appearance was poor.
実施例２〜３、比較例４〜５
ジアミン類として４．４−一ジアミノジフェニルエーテ
ル／２．２−−ビス［４−（４−アミノフェノキシ）フ
ェニル］プロパン（実施例２）およびＮ、Ｎ−−ビス（
３−アミノフェニル）テレフタルアミド（実施例３）を
用い、表１に示す組成で重合した。Examples 2-3, Comparative Examples 4-5 Diamines include 4.4-monodiaminodiphenyl ether/2.2-bis[4-(4-aminophenoxy)phenyl]propane (Example 2) and N,N- −Bis(
Polymerization was carried out using 3-aminophenyl) terephthalamide (Example 3) with the composition shown in Table 1.
また、比較例４．５は実施例２．３のフッ素含有カルボ
ン酸クロライドの添加をしないで重合を行なったもので
ある。Furthermore, in Comparative Example 4.5, polymerization was carried out without adding the fluorine-containing carboxylic acid chloride of Example 2.3.
これらの重合体の元素分析結果は理論値と一致した。こ
の重合体をブラベンダーエクストルーダーで溶融混錬し
た後、射出成形を行ない、摺動測定用の試験片を作成し
た。The elemental analysis results of these polymers were in agreement with the theoretical values. This polymer was melt-kneaded using a Brabender extruder and then injection molded to prepare test pieces for sliding measurement.
試験片の摩擦・摩耗特性を測定し、表１に示した。The friction and wear characteristics of the test pieces were measured and shown in Table 1.
ジアミン類として４．４−一ジアミノジフェニルエーテ
ル／２．２−−ビス［４−（４−アミノフェノキシ）フ
ェニル］プロパンを用いた実施例２はフ・ツ素含有カル
ボン酸クロライドを用いない比較例４に比べて耐摩擦・
摩耗特性が優れていた。Example 2 using 4.4-monodiaminodiphenyl ether/2.2-bis[4-(4-aminophenoxy)phenyl]propane as diamines is Comparative Example 4 without using fluorine-containing carboxylic acid chloride. Friction resistance compared to
It had excellent wear characteristics.
またジアミンとしてＮ、Ｎ−−ビス（３−アミノフェニ
ル）テレフタルアミドを用いた実施例３もフッ素含有カ
ルボン酸クロライドを用いない比軟例５に比べて耐摩擦
・摩耗特性が優れていた。Further, Example 3 in which N,N--bis(3-aminophenyl)terephthalamide was used as the diamine also had superior friction and abrasion resistance compared to Example 5 in which no fluorine-containing carboxylic acid chloride was used.
実施例４．５
フッ素含有カルボン酸クロライドとして（Ｉ３）および
（Ｃ）を用い、表１に示ず組成で重合を行なった。Example 4.5 Using (I3) and (C) as fluorine-containing carboxylic acid chlorides, polymerization was carried out with compositions not shown in Table 1.
これらの重合体の元素分析結果は理論値とよく一致した
。続いてこの重合体粉末をブラベンダーエクストルーダ
ーで溶融混練した後、射出成形を行なって試験片を得た
。The elemental analysis results of these polymers were in good agreement with the theoretical values. Subsequently, this polymer powder was melt-kneaded using a Brabender extruder, and then injection molded to obtain a test piece.
この試験片の摺動特性を測定し、表１に示したが、フッ
素含有カルボン酸クロライドを添加しない比較例１に比
べて各々耐摩擦・摩耗特性が優れており・、成形品の外
観も良好であった。The sliding properties of this test piece were measured and are shown in Table 1. Compared to Comparative Example 1 in which fluorine-containing carboxylic acid chloride was not added, the friction and abrasion properties were superior, and the appearance of the molded product was also good. Met.
実施例６
実施例１において、フッ素含有カルボン酸クロライド（
Ａ）の代わりに、フッ素含有カルボン酸無水物（Ｄ）を
用いるほかは実質的に同様な方法で重合および成形を行
ない、摺動試験を行なった。Example 6 In Example 1, fluorine-containing carboxylic acid chloride (
Polymerization and molding were carried out in substantially the same manner except that a fluorine-containing carboxylic acid anhydride (D) was used instead of A), and a sliding test was conducted.
結果は、摩耗重量４．ＯＲ／−・ｈ、動摩擦係数０．２
１と優れており、成形品の外観も良好であった。The result is a wear weight of 4. OR/-・h, dynamic friction coefficient 0.2
1, and the appearance of the molded product was also good.
〈発明の効果〉
本発明の芳香族ポリアミドイミド樹脂および本発明の製
造方法により得られる芳香族ポリアミドイミド樹脂は、
従来の芳香族ポリアミドイミド樹脂およびフッ素樹脂充
填芳香族ポリアミドイミド樹脂組成物に比べて、耐摩擦
・摩耗特性が改善されており、かつ成形品の表面も良好
である。これは、パーフロロ炭化水素基が共有結合によ
り分子鎖末端に導入されたためと考えられる。<Effects of the Invention> The aromatic polyamide-imide resin of the present invention and the aromatic polyamide-imide resin obtained by the production method of the present invention are as follows:
Compared to conventional aromatic polyamide-imide resins and fluororesin-filled aromatic polyamide-imide resin compositions, the friction and wear resistance properties are improved, and the surface of the molded product is also good. This is considered to be because the perfluorinated hydrocarbon group was introduced at the end of the molecular chain through a covalent bond.
こうして得られた芳香族ポリアミドイミド樹脂は、優れ
た摺動特性、耐熱性、機械特性を有しており、電気・電
子機器部品、自動車部品、事務機器部品、航空機部品な
どに有用である。The aromatic polyamide-imide resin thus obtained has excellent sliding properties, heat resistance, and mechanical properties, and is useful for electrical/electronic equipment parts, automobile parts, office equipment parts, aircraft parts, etc.
Claims (2)
（II）で表わされるフッ素含有官能基を持ち、かつ、Ｎ
−メチルピロリドン中、濃度０．５ｇ／ｄｌ、温度３０
℃の条件で測定した対数粘度が０．２〜３．０ｄｌ／ｇ
の範囲である芳香族ポリアミドイミド樹脂。Ｒ＿ｆ−Ｃ
Ｏ−（ I ） ▲数式、化学式、表等があります▼（II） （式中Ｒ＿ｆは、水素原子の半数以上がフッ素原子に置
き換った炭素数１〜１０の１価の脂肪族残基を示す。）(1) It has a fluorine-containing functional group represented by the following general formula (I) and/or (II) at the end of the molecular chain, and
- in methylpyrrolidone, concentration 0.5 g/dl, temperature 30
Logarithmic viscosity measured at ℃ condition is 0.2 to 3.0 dl/g
Aromatic polyamideimide resins in the range of. R_f-C
O-(I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) (In the formula, R_f is a monovalent aliphatic residue with 1 to 10 carbon atoms in which more than half of the hydrogen atoms are replaced with fluorine atoms. )
ジイソシアネートとを、有機極性溶媒中で反応させ、芳
香族ポリアミドイミド樹脂を製造する工程において、下
記一般式（III）および／または（IV）で表わされるフ
ッ素含有カルボン酸またはそれから誘導される酸塩化物
、酸無水物、エステルを添加し、分子鎖末端に、下記一
般式（ I ）および／または（II）で表わされるフッ素
含有官能基を導入することを特徴とする芳香族ポリアミ
ドイミド樹脂の製造方法。 Ｒ＿ｆ−ＣＯ−（ I ） ▲数式、化学式、表等があります▼（II） Ｒ＿ｆ−ＣＯＯＨ（III） ▲数式、化学式、表等があります▼（IV） （式中Ｒ＿ｆは、水素原子の半数以上がフッ素原子に置
き換つた炭素数１〜１０の１価の脂肪族残基を示す。）(2) In the step of producing an aromatic polyamideimide resin by reacting an aromatic tricarboxylic acid with a diamine and/or diisocyanate in an organic polar solvent, a compound represented by the following general formula (III) and/or (IV) Adding a fluorine-containing carboxylic acid or an acid chloride, acid anhydride, or ester derived therefrom to introduce a fluorine-containing functional group represented by the following general formula (I) and/or (II) at the molecular chain end. A method for producing an aromatic polyamide-imide resin, characterized by: R_f-CO-(I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) R_f-COOH(III) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(IV) (In the formula, R_f is more than half of the hydrogen atoms indicates a monovalent aliphatic residue having 1 to 10 carbon atoms in which the fluorine atom is substituted.)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16925388A JPH0218422A (en) | 1988-07-06 | 1988-07-06 | Aromatic polyamide-imide resin and production hereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16925388A JPH0218422A (en) | 1988-07-06 | 1988-07-06 | Aromatic polyamide-imide resin and production hereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0218422A true JPH0218422A (en) | 1990-01-22 |
Family
ID=15883083
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP16925388A Pending JPH0218422A (en) | 1988-07-06 | 1988-07-06 | Aromatic polyamide-imide resin and production hereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0218422A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5521276A (en) * | 1993-07-05 | 1996-05-28 | Korea Research Institute Of Chemical Technology | Polyamideimide resins containing isophorone diamine structures |
| US5532334A (en) * | 1993-11-12 | 1996-07-02 | Korea Research Institute Of Chemical Technology | Process for preparing polyamideimide resins having high molecular weight |
| US5955568A (en) * | 1996-04-22 | 1999-09-21 | Korea Research Institute Of Chemical Technology | Process for preparing polyamideimide resins by direct polymerization |
| US7192510B2 (en) | 2002-12-13 | 2007-03-20 | Canon Kabushiki Kaisha | Fluid control device and method of manufacturing the same |
| JP2007232136A (en) * | 2006-03-02 | 2007-09-13 | Nichias Corp | Shim for disk brake and its manufacturing method it |
-
1988
- 1988-07-06 JP JP16925388A patent/JPH0218422A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5521276A (en) * | 1993-07-05 | 1996-05-28 | Korea Research Institute Of Chemical Technology | Polyamideimide resins containing isophorone diamine structures |
| US5532334A (en) * | 1993-11-12 | 1996-07-02 | Korea Research Institute Of Chemical Technology | Process for preparing polyamideimide resins having high molecular weight |
| US5955568A (en) * | 1996-04-22 | 1999-09-21 | Korea Research Institute Of Chemical Technology | Process for preparing polyamideimide resins by direct polymerization |
| US7192510B2 (en) | 2002-12-13 | 2007-03-20 | Canon Kabushiki Kaisha | Fluid control device and method of manufacturing the same |
| JP2007232136A (en) * | 2006-03-02 | 2007-09-13 | Nichias Corp | Shim for disk brake and its manufacturing method it |
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