CN103254424A - Polyamide resin and polyamide composition composed thereof - Google Patents
Polyamide resin and polyamide composition composed thereof Download PDFInfo
- Publication number
- CN103254424A CN103254424A CN2013101862487A CN201310186248A CN103254424A CN 103254424 A CN103254424 A CN 103254424A CN 2013101862487 A CN2013101862487 A CN 2013101862487A CN 201310186248 A CN201310186248 A CN 201310186248A CN 103254424 A CN103254424 A CN 103254424A
- Authority
- CN
- China
- Prior art keywords
- polyamide resin
- reinforcing filler
- brominated
- resin
- daiamid composition
- 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
- 229920006122 polyamide resin Polymers 0.000 title claims abstract description 31
- 239000000203 mixture Substances 0.000 title claims abstract description 26
- 239000004952 Polyamide Substances 0.000 title abstract 3
- 229920002647 polyamide Polymers 0.000 title abstract 3
- 239000012763 reinforcing filler Substances 0.000 claims abstract description 30
- 239000003063 flame retardant Substances 0.000 claims abstract description 26
- 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 claims abstract description 13
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 5
- SYECJBOWSGTPLU-UHFFFAOYSA-N hexane-1,1-diamine Chemical compound CCCCCC(N)N SYECJBOWSGTPLU-UHFFFAOYSA-N 0.000 claims abstract description 5
- YQLZOAVZWJBZSY-UHFFFAOYSA-N decane-1,10-diamine Chemical compound NCCCCCCCCCCN YQLZOAVZWJBZSY-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229920003656 Daiamid® Polymers 0.000 claims description 17
- -1 agalmatolite Chemical compound 0.000 claims description 16
- 239000000835 fiber Substances 0.000 claims description 15
- 239000003365 glass fiber Substances 0.000 claims description 9
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 claims description 6
- 238000001746 injection moulding Methods 0.000 claims description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 4
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 4
- OCKPCBLVNKHBMX-UHFFFAOYSA-N butylbenzene Chemical compound CCCCC1=CC=CC=C1 OCKPCBLVNKHBMX-UHFFFAOYSA-N 0.000 claims description 4
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 239000000919 ceramic Substances 0.000 claims description 4
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 claims description 4
- 239000003822 epoxy resin Substances 0.000 claims description 4
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 4
- 239000010452 phosphate Substances 0.000 claims description 4
- 150000003014 phosphoric acid esters Chemical class 0.000 claims description 4
- 229920000647 polyepoxide Polymers 0.000 claims description 4
- ODLMAHJVESYWTB-UHFFFAOYSA-N propylbenzene Chemical compound CCCC1=CC=CC=C1 ODLMAHJVESYWTB-UHFFFAOYSA-N 0.000 claims description 4
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 4
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 4
- 239000010456 wollastonite Substances 0.000 claims description 4
- 229910052882 wollastonite Inorganic materials 0.000 claims description 4
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 claims description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 3
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 3
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- 229910052744 lithium Inorganic materials 0.000 claims description 3
- 229910052618 mica group Inorganic materials 0.000 claims description 3
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- AQPHBYQUCKHJLT-UHFFFAOYSA-N 1,2,3,4,5-pentabromo-6-(2,3,4,5,6-pentabromophenyl)benzene Chemical group BrC1=C(Br)C(Br)=C(Br)C(Br)=C1C1=C(Br)C(Br)=C(Br)C(Br)=C1Br AQPHBYQUCKHJLT-UHFFFAOYSA-N 0.000 claims description 2
- DGZQEAKNZXNTNL-UHFFFAOYSA-N 1-bromo-4-butan-2-ylbenzene Chemical class CCC(C)C1=CC=C(Br)C=C1 DGZQEAKNZXNTNL-UHFFFAOYSA-N 0.000 claims description 2
- 239000005995 Aluminium silicate Substances 0.000 claims description 2
- 229910052582 BN Inorganic materials 0.000 claims description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 2
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 2
- 229920000271 Kevlar® Polymers 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- 239000004793 Polystyrene Substances 0.000 claims description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910021536 Zeolite Inorganic materials 0.000 claims description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 2
- RJDOZRNNYVAULJ-UHFFFAOYSA-L [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[F-].[F-].[Mg++].[Mg++].[Mg++].[Al+3].[Si+4].[Si+4].[Si+4].[K+] Chemical compound [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[F-].[F-].[Mg++].[Mg++].[Mg++].[Al+3].[Si+4].[Si+4].[Si+4].[K+] RJDOZRNNYVAULJ-UHFFFAOYSA-L 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 2
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 235000012211 aluminium silicate Nutrition 0.000 claims description 2
- OJMOMXZKOWKUTA-UHFFFAOYSA-N aluminum;borate Chemical compound [Al+3].[O-]B([O-])[O-] OJMOMXZKOWKUTA-UHFFFAOYSA-N 0.000 claims description 2
- 239000010425 asbestos Substances 0.000 claims description 2
- 239000011324 bead Substances 0.000 claims description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 230000031709 bromination Effects 0.000 claims description 2
- 238000005893 bromination reaction Methods 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 2
- 239000000920 calcium hydroxide Substances 0.000 claims description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 2
- 239000004917 carbon fiber Substances 0.000 claims description 2
- 239000004927 clay Substances 0.000 claims description 2
- 229910052570 clay Inorganic materials 0.000 claims description 2
- 238000002485 combustion reaction Methods 0.000 claims description 2
- 229920006037 cross link polymer Polymers 0.000 claims description 2
- 239000013078 crystal Substances 0.000 claims description 2
- SRONXYPFSAKOGH-UHFFFAOYSA-N cyclopentadecane Chemical class C1CCCCCCCCCCCCCC1 SRONXYPFSAKOGH-UHFFFAOYSA-N 0.000 claims description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims description 2
- 239000010440 gypsum Substances 0.000 claims description 2
- 229910052602 gypsum Inorganic materials 0.000 claims description 2
- 239000003112 inhibitor Substances 0.000 claims description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000004761 kevlar Substances 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000001095 magnesium carbonate Substances 0.000 claims description 2
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 2
- 229960001708 magnesium carbonate Drugs 0.000 claims description 2
- 235000014380 magnesium carbonate Nutrition 0.000 claims description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 2
- 239000000347 magnesium hydroxide Substances 0.000 claims description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 2
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000395 magnesium oxide Substances 0.000 claims description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 2
- 239000000391 magnesium silicate Substances 0.000 claims description 2
- 229910052919 magnesium silicate Inorganic materials 0.000 claims description 2
- 235000019792 magnesium silicate Nutrition 0.000 claims description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- 239000010445 mica Substances 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N o-dimethylbenzene Natural products CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 2
- 229920006287 phenoxy resin Polymers 0.000 claims description 2
- 239000013034 phenoxy resin Substances 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- 239000004417 polycarbonate Substances 0.000 claims description 2
- 229920000515 polycarbonate Polymers 0.000 claims description 2
- 229920013636 polyphenyl ether polymer Polymers 0.000 claims description 2
- 229920002223 polystyrene Polymers 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 229910052895 riebeckite Inorganic materials 0.000 claims description 2
- 239000010980 sapphire Substances 0.000 claims description 2
- 229910052594 sapphire Inorganic materials 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- 229960001866 silicon dioxide Drugs 0.000 claims description 2
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000000454 talc Substances 0.000 claims description 2
- 235000012222 talc Nutrition 0.000 claims description 2
- 229910052623 talc Inorganic materials 0.000 claims description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 2
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 claims description 2
- 239000010457 zeolite Substances 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims 1
- 229920005989 resin Polymers 0.000 abstract description 12
- 239000011347 resin Substances 0.000 abstract description 12
- 238000005476 soldering Methods 0.000 abstract description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 abstract 2
- 235000011037 adipic acid Nutrition 0.000 abstract 1
- 239000001361 adipic acid Substances 0.000 abstract 1
- 239000002932 luster Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 36
- 150000001875 compounds Chemical class 0.000 description 26
- 125000004665 trialkylsilyl group Chemical group 0.000 description 16
- 238000012360 testing method Methods 0.000 description 12
- 150000001408 amides Chemical class 0.000 description 11
- 150000001282 organosilanes Chemical class 0.000 description 6
- 238000004448 titration Methods 0.000 description 6
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 5
- 239000007822 coupling agent Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 2
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 2
- OSSMYOQKNHMTIP-UHFFFAOYSA-N 5-[dimethoxy(methyl)silyl]pentane-1,3-diamine Chemical compound CO[Si](C)(OC)CCC(N)CCN OSSMYOQKNHMTIP-UHFFFAOYSA-N 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 150000008064 anhydrides Chemical group 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 239000012757 flame retardant agent Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 2
- RINCXYDBBGOEEQ-UHFFFAOYSA-N succinic anhydride Chemical compound O=C1CCC(=O)O1 RINCXYDBBGOEEQ-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 1
- NMUBRRLYMADSGF-UHFFFAOYSA-N 3-triethoxysilylpropan-1-ol Chemical compound CCO[Si](OCC)(OCC)CCCO NMUBRRLYMADSGF-UHFFFAOYSA-N 0.000 description 1
- YATIYDNBFHEOFA-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-ol Chemical compound CO[Si](OC)(OC)CCCO YATIYDNBFHEOFA-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Chemical class 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910000085 borane Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- ZWTJVXCCMKLQKS-UHFFFAOYSA-N diethoxy(ethyl)silicon Chemical compound CCO[Si](CC)OCC ZWTJVXCCMKLQKS-UHFFFAOYSA-N 0.000 description 1
- GAURFLBIDLSLQU-UHFFFAOYSA-N diethoxy(methyl)silicon Chemical compound CCO[Si](C)OCC GAURFLBIDLSLQU-UHFFFAOYSA-N 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- PKTOVQRKCNPVKY-UHFFFAOYSA-N dimethoxy(methyl)silicon Chemical compound CO[Si](C)OC PKTOVQRKCNPVKY-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- YSLVSGVAVRTLAV-UHFFFAOYSA-N ethyl(dimethoxy)silane Chemical compound CC[SiH](OC)OC YSLVSGVAVRTLAV-UHFFFAOYSA-N 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 235000021050 feed intake Nutrition 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000002530 phenolic antioxidant Substances 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000003825 pressing Methods 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
- 238000011160 research Methods 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 229920006012 semi-aromatic polyamide Polymers 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- 238000007655 standard test method Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 230000002522 swelling effect Effects 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- DOEHJNBEOVLHGL-UHFFFAOYSA-N trichloro(propyl)silane Chemical compound CCC[Si](Cl)(Cl)Cl DOEHJNBEOVLHGL-UHFFFAOYSA-N 0.000 description 1
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000013022 venting Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/265—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from at least two different diamines or at least two different dicarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a polyamide resin, which consists of the following components: a component A which includes 40-48mol% of decamethylene diamine and 2-10mol/% of hexane diamine; and a component B which includes 40-48mol% of terephthalic acid and 2-10mol/% of adipic acid. A polyamide composition containing the polyamide resin comprises the following components in percentage by weight: 30-99.9% polyamide resin, 0-60% reinforcing filler, 0-50% of flame retardant, and 0.1 to 10% of other auxiliary agents. The polyamide resin and the polyamide composition composed thereof have the advantages that with relatively high brightness, the resin and the composition can be applied to situations in which the requirement on product luster is relatively high; and with strong heat resistance, the resin and the composition can be applied to situations in which the reflow soldering temperature exceeds 270 DEG C, for example.
Description
Technical field
The present invention relates to polymeric material field, particularly a kind of polyamide resin and by its daiamid composition of forming.
Background technology
Polymeric amide is because having good comprehensive performances, comprise mechanical property, thermotolerance, wearability, chemical proofing and self lubricity, and frictional coefficient is low, certain flame retardant resistance is arranged, be easy to processing etc., it extensively is suitable for improves aspects such as performance and broadened application scope with glass fibre and other filler filling enhancing modified.In recent years semiaromatic polyamide composition because its resistance toheat and mechanical property are more excellent by focus development.
A well known fact is, polymeric amide be easy to oxidized or high temperature under produce and decompose, cause the color of resin obfuscation, have a strong impact on its quality.Therefore the improvement of polymeric amide brightness becomes an important research project.
Summary of the invention
For the shortcoming and deficiency that overcome prior art, primary and foremost purpose of the present invention is to provide the polyamide resin of a kind of high brightness and high heat resistance.
A kind of polyamide resin, by mole per-cent, formed by following component:
The decamethylene diamine of component A:40-48mol% and the hexanediamine of 2-10mol%;
The terephthalic acid of B component: 40-48mol% and the hexanodioic acid of 2-10mol%.
Described polyamide resin be higher than 270
oC is preferably 280
oC ~ 320
oC; Melting point resin is too low, goods easy deformation under the pyroprocessing of reflow soldering; Melting point resin is too high, causes its processing characteristics to descend; And fusing point is too high near decomposition temperature, and the goods various aspects of performance is all descended.
Obtain the brightness value L of colour table after the injection moulding of described polyamide resin greater than 75.0, be preferably more than 76.0; The resin brightness value is too low, causes its goods obfuscation, and influence is finally used.
A kind of daiamid composition that comprises described polyamide resin by weight percentage, comprises following component:
Polyamide resin 30 ~ 99.9%;
Reinforcing filler 0 ~ 60%;
Fire retardant 0 ~ 50%;
Other auxiliary agents 0 ~ 10%;
The content of described reinforcing filler is preferably 15-40%; Filler content is low excessively, causes the daiamid composition mechanical property relatively poor; Filler content is too high, and the daiamid composition product surface is floating fine serious, influences product appearance.
Being shaped as of described reinforcing filler is fibrous, and its mean length is 0.01 ~ 20mm, is preferably 0.1 ~ 6mm; Its length-to-diameter ratio is 5 ~ 2000:1, is preferably 30 ~ 600:1, when fibrous reinforcing filler content is in above-mentioned scope, and the high temperature rigid that daiamid composition will show high heat distortion temperature and increase, above-mentioned size can obtain fiber measurement by milscale.
Described reinforcing filler is inorganic reinforcing filler or organic reinforcing filler;
Described inorganic reinforcing filler is selected from one or more of glass fibre, potassium titanate fiber, metalclad glass fibre, ceramic fiber, wollastonite fibre, metallic carbide fibres, metal-cured fiber, fibrous magnesium silicate, sapphire whisker, silicon carbide fiber, gypsum fiber or boron fibre, is preferably glass fibre; Use glass fibre not only can improve the mouldability of daiamid composition, and can improve mechanical property for example tensile strength, flexural strength and modulus in flexure, and the heat-drawn wire when improving thermotolerance for example the thermoplastic resin composition carrying out molding.
Described organic reinforcing filler is selected from Kevlar and/or carbon fiber.
Being shaped as of described reinforcing filler is non-fibrous, for example Powdered, particulate state, tabular, needle-like, fabric or felted, its median size is 0.001~10 μ m, is preferably 0.01~5 μ m, will cause the melt processable of polyamide resin difference less than 0.001 μ m when the median size of reinforcing filler; When the median size of reinforcing filler greater than 10 μ m, will cause bad injection moulding product appearance.The median size of above-mentioned reinforcing filler is measured by absorption method, and it can be selected from potassium titanate crystal whisker, ZnOw, aluminium borate whisker, wollastonite, zeolite, sericite, kaolin, mica, talcum, clay, agalmatolite, wilkinite, polynite, lithium montmorillonite, synthetic mica, asbestos, silico-aluminate, aluminum oxide, silicon oxide, magnesium oxide, zirconium white, titanium oxide, ferric oxide, calcium carbonate, magnesiumcarbonate, rhombspar, calcium sulfate, barium sulfate, magnesium hydroxide, calcium hydroxide, aluminium hydroxide, granulated glass sphere, ceramic bead, boron nitride, one or more of silicon carbide or silicon-dioxide.These reinforcing fillers can be hollow; In addition, for swelling property layered silicates such as wilkinite, polynite, lithium montmorillonite, synthetic micas, can use and adopt organic ammonium salt that interlayer ion is carried out organic montmorillonoid after the cationic exchange.
In order to make daiamid composition obtain more good mechanical property, can adopt coupling agent that inorganic reinforcing filler is carried out functional processing, wherein coupling agent is selected from isocyanic ester based compound, organosilane based compound, organic titanate based compound, organo-borane based compound, epoxy compounds; Be preferably the organosilane based compound;
Wherein, described organosilane based compound be selected from alkoxysilane compound containing trialkylsilyl group in molecular structure, the alkoxysilane compound containing trialkylsilyl group in molecular structure that contains sulfydryl, the alkoxysilane compound containing trialkylsilyl group in molecular structure that contains urea groups, the alkoxysilane compound containing trialkylsilyl group in molecular structure that contains isocyanate group that contain epoxy group(ing), contain amino alkoxysilane compound containing trialkylsilyl group in molecular structure, contain hydroxyl alkoxysilane compound containing trialkylsilyl group in molecular structure, contain the carbon-to-carbon unsaturated group alkoxysilane compound containing trialkylsilyl group in molecular structure, contain one or more of alkoxysilane compound containing trialkylsilyl group in molecular structure of anhydride group.
The described alkoxysilane compound containing trialkylsilyl group in molecular structure that contains epoxy group(ing) is selected from one or more of γ-glycidoxypropyltrime,hoxysilane, γ-glycidoxy propyl-triethoxysilicane, β-(3,4-epoxycyclohexyl) ethyl trimethoxy silane;
The described alkoxysilane compound containing trialkylsilyl group in molecular structure that contains sulfydryl is selected from γ-Qiu Jibingjisanjiayangjiguiwan and/or γ-sulfydryl propyl-triethoxysilicane;
The described alkoxysilane compound containing trialkylsilyl group in molecular structure that contains urea groups is selected from one or more of γ-urea groups propyl-triethoxysilicane, γ-urea groups propyl trimethoxy silicane, γ-(2-urea groups ethyl) TSL 8330;
The described alkoxysilane compound containing trialkylsilyl group in molecular structure that contains isocyanate group is selected from one or more of γ-isocyanate group propyl-triethoxysilicane, γ-isocyanate group propyl trimethoxy silicane, γ-isocyanate group propyl group methyl dimethoxysilane, γ-isocyanate group propyl group methyldiethoxysilane, γ-isocyanate group propyl group ethyl dimethoxy silane, γ-isocyanate group propyl group ethyl diethoxy silane, γ-isocyanate group propyltrichlorosilan;
Describedly contain amino alkoxysilane compound containing trialkylsilyl group in molecular structure and be selected from one or more of γ-(2-amino-ethyl) aminopropyl methyl dimethoxysilane, γ-(2-amino-ethyl) TSL 8330, gamma-amino propyl trimethoxy silicane;
The described alkoxysilane compound containing trialkylsilyl group in molecular structure that contains hydroxyl is selected from γ-hydroxypropyl Trimethoxy silane and/or γ-hydroxypropyl triethoxyl silane;
The described alkoxysilane compound containing trialkylsilyl group in molecular structure that contains the carbon-to-carbon unsaturated group is selected from one or more of γ-methacryloxypropyl trimethoxy silane, vinyltrimethoxy silane, N-β-(N-vinyl benzyl amino-ethyl)-gamma-amino propyl trimethoxy silicane hydrochloride;
The described alkoxysilane compound containing trialkylsilyl group in molecular structure that contains anhydride group is selected from 3-trimethoxy-silylpropyl succinyl oxide;
Described organosilane based compound is preferably γ-methacryloxypropyl trimethoxy silane, γ-(2-amino-ethyl) aminopropyl methyl dimethoxysilane, γ-(2-amino-ethyl) TSL 8330, gamma-amino propyl trimethoxy silicane or 3-trimethoxy-silylpropyl succinyl oxide.
Can adopt above-mentioned organosilane based compound that inorganic reinforcing filler is carried out surface treatment according to the method for routine, and then itself and polyamide resin are carried out melting mixing, to prepare described daiamid composition; Also can directly in inorganic reinforcing filler and polyamide resin melting mixing, add the organosilane based compound and carry out in-situ blending;
Wherein, the consumption of described coupling agent is with respect to 0.05 ~ 10wt% of inorganic reinforcing filler weight, is preferably 0.1 ~ 5wt%; When the consumption of coupling agent during less than 0.05wt%, it does not reach the effect of tangible improved mechanical properties; When the consumption of coupling agent during greater than 10wt%, inorganic reinforcing filler condenses easily, and disperses bad risk in polyamide resin, finally causes mechanical property to descend.
Described fire retardant is the composition of fire retardant or fire retardant and fire-retardant assistance agent, and its content is preferably 10 ~ 40wt%; The low excessively flame retardant effect variation that causes of flame retardant agent content, the too high material property that causes of flame retardant agent content descends.
Described fire retardant is halogenated flame retardant or halogen-free flame retardants;
Described halogenated flame retardant is selected from one or more of brominated Polystyrene, brominated polyphenylether, brominated bisphenol a type epoxy resin, brominated styrene-copolymer-maleic anhydride, brominated epoxy resin, bromination phenoxy resin, decabromodiphynly oxide, decabromodiphenyl, brominated polycarbonate, perbromo-three cyclopentadecanes or brominated aromatic cross-linked polymer, is preferably preferred brominated Polystyrene;
Described halogen-free flame retardants is selected from one or more of the fire retardant that contains nitrogen combustion inhibitor, phosphonium flame retardant or nitrogenous and phosphorus; Be preferably phosphonium flame retardant.
It is that phosphoric acid ester, butylbenzene are one or more of phosphoric acid ester or hypophosphite that described phosphonium flame retardant is selected from monophosphate aryl phosphate ester, bis phosphoric acid aryl phosphate ester, alkyl phosphonic acid dimethyl ester, triphenylphosphate, Tritolyl Phosphate, tricresyl phosphate (dimethylbenzene) ester, propyl benzene; Be preferably hypophosphite;
Described hypophosphite has the hypophosphite of following structure formula I:
In the formula, R
1, R
2Identical or different, be expressed as straight chain or contain alkyl and/or aryl or the phenyl of 1 ~ 6 carbon atom of side chain; M is Mg, Ca, Al, Zn, Bi, Mn, Na, K or by protonated nitrogenous base; M is 1 ~ 3.
Described other auxiliary agents are selected from one or more of softening agent, thickening material, antistatic agent, releasing agent, toner, staining agent or nucleator.
The present invention compared with prior art has following beneficial effect:
1) polyamide resin of the present invention prepares by specific repeating unit, obtains the brightness value L of colour table after the injection moulding greater than 75.0, has higher brightness, can be applied to the occasion that product color is had relatively high expectations;
2) fusing point of polyamide resin of the present invention is higher than 270
oC, thermotolerance is strong, can be applied to surpass 270 as the reflow soldering temperature
oThe occasion of C;
3) daiamid composition for preparing gained by polyamide resin of the present invention also has high brightness and strong thermotolerance, can be applied to the occasion that product color, thermotolerance are had relatively high expectations.
Embodiment
Further specify the present invention below by embodiment, following examples are preferred implementation of the present invention, but embodiments of the present invention are not subjected to the restriction of following embodiment.
The testing method of gained polymeric amide relative viscosity: with reference to GB12006.1-89, polymeric amide viscosity number measuring method; Concrete testing method is: 25 ± 0.01
OC98% the vitriol oil in to measure concentration be the relative viscosity η r of the polymeric amide of 0.25g/dl;
The testing method of the fusing point of polymeric amide: with reference to ASTM D3418-2003, Standard Test Method for Transition Temperatures of Polymers By Differential Scanning Calorimetry; Concrete testing method is: the fusing point that adopts Perkin Elmer Dimond dsc analysis instrument specimen; Nitrogen atmosphere, flow velocity are 40mL/min; Elder generation is with 10 during test
oC/min is warming up to 340
oC is 340
OCKeep 2min, then with 10
oC/min is cooled to 50
oC is again with 10
oC/min is warming up to 340
oC is made as fusing point with endotherm peak temperature at this moment
T m
The testing method of gained polymeric amide terminal amino group content: with full-automatic current potential titration apparatus titration sample terminal amino group content; Get the 0.5g polymkeric substance, add phenol 45mL and anhydrous methanol 3mL, reflux after the observation sample dissolves fully, is chilled to room temperature, with the hydrochloric acid standard solution titration terminal amino group content of having demarcated;
The testing method of gained polymeric amide content of carboxyl end group: with full-automatic current potential titration apparatus titration sample content of carboxyl end group; Get the 0.5g polymkeric substance, add ortho-cresol 50mL, the dissolving that refluxes is put cold back and is added 400 μ L formaldehyde solutions rapidly, with the KOH-ethanolic soln titration content of carboxyl end group of having demarcated;
The testing method of gained polyamide resin brightness L value: use the Standard colour board mould, after getting the 3000g polymer particle and carrying out injection moulding, obtain the colour table of one-sided smooth.Place reason to obtain the brightness value L value on the precious Color-Eye7000A computer color measurement instrument this colour table;
Tensile strength: measure according to ISO 527-2, test condition is 23
oC and 10mm/min;
Elongation at break: measure according to ISO 527-2, test condition is 23
oC and 10mm/min;
Flexural strength and modulus in flexure: measure according to ISO 178, test condition is 23
oC and 2mm/min;
The socle girder notched Izod impact strength: measure according to ISO 180/1A, test condition is 23
oC, the breach type is the A type.
Embodiment 1 ~ 4 and Comparative Examples 1 ~ 14
In the autoclave pressure of being furnished with magnetic force coupling stirring, prolong, gas phase mouth, charging opening, pressure venting, add reaction raw materials in the ratio in the form; Add phenylformic acid, sodium hypophosphite and deionized water again; The phenylformic acid amount of substance is 2.5% of diamines, diacid, lactan and the total amount of substance of amino acid, and sodium hypophosphite weight is 0.1% of outer other weight that feed intake of deionizing water, and deionized water weight is 30% of the weight that always feeds intake; Vacuumize and charge into high pure nitrogen as protection gas, be warmed up to 220 under agitation 2 hours
oC, with reaction mixture 220
oC stirred 1 hour, under agitation made the temperature of reactant be elevated to 230 then
oC; Be reflected at 230
oProceed 2 hours under the constant temperature of C and the constant voltage of 2.2MPa, by remove formed water keep-up pressure constant, the reaction finish after discharging, prepolymer is in 80
oVacuum-drying is 24 hours under the C, obtains prepolymer product, and described prepolymer product is 250
oSolid-phase tack producing is 10 hours under C, the 50Pa vacuum condition, obtains polymeric amide.The relative viscosity of polymeric amide, fusing point and brightness L value are listed in the table 1.
Table 1
? | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Comparative Examples 1 | Comparative Examples 2 | Comparative Examples 3 | Comparative Examples 4 | Comparative Examples 5 | Comparative Examples 6 |
Terephthalic acid/mol | 18 | 19 | 16 | 24 | 9 | 11 | 14 | 10 | 24.5 | 25 |
Hexanodioic acid/mol | 2 | 1 | 4 | 1 | 11 | 9 | 6 | 10 | 0.5 | 0 |
1/mol | 18 | 19 | 16 | 24 | 0 | 0 | 14 | 10 | 24.5 | 25 |
Hexanediamine/mol | 2 | 1 | 4 | 1 | 20 | 20 | 6 | 10 | 0.5 | 0 |
End amino/mol/t | 38 | 44 | 40 | 45 | 40 | 38 | 41 | 48 | 39 | 45 |
End carboxyl/mol/t | 92 | 89 | 78 | 96 | 82 | 71 | 95 | 101 | 98 | 88 |
Relative viscosity | 2.220 | 2.231 | 2.244 | 2.250 | 2.233 | 2.228 | 2.238 | 2.201 | 2.232 | 2.271 |
Fusing point/ oC | 292 | 304 | 276 | 309 | 292 | 311 | 251 | 240 | 311 | 316 |
Resin brightness (L) | 78.1 | 79.3 | 78.6 | 78.9 | 70.2 | 71.1 | 69.3 | 68.2 | 66.7 | 68.2 |
Continuous table 1
? | Comparative Examples 7 | Comparative Examples 8 | Comparative Examples 9 | Comparative Examples 10 | Comparative Examples 11 | Comparative Examples 12 | Comparative Examples 13 | Comparative Examples 14 |
Terephthalic acid/mol | 18 | 19 | 24.5 | 25 | 18 | 19 | 11 | 9 |
Hexanodioic acid/mol | 7 | 6 | 0.5 | 0 | 2 | 1 | 9 | 11 |
1/mol | 24.5 | 25 | 18 | 19 | 14 | 10 | 16 | 19 |
Hexanediamine/mol | 0.5 | 0 | 7 | 6 | 6 | 10 | 4 | 1 |
End amino/mol/t | 40 | 32 | 38 | 47 | 42 | 37 | 34 | 46 |
End carboxyl/mol/t | 101 | 95 | 97 | 87 | 91 | 85 | 96 | 89 |
Relative viscosity | 2.223 | 2.263 | 2.259 | 2.245 | 2.260 | 2.280 | 2.246 | 2.215 |
Fusing point/ oC | 275 | 277 | 301 | 296 | 289 | 304 | 269 | 255 |
Resin brightness (L) | 67.5 | 66.9 | 67.9 | 69.9 | 70.3 | 68.5 | 67.6 | 69.0 |
From embodiment 1 ~ 4 and Comparative Examples 1 ~ 14 more as can be seen, the brightness L value of embodiment gained 10T resin of the present invention is all more than 78, and the resinoid brightness L of Comparative Examples 6T value is all about 70, its brightness L value is far below the embodiment resin.And among the Comparative Examples 10T/66,66 content are when 30mol% is above, and the fusing point of polyamide resin is reduced to 250
oBelow the C, this just means its stable on heating decline, can't be used for heat-resisting place of having relatively high expectations, and surpasses 270 as the reflow soldering temperature
oThe occasion of C.
Embodiment 5 ~ 8 and Comparative Examples 15 ~ 21
The prescription of pressing table 2 with polyamide resin, fire retardant, other auxiliary agents high-speed mixer and mixing evenly after, add in the twin screw extruder by main spout, reinforcing filler is fed by side feeding scale side, extrudes, cross water cooling, obtain described daiamid composition after granulation and the drying.Wherein, extrusion temperature is 330
oC.
Prescription is weight part in table 2 following table
? | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 | Comparative Examples 15 | Comparative Examples 16 | Comparative Examples 17 | Comparative Examples 18 | Comparative Examples 19 | Comparative Examples 20 | Comparative Examples 21 |
Polyamide resin | Embodiment 1 | Embodiment 1 | Embodiment 4 | Embodiment 4 | Comparative Examples 1 | Comparative Examples 3 | Comparative Examples 5 | Comparative Examples 7 | Comparative Examples 9 | Comparative Examples 11 | Comparative Examples 13 |
Resin content | 70 | 50 | 30 | 99.9 | 70 | 50 | 70 | 50 | 99.9 | 70 | 30 |
Glass fibre | 29 | 30 | 60 | 0 | 29 | 30 | 29 | 30 | 0 | 29 | 60 |
Hypophosphite fire retardant | 0 | 15 | 5 | 0 | 0 | 15 | 0 | 15 | 0 | 0 | 5 |
Polybutene | 0 | 2 | 2 | 0 | 0 | 2 | 0 | 2 | 0 | 0 | 2 |
Dipentaerythritol | 0 | 1 | 1 | 0 | 0 | 1 | 0 | 1 | 0 | 0 | 1 |
Zinc borate | 0 | 1 | 1 | 0 | 0 | 1 | 0 | 1 | 0 | 0 | 1 |
Phenolic antioxidant | 0.5 | 0.5 | 0.5 | 0.05 | 0.5 | 0.5 | 0.5 | 0.5 | 0.05 | 0.5 | 0.5 |
Polyethylene wax | 0.5 | 0.5 | 0.5 | 0.05 | 0.5 | 0.5 | 0.5 | 0.5 | 0.05 | 0.5 | 0.5 |
Resin brightness (L) | 79.4 | 77.6 | 80.3 | 79.8 | 80.3 | 76.3 | 68.3 | 71.6 | 66.1 | 67.2 | 63.2 |
Tensile strength/MPa | 181 | 232 | 185 | 179 | 138 | 162 | 190 | 183 | 176 | 172 | 218 |
Elongation at break/% | 3.2 | 2.2 | 3.3 | 3.1 | 2.8 | 2.6 | 3.1 | 3.1 | 3.0 | 3.3 | 2.1 |
Flexural strength/MPa | 267 | 336 | 261 | 258 | 197 | 224 | 273 | 265 | 251 | 247 | 330 |
Modulus in flexure/MPa | 8343 | 14312 | 8167 | 8437 | 9324 | 10386 | 8612 | 8572 | 8629 | 8273 | 14721 |
Socle girder notched Izod impact strength/kJ/m 2 | 11.7 | 14.7 | 12.3 | 11.4 | 8.9 | 9.1 | 11.0 | 10.4 | 11.8 | 12.3 | 13.6 |
From the embodiment 5 ~ 8 of table 2 and Comparative Examples 15 ~ 21 more as can be seen, the composition that the composition that the embodiment of the present application prepares prepares than Comparative Examples has more outstanding brightness L value, its brightness value is better than Comparative Examples, can be applied to the occasion that product color is had relatively high expectations.
Claims (9)
1. a polyamide resin is characterized in that, by mole per-cent, is made up of following component:
The decamethylene diamine of component A:40-48mol% and the hexanediamine of 2-10mol%;
The terephthalic acid of B component: 40-48mol% and the hexanodioic acid of 2-10mol%.
2. polyamide resin according to claim 1 is characterized in that, described polyamide resin be higher than 270
oC is preferably 280 ~ 330
oC.
3. polyamide resin according to claim 1 is characterized in that, obtains the brightness value L of colour table after the injection moulding of described polyamide resin greater than 75.0, is preferably more than 76.0.
4. daiamid composition that comprises each described polyamide resin of claim 1 ~ 3, percentage ratio meter by weight comprises following component:
Polyamide resin 30 ~ 99.9%;
Reinforcing filler 0 ~ 60%;
Fire retardant 0 ~ 50%;
Other auxiliary agents 0.1 ~ 10%.
5. daiamid composition according to claim 4 is characterized in that, being shaped as of described reinforcing filler is fibrous, and its mean length is 0.01-20mm, is preferably 0.1 ~ 6mm; Its length-to-diameter ratio is 5 ~ 2000:1, is preferably 30 ~ 600:1; The content of described reinforcing filler is 10 ~ 50wt%.
6. daiamid composition according to claim 5, it is characterized in that, described reinforcing filler is inorganic reinforcing filler or organic reinforcing filler, described inorganic reinforcing filler is selected from one or more of glass fibre, potassium titanate fiber, metalclad glass fibre, ceramic fiber, wollastonite fibre, metallic carbide fibres, metal-cured fiber, fibrous magnesium silicate, sapphire whisker, silicon carbide fiber, gypsum fiber or boron fibre, is preferably glass fibre; Described organic reinforcing filler is selected from Kevlar and/or carbon fiber.
7. daiamid composition according to claim 4, it is characterized in that, being shaped as of described reinforcing filler is non-fibrous, its median size is 0.001~10 μ m, be preferably 0.01~5 μ m, be selected from potassium titanate crystal whisker, ZnOw, aluminium borate whisker, wollastonite, zeolite, sericite, kaolin, mica, talcum, clay, agalmatolite, wilkinite, polynite, lithium montmorillonite, synthetic mica, asbestos, silico-aluminate, aluminum oxide, silicon oxide, magnesium oxide, zirconium white, titanium oxide, ferric oxide, calcium carbonate, magnesiumcarbonate, rhombspar, calcium sulfate, barium sulfate, magnesium hydroxide, calcium hydroxide, aluminium hydroxide, granulated glass sphere, ceramic bead, boron nitride, one or more of silicon carbide or silicon-dioxide.
8. daiamid composition according to claim 4, it is characterized in that, described fire retardant is halogenated flame retardant or halogen-free flame retardants, described halogenated flame retardant is selected from one or more of brominated Polystyrene, brominated polyphenylether, brominated bisphenol a type epoxy resin, brominated styrene-copolymer-maleic anhydride, brominated epoxy resin, bromination phenoxy resin, decabromodiphynly oxide, decabromodiphenyl, brominated polycarbonate, perbromo-three cyclopentadecanes or brominated aromatic cross-linked polymer, is preferably preferred brominated Polystyrene; Described halogen-free flame retardants is selected from one or more of the fire retardant that contains nitrogen combustion inhibitor, phosphonium flame retardant or nitrogenous and phosphorus; Be preferably phosphonium flame retardant; The content of described fire retardant is 10 ~ 40wt%.
9. daiamid composition according to claim 8, it is characterized in that it is that phosphoric acid ester, butylbenzene are one or more of phosphoric acid ester, hypophosphite that described phosphonium flame retardant is selected from monophosphate aryl phosphate ester, bis phosphoric acid aryl phosphate ester, alkyl phosphonic acid dimethyl ester, triphenylphosphate, Tritolyl Phosphate, tricresyl phosphate (dimethylbenzene) ester, propyl benzene; Be preferably the hypophosphite with following structure formula I:
In the formula, R
1, R
2Identical or different, be expressed as straight chain or contain alkyl and/or aryl or the phenyl of 1 ~ 6 carbon atom of side chain; M is Mg, Ca, Al, Zn, Bi, Mn, Na, K or by protonated nitrogenous base; M is 1 ~ 3.
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CN2013101862487A CN103254424A (en) | 2013-05-20 | 2013-05-20 | Polyamide resin and polyamide composition composed thereof |
CN201310721601.7A CN103804683B (en) | 2013-05-20 | 2013-12-24 | A kind of polyamide resin and consisting of daiamid composition |
PCT/CN2014/070041 WO2014187153A1 (en) | 2013-05-20 | 2014-01-02 | Polyamide resin and polyamide combination formed of same |
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CN201310721601.7A Active CN103804683B (en) | 2013-05-20 | 2013-12-24 | A kind of polyamide resin and consisting of daiamid composition |
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WO2014187153A1 (en) * | 2013-05-20 | 2014-11-27 | 金发科技股份有限公司 | Polyamide resin and polyamide combination formed of same |
CN104262952A (en) * | 2014-09-19 | 2015-01-07 | 金发科技股份有限公司 | Low-pH-value polyamide molding composition |
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-
2013
- 2013-05-20 CN CN2013101862487A patent/CN103254424A/en active Pending
- 2013-12-24 CN CN201310721601.7A patent/CN103804683B/en active Active
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- 2014-01-02 WO PCT/CN2014/070041 patent/WO2014187153A1/en active Application Filing
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Also Published As
Publication number | Publication date |
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CN103804683B (en) | 2016-06-01 |
WO2014187153A1 (en) | 2014-11-27 |
CN103804683A (en) | 2014-05-21 |
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