JPS63117035A - Thermosplastic polyether-imide-amide - Google Patents
Thermosplastic polyether-imide-amideInfo
- Publication number
- JPS63117035A JPS63117035A JP26202886A JP26202886A JPS63117035A JP S63117035 A JPS63117035 A JP S63117035A JP 26202886 A JP26202886 A JP 26202886A JP 26202886 A JP26202886 A JP 26202886A JP S63117035 A JPS63117035 A JP S63117035A
- Authority
- JP
- Japan
- Prior art keywords
- acid
- polymer
- carbon atoms
- amide
- parts
- 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
- -1 aliphatic diamine Chemical class 0.000 claims abstract description 53
- 239000000203 mixture Substances 0.000 claims abstract description 13
- 150000003839 salts Chemical class 0.000 claims abstract description 12
- 150000001875 compounds Chemical class 0.000 claims abstract description 9
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 8
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 claims abstract description 7
- 150000003951 lactams Chemical class 0.000 claims abstract description 7
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 26
- 239000004697 Polyetherimide Substances 0.000 claims description 19
- 150000001408 amides Chemical class 0.000 claims description 19
- 229920001601 polyetherimide Polymers 0.000 claims description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- RAABOESOVLLHRU-UHFFFAOYSA-N diazene Chemical compound N=N RAABOESOVLLHRU-UHFFFAOYSA-N 0.000 claims description 3
- 229910000071 diazene Inorganic materials 0.000 claims description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 abstract description 24
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 abstract description 20
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 abstract description 12
- 239000004952 Polyamide Substances 0.000 abstract description 7
- 229920002647 polyamide Polymers 0.000 abstract description 7
- 239000000126 substance Substances 0.000 abstract description 7
- 229920001971 elastomer Polymers 0.000 abstract description 5
- SLXKOJJOQWFEFD-UHFFFAOYSA-N 6-aminohexanoic acid Chemical compound NCCCCCC(O)=O SLXKOJJOQWFEFD-UHFFFAOYSA-N 0.000 abstract description 4
- 239000000806 elastomer Substances 0.000 abstract description 4
- 125000002947 alkylene group Chemical group 0.000 abstract description 2
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 abstract 1
- 229920000642 polymer Polymers 0.000 description 38
- 239000002253 acid Substances 0.000 description 27
- 238000006116 polymerization reaction Methods 0.000 description 20
- 230000000704 physical effect Effects 0.000 description 10
- PBLZLIFKVPJDCO-UHFFFAOYSA-N 12-aminododecanoic acid Chemical compound NCCCCCCCCCCCC(O)=O PBLZLIFKVPJDCO-UHFFFAOYSA-N 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 150000004985 diamines Chemical class 0.000 description 6
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 6
- 230000007062 hydrolysis Effects 0.000 description 6
- 238000006460 hydrolysis reaction Methods 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 4
- 239000004721 Polyphenylene oxide Substances 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229920000728 polyester Polymers 0.000 description 4
- 229920000570 polyether Polymers 0.000 description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 4
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-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
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 150000008064 anhydrides Chemical class 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- 229920001451 polypropylene glycol Polymers 0.000 description 3
- RYRZSXJVEILFRR-UHFFFAOYSA-N 2,3-dimethylterephthalic acid Chemical compound CC1=C(C)C(C(O)=O)=CC=C1C(O)=O RYRZSXJVEILFRR-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 150000004982 aromatic amines Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000012965 benzophenone Substances 0.000 description 2
- 150000008366 benzophenones Chemical class 0.000 description 2
- 150000001565 benzotriazoles Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
- TVIDDXQYHWJXFK-UHFFFAOYSA-N dodecanedioic acid Chemical compound OC(=O)CCCCCCCCCCC(O)=O TVIDDXQYHWJXFK-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 239000004611 light stabiliser Substances 0.000 description 2
- YDSWCNNOKPMOTP-UHFFFAOYSA-N mellitic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(O)=O)=C(C(O)=O)C(C(O)=O)=C1C(O)=O YDSWCNNOKPMOTP-UHFFFAOYSA-N 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 2
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- LWBHHRRTOZQPDM-UHFFFAOYSA-N undecanedioic acid Chemical compound OC(=O)CCCCCCCCCC(O)=O LWBHHRRTOZQPDM-UHFFFAOYSA-N 0.000 description 2
- MRERMGPPCLQIPD-NBVRZTHBSA-N (3beta,5alpha,9alpha,22E,24R)-3,5,9-Trihydroxy-23-methylergosta-7,22-dien-6-one Chemical compound C1C(O)CCC2(C)C(CCC3(C(C(C)/C=C(\C)C(C)C(C)C)CCC33)C)(O)C3=CC(=O)C21O MRERMGPPCLQIPD-NBVRZTHBSA-N 0.000 description 1
- PWGJDPKCLMLPJW-UHFFFAOYSA-N 1,8-diaminooctane Chemical compound NCCCCCCCCN PWGJDPKCLMLPJW-UHFFFAOYSA-N 0.000 description 1
- AOGDNNLIBAUIIX-UHFFFAOYSA-N 1-n,4-n-dinaphthalen-1-ylbenzene-1,4-diamine Chemical compound C1=CC=C2C(NC=3C=CC(NC=4C5=CC=CC=C5C=CC=4)=CC=3)=CC=CC2=C1 AOGDNNLIBAUIIX-UHFFFAOYSA-N 0.000 description 1
- QFGCFKJIPBRJGM-UHFFFAOYSA-N 12-[(2-methylpropan-2-yl)oxy]-12-oxododecanoic acid Chemical compound CC(C)(C)OC(=O)CCCCCCCCCCC(O)=O QFGCFKJIPBRJGM-UHFFFAOYSA-N 0.000 description 1
- DKCPKDPYUFEZCP-UHFFFAOYSA-N 2,6-di-tert-butylphenol Chemical compound CC(C)(C)C1=CC=CC(C(C)(C)C)=C1O DKCPKDPYUFEZCP-UHFFFAOYSA-N 0.000 description 1
- QUBNFZFTFXTLKH-UHFFFAOYSA-N 2-aminododecanoic acid Chemical compound CCCCCCCCCCC(N)C(O)=O QUBNFZFTFXTLKH-UHFFFAOYSA-N 0.000 description 1
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 1
- UFFRSDWQMJYQNE-UHFFFAOYSA-N 6-azaniumylhexylazanium;hexanedioate Chemical compound [NH3+]CCCCCC[NH3+].[O-]C(=O)CCCCC([O-])=O UFFRSDWQMJYQNE-UHFFFAOYSA-N 0.000 description 1
- UQXNEWQGGVUVQA-UHFFFAOYSA-N 8-aminooctanoic acid Chemical compound NCCCCCCCC(O)=O UQXNEWQGGVUVQA-UHFFFAOYSA-N 0.000 description 1
- DPUOLQHDNGRHBS-UHFFFAOYSA-N Brassidinsaeure Natural products CCCCCCCCC=CCCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-UHFFFAOYSA-N 0.000 description 1
- GHKOFFNLGXMVNJ-UHFFFAOYSA-N Didodecyl thiobispropanoate Chemical compound CCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCC GHKOFFNLGXMVNJ-UHFFFAOYSA-N 0.000 description 1
- 239000003508 Dilauryl thiodipropionate Substances 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 1
- 238000012695 Interfacial polymerization Methods 0.000 description 1
- KEQFTVQCIQJIQW-UHFFFAOYSA-N N-Phenyl-2-naphthylamine Chemical compound C=1C=C2C=CC=CC2=CC=1NC1=CC=CC=C1 KEQFTVQCIQJIQW-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 241000860832 Yoda Species 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229920006125 amorphous polymer Polymers 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- YDLSUFFXJYEVHW-UHFFFAOYSA-N azonan-2-one Chemical compound O=C1CCCCCCCN1 YDLSUFFXJYEVHW-UHFFFAOYSA-N 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 239000001273 butane Substances 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
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- WTNDADANUZETTI-UHFFFAOYSA-N cyclohexane-1,2,4-tricarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)C(C(O)=O)C1 WTNDADANUZETTI-UHFFFAOYSA-N 0.000 description 1
- YQLZOAVZWJBZSY-UHFFFAOYSA-N decane-1,10-diamine Chemical compound NCCCCCCCCCCN YQLZOAVZWJBZSY-UHFFFAOYSA-N 0.000 description 1
- 235000019304 dilauryl thiodipropionate Nutrition 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- FPTWDYRUZZWASE-UHFFFAOYSA-N ethene-1,1,2-tricarboxylic acid Chemical compound OC(=O)C=C(C(O)=O)C(O)=O FPTWDYRUZZWASE-UHFFFAOYSA-N 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 229920002457 flexible plastic Polymers 0.000 description 1
- 229920005570 flexible polymer Polymers 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000012208 gear oil Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- PWSKHLMYTZNYKO-UHFFFAOYSA-N heptane-1,7-diamine Chemical compound NCCCCCCCN PWSKHLMYTZNYKO-UHFFFAOYSA-N 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 239000010705 motor oil Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- BTHGHFBUGBTINV-UHFFFAOYSA-N naphthalene-2,3,6-tricarboxylic acid Chemical compound C1=C(C(O)=O)C(C(O)=O)=CC2=CC(C(=O)O)=CC=C21 BTHGHFBUGBTINV-UHFFFAOYSA-N 0.000 description 1
- SXJVFQLYZSNZBT-UHFFFAOYSA-N nonane-1,9-diamine Chemical compound NCCCCCCCCCN SXJVFQLYZSNZBT-UHFFFAOYSA-N 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- KZAUOCCYDRDERY-UHFFFAOYSA-N oxamyl Chemical compound CNC(=O)ON=C(SC)C(=O)N(C)C KZAUOCCYDRDERY-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- DXGLGDHPHMLXJC-UHFFFAOYSA-N oxybenzone Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1 DXGLGDHPHMLXJC-UHFFFAOYSA-N 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 229940116351 sebacate Drugs 0.000 description 1
- CXMXRPHRNRROMY-UHFFFAOYSA-L sebacate(2-) Chemical compound [O-]C(=O)CCCCCCCCC([O-])=O CXMXRPHRNRROMY-UHFFFAOYSA-L 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- DXNCZXXFRKPEPY-UHFFFAOYSA-N tridecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCC(O)=O DXNCZXXFRKPEPY-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〈産業上の利用分野〉
本発明は射出成形・押出成形等の加工性、機械的性質、
エラストマ特性（特に柔軟性）及び耐加水分解性、耐オ
イル性等の化学的性質に優れたポリエーテルイミドアミ
ドに関する。さらに詳しくは、本発明は上記特性を有す
るラクタム、アミノカルボン酸、脂肪族ジアミンと実質
的に等モルの脂肪ルジカルボン酸から選ばれた化合物、
脂肪族ジアミン及びポリオキシアルキレンジイミドニ酸
からなるポリエーテルイミドアミドに関するものである
。[Detailed Description of the Invention] <Industrial Application Field> The present invention is applicable to injection molding, extrusion molding, etc. processability, mechanical properties,
This invention relates to a polyetherimide amide that has excellent elastomer properties (especially flexibility) and chemical properties such as hydrolysis resistance and oil resistance. More specifically, the present invention provides a compound selected from lactams having the above characteristics, aminocarboxylic acids, aliphatic dicarboxylic acids in substantially equimolar amounts to aliphatic diamines,
The present invention relates to a polyetherimide amide consisting of an aliphatic diamine and a polyoxyalkylene diimidonic acid.
〈従来の技術〉
ポリマー主鎖中にポリエステル繰返し単位、ポリエーテ
ル繰返し単位及びイミド結合を有するポリエーテルイミ
ドエステルが特開昭６１−１０８６２６号公報に記載さ
れている。<Prior Art> A polyetherimide ester having a polyester repeating unit, a polyether repeating unit, and an imide bond in the polymer main chain is described in JP-A-61-108626.
〈発明が解決しようとする問題点〉
前記特開昭６１−１０８６２６号公報で開示されたポリ
エーテルイミドエステルは、加工性、物理的性質は優れ
ているが、柔軟性、柔軟な領域における射出成形性及び
耐加水分解性、耐オイル性等の化学的性質については不
十分である。<Problems to be Solved by the Invention> The polyetherimide ester disclosed in JP-A No. 61-108626 has excellent processability and physical properties, but is difficult to injection mold in the soft and flexible region. Chemical properties such as durability, hydrolysis resistance, and oil resistance are insufficient.
よって、本発明は、加工性、物理的性質に優れ、さらに
柔軟性及び耐加水分解性、耐オイル性などの化学的性質
にも優れたエラストマを提供する目的でなされた。Therefore, the present invention was made with the object of providing an elastomer that has excellent processability and physical properties, and also has excellent chemical properties such as flexibility, hydrolysis resistance, and oil resistance.
〈問題点を解決するための手段〉
その結果、上記の目的は、ＣＡ）炭素原子数６以上のラ
クタム、炭素原子数６以上のアミノカルボン酸、炭素数
６〜２０の脂肪族ジアミン（ａ）と実質的に（ａ）と等
モルの炭素数６〜１５の脂肪族ジカルボン酸（ｂ）の塩
及び炭素数６〜２０の脂肪族ジアミン（ａ）と実質的に
（ａ）と等モルの炭素数６〜１５の脂肪族ジカルボン酸
（ｂ）の混合物から選ばれた一種または二種以上の化合
物、
（Ｂ）炭素数６〜２０の脂肪族ジアミン及び（Ｃ）ポリ
オキシアルキレンジイミドニ酸からなるポリエーテルイ
ミドアミドによって、達成されることを見出した。<Means for Solving the Problems> As a result, the above objectives are as follows: CA) Lactams having 6 or more carbon atoms, aminocarboxylic acids having 6 or more carbon atoms, aliphatic diamines having 6 to 20 carbon atoms (a) A salt of an aliphatic dicarboxylic acid (b) having 6 to 15 carbon atoms in substantially the same molar amount as (a) and a salt of an aliphatic diamine having 6 to 20 carbon atoms (a) in substantially the same molar amount as (a). One or more compounds selected from a mixture of aliphatic dicarboxylic acids (b) having 6 to 15 carbon atoms, (B) aliphatic diamines having 6 to 20 carbon atoms, and (C) polyoxyalkylene diimidonic acid. It has been found that this can be achieved by using polyetherimide amide.
以下、本発明の構成を詳述する。Hereinafter, the configuration of the present invention will be explained in detail.
本発明のポリエーテルイミドアミドにおける（Ａ）成分
は、炭素原子数６以上のラクタム、炭素原子数６以上の
アミノカルボン酸、炭素数６〜２０の脂肪族ジアミン（
ａ）と実質的に（ａ）と等モルの炭素数６〜１５の脂肪
族ジカルボン酸（ｂ）の塩、及び炭素数６〜２０の脂肪
族ジアミン（ａ）と実質的に（ａ）と等モルの炭素数６
〜１５の脂肪族ジカルボン酸（ｂ）の混合物から選ばれ
た一種または二種以上の化合物である。Component (A) in the polyetherimide amide of the present invention includes a lactam having 6 or more carbon atoms, an aminocarboxylic acid having 6 or more carbon atoms, an aliphatic diamine having 6 to 20 carbon atoms (
a) and a salt of an aliphatic dicarboxylic acid (b) having 6 to 15 carbon atoms in substantially equimolar amounts as (a), and an aliphatic diamine having 6 to 20 carbon atoms (a) and substantially (a) Equimolar carbon number 6
It is one or more compounds selected from a mixture of ~15 aliphatic dicarboxylic acids (b).
上記炭素原子数６以上のラクタムとしては、カプロラク
タム、エナントラクタム、カプリルラクタム、ラウロラ
クタムなどが挙げられるが、特にカプロラクタム、ラウ
ロラクタム等が好ましい。Examples of the lactam having 6 or more carbon atoms include caprolactam, enantlactam, capryllactam, and laurolactam, with caprolactam, laurolactam, and the like being particularly preferred.
炭素原子数６以上のアミノカルボン酸としては、ω−ア
ミノカプロン酸、ω−アミノエナンｌ−酸、ω−アミノ
カプリル酸、ω−・アミノペラルゴン酸、ω−アミノカ
プリン酸、ω−アミノウンデカン酸、ω−アミノドデカ
ン酸等が挙げられるが、特にω−アミノカプロン酸、ω
−アミノウンデカン酸、ω−アミノドデカン酸等が好ま
しい。Examples of aminocarboxylic acids having 6 or more carbon atoms include ω-aminocaproic acid, ω-aminoenanic acid, ω-aminocaprylic acid, ω-aminopelargonic acid, ω-aminocapric acid, ω-aminoundecanoic acid, ω -Aminododecanoic acid, etc., especially ω-aminocaproic acid, ω-aminocaproic acid, etc.
-aminoundecanoic acid, ω-aminododecanoic acid, etc. are preferred.
炭素数６〜２０の脂肪族ジアミン（ａ）としては、ヘキ
サメチレンジアミン、ヘプ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、デカメチレ
ンジアミン、ドカメチレンジアミン、ヘキサデカメチレ
ンジアミン等が挙げられるが、特にヘキサメチレンジア
ミン等が好ましい炭素数６〜１５の脂肪族ジカルボン酸
（ｂ）としては、アジピン酸、ピメリン酸、スペリン酸
、アゼライン酸、セバシン酸、ウンデカンジ酸、ドデカ
ンジ酸、ブラシル酸等が挙げられるが、中でもアジピン
酸、セバシン酸、ドデカンジ酸等が好ましい。Examples of the aliphatic diamine (a) having 6 to 20 carbon atoms include hexamethylene diamine, heptamethylene diamine, octamethylene diamine, nonamethylene diamine, decamethylene diamine, docamethylene diamine, hexadecamethylene diamine, etc. Examples of the aliphatic dicarboxylic acid (b) having 6 to 15 carbon atoms, preferably hexamethylene diamine, include adipic acid, pimelic acid, superric acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, brassylic acid, etc. Among them, adipic acid, sebacic acid, dodecanedioic acid and the like are preferred.
これら脂肪族ジアミン（ａ）と、脂肪族ジカルボン（ｂ
）は、実質的に等モルの塩または混合物で重合に供され
る。These aliphatic diamines (a) and aliphatic dicarbons (b)
) is subjected to polymerization in substantially equimolar salts or mixtures.
（Ｂ）成分である炭素数６〜２０の脂肪族ジアミンとし
ては、前記（Ａ）成分の炭素数６〜２０の脂肪族ジアミ
ン（ａ）と同様のものが挙げられる。Examples of the aliphatic diamine having 6 to 20 carbon atoms as component (B) include those similar to the aliphatic diamine having 6 to 20 carbon atoms (a) as component (A).
（Ｃ）成分であるポリオキシアルキレンジイミド二酸は
、トリカルボン酸化合物と、高分子量ポリオキシアルキ
レンジアミンとのイミド化反応により得られるものであ
る。The polyoxyalkylene diimide diacid which is the component (C) is obtained by an imidization reaction between a tricarboxylic acid compound and a high molecular weight polyoxyalkylene diamine.
高分子量ポリオキシアルキレンジアミンは、ポリ（アル
キレジオキシド）グリコールから誘導されるものが通常
用いられる。High molecular weight polyoxyalkylene diamines derived from poly(alkylene dioxide) glycols are usually used.
高分子量ポリオキシアルキレンジアミンの分子量は重合
時に粗大な相分離を起こさず、低温特性や機械的性質が
優れる分子量領域が選択され、数平均分子量で約６００
〜１２．ｏｏｏの範囲が好ましく、特に約９００〜４０
００の範囲のものが好ましく用いられる。The molecular weight of the high molecular weight polyoxyalkylene diamine is selected from a molecular weight range that does not cause coarse phase separation during polymerization and has excellent low temperature properties and mechanical properties, and has a number average molecular weight of approximately 600.
~12. ooo range is preferred, especially about 900-40
A value in the range of 00 is preferably used.
前記ポリ（アルキレンオキシド）グリコールとしては、
ポリ（エチレンオキシド）り刃コール、ポリ（プロピレ
ンオキシド）グリコール、ポリ（テトラメチレンオキシ
ド）グリコール、ポリ（ヘキサメチレンオキシド）グリ
コール、プロピレンオキシドで末端封鎖したポリ（エチ
レンオキシド）グ１７コールを含めたエチレンオキシド
とテトラヒドロフランとのランダムまたはブロック共重
合体等が挙げられる。中でもプロピレンオキシドで末端
封鎖したポリ（エチレンオキシド）グリコール及びポリ
（プロピレンオキシド）グリコール等が特に好ましく用
いられる。As the poly(alkylene oxide) glycol,
Ethylene oxide and tetrahydrofuran, including poly(ethylene oxide) glycol, poly(propylene oxide) glycol, poly(tetramethylene oxide) glycol, poly(hexamethylene oxide) glycol, and propylene oxide end-capped poly(ethylene oxide) glycol. Examples include random or block copolymers with. Among them, poly(ethylene oxide) glycol and poly(propylene oxide) glycol terminal-capped with propylene oxide are particularly preferably used.
また、トリカルボン酸化合物とし７てはイミド化可能な
２つの隣接カルボキシル基を含有する下記一般式（Ｉ）
で示される化合物、もしくはアミド化可能なカルボキシ
ル基を含有する下記一般式（■）で示される酸無水物等
が挙げられる。Further, as the tricarboxylic acid compound 7, the following general formula (I) containing two adjacent carboxyl groups that can be imidized is used.
Examples thereof include compounds represented by the above, and acid anhydrides represented by the following general formula (■) containing an amidatable carboxyl group.
上記アミド化可能なカルボキシル基は、アミド化可能で
あれば特に制限はないが、実質的にイミド化不能である
ことが好ましい。The above-mentioned amidatable carboxyl group is not particularly limited as long as it is amidatable, but it is preferably substantially imidizable.
（ここでＲは三価の有機基、好ましくは三価の炭素原子
数２〜２０の脂肪族、芳香族または脂環式有機基である
。Ｒ−は、好ましくは水素、または−価の炭素原子数１
〜６の脂肪族及び／又は脂環式基及び炭素原子数６〜１
２の芳香族基で、特に好ましくは水素である。）
具体的には、１〜リメリツト酸、２，６．７−ナフタレ
ントリカルボン酸、３．３’、４−ジフェニル１〜リカ
ルボン酸、３．３’、４−ベンゾフェノントリカルボン
酸、１，３．４−シクロペンタントリカルホ゛ン酸、２
．２’、３−ジフェニルトリカルボン酸、ジフェニルス
ルホン−３，３“、４−トリカルボン酸、エチレントリ
カルボン酸、１，２．４−ブタン１〜リカルボン酸、３
，４−ジカルボキシフェニル−３−カルボキシフェニル
エーテル、１，３．４−シクロヘキサントリカルボン酸
等、及び上記ｌ・リカルボン酸の２つの隣接カルボキシ
ル基が閉環した状態の酸無水物が挙げられ、中でもトリ
メリット酸またはその無水物が好ましい。(Here, R is a trivalent organic group, preferably a trivalent aliphatic, aromatic or alicyclic organic group having 2 to 20 carbon atoms. R- is preferably hydrogen or a -valent carbon Number of atoms: 1
~6 aliphatic and/or cycloaliphatic groups and 6 to 1 carbon atoms
2 is an aromatic group, and hydrogen is particularly preferred. ) Specifically, 1-limellitic acid, 2,6.7-naphthalenetricarboxylic acid, 3.3',4-diphenyl1-licarboxylic acid, 3.3',4-benzophenonetricarboxylic acid, 1,3.4 -Cyclopentanetricarphonic acid, 2
．． 2',3-diphenyltricarboxylic acid, diphenylsulfone-3,3'', 4-tricarboxylic acid, ethylenetricarboxylic acid, 1,2,4-butane 1-ricarboxylic acid, 3
, 4-dicarboxyphenyl-3-carboxyphenyl ether, 1,3,4-cyclohexanetricarboxylic acid, and acid anhydrides in which two adjacent carboxyl groups of the above l-licarboxylic acid are ring-closed. Mellitic acid or its anhydride is preferred.
ポリオキシアルキレンジイミドニ酸即ち（Ｃ）成分は、
既知のイミド化反応により例えば、溶融合成、または溶
液系での合成により製造することができる。このような
反応は、水を排除しながら、あるいは溶液系では溶媒ま
たは共沸（溶媒）混合物を還流させながら、１００℃〜
３００℃、好ましくは約１２０ ’Ｃ〜２５０°Ｃの温
度で行われる。Polyoxyalkylene diimidonic acid, that is, component (C), is
It can be produced by known imidization reactions, for example, by melt synthesis or solution-based synthesis. Such reactions are carried out at temperatures between 100° C. and refluxing the solvent or azeotropic (solvent) mixture, with exclusion of water or, in solution systems, with refluxing of the solvent or azeotropic (solvent) mixture.
It is carried out at a temperature of 300°C, preferably about 120'C to 250°C.
本発明のポリエーテルイミドアミドを得るには（Ｂ）成
分と（Ｃ）成分は等モル量使用することが必要である。In order to obtain the polyetherimide amide of the present invention, it is necessary to use equimolar amounts of component (B) and component (C).
ここで（Ｂ）成分と（Ｃ）成分は混合物の形で使用して
もよいが、好ましくは塩を形成して用いる。Although component (B) and component (C) may be used in the form of a mixture, they are preferably used in the form of a salt.
さらに好ましい物性のポリマを得るためには、上記（Ｂ
）成分と（Ｃ）成分から形成される長鎖ポリエーテルイ
ミドアミド単位は（Ａ）成分、（Ｂ）成分及び（Ｃ）成
分から形成されるポリマ全量に対し、対衝撃性、耐寒性
などの改善効果が顕著であることから５重量％以上、物
理的性質の点から９５重量％以下で共重合させることが
好ましい。In order to obtain a polymer with more preferable physical properties, the above (B
The long-chain polyetherimide amide unit formed from components () and (C) has properties such as impact resistance and cold resistance relative to the total amount of the polymer formed from components (A), (B), and (C). It is preferable to copolymerize in an amount of 5% by weight or more because the improvement effect is remarkable, and 95% by weight or less from the viewpoint of physical properties.
（Ｂ）成分と（Ｃ）成分から形成される長鎖ポリエーテ
ルイミドアミド単位が全ポリマ中５〜約２５重量％の範
囲で共重合されていると、得られるポリエーテルイミド
アミドは強度が高く、かつ低温においても優れた耐衝撃
性を有する、いわゆる可塑化ナイロンのような柔軟プラ
スチックに対応する弾性率領域に属するポリマとなる。When long-chain polyetherimide amide units formed from components (B) and (C) are copolymerized in a range of 5 to about 25% by weight based on the total polymer, the resulting polyetherimideamide has high strength. The polymer has excellent impact resistance even at low temperatures and has an elastic modulus in the region corresponding to flexible plastics such as so-called plasticized nylon.
また、長鎖ポリエーテル、イミドアミド単位が全ポリマ
中約２５〜約７５重量％の範囲で共重合されたポリエー
テルイミドアミドはいわゆる熱可塑性エラス１ヘマとし
て分類される物理的性質を有し、低温から高温にわたる
広い温度領域で優れた耐永久歪性と適度な弾性率等のゴ
ム的性質を有しているまた、長鎖ポリエーテルイミドア
ミド単位が全ポリマ巾約７５〜９５重量％の範囲で°共
重合されたポリニーデルイミドアミドは極めて柔軟で異
種のポリマに柔軟性や耐衝撃性を付与する改質ポリマと
して使用し得る池、単独でも接着剤、コーティング被覆
などの用途に適用し得る６いずれにしても長鎖ポリエー
テルイミドアミド単位を共重合することにより特に射出
成形性に優れたポリエーテルイミドアミドが得られる。In addition, polyether imidamide, which is copolymerized with long chain polyether and imidoamide units in a range of about 25 to about 75% by weight based on the total polymer, has physical properties that can be classified as so-called thermoplastic elastomer. It has rubber properties such as excellent permanent deformation resistance and moderate elastic modulus in a wide temperature range from to °Copolymerized polyamide amide is extremely flexible and can be used as a modified polymer to impart flexibility and impact resistance to dissimilar polymers, and can also be used alone in applications such as adhesives and coatings. 6. In any case, by copolymerizing long-chain polyetherimide amide units, a polyetherimide amide with particularly excellent injection moldability can be obtained.
本発明のポリエーテルイミドアミドは、慣例のポリアミ
ド重合法により得られる。なお、ポリアミドの重合法に
は溶融重合、界面重合、溶液重合、塊状重合、固相重合
及びこｒしらの方法を組合わせた方法がある。重合触媒
は、特に必要ではないが、酸（鉱酸、有機酸）または塩
基を添加し、でもよい。一般に、こｈらの添加により重
合速度が加速されることが知られでいる。中でもリン酸
の効果が最も大きい。また、リン酸エステルも好ましい
。さらに短時間で重合を終了させたい場合は、重合の後
半で減圧にするとよい。The polyetherimide amide of the invention is obtained by conventional polyamide polymerization methods. Polyamide polymerization methods include melt polymerization, interfacial polymerization, solution polymerization, bulk polymerization, solid phase polymerization, and a combination of these methods. Although not particularly necessary, an acid (mineral acid, organic acid) or base may be added to the polymerization catalyst. It is generally known that the addition of these compounds accelerates the polymerization rate. Among them, phosphoric acid has the greatest effect. Also preferred are phosphoric acid esters. If it is desired to complete the polymerization in an even shorter period of time, the pressure may be reduced during the latter half of the polymerization.
本発明のポリエーテル・ｒミドアミドを製造する際に安
定剤を添加し、熱、酸化、紫外線等に対し、安定化をは
かるのが好ましい。これらの安定剤はポリエーテルイミ
ドアミドの重合時、重合終了時、もしくは重合後成形前
に添加される。好適な酸化防止剤にはヒンダードフェノ
ール類、芳香族アミン類がある。また耐光安定剤にはヒ
ンダードアミン類、ベンゾフェノン類、ベンゾトリアゾ
ール類等がある。When producing the polyether/ramide amide of the present invention, it is preferable to add a stabilizer to stabilize it against heat, oxidation, ultraviolet rays, etc. These stabilizers are added during polymerization of polyetherimide amide, at the end of polymerization, or after polymerization and before molding. Suitable antioxidants include hindered phenols and aromatic amines. Further, light stabilizers include hindered amines, benzophenones, benzotriazoles, and the like.
ヒンダードフェノール類の例としては、１，３．５−ト
リス−（２−ヒドロキシエチル）−３−１〜リアジン−
２，４，６−（１ｔｌ、３１ｉ、５１１） ｌ〜リオ
ンの３，５−ジ−ｔ−ブチル−４−ヒドロキシヒドロ桂
皮酸トリエステル、４，４“−ビス（２，６−ジーｔ−
ブチルフェノール） 、１，３．５−トリメチル−２，
４，６−１−リス（３，５−ジー［−ブチル−４−ヒド
ロキシベンジル）ベンゼン、４，４°−ブチリデン−ビ
ス（６−ｔ−ブチルーロｌ−クレゾール）、Ｎ、Ｎ’−
ヘキサメチレンビス（３，５−ジーし一ブチルー４−ヒ
ドロキシーヒドロシンナムアミド）、ペンタエリスリチ
ル−テトラキス［３−（３，５−ジ−ｔ−ブチル−４−
ヒドロキシフェニル）プロピオネート］ 、２．２−千
オジエチレンビス［３−（３，５−ジー℃−ブチルー４
−ヒドロキシフェニル）プロピオネート１等が挙げられ
る。Examples of hindered phenols include 1,3,5-tris-(2-hydroxyethyl)-3-1~riazine-
2,4,6-(1tl, 31i, 511) 3,5-di-t-butyl-4-hydroxyhydrocinnamic acid triester, 4,4"-bis(2,6-di-t-
butylphenol), 1,3.5-trimethyl-2,
4,6-1-Lis(3,5-di[-butyl-4-hydroxybenzyl)benzene, 4,4°-butylidene-bis(6-t-butyluro-l-cresol), N,N'-
Hexamethylenebis(3,5-di-t-butyl-4-hydroxy-hydrocinnamamide), pentaerythrityl-tetrakis[3-(3,5-di-t-butyl-4-
hydroxyphenyl)propionate], 2.2-thousandodiethylenebis[3-(3,5-diC-butyl-4
-hydroxyphenyl) propionate 1 and the like.
芳香族アミン類としては４，４−ビス（４−α、α−ジ
メチルベンジル）ジフェニルアミン、Ｎ、Ｎ’−ジ−ナ
フチル−ｐ−フェニレンジアミン、Ｎ、Ｎ’−ビス（１
−メヂルＩ＼ブチル）−叶フェニレンジアミン、フェニ
ル−β−ナフチルアミン等が挙げられる。Aromatic amines include 4,4-bis(4-α,α-dimethylbenzyl)diphenylamine, N,N'-di-naphthyl-p-phenylenediamine, N,N'-bis(1
Examples include -medyl I\butyl)-phenylenediamine, phenyl-β-naphthylamine, and the like.
また、ヒンダードフェノール類はジラウリルチオジプロ
ピオネートのようなチオエーテル化合物あるいはトリフ
ェニルフォスファイトのような亜リン酸化合物を併用す
ると、さらに優れた効果が得られる。Furthermore, when the hindered phenols are used in combination with a thioether compound such as dilauryl thiodipropionate or a phosphorous acid compound such as triphenylphosphite, even more excellent effects can be obtained.
ヒンダードアミン類の例として、ビス（１，２，２，６
，６−ベンタメチルー４−ピペリジル）セバケート等が
挙げられ、紫外線吸収剤のベンゾフェノン類としては、
２−ヒドロキシ−４−メトキシベンゾフェノン等が挙げ
られ、またベンゾトリアゾール類には、２−β−ｒ−ブ
チルー５−、メチルー２−ヒドロキシフェニル）−５−
クロロベンゾ）・リアゾール等が挙げられる。このよう
な光安定剤の添加により、紫外光に対する安定化が得ら
れる。Examples of hindered amines include bis(1,2,2,6
, 6-bentamethyl-4-piperidyl) sebacate, etc., and the benzophenones of ultraviolet absorbers include:
Examples include 2-hydroxy-4-methoxybenzophenone, and benzotriazoles include 2-β-r-butyl-5-, methyl-2-hydroxyphenyl)-5-
Examples include chlorobenzo) and riazole. The addition of such a light stabilizer provides stabilization against ultraviolet light.
また、■・リカルボン酸を少量添加することも望ましい
。It is also desirable to add a small amount of (1)-ricarboxylic acid.
この添加により、残留する未反応アミンど全て反応し、
ポリマの粘度上昇が助けられる。添加する適量はポリオ
キシアルキレンジアミドニ酸のモル数の２０モル％以下
、より好ましくは１０モル％以下である。これ以上添加
するとゲル化等がおきて、有益な物性を損なうおそれが
ある。また、添加するトリカルボン
シドニ酸の成分と同しにすることが好ましいが、このこ
とは必ずしも必要ではない。By this addition, all remaining unreacted amine reacts,
Helps increase the viscosity of the polymer. The appropriate amount to be added is 20 mol % or less, more preferably 10 mol % or less, based on the number of moles of polyoxyalkylene diamide diacid. If more than this is added, gelation etc. may occur, which may impair useful physical properties. Further, although it is preferable to use the same components as the tricarboxydonic acid to be added, this is not always necessary.
さらに本発明のポリエーテルイミドアミドには耐加水分
解改良剤、着色剤（顔料、染料）、帯電防止剤、導電剤
、難燃剤、補強剤、充填剤、滑剤、核剤、離型剤、可塑
剤、接着助剤、粘着剤等を任意に含有せしめることがで
きる。Furthermore, the polyetherimide amide of the present invention includes hydrolysis resistance improvers, colorants (pigments, dyes), antistatic agents, conductive agents, flame retardants, reinforcing agents, fillers, lubricants, nucleating agents, mold release agents, plasticizers, etc. Agents, adhesion aids, adhesives, etc. can be optionally contained.
〈実施例〉
以下、実施例によって、本発明を説明する。なお、実施
例中特にことわらない限り、部数は重量部を意味する。<Examples> The present invention will be described below with reference to Examples. In addition, unless otherwise specified in the examples, parts mean parts by weight.
融点は試料を８０℃で１８時間真空乾燥した後、ＤＳＣ
により測定し、相対粘度（ηｒ）はＯ−クロロフェノー
ル中２５℃、０．５％濃度で測定した。また、機械的性
質は下記の方法により測定した。The melting point was determined by DSC after vacuum drying the sample at 80°C for 18 hours.
The relative viscosity (ηr) was measured in O-chlorophenol at 25° C. at a concentration of 0.5%. In addition, mechanical properties were measured by the following method.
引張弾性率 ＡＳＴ）Ｉ Ｄ−６３８破断応
カ ツノ
破断伸び ツノ
シヨアＤ硬度 ＡＳＴ）ｌ Ｄ−２２４弾性回
復率（５０％伸長） 八ＳＴ）ｌ ［）−４１２また、
実施例中で用いている″シェフアミン″ＥＤはテキサ：
トケミカル・カンパニー製のポリ（エチレンオキシド）
グリコールの両末端にプロピレンオキシドを付加させた
ポリ（アルキレンオキシド）グリコールから誘導された
ポリオキシアルキレンジアミンである。Tensile modulus AST)I D-638 Break stress Horn break elongation Horn shore D hardness AST)l D-224 Elastic recovery rate (50% elongation) 8ST)l [)-412 Also,
"Chefamine" ED used in the examples is Texas:
Poly(ethylene oxide) manufactured by To Chemical Company
It is a polyoxyalkylene diamine derived from poly(alkylene oxide) glycol with propylene oxide added to both ends of the glycol.
また、″シェフアミン″′Ｄは同じくテキサコ・ケミカ
ル・カンパニー製のポリ（プロピレンオキシド）グリコ
ールから誘導されたポリオキシアルキレンジアミンであ
る。"Chefamine" D is a polyoxyalkylene diamine derived from poly(propylene oxide) glycol, also manufactured by Texaco Chemical Company.
なお、ここでいうポリアミド単位とは（Ａ）成分から形
成されるハードセグメントを長鎖ポリエーテルイミドア
ミド単位とは（Ｂ）成分と（Ｃ）成分から形成されるソ
フトセグメントを表わす。Note that the polyamide unit herein refers to a hard segment formed from component (A), and the long chain polyetherimide amide unit refers to a soft segment formed from components (B) and (C).
実施例１
数平均分子１１１８０の′”シェフアミン” ＥＤ９０
０１００部と無水トリメリット酸３２．５部を窒素気流
下撹拌して１５０℃で留出する水を除去しながら、３時
間反応させてポリオキシアルキレンジイミドニ酸を作っ
た。得られたポリオキシアルキレンジイミドニ酸をイオ
ン交換水に溶解し、撹拌しながら、ヘキサメチレンジア
ミンを滴下して温調し１，３０％の塩水溶液を作った。Example 1 ``Chefamine'' ED90 with number average molecular weight 11180
0100 parts of trimellitic anhydride and 32.5 parts of trimellitic anhydride were stirred under a nitrogen stream and reacted for 3 hours while removing distilled water at 150°C to produce polyoxyalkylene diimidonic acid. The obtained polyoxyalkylene diimidonic acid was dissolved in ion-exchanged water, and while stirring, hexamethylene diamine was added dropwise to adjust the temperature to prepare a 1.30% aqueous salt solution.
この３０％塩水溶液８５．２部とω−アミノドデカン酸
８１．９部と′°イルガノックス” １０９８ （酸化
防止剤）０．２部及びトリフェニルホスファイト０．０
１部をヘリカルリボン撹拌翼を備えた反応容器に仕込み
、窒素気流下、２５０℃で３時間４５分重合させると、
２２ｐｐｍでトルク５．０ｋｇ−ａｍに達し、粘稠で無
色透明な溶融ポリマが得られ、このポリマをガツトとし
て水中に吐出すると結晶化して白化した。このポリマは
ポリアミド単位を７５重量％含有するものである。85.2 parts of this 30% aqueous salt solution, 81.9 parts of ω-aminododecanoic acid, 0.2 parts of ``Irganox'' 1098 (antioxidant), and 0.0 parts of triphenylphosphite.
One part was placed in a reaction vessel equipped with a helical ribbon stirring blade and polymerized at 250°C for 3 hours and 45 minutes under a nitrogen stream.
A torque of 5.0 kg-am was reached at 22 ppm, and a viscous, colorless and transparent molten polymer was obtained. When this polymer was discharged into water as a gut, it crystallized and turned white. This polymer contains 75% by weight of polyamide units.
ここで得られたポリマをホラ１〜プレスにより約１−の
厚みのシートとし、このシートからダンベル試験片を打
抜き、機械的強度等を測定した。なお硬度はこのシート
を４枚重ねて測定した値である。The polymer thus obtained was pressed into a sheet having a thickness of about 1 mm, and dumbbell test pieces were punched out from this sheet to measure mechanical strength and the like. Note that the hardness is a value measured by stacking four of these sheets.
また、表１のように組成比を変えて重合し、同様に物性
を測定した。結果を表１に湿す。なお、ポリアミド単位
が２０重量％であるＮｏ、３のポリマもガツトを水中に
吐出するとまもなく結晶化して半透明となり硬度７８Ａ
の柔軟なポリマが得られた。Further, as shown in Table 1, polymerization was carried out by changing the composition ratio, and the physical properties were measured in the same manner. The results are shown in Table 1. In addition, when the polymer No. 3, which has a polyamide unit content of 20% by weight, is discharged into water, it immediately crystallizes, becomes translucent, and has a hardness of 78A.
A flexible polymer was obtained.
表１
実施例２
数平均分子量２２８０の″シェフアミン” ＥＤ２００
１１００重量部と無水トリメリット酸８．４部から実施
例１と同様の方法でポリオキシアルキレンジイミドニ酸
を合成した。この水溶液にヘキサメチレンジアミンを滴
下し、３０％塩水溶液を調整した。このポリオキシアル
キレンジイミドニ酸とへキサメチレンジアミンの等モル
塩の３０％水溶液と、ε−カプロラクタムと′°イルカ
′ノックス” １０９８（０，２部対ポリマ）を表２に
示すような共重合組成となるように反応容器に仕込み、
実施例１と同様の方法で重合してポリマを作り、物性を
測定した。結果と表２に示す。Table 1 Example 2 “Chefamine” ED200 with number average molecular weight 2280
Polyoxyalkylene diimidonic acid was synthesized from 1100 parts by weight and 8.4 parts of trimellitic anhydride in the same manner as in Example 1. Hexamethylene diamine was added dropwise to this aqueous solution to prepare a 30% salt aqueous solution. A 30% aqueous solution of an equimolar salt of polyoxyalkylene diimidonic acid and hexamethylene diamine was copolymerized with ε-caprolactam and '°Iruka'Knox' 1098 (0.2 parts to polymer) as shown in Table 2. Pour into a reaction container so that the composition is as follows.
A polymer was prepared by polymerization in the same manner as in Example 1, and its physical properties were measured. The results are shown in Table 2.
実施例３
数平均分子址８７０の″シェフアミン“’ ＥＤ６００
１００重量部と無水トリメリット酸４４．１部を実施例
１と同様の方法で反応させた後、ヘキサメチレンジアミ
ンで温調し、ポリオキシアルキレンジイミドニ酸とへキ
サメチレンジアミンの等モル塩の３０％水溶液を得た。Example 3 “Chefamine” ED600 with number average molecular weight 870
After reacting 100 parts by weight and 44.1 parts of trimellitic anhydride in the same manner as in Example 1, the temperature was controlled with hexamethylene diamine, and an equimolar salt of polyoxyalkylene diimidonic acid and hexamethylene diamine was reacted. A 30% aqueous solution was obtained.
この等モル塩の３０％水溶液、ヘキサメヂレンジアミン
ーアジピン酸塩及び″イルカソックス” １０９８ （
０，２部対ポリマ）を表３のような共重合組成比になも
ように反応容器に仕込み、重合温度を２７０°Ｃとする
以外は実施例１と同様の方法で重合してポリマを作り、
物性を測定した。結果を表３に示す。A 30% aqueous solution of this equimolar salt, hexamethylenediamine-adipate and "Irukasox" 1098 (
0.2 parts of polymer) were charged into a reaction vessel at the copolymerization composition ratio as shown in Table 3, and the polymer was polymerized in the same manner as in Example 1 except that the polymerization temperature was 270°C. Making,
Physical properties were measured. The results are shown in Table 3.
表３
実施例４
数平均分子−ｘ２１ｏｏの″”シェフアミン” ０２０
００１００重址部と無水トリスリット酸１８３部から実
施例１と同様の方法でポリオキジアルキレンジ、イミド
ニ酸を合成した。このポリオキシアルキレンジイミドニ
酸８４７部、ヘキサメチレニ／ジアミン４０，１部、ω
−アミノドデカン酸１７７３部、パイルガノックス”１
０９８ ５部を、撹拌装置を備えたステンレス製５′Ｊ
オートクレーブに仕込み、加圧下、２５０°Ｃで１時間
反応させた。その後１時間かけて放圧し、窒素気流下２
５０℃で４時間３０分重合し、ポリマを得た。このポリ
マの物性は以下に示すようなものであった。Table 3 Example 4 “Chefamine” with number average molecule-x21oo 020
Polyoxydialkylene diimidonic acid was synthesized from 183 parts of trislitic anhydride and 183 parts of trislitic anhydride in the same manner as in Example 1. 847 parts of this polyoxyalkylene diimidonic acid, 40.1 parts of hexamethylene diamine, ω
-1773 parts of aminododecanoic acid, 1 part of Pyleganox
098 5 parts in a stainless steel 5'J equipped with a stirring device
The mixture was placed in an autoclave and reacted under pressure at 250°C for 1 hour. After that, the pressure was released for 1 hour, and the pressure was released for 2 hours under nitrogen flow.
Polymerization was carried out at 50°C for 4 hours and 30 minutes to obtain a polymer. The physical properties of this polymer were as shown below.
ηｒ １．６０部ｍ （’Ｃ）
１６Ｂ引張弾性率（ｋｇ−ｃｉ）
１９００破断応力（ｋｇ−ａａ） ４１
０破旨伸び（％） ３５０
ショア硬度 ５５Ｄ
弾性回復率（％）（５０％伸長）６５
比較例１
実施例１で用いたものと同様のポリオキシアルキレンジ
イミドニ酸７７．３部、ジメチルテレフタル酸１７．６
部、１，４−ブタンジオール２１．６部、”パイルガノ
ックス”１０９８（酸化防止剤）０．２部をテトラブチ
ルチタネート触媒０゜０５部とともにヘリカルリボン撹
拌翼を備えた反応容器に仕込み、１８０°Ｃに加熱して
理論量のメタノールを留出させた。ηr 1.60 partsm ('C)
16B tensile modulus (kg-ci)
1900 breaking stress (kg-aa) 41
0 Elongation at break (%) 350 Shore hardness 55D Elastic recovery rate (%) (50% elongation) 65 Comparative example 1 77.3 parts of polyoxyalkylene diimidonic acid similar to that used in Example 1, dimethyl terephthalic acid 17.6
1,4-butanediol, 21.6 parts, and 0.2 parts of "Pile Ganox" 1098 (antioxidant) were charged together with 0.05 parts of tetrabutyl titanate catalyst into a reaction vessel equipped with a helical ribbon stirring blade. The mixture was heated to 180°C to distill off the theoretical amount of methanol.
テトラブチルチタネート触媒０．０３部を追加した後、
減圧及び昇温プログラムに従って、４５分で２５０℃、
ｌｍｍＨｇ以下の重合条件にもたらした。この条件にて
８時間１５分重合したが、２２１− ｐ ｍでトルク２
．５ｋｇ−■に達したところで頭打ちとなり、それ以上
トルクが上昇しなくなった。このポリマをガツトとして
水中に吐出したが、結晶化せず、無定形のポリマしか得
られなかった。このポリマはポリブチレンテレフタレー
トからなるハードセグメントであるポリエステル単位を
２０重量％含有し、実施例１のＮ０１３のポリマと比較
されるものである。After adding 0.03 parts of tetrabutyl titanate catalyst,
250°C in 45 minutes according to the depressurization and temperature increase program;
The polymerization conditions were brought to below 1 mmHg. Polymerization was carried out for 8 hours and 15 minutes under these conditions, but the torque was 2 at 221-pm.
．． When it reached 5 kg-■, it reached a plateau and the torque did not increase any further. This polymer was discharged into water as a gut, but it did not crystallize and only an amorphous polymer was obtained. This polymer contains 20% by weight of polyester units, which are hard segments made of polybutylene terephthalate, and is compared with polymer No. 13 of Example 1.
参考例１
実施例１で用いたものと同様のポリオキシアルキレンジ
イミドニ酸６０．８部、ジメチルテレフタル酸３２．６
部、１．４−ブタンジオール３１．３部を原料に用い、
比較例１と同様の方法でポリマを重合し、６時間３０分
の重合でトルク５゜Ｏｋｇ−■のポリマを得た。このポ
リマはハードポリエステル単位を３７重量％含有するも
のであり、融点１７５℃、硬度は実施例１のｆ’Ｊｏ、
２のポリマと同じ４０Ｄであった。Reference Example 1 60.8 parts of polyoxyalkylene diimidonic acid similar to that used in Example 1, 32.6 parts of dimethyl terephthalic acid
using 31.3 parts of 1,4-butanediol as a raw material,
A polymer was polymerized in the same manner as in Comparative Example 1, and a polymer with a torque of 5°Okg-■ was obtained by polymerization for 6 hours and 30 minutes. This polymer contains 37% by weight of hard polyester units, has a melting point of 175°C, and a hardness of f'Jo of Example 1.
The polymer was 40D, which is the same as No. 2 polymer.
９考例２
実施例１で用いたものと同様のポリオキシアルキレンジ
イミドニ１２４．１部、ジメチルプレフタル酸６６．１
部、１．４−ブタンジオール５４．６部を原料に用い、
比較例１と同様の方法でポリマを重合し、４時間２０分
の重合でトルク５゜０ｋｇ−（１）のポリマを得た。こ
のポリマはハードポリエステル単位を７５重量％含有し
、実施例１のＮｏ、１のボ刀”マと比較されるものであ
る。9 Example 2 124.1 parts of polyoxyalkylene diimide similar to that used in Example 1, 66.1 parts of dimethylprephthalic acid
parts, using 54.6 parts of 1,4-butanediol as a raw material,
A polymer was polymerized in the same manner as in Comparative Example 1, and a polymer with a torque of 5.0 kg-(1) was obtained by polymerization for 4 hours and 20 minutes. This polymer contains 75% by weight of hard polyester units and is compared with the No. 1 bottom polymer of Example 1.
実施例５、比較例２
実施例１のＮｏ、２のポリマと参考例１のポリマの射出
成形性を比較するために、日ｍＮ７０Ａ射出成形機によ
りＪＩＳ２号ダンベル試験片を成形した。結果を表４に
示す。Example 5, Comparative Example 2 In order to compare the injection moldability of the polymers No. 2 of Example 1 and the polymer of Reference Example 1, JIS No. 2 dumbbell test pieces were molded using a JIS mN70A injection molding machine. The results are shown in Table 4.
表４
本発明のポリエーテルイミドアミドはショア硬度４０Ｄ
の柔軟なものでもハイサイクルで成形できる。Table 4 The polyetherimide amide of the present invention has a Shore hardness of 40D.
Even flexible materials can be molded in high cycles.
実施例６．比較例３
実施例１のＮｏ、１のポリマと、参考例２のポリマのダ
ンベル試験片を水と共にステンレス製耐圧ボンベに入れ
て１００℃で熱処理し、破断応力／破断伸びの変化を追
うことによって、耐加水分解性を調べた。結果を表５に
示す。Example 6. Comparative Example 3 Dumbbell test pieces of the polymer No. 1 of Example 1 and the polymer of Reference Example 2 were placed in a stainless steel pressure cylinder with water and heat treated at 100°C, and the changes in breaking stress/breaking elongation were followed. , the hydrolysis resistance was investigated. The results are shown in Table 5.
表５
本発明のポリエーテルイミドアミドは優れた耐加水分解
性を有する。Table 5 The polyetherimide amide of the present invention has excellent hydrolysis resistance.
実施例７、比較例８
実施例１のＮｏ、２のポリマと、参考例２のポリマのダ
ンベル試験片をＡＳＴＭ Ｎｏ、３オイル、エンジン
オイル（“°出光アポロイルジーゼ゛ルモチーフ“°。Example 7, Comparative Example 8 Dumbbell test pieces of the polymers No. 2 of Example 1 and the polymer of Reference Example 2 were tested with ASTM No. 3 oil, engine oil ("Idemitsu Apollo Oil Diesel Motif").
５３１０） 、ギアオイル（″°出光ダフニ”ＣＥコン
パウンド）、ブレーキ液（°”１〜ヨダ’２４００ＤＯ
Ｔ）のそれぞれに１００℃で３週間浸漬し、破断応力／
′破断伸びの変化を調べた。結果分表６に示す。5310), gear oil ("°Idemitsu Daphuni" CE compound), brake fluid (°"1~Yoda'2400DO
T) at 100°C for 3 weeks, and the breaking stress/
'Changes in elongation at break were investigated. The results are shown in Table 6.
〈発明の効果〉
本発明のポリエーテルイミドアミドは加工性、機械的性
質、エラストマ特性、化学的性質に優れている。<Effects of the Invention> The polyetherimide amide of the present invention has excellent processability, mechanical properties, elastomer properties, and chemical properties.
Claims (1)
のアミノカルボン酸、炭素数６〜２０の脂肪族ジアミン
（ａ）と実質的に（ａ）と等モルの炭素数６〜１５の脂
肪族ジカルボン酸（ｂ）の塩及び炭素数６〜２０の脂肪
族ジアミン（ａ）と実質的に（ａ）と等モルの炭素数６
〜１５の脂肪族ジカルボン酸（ｂ）の混合物から選ばれ
た一種または二種以上の化合物、（Ｂ）炭素数６〜２０
の脂肪族ジアミン及び（Ｃ）ポリオキシアルキレンジイ
ミド二酸 からなるポリエーテルイミドアミド。Scope of Claims: (A) A lactam having 6 or more carbon atoms, an aminocarboxylic acid having 6 or more carbon atoms, an aliphatic diamine having 6 to 20 carbon atoms, and substantially equimolar amounts of (a) to (a). Salt of aliphatic dicarboxylic acid (b) having 6 to 15 carbon atoms and aliphatic diamine (a) having 6 to 20 carbon atoms and substantially equimolar carbon number 6 to (a).
- One or more compounds selected from a mixture of 15 aliphatic dicarboxylic acids (b), (B) having 6 to 20 carbon atoms
A polyetherimide amide comprising an aliphatic diamine and (C) a polyoxyalkylene diimide diacid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26202886A JPS63117035A (en) | 1986-11-05 | 1986-11-05 | Thermosplastic polyether-imide-amide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26202886A JPS63117035A (en) | 1986-11-05 | 1986-11-05 | Thermosplastic polyether-imide-amide |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63117035A true JPS63117035A (en) | 1988-05-21 |
Family
ID=17370020
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP26202886A Pending JPS63117035A (en) | 1986-11-05 | 1986-11-05 | Thermosplastic polyether-imide-amide |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63117035A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH023428A (en) * | 1987-12-31 | 1990-01-09 | General Electric Co (Ge) | High-molecular amide |
| WO2016163417A1 (en) * | 2015-04-07 | 2016-10-13 | ユニチカ株式会社 | Polyamide-imide, raw material salt for polyamide-imide, and methods respectively for producing these compounds |
| JP2017186560A (en) * | 2016-04-05 | 2017-10-12 | ユニチカ株式会社 | Polyamide-imide precursor solution |
| US10501415B2 (en) | 2015-04-07 | 2019-12-10 | Unitika Ltd. | Method for producing bisimide dicarboxylic acid |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60158222A (en) * | 1984-01-27 | 1985-08-19 | Ube Ind Ltd | Production of polyether-imide-amide |
-
1986
- 1986-11-05 JP JP26202886A patent/JPS63117035A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60158222A (en) * | 1984-01-27 | 1985-08-19 | Ube Ind Ltd | Production of polyether-imide-amide |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH023428A (en) * | 1987-12-31 | 1990-01-09 | General Electric Co (Ge) | High-molecular amide |
| WO2016163417A1 (en) * | 2015-04-07 | 2016-10-13 | ユニチカ株式会社 | Polyamide-imide, raw material salt for polyamide-imide, and methods respectively for producing these compounds |
| CN107428936A (en) * | 2015-04-07 | 2017-12-01 | 尤尼吉可株式会社 | Polyamidoimide, polyamidoimide raw material salt and their manufacture method |
| JPWO2016163417A1 (en) * | 2015-04-07 | 2018-02-01 | ユニチカ株式会社 | Polyamideimide, polyamideimide raw material salt and production method thereof |
| US10501415B2 (en) | 2015-04-07 | 2019-12-10 | Unitika Ltd. | Method for producing bisimide dicarboxylic acid |
| US10584212B2 (en) | 2015-04-07 | 2020-03-10 | Unitika Ltd. | Polyamide-imide, raw material salt of polyamide-imide, and production method thereof |
| JP2017186560A (en) * | 2016-04-05 | 2017-10-12 | ユニチカ株式会社 | Polyamide-imide precursor solution |
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