CN1159457A - Low profile additives for polyester resin systems based on asymmetric glycols and aromatic diacids - Google Patents
Low profile additives for polyester resin systems based on asymmetric glycols and aromatic diacids Download PDFInfo
- Publication number
- CN1159457A CN1159457A CN97100595A CN97100595A CN1159457A CN 1159457 A CN1159457 A CN 1159457A CN 97100595 A CN97100595 A CN 97100595A CN 97100595 A CN97100595 A CN 97100595A CN 1159457 A CN1159457 A CN 1159457A
- Authority
- CN
- China
- Prior art keywords
- acid
- additive
- glycol
- compound
- mixture
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000654 additive Substances 0.000 title claims abstract description 145
- 125000003118 aryl group Chemical group 0.000 title claims description 12
- 150000002334 glycols Chemical class 0.000 title abstract description 4
- 229920001225 polyester resin Polymers 0.000 title description 4
- 239000004645 polyester resin Substances 0.000 title description 4
- 230000000996 additive effect Effects 0.000 claims abstract description 138
- 239000002253 acid Substances 0.000 claims abstract description 69
- -1 polyethylene terephthalate Polymers 0.000 claims abstract description 39
- 229920000728 polyester Polymers 0.000 claims abstract description 37
- 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 24
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 17
- 229920001169 thermoplastic Polymers 0.000 claims abstract description 17
- 239000004416 thermosoftening plastic Substances 0.000 claims abstract description 14
- 229920000139 polyethylene terephthalate Polymers 0.000 claims abstract description 9
- 239000005020 polyethylene terephthalate Substances 0.000 claims abstract description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 7
- 150000001491 aromatic compounds Chemical class 0.000 claims abstract 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 213
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 70
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 60
- 239000000203 mixture Substances 0.000 claims description 48
- 229920005989 resin Polymers 0.000 claims description 46
- 239000011347 resin Substances 0.000 claims description 46
- UXFQFBNBSPQBJW-UHFFFAOYSA-N 2-amino-2-methylpropane-1,3-diol Chemical compound OCC(N)(C)CO UXFQFBNBSPQBJW-UHFFFAOYSA-N 0.000 claims description 28
- AIDLAEPHWROGFI-UHFFFAOYSA-N 2-methylbenzene-1,3-dicarboxylic acid Chemical compound CC1=C(C(O)=O)C=CC=C1C(O)=O AIDLAEPHWROGFI-UHFFFAOYSA-N 0.000 claims description 26
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 26
- 150000001875 compounds Chemical class 0.000 claims description 24
- 239000004593 Epoxy Substances 0.000 claims description 19
- 150000002118 epoxides Chemical class 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 17
- 125000001931 aliphatic group Chemical group 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 150000002009 diols Chemical class 0.000 claims description 13
- 238000011084 recovery Methods 0.000 claims description 13
- 239000000126 substance Substances 0.000 claims description 13
- 150000002148 esters Chemical class 0.000 claims description 12
- 150000008065 acid anhydrides Chemical class 0.000 claims description 11
- 239000012948 isocyanate Substances 0.000 claims description 10
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical group OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 10
- 238000005809 transesterification reaction Methods 0.000 claims description 10
- 229920006337 unsaturated polyester resin Polymers 0.000 claims description 10
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 8
- 229920006305 unsaturated polyester Polymers 0.000 claims description 8
- 239000000178 monomer Substances 0.000 claims description 7
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 6
- JFCQEDHGNNZCLN-UHFFFAOYSA-N glutaric acid Chemical compound OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 claims description 6
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 claims description 6
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 6
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 4
- MNAHQWDCXOHBHK-UHFFFAOYSA-N 1-phenylpropane-1,1-diol Chemical compound CCC(O)(O)C1=CC=CC=C1 MNAHQWDCXOHBHK-UHFFFAOYSA-N 0.000 claims description 3
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 3
- FYIBGDKNYYMMAG-UHFFFAOYSA-N ethane-1,2-diol;terephthalic acid Chemical compound OCCO.OC(=O)C1=CC=C(C(O)=O)C=C1 FYIBGDKNYYMMAG-UHFFFAOYSA-N 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims 9
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims 6
- 150000005690 diesters Chemical class 0.000 claims 4
- 150000002513 isocyanates Chemical class 0.000 claims 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims 2
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims 2
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims 2
- HCPOCMMGKBZWSJ-UHFFFAOYSA-N ethyl 3-hydrazinyl-3-oxopropanoate Chemical compound CCOC(=O)CC(=O)NN HCPOCMMGKBZWSJ-UHFFFAOYSA-N 0.000 claims 2
- 235000006408 oxalic acid Nutrition 0.000 claims 2
- 229940106691 bisphenol a Drugs 0.000 claims 1
- 238000000605 extraction Methods 0.000 claims 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims 1
- 150000007513 acids Chemical class 0.000 abstract description 2
- 239000004615 ingredient Substances 0.000 abstract description 2
- 239000003677 Sheet moulding compound Substances 0.000 abstract 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 22
- 239000000463 material Substances 0.000 description 19
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 15
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 14
- 229920001187 thermosetting polymer Polymers 0.000 description 13
- 238000004458 analytical method Methods 0.000 description 12
- 230000029087 digestion Effects 0.000 description 11
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
- 230000008602 contraction Effects 0.000 description 8
- JIGUICYYOYEXFS-UHFFFAOYSA-N 3-tert-butylbenzene-1,2-diol Chemical compound CC(C)(C)C1=CC=CC(O)=C1O JIGUICYYOYEXFS-UHFFFAOYSA-N 0.000 description 7
- 239000011521 glass Substances 0.000 description 7
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 6
- KUBDPQJOLOUJRM-UHFFFAOYSA-N 2-(chloromethyl)oxirane;4-[2-(4-hydroxyphenyl)propan-2-yl]phenol Chemical compound ClCC1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 KUBDPQJOLOUJRM-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- CFQZKFWQLAHGSL-FNTYJUCDSA-N (3e,5e,7e,9e,11e,13e,15e,17e)-18-[(3e,5e,7e,9e,11e,13e,15e,17e)-18-[(3e,5e,7e,9e,11e,13e,15e)-octadeca-3,5,7,9,11,13,15,17-octaenoyl]oxyoctadeca-3,5,7,9,11,13,15,17-octaenoyl]oxyoctadeca-3,5,7,9,11,13,15,17-octaenoic acid Chemical compound OC(=O)C\C=C\C=C\C=C\C=C\C=C\C=C\C=C\C=C\OC(=O)C\C=C\C=C\C=C\C=C\C=C\C=C\C=C\C=C\OC(=O)C\C=C\C=C\C=C\C=C\C=C\C=C\C=C\C=C CFQZKFWQLAHGSL-FNTYJUCDSA-N 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 238000006471 dimerization reaction Methods 0.000 description 5
- 239000000395 magnesium oxide Substances 0.000 description 5
- 239000012492 regenerant Substances 0.000 description 5
- 238000007711 solidification Methods 0.000 description 5
- 230000008023 solidification Effects 0.000 description 5
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- 230000034659 glycolysis Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000000206 moulding compound Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000010298 pulverizing process Methods 0.000 description 4
- 230000000452 restraining effect Effects 0.000 description 4
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 description 3
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 3
- 239000004641 Diallyl-phthalate Substances 0.000 description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 3
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 3
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 230000032050 esterification Effects 0.000 description 3
- 238000005886 esterification reaction Methods 0.000 description 3
- 229940051250 hexylene glycol Drugs 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 3
- 229920002635 polyurethane Polymers 0.000 description 3
- 239000004814 polyurethane Substances 0.000 description 3
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 2
- 229940058015 1,3-butylene glycol Drugs 0.000 description 2
- CWPKTBMRVATCBL-UHFFFAOYSA-N 3-[1-[1-[(2-methylphenyl)methyl]piperidin-4-yl]piperidin-4-yl]-1h-benzimidazol-2-one Chemical compound CC1=CC=CC=C1CN1CCC(N2CCC(CC2)N2C(NC3=CC=CC=C32)=O)CC1 CWPKTBMRVATCBL-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- 239000004322 Butylated hydroxytoluene Substances 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 2
- 125000005250 alkyl acrylate group Chemical group 0.000 description 2
- 230000031709 bromination Effects 0.000 description 2
- 238000005893 bromination reaction Methods 0.000 description 2
- 235000019437 butane-1,3-diol Nutrition 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 229940095259 butylated hydroxytoluene Drugs 0.000 description 2
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N ethyl acetate Substances CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 229920001903 high density polyethylene Polymers 0.000 description 2
- 239000004700 high-density polyethylene Substances 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 235000012204 lemonade/lime carbonate Nutrition 0.000 description 2
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000005935 nucleophilic addition reaction Methods 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 2
- 229920001567 vinyl ester resin Polymers 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 1
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical class O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 1
- SLGGJMDAZSEJNG-UHFFFAOYSA-N 2-(2-hydroxyethoxy)ethanol;terephthalic acid Chemical compound OCCOCCO.OC(=O)C1=CC=C(C(O)=O)C=C1 SLGGJMDAZSEJNG-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- WEHZNZTWKUYVIY-UHFFFAOYSA-N 3-oxabicyclo[3.2.2]nona-1(7),5,8-triene-2,4-dione Chemical compound O=C1OC(=O)C2=CC=C1C=C2 WEHZNZTWKUYVIY-UHFFFAOYSA-N 0.000 description 1
- LNYYKKTXWBNIOO-UHFFFAOYSA-N 3-oxabicyclo[3.3.1]nona-1(9),5,7-triene-2,4-dione Chemical compound C1=CC(C(=O)OC2=O)=CC2=C1 LNYYKKTXWBNIOO-UHFFFAOYSA-N 0.000 description 1
- SGYAMNNIKRWVKZ-UHFFFAOYSA-N 6-(furan-2-yl)hexa-3,5-dien-2-one Chemical compound CC(=O)C=CC=CC1=CC=CO1 SGYAMNNIKRWVKZ-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- HSKNIMOEWAXVTR-UHFFFAOYSA-N CC(O)=O.CC(O)=O.CC(O)=O.P Chemical compound CC(O)=O.CC(O)=O.CC(O)=O.P HSKNIMOEWAXVTR-UHFFFAOYSA-N 0.000 description 1
- GEZVVKMYDDZWFP-UHFFFAOYSA-N CC1=C(C(=O)O)C=CC=C1C(=O)O.C(C1=CC=C(C(=O)O)C=C1)(=O)O Chemical compound CC1=C(C(=O)O)C=CC=C1C(=O)O.C(C1=CC=C(C(=O)O)C=C1)(=O)O GEZVVKMYDDZWFP-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- OWIKHYCFFJSOEH-UHFFFAOYSA-N Isocyanic acid Chemical compound N=C=O OWIKHYCFFJSOEH-UHFFFAOYSA-N 0.000 description 1
- AYDQIZKZTQHYIY-UHFFFAOYSA-N OC(=O)C1(C)CC(C(O)=O)=CC=C1 Chemical compound OC(=O)C1(C)CC(C(O)=O)=CC=C1 AYDQIZKZTQHYIY-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 229920006387 Vinylite Polymers 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical class CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-N anhydrous cyanic acid Natural products OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- XZKRXPZXQLARHH-UHFFFAOYSA-N buta-1,3-dienylbenzene Chemical compound C=CC=CC1=CC=CC=C1 XZKRXPZXQLARHH-UHFFFAOYSA-N 0.000 description 1
- UPIWXMRIPODGLE-UHFFFAOYSA-N butyl benzenecarboperoxoate Chemical compound CCCCOOC(=O)C1=CC=CC=C1 UPIWXMRIPODGLE-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 235000019628 coolness Nutrition 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 1
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 150000007520 diprotic acids Chemical class 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- 235000019359 magnesium stearate Nutrition 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 description 1
- HRRDCWDFRIJIQZ-UHFFFAOYSA-N naphthalene-1,8-dicarboxylic acid Chemical compound C1=CC(C(O)=O)=C2C(C(=O)O)=CC=CC2=C1 HRRDCWDFRIJIQZ-UHFFFAOYSA-N 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- PSXNDMJWRZYVTM-UHFFFAOYSA-N octanoic acid butyl ester Natural products CCCCCCCC(=O)OCCCC PSXNDMJWRZYVTM-UHFFFAOYSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000005502 peroxidation Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004597 plastic additive Substances 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 238000012667 polymer degradation Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- YTZKOQUCBOVLHL-UHFFFAOYSA-N tert-butylbenzene Chemical compound CC(C)(C)C1=CC=CC=C1 YTZKOQUCBOVLHL-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000010136 thermoset moulding Methods 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 229940005605 valeric acid Drugs 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/06—Unsaturated polyesters
-
- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
-
- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/672—Dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/05—Alcohols; Metal alcoholates
- C08K5/053—Polyhydroxylic alcohols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/092—Polycarboxylic acids
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
- Reinforced Plastic Materials (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
This invention is a thermoplastic saturated polyester low profile additive (low profile additive) useful in sheet molding compounds for parts, especially vehicle parts, the additive has a major component derived from aromatic compounds such as terephthalic acid including recycled polyethylene terephthalate. Asymmetrical glycols are an important ingredient and can be used to digest recycled PET to make oligomeric glycols which are reacted with acids having fewer than 12 carbon atoms to make one of the low profile additives of this invention.
Description
The present invention relates to low-smoothness (low profile) additive of thermoplasticity saturated polyester, this additive is used for making moulded piece with unsaturated polyester and unsaturated monomer, particularly automobile component.These additives are by major part is made for the unsaturated diacid of aromatic diacid and glycol reaction, and the part of described glycol is asymmetric glycol.According to one aspect of the present invention, the reagent that contains aromatic diacid adopts asymmetric glycol to make the glycolysis of ground polyethylene terephthalate form a low-molecular-weight oligomeric diol and obtains.
With plastic material, for example glass fibre enhanced thermosetting polyester resin becomes more and more general as the outer component of automobile and truck.The successful use of these solidified resin materials is to form several metallic elements because they have high strength, high heat impedance and they can be molded as a plastic items rather than resemble the metallic substance.But because their essence limits, the thermosetting resin mixture is difficult to obtain surface property after molded and is not subjected to the badly damaged component.Along with the more and more higher requirement of human consumer to quality product, the material supplier and the moulded product producer have carried out continuous effort, to improve the surface flatness and the dimensional stability of mixture component.
A series of thermoplastic polymer additive is used to improve the surface quality of molded thermosetting resin component.These materials are known as low-smoothness additive, because they reduce surfaceness and improve surface flatness or " profile (profile) " by the contraction that reduces resin in the molded, cured process of resin as the part of thermosetting resin.If there is a large amount of cure shrinkage to produce, its surperficial cross section is coarse, can find that it has big Feng Hegu under the situation that high power is amplified.If cure shrinkage reduces, the surface is then more smooth, and it is more level and smooth that its cross section also seems, has lower peak and more shallow paddy.A kind of purpose of effective low-smoothness additive is that the gap between the highest peak and the most shallow paddy is reduced to minimum.But, even best low-smoothness additive can not make the product that obtains have specular surface.
In the solidification process of unsaturated polyester resin and vinyl ester resin, the example that reacts the thermoplastic polymer of contraction and improvement surface flatness with control as low-smoothness additive comprises polystyrene, polyester, polymethylmethacrylate, polyvinyl acetate, polyurethane, polyoxyethylene glycol and their various multipolymers.
The United States Patent (USP) 3,959,209 of Koppers has exemplified and has reduced its contraction to prepare the thermoplastic polymers with level and smooth and high-quality ostentatious goods effectively in the solidification process of compositions of thermosetting resin.At United States Patent (USP) 3,959, in 209, some homopolymer have been exemplified, as the homopolymer of ethene, vinylbenzene, Vinyl toluene, alkyl methacrylate, alkyl acrylate; Various multipolymers are as the multipolymer of vinylchlorid and vinyl-acetic ester, vinylbenzene and acrylonitrile, methyl methacrylate and alkyl acrylate, methyl methacrylate and vinylbenzene, methyl methacrylate and acrylamide.
The thermoplasticity low-smoothness additive can improve other character of thermosetting moulding compound sometimes.The United States Patent (USP) 4 of Olin, 421,894 have described a kind of polyurethane oligopolymer properties-correcting agent that joins in the thermosetting polyester resin composition, and except reducing the contraction in the solidification process, this properties-correcting agent can also make common easily crisp thermosetting resin have improved shock resistance.
In the Kunststoffe publication of nineteen eighty-three, Krolikowski is according to the increase to the shrinkage value of corresponding modified unsaturated polyester resin system, various thermoplastic additive are sorted: high density polyethylene(HDPE), the multipolymer of vinyl-acetic ester and diallyl phthalate, polycaprolactone, polystyrene, polymethylmethacrylate, the multipolymer of poly-hydroxy ester and vinylbenzene and diallyl phthalate.
The United States Patent (USP) 5 of Ashland Oil, Inc, 116,917 have described a kind of saturated polyester low-smoothness additive that is used for vinyl ester resin systems, and this additive is that the ethylene oxide/propylene oxide multi-ether polyol of mol ratio in the scope of 0.1-0.9 by diprotic acid and ethylene oxide/propylene oxide makes.
In these additives, more general low-smoothness additive is a thermoplastic polyester.It has versatility is because can prepare multiple polyester copolymer at an easy rate, therefore can to interested be the polyester low-smoothness additive that the resin design of base goes out to have specific function with the unsaturated polyester.The most general vibrin low-smoothness additive is obtained by aliphatic dibasic acids or acid anhydrides such as pentanedioic acid, hexanodioic acid, sebacic acid or nonane diacid or its acid anhydrides and glycol based on oxyethane or propylene oxide.These low-smoothness additives are preparation and allotment easily usually, has good consistency in vinylbenzene and basic resin, and demonstrates the ability that good control is shunk, can high-quality combination with decorative surfaces.
When mechanical property is at the crucial moment, although this is uncommon, low-smoothness additive also can be prepared with glycol or lactone by aromatic dibasic acid or its acid anhydrides such as Tetra hydro Phthalic anhydride, isophthalic anhydride and terephthalic anhydride etc.The usually more difficult preparation of this kind resin, the solvability in vinylbenzene be relatively poor, relatively poor with other the consistency of vibrin, and demonstrate bigger cure shrinkage and relatively poor surface flatness usually.But their toughness is higher usually, has higher glass transition temp and fusing point, and has higher anti-transesterification.Its high tenacity can be so that composite elements has the physical strength under the enhanced physical strength, particularly high temperature.Because normally pre-mixing before use and storage of moulding compound, therefore between low-smoothness additive and basic resin, always exist transesterification takes place may.Therefore this transesterification causes the reduction of the effective concentration of low-smoothness additive, causes the loss of the control of shrinking and the reduction of surface flatness.Therefore, what wish most is to find and prepare such low-smoothness additive from aromatic diacid, this additive can be used for preparing have excellent anti-transesterification, the moulding compound of enhanced physical strength and excellent surface flatness.
In view of this, low-smoothness additive of the present invention mainly is to make from m-phthalic acid and terephthalic acid and a series of symmetry and asymmetric dihydroxy alcohol or glycol.Can obtain following conclusion thus:
(1) anti-transesterification mainly is the function of aromatic diacid content and the mol ratio that approximately is proportional to aromatic diacid and aliphatic diacid.When diacid mainly was aromatic diacid, anti-transesterification was best.
(2) for polymkeric substance with high aromatic diacid content:
(a) consistency and the validity that reduces cure shrinkage and improve surface flatness mainly are the functions of the number-average molecular weight (Mn) of the kind of employed glycol and structure and polymkeric substance in vinylbenzene and unsaturated basic resin,
(b) with containing a large amount of asymmetric materials such as propylene, two propylene, polypropylene and 2-methyl isophthalic acid, when the diol mixture of ammediol prepares low-smoothness additive, demonstrate the effect of increase,
(c) compare with other asymmetric glycol, adopt and contain a large amount of 2-methyl isophthalic acids, the low-smoothness additive of the diol mixture preparation of ammediol is effective in more basic resin,
(d) for the low-smoothness additive of same concentrations, the mechanical properties of composition increases with the increase of the mechanical properties of low-smoothness additive.
The present invention relates to a kind of resin combination that is used to form solidified moulded product such as automobile component, said composition comprises a kind of thermoset unsaturated polyester resin, one or more can with the ethylenically unsaturated monomer of described unsaturated polyester copolymerization, and a kind of low-smoothness additive, this additive can be compatible with uncured resin molded composition and be become in undersaturated polyester and monomeric solidify reaction process and do not dissolve or incompatible.The number-average molecular weight of additive of the present invention (Mn) is 3, and 000-20 is between 000.This molecular weight can reach by by the end acidic group of polyester or hydroxyl end groups polyester and polyfunctional epoxide or isocyanic ester being coupled together after esterification or the esterification.
Thermoplasticity low-smoothness additive component of the present invention is that esterification or the digestion by dicarboxylic acid or its acid anhydrides and glycol makes.Acidic group that also can be by polyester after the digestion or hydroxyl end groups couple together polyester and polyfunctional epoxide or isocyanic ester to regulate its number-average molecular weight.This method is that the those of ordinary skill of polyester art is known.Typical reagent comprises diacid such as hexanodioic acid, phthalic acid (acid anhydride), m-phthalic acid and terephthalic acid, and glycol such as ethylene glycol, propylene glycol and dipropylene glycol, 2-methyl isophthalic acid, ammediol, 1,4-butyleneglycol and hexylene glycol.
The link molecule that is suitable for comprises glycidyl ether, linear phenolic resin, lipid acid and ester, two pure and mild polyether glycols, the polyamines of polyepoxide such as dihydroxyphenyl propane and can obtain the tetrahydrobenzene of aliphatic epoxide.Polymeric polyisocyanate is public as xylene diisocyanate (TDI) and two pairs of phenylene esters of isocyanic acid methylene radical (MDI).
The diglycidyl ether that preferred epoxy connection compound is a dihydroxyphenyl propane " 4,4 '-(1-methyl ethylidene) bis-phenol polymkeric substance and chloromethyloxirane " CAS#25068-38-6 " ".If polyester oligomer is that then they can be attached in the polyepoxide at an easy rate by nucleophilic addition(Adn) by the group end capping that reaction obtains acidic group that passes through of nucleophilic functional group such as acidic group or any other.
If very difficult, then can digest (cooked) to resin and obtain hydroxyl end groups with the nucleophilic addition(Adn) of epoxy compounds.Adopt polyfunctional isocyanic ester such as TDI or MDI, can at an easy rate this quasi-oligomer be coupled together and form polyurethane.
The content of polyfunctional epoxy compounds or isocyanic ester connection portion is generally less than 15% (weight) in final low-smoothness additive product; Preferably less than 10% (weight); Especially preferably less than 5% (weight).The common average out to 1000-9000 of Mn that is suitable for polyester prepolyer of the present invention, and the Mn of prepared final low-smoothness additive is 3000-20000, is preferably 6000-16000.
Low-smoothness additive of the present invention is joined in the thermoset moulding compound to control the contraction in its solidification process.Employed thermosetting resin can comprise unsaturated polyester commonly used, Vinylite and the unsaturated polyester resin hybrid that contains epoxy or urethane connector.Described low-smoothness additive can be any the effective level ratio use.Preferably, in the unsaturated polyester resin of 100 weight parts and copolymerizable solvent, the add-on of described low-smoothness additive is the 5-30 weight part.Particularly preferably be, in the unsaturated polyester resin of 100 weight parts and copolymerizable solvent, the add-on of described low-smoothness additive is the 8-20 weight part.
Described thermoset unsaturated polyester resin is those of ordinary skill known method and the reagent that adopts polyester art, makes the reaction of dicarboxylic acid or its acid anhydrides and glycol and prepares.Typical reagent comprises diacid and its acid anhydrides such as phthalic acid, phthalate anhydride, and toxilic acid, maleic anhydride, and glycol, as ethylene glycol, Diethylene Glycol, propylene glycol, butyleneglycol and hexylene glycol.Formed polyester and additive are dissolved in the active copolymerizable solvent, and with its diluted for use.This type of copolymerizable solvent comprises alefinically unsaturated compounds such as vinylbenzene, Vinyl toluene, methacrylic ester, acrylate, Vinylstyrene, various polyfunctional acrylate and methacrylic ester and diallyl phthalate.
The polymerization and the curing that contain the vibrin system of additive are to adopt various known method, preferably carry out in the presence of a kind of polymerizing catalyst.Solidification value depends on employed catalyzer.Normally used catalyzer is catalyzer such as the superoxide and the azo compound that can produce radical.Typical peroxide catalyst is organo-peroxide and hydroperoxide, as benzoyl peroxide, dicumyl peroxide, methyl-ethyl-ketone peroxide, peroxidation lauryl, pimelinketone superoxide, t-butylperoxyl benzoate, tert-butyl hydroperoxide, tert.-butylbenzene hydroperoxide, cumene hydroperoxide and mistake butyl caprylate.Typical azo compound is that azo two isobutyls are fine, 2-tertiary butyl azo-2-cyano group-4-methylpentane and 4-5-butyl azo-4-cyano group-valeric acid.Preferred catalyzer is a t-butylperoxyl benzoate.In the thermosetting resin of 100 weight parts, reactive solvent and low-smoothness additive, catalyst consumption is generally the 0.1-10 weight part.
Composition of the present invention also can contain other standard ingredient, as filler (broken solid such as the lime carbonate of fine powder for example, clay, aluminum oxide, talcum or glass microsphere) and other strongthener (as, the glass fibre of pulverizing, carbon fiber, fibrous magnesium silicate or boron nitride must be brilliant).Other component can comprise inner pattern releasing agent applicable, for example calcium stearate, Magnesium Stearate or sodium stearate.Also can add pigment, dyestuff, stablizer and viscosity modifier (for example the oxide compound and the oxyhydroxide of II family metal, as magnesium oxide).The low contraction or the shock resistance additive that also can comprise other.In a typical prescription,, contain the strongthener that consumption is the 20-300 weight part and the filler of 50-1000 weight part usually in the thermosetting resin of 100 weight parts, reactive solvent and low-smoothness additive oligopolymer.
According to one aspect of the present invention, a kind of saturated polyester low-smoothness additive is provided, and this additive is that the employing major part is that the diacid of aliphatic dicarboxylic acid and the diol mixture reaction that contains linear and asymmetric glycol obtain for saturated aromatic dicarboxylic acid, small portion.Described polyester can further be connected with epoxy or isocyanate compound.
According to another aspect of the present invention, a kind of saturated polyester low-smoothness additive is provided, this additive adopts asymmetric two pure and mild saturated aliphatic acids that the recovery polyethylene terephthalate polymer ethylene glycolization and the digestion of pulverizing are obtained.This polyester also can be connected with polyfunctional epoxy or isocyanate compound.This second kind of polyester contains 50% the regenerant of having an appointment.
Among the present invention, described asymmetric glycol is following those:
Propylene glycol
The 2-methyl isophthalic acid, ammediol
Dipropylene glycol
X 〉=3, polypropylene glycol
1,3 butylene glycol
Most preferred asymmetric glycol is the 2-methyl isophthalic acid, ammediol.
Described symmetric glycol is following those:
Neopentyl glycol HO-CH
2-CH
2-OH ethylene glycol HO-CH
2-CH
2-O-CH
2-CH
2-OH
Diethylene Glycol
Polyoxyethylene glycol, x 〉=3HO-CH
2-CH
2-CH
2-CH
2-OH 1,4-butyleneglycol (butyleneglycol) HO-CH
2-CH
2-CH
2-OH 1, ammediol (positive propylene glycol) HO-CH
2-CH
2-CH
2-CH
2-CH
2-CH
2-CH
2-OH
1, the 6-hexylene glycol
Provide a kind of low-smoothness additive more on the one hand according to of the present invention, most of aromatic hydroxy compound of this additive, it is the oligopolymer that obtains from the recovery polyethylene terephthalate of pulverizing (PET).Contain at least 25% recovery component because the automaker wishes to be used to make the composition of automobile component, each component that is used for making component all should contain the recovery component of this content.Use of the present invention a kind of low-smoothness additive of the PET preparation of reclaiming to provide a kind of component concentration that reclaims to be about 50% low-smoothness additive.
The recovery polyethylene terephthalate of pulverizing can be the various forms that obtains from many waste recovery center, as film, ampuliform and blocky polyethylene terephthalate.A collection centre is the Flo-Rida-Low that boils, the resin retrieval management company of Tan Mupa.
The United States Patent (USP) 4 of Owens Corning, 054,561 use carbon atoms to prepare additive more than 12 dimerization and trimer acid and from recovery terephthalic acid ester oligomer and symmetrical glycol that PET obtains, the additive that obtains has moderate contraction controllability, and the surface quality of molded component is poor.High-molecular weight dimerization/trimer acid also makes the content of the regenerant in the low-smoothness additive low to the degree that can not receive.
Have been found that by using various glycol digestion PET to use the terephthalic acid ester oligomer reaction of low-molecular-weight acid and recovery can make the saturated polyester low-smoothness additive with satisfied low-smoothness characteristic of the present invention simultaneously.Use less acid can obtain the excellent surface quality and the content of acceptable regenerant.
The following examples have been described the preparation and the evaluation of the low-smoothness additive in the present invention and the United States Patent (USP) 4,054,561.Unless specialize, all umbers all are parts by weight, and all units all are metric units.All reference of being addressed herein all are incorporated herein by reference document.Low-smoothness additive #1: be connected with epoxide
Following raw material joined in one 4 liters the resin kettle:
M-phthalic acid: 1614.0g (9.7 moles)
Hexanodioic acid 157.7g (1.08 moles)
The 2-methyl isophthalic acid, ammediol 583.5g
Diethylene Glycol 286.9g
Ethylene glycol 73.8g
Poly(oxyethylene glycol) 400 172.0g
This mixture slowly is heated to 225 ℃, remove water wherein and keep 15-16 hour until its acid number be 26.8 and hydroxyl value be about 4.Cool the temperature to 171 ℃ and add about 130 gram EPON828 Resins, epoxy (shell chemical company) and 2.8 and restrain tetrabutylphosphoniuacetate acetate (70%NV in the methyl alcohol) " Johnson Matthye, Alfa Aesar, Ward Hill MA 01835-0747; Product code: 56179 ".After about 50 minutes, acid number reduces to 10.0 170 ℃ of maintenances.About 2600 gram polymeric articles are dissolved in the tert-butyl catechol that obtains 50% non-volatile matter in the vinylbenzene and use 200ppm to be suppressed.Adopt end-group analysis, the number-average molecular weight (Mn) of the polyester low-smoothness additive that records is about 8000.Low-smoothness additive #2: be not connected with epoxide
Following raw material joined in one 3 liters the resin kettle:
M-phthalic acid: 1317.6g (7.9 moles)
Hexanodioic acid 128.8g (0.9 mole)
The 2-methyl isophthalic acid, ammediol 471.5g
Diethylene Glycol 231.8g
Ethylene glycol 59.6g
Poly(oxyethylene glycol) 400 139.0g
Fascat 4100 catalyzer 2.0g
This mixture slowly is heated to 225 ℃, removes to anhydrate and keep being 39 and adding 1 gram Fascat, 4100 catalyzer (M﹠amp until its acid number in about 9 hours; T chemical company, Rahway, NJ).15 hours and acid number are about at 31 o'clock, add 1 gram Fascat catalyzer again.When acid number does not have considerable change in 3 hours, detect hydroxyl value and find that hydroxyl value is about 2.Temperature reduced and add diol mixtures in about 35 gram initial charge.In subsequently 9 hours, acid number is reduced to 12.3.About 2000 gram polymeric articles are dissolved in the tert-butyl catechol that obtains 50% non-volatile matter in the vinylbenzene and use 200ppm to be suppressed.Adopt end-group analysis, the number-average molecular weight (Mn) of the polyester low-smoothness additive that records is about 7400.Low-smoothness additive #3: use asymmetric glycol
Attempt using the 1-methyl isophthalic acid, ammediol (1,3 butylene glycol) replaces the 2-methyl isophthalic acid among the low-smoothness additive #1, and ammediol prepares the third low-smoothness additive #3.Digestion is carried out reaching about 37 until acid number reposefully, and reaction stops.Hydroxy value measuring shows that hydroxyl value is about 13, and this hydroxyl value is enough to proceed polymerization.Attempt by adding catalyzer and temperature being elevated to 235 ℃ so that reaction forces to carry out but not success, and continue " digestion " and just make polymer degradation and make the acid number increase.Stop to prepare and will discard for the polymkeric substance of making.Low-smoothness additive #4: use symmetrical glycol
According to following method, from the glycolysis product of Diethylene Glycol (a kind of symmetrical glycol) and ethylene glycol terephthalate (PET) and the low-smoothness additive that hexanodioic acid makes high regenerant content.PET and 900 gram Diethylene Glycols (1/0.8 mol ratio) are heated to 220 ℃ and be incubated 4 hours.
The PET and 424 of the glycolysis diacid of restraining oneself is joined in one 2 liters the resin kettle and slowly is heated to 226 ℃ to remove moisture.Acid number reaches 21.2 after 6 hours, and hydroxyl value is about 13.Add about 19 restrain oneself diacid and continue reaction 6 hours so that acid number reduces to 25.0, hydroxyl value is reduced to 3-4.With reactor cooling to 185 ℃ and add 57.9 gram EPON828 Resins, epoxy and 2.8 gram bromination tetramethyl-catalyzer.Acid number reduces to 7.8 in one hour.About 1250 gram polymeric articles are dissolved in the tert-butyl catechol that obtains 50% non-volatile matter in the vinylbenzene and use 200ppm to be suppressed.Adopt end-group analysis, the number-average molecular weight of the product that records (Mn) is about 9930.Low-smoothness additive #5: use asymmetric glycol
According to following method, from the 2-methyl isophthalic acid, the glycolysis product of 3 propylene glycol and ethylene glycol terephthalate (PET) and hexanodioic acid make the low-smoothness additive of high regenerant content:
PET??????????????????1361.7g
The 2-methyl isophthalic acid, ammediol 638.3g
Hexanodioic acid 1035.4g
PET and glycol joined in one 4 liters the resin kettle, be heated to 220-222 ℃ and be incubated about 4 hours.After the cooling, product is the soft paste that fully digests.Add hexanodioic acid and kilfoam A and temperature is elevated to 225 ℃.When acid number reduces to 24.5 and hydroxyl value when being 2-3, with reactor cooling to 180 ℃.At this moment, add 133 gram EPON828 Resins, epoxy and 2.04 gram bromination tetrabutyl catalyzer.Acid number reduces to 10.0 in 45 minutes.About 2850 gram polymeric articles are dissolved in the tert-butyl catechol that obtains 50% non-volatile matter in the vinylbenzene and use 200ppm to be suppressed.Adopt end-group analysis, the molecular weight of the polyester low-smoothness additive that records is about 8980.Low-smoothness additive #6: use symmetrical glycol
Following raw material joined in one 4 liters the resin kettle:
M-phthalic acid: 1632.7g
Hexanodioic acid 152.3g
Neopentyl glycol (NPG) 650.5g
Diethylene Glycol (DEG) 276.8g
Ethylene glycol 71.3g
Poly(oxyethylene glycol) 400 166.8g
This mixture slowly is heated to 225 ℃, except that anhydrating and keeping 15-16 hour, adds 1.2 gram Fascat4100 catalyzer (M﹠amp; T chemical company, Rahway, NJ).The analysis revealed acid number is 43.1 and hydroxyl value is about 13.6, therefore adds 12 gram NPG and 8 gram DEG.Acid number is to stop digestion at 34.6 o'clock.The analysis revealed hydroxyl value is about 0.Close nitrogen gas stream this moment and add 21 gram NPG and 11 gram DEG.In about 8 hours, acid number reduces to 25.4.Cool the temperature to 160 ℃ and add 113 gram EPON828 Resins, epoxy (shell chemical company) and 2.7 and restrain tetrabutylphosphoniuacetate acetate.After about 65 minutes, acid number reduces to 8.5 165 ℃ of maintenances.About 2600 gram polymeric articles are dissolved in the tert-butyl catechol that obtains 50% non-volatile matter in the vinylbenzene and use 200ppm to be suppressed.Adopt end-group analysis, the molecular weight of the polyester low-smoothness additive that records is about 8950.Low-smoothness additive #7: use symmetrical glycol
Low-smoothness additive #7 adopts the diol mixture by the neopentyl glycol of the Diethylene Glycol and 40% (mole) of 60% (mole) to replace the 2-methyl isophthalic acid, and the recovery PET of ammediol digestion makes.The raw material that adds in 4 liters the resin kettle is:
PET?????????????1291.6g
DEG??????????????428.6g
NPG??????????????279.8g
Hexanodioic acid 1004.0g
Fascat?4100????????2.5g
At first add two pure and mild 960 gram PET.Begin in glycol, after the dissolving, to add remaining PET at polymkeric substance.The still temperature is set at 235 ℃, but begins violent boiling 225 ℃ the time.Add 2ppm kilfoam A and can eliminate foam.PET was digested about 4 hours and add hexanodioic acid so that the PET repolymerization.Water is removed the still temperature rises to 225 ℃ 8 hours from 165 ℃ in.226 ℃ after 6 hours, acid number is 37.8 and adds 1.25 gram Fascat4100 catalyzer.226 ℃ after 9 hours, acid number is 31.4 and hydroxyl value is 17.7.Acid number and hydroxyl value difference are regulated with 24 diacid of restraining oneself.Reactor 226 ℃ of insulations 6 hours, when being 28.9, acid number is added 1.2 gram Fascat4100 catalyzer.Digested 4 hours, acid number reduces to 26.2 again.With reactor cooling to 175 ℃ and add the tetrabutylphosphoniuacetate acetate phosphorus father-in-law catalyzer of 108 gram Epon828 and 2.9 grams 70%.In about 75 minutes, acid number reduces to 13.1, and with 2550 gram polymkeric substance coolings and be dissolved in the vinylbenzene that is subjected to press down and obtain 50% non-volatile matter.Low-smoothness additive #8: be connected with diethyl cyanic acid toluene ester
Following raw material joined in one 4 liters the resin kettle to form polymer precursor:
M-phthalic acid: 2821.0g
Hexanodioic acid 275.3g
The 2-methyl isophthalic acid, ammediol 1019.7g
Diethylene Glycol 501.4g
Ethylene glycol 129.0g
Poly(oxyethylene glycol) 400 301.3g
This mixture slowly is heated to 225 ℃, remove anhydrate and keep about 20 hours until its acid number be 12.9 and hydroxyl value be about 14.About 800 gram polymer dissolution are restrained in the vinylbenzene as 800 of inhibitor in restraining tert-butyl catechol with 0.28.After adding 12.5 gram toluene-2,4-diisocyanates, mixture is warmed to about 70 ℃ under nitrogen gas stream.Add about 1.6 gram dibutyl tin laurates and be incubated about 3 hours as catalyzer and under this temperature.It is complete to guarantee all isocyanic ester consumption to add about 3.7 gram 2-Ethylhexyl Alcohols.Ultimate analysis shows that acid number is about 13, and the per-cent of non-volatile matter is about 50.3, and viscosity (Brookfield, 2# rotor) is about 730cps.The number-average molecular weight that adopts end-group analysis to record is about 7500.Low-smoothness additive #9: symmetrical glycol, expand without epoxide
Following raw material joined in one 4 liters the resin kettle:
M-phthalic acid: 1633.0g
Hexanodioic acid 152.3g
Neopentyl glycol (NPG) 651.0g
Diethylene Glycol (DEG) 276.8g
Ethylene glycol 71.2g
Poly(oxyethylene glycol) 400 166.8g
This mixture slowly is heated to 225 ℃, remove to anhydrate and after insulation 14-15 hour, the analysis revealed acid number be 43.2 and hydroxyl value be about 27.5.Add about 19 gram NPG, 7 gram EG and 17 gram DEG.At acid number is to slow down " digestion " at 34.9 o'clock once more.Analyze and show that hydroxyl value is about 16.Reduce nitrogen flow and add 3 gram EG, 7.2 gram DEG and 8.1 gram NPG.When acid number slowly reduced, adding 1.25 gram Fascat4100 and keeping temperature was 225 ℃." digestion " 10-11 hour again when acid number reduces to 12.4, stops digestion.About 2500 gram polymeric articles are dissolved in and obtain 50% non-volatile matter in the vinylbenzene.And suppress with the tert-butyl catechol of 300ppm.Adopt end-group analysis, the number-average molecular weight (Mn) of the polyester low-smoothness additive that records is about 7800.
Following table 1 shows and adopts asymmetric glycol 2-methyl isophthalic acid, the low-smoothness additive (LPA#1) that ammediol makes and further is connected with epoxide, adopt the 2-methyl isophthalic acid, ammediol makes and does not have the low-smoothness additive (LPA#2) of epoxide expansion, the low-smoothness additive (LPA#6) that adopts symmetrical glycol neopentyl glycol to make and further be connected with epoxide, adopt symmetrical glycol dimethyltrimethylene glycol to make and do not have the low-smoothness additive (LPA#9) and the asymmetric glycol 2-methyl isophthalic acid of employing of epoxide expansion, ammediol makes and the comparative result of the low-smoothness additive (LPA#8) that further is connected with isocyanic ester.
| Table 1 | |||||
| Prescription | ????A | ????B | ????C | ????D | ????E |
| ?Q6585 | ??65.0 | ???65.0 | ??65.0 | ???65.0 | ???65.0 |
| ?LPA#1 1 | ??28.0 | ?????- | ????- | ????- | ????- |
| ?LPA#2 | ???- | ???28.0 | ????- | ????- | ????- |
| ?LPA#6 2 | ???- | ?????- | ??28.0 | ????- | ????- |
| ?LPA#8 3 | ???- | ?????- | ????- | ???28.0 | ????- |
| ?LPA#9 | ???- | ?????- | ????- | ????- | ???28.0 |
| Vinylbenzene | ???7.0 | ????7.0 | ???7.0 | ????7.0 | ????7.0 |
| 12% cobalt naphthenate | ???0.1 | ????0.1 | ???0.1 | ????0.1 | ????0.1 |
| BHT (butylated hydroxytoluene) | ???0.1 | ????0.1 | ???0.1 | ????0.1 | ????0.1 |
| The TBPB butyl perbenzoate | ???1.5 | ????1.5 | ???1.5 | ????1.5 | ????1.5 |
| B-side 33%MgO dispersion liquid | ???2.7 | ????2.7 | ???2.7 | ????2.7 | ????2.7 |
| Surface quality, ashland LORIA index (ashland index on A level surface is lower than 100) ashland LORIA unit describe is in United States Patent (USP) 4, in 853,777 | ????80 | ?103，103， ????115 | ???108 | ????113 | ????145 |
1 asymmetric two pure and mild symmetrical glycol, the epoxide expansion
2 symmetrical glycol, the epoxide expansion
3 symmetries, two pure and mild asymmetric glycol, the isocyanic ester expansion
Prescription B shows the surface quality of being extra-large, and the prescription A when LPA (low-smoothness additive) expands with epoxide demonstrates excellent surface quality.
Prescription B is better than the prescription E that is only made by the mixture of symmetrical glycol.
Table 1 data presentation, although neopentyl glycol and the result (LPA#6) who obtains with the epoxide propagation energy, adopting the 2-methyl isophthalic acid, during ammediol, also can obtain better result during not even with epoxide expansion (LPA#2), adopt the 2-methyl isophthalic acid, the result that ammediol and the low-smoothness additive of expanding with epoxide of the present invention (LPA#1) obtain is best.
Following table 2 has shown the performance of the low-smoothness additive (LPA#4) that contains terephthalic acid-Diethylene Glycol (a kind of symmetrical glycol) and has contained terephthalic acid-2-methyl isophthalic acid, the comparative result of the performance of the low-smoothness additive (LPA#5) of ammediol (a kind of asymmetric glycol).Two kinds of low-smoothness additives are all expanded to increase its molecular weight with epoxide.
| Table 2 is from reclaiming the low-smoothness additive that PET makes | ||
| Composition | ????#1 | ????#2 |
| ??Q6585 | ????65.0 | ????65.0 |
| Low-smoothness additive #4 | ????28.0 | ?????-- |
| Low-smoothness additive #5 | ?????-- | ????28.0 |
| Vinylbenzene | ????7.0 | ????7.0 |
| Lime carbonate | ????200 | ????200 |
| 12% naphthalic acid cobalt | ????0.1 | ????0.1 |
| 2,6 ditertiary butyl p cresol | ????0.1 | ????0.1 |
| T-butyl perbenzoate | ????1.5 | ????1.5 |
| B-Side, the 33%MgO dispersion liquid | ????2.7 | ????2.7 |
| Surface quality, ashland index | ????86 | ????75 |
The data presentation of table 2, the low-smoothness additive #4 that the mixture of employing ethylene glycol and Diethylene Glycol (symmetrical glycol) makes and employing ethylene glycol and 2-methyl isophthalic acid, the LPA#5 of the mixture preparation of ammediol can reach A level car surface quality index (ashland surface quality index is lower than 100).Adopt asymmetric 2-methyl isophthalic acid, the low-smoothness additive #5 of ammediol preparation has obtained the good surface quality near top grade category-A index (70).Two kinds of low-smoothness additives that prepare from the PET deutero-oligomeric diol that reclaims can both make acceptable component.With United States Patent (USP) 4,054,561 comparing embodiment
A) according to United States Patent (USP) 4,054,561 make thermoplastic additive.Made PET oligopolymer and diol monomer by the mixture that will reclaim PET, ethylene glycol and Diethylene Glycol in 3-4 hour 230 ℃ of reactions.In oligopolymer, add extra glycol to obtain forming at United States Patent (USP) 4,054 561 second hurdles, the mixture of described preferable range between 45-55 is capable.To the analysis revealed of mixture, hydroxyl value is about 550.Use acid number to be about Empol1018 dimerization/trimer acid of 197.Calculating shows, according to United States Patent (USP) 4,054,561, prepare an acid number be about 30 and hydroxyl value be about 525 gram oligopolymer of thermoplastic additive needs and the 1660 gram dimeracids (weight ratio is 3.16) of 5-10, this weight ratio is in the scope of 1.3-3.5.The acid number of the finished product is about 26, and the solubleness in vinylbenzene is 50%N.V. (non-volatile matter).But, restraining in the resin modified PET standard recipe of ashland ENVIREZ8030 of vinylbenzene (in the prescription resins of 100 grams) with the 50%NV additive and 10.5 that contains 57.5,32.0, it is undissolved.This solution is divided into rarer upper layer (～40%) and thicker lower layer (～60%, in 1-1.5 hour) rapidly.According to standard program, add filler, releasing agent, initiator, inhibitor, MgO thickening material and glass to form a sheet material molding compound.Usual higher of consistency ratio produces the problem that glass (glass wet-out) soaks into.The rapid multiviscosisty of sheet material and after 2 days, be that the paste of about 5,000 ten thousand cps is molded as 12 * 12 sheet material with viscosity.Notice that some resin isolation comes out and make the glass spine come out from the edge of sheet material.Plate surface is matt and protruding bubble and a large amount of glass traces are arranged.Sheet material have to a certain degree curl therefore can not be as car body sheet material.Because the surface is too coarse, can not carry out quantitative analysis to surface quality.
Comparative Examples B
According to United States Patent (USP) 4,051,561, by significantly reducing by second kind of thermoplastic additive B of ratio preparation of dimerization/trimer acid and diol mixture.In order to finish this process and to keep product to have similar number-average molecular weight and acid number, need to regulate diol mixture to increase oligomer and to reduce hydroxyl value.This new diol mixture is to react at 235 ℃ by the mixture that makes the PET that oligopolymer (hydroxyl value is about 550) that 613 grams obtain from Comparative Example A An and 387 grams reclaim to make in 3.5-4 hour.Obtain hydroxyl value thus and be about 325 oligomer mixture.Subsequently with 436 gram oligopolymer and 842 gram Empol0108 dimeracid reactions.Except that anhydrating and temperature slowly being risen to 225 ℃, reach 280 until acid number.The polymer dissolution that forms is obtained 50% non-volatile matter in being subjected to the vinylbenzene that presses down.(be unusual heavy-gravity when polymkeric substance and cinnamic mixture room temperature, and be paste).A compares with the comparative heat plastic additive, standard recipe thing shown in the table 3 is blended in the ashland ENVIREZ8030 basic resin with preparation sheet material molding compound, this thermoplastic additive also is insoluble in the described resin title complex, in 2-2.5 hour, liquid resin is separated into approximately equate two-layer.Compare with the sample that uses low-smoothness additive #4, the viscosity of the paste of the filling of use thermoplastic additive B is the former about 2 times (52000cps is to 98600cps).To reach 5,000 5 hundred ten thousand cps until the viscosity of paste by the sheet material multiviscosisty that thermoplastic additive B makes.Then with its 1000psi and 300 compacting 90-120 second to be molded as 12 * 12 sheet material.Formed sheet material is better than the sheet material that formed by thermoplastic additive A.Do not observed protruding bubble.Contraction is controlled to be medium.The surface of sheet material is very gloomy, and can be observed the glass trace.Carried out the LORIA surface quality measurement, the part of sheet material can produce surface reflection (table 3) very difficultly.This measurement result (151) is worse than greatly uses #4 hour measurement result of low-smoothness additive (111).Although be difficult to measure, this is a getable best result when using thermoplastic additive B.
Shown in the following table 3 is the low-smoothness additive #4 that contains terephthalic acid in the table 2 and #5 at the comparative result that contains from the basic resin that reclaims the terephthalic acid that polyethylene terephthalate obtains.
Table 3 also shows and United States Patent (USP) 4,054, the comparison test result of 561 embodiment A and B.
The surface quality of * plate is too poor, so that LORIA can not analyze its surface quality.
| Table 3 reclaims the recovery low-smoothness additive in the PET basic resin | ||||
| Prescription | ????1 | ????2 | ????3 | ????4 |
| Ashland Envirez 8030 resins | 57.5 | ?57.5 | ?57.5 | ?57.5 |
| Vinylbenzene | 10.5 | ?10.5 | ?10.5 | ?10.5 |
| ?LPA#5 | 32.0 | ?32.0 | ??- | ???- |
| ?LPA#4 | ?- | ??- | ??- | ???- |
| Thermoplastic additive A | ?- | ??- | ?32.0 | ???- |
| Thermoplastic additive B | ?- | ??- | ??- | ?32.0 |
| 12% cobalt curing accelerator | 0.1 | ?0.1 | ?0.1 | ?0.1 |
| 1,10% solution among the 4-benzoquinones inhibitor Dowenol | 0.42 | ?0.42 | ?0.42 | ?0.42 |
| The Lupersol PDO catalyzer peroxide-2 ethyl hexanoic acid tert-butyl ester | 0.27 | ?0.27 | ?0.27 | ?0.27 |
| The TBPB catalyzer, t-butylperoxyl benzoate | 1.5 | ?1.5 | ?1.5 | ?1.5 |
| Zinic stearas | 4.5 | ?4.5 | ?4.5 | ?4.5 |
| Pearl filler | 190 | ?190 | ?190 | ?190 |
| B-Side (33%MgO dispersion liquid) | 2.4 | ?2.4 | ?2.4 | ?2.4 |
| Ashland index | 100 | ?111 | ?n/a ＊＊ | ?151 |
The data presentation of table 3, the mixture (symmetrical glycol) that makes spent glycol and Diethylene Glycol are (#4) and make spent glycol and 2-methyl isophthalic acid, the result that the mixture of ammediol (asymmetric glycol) (#5) can both obtain.Use asymmetric glycol (#5) can obtain excellent surface quality.
Table 3 has also shown United States Patent (USP) 4,054,564 results that use dimerization/trimer acid to obtain.Compare with the surface quality index 100 or 111 of Diethylene Glycol of the present invention/recovery PET low-smoothness additive and asymmetric glycol/PET low-smoothness additive, ashland surface quality index is 151.The surface quality index changes to 100 or 111 from 151 and shows that saturated polyester low-smoothness additive of the present invention compares with the low smooth additive the documents, and the low-smoothness properties is had tangible improvement.
Claims (32)
1, a kind of thermoplasticity saturated resin surface quality additive that uses with unsaturated polyester resin and unsaturated monomer, it can be resisted and described unsaturated polyester generation transesterification, and number-average molecular weight is 3,000-10,000, this additive comprises:
A) mixture of saturated difunctional's compound, the major part of this mixture is a kind of aromatic compound that is selected from m-phthalic acid, phthalic acid or terephthalic acid or ester or phthalic anhydride, and small portion is a kind of aliphatic cpd that are selected from aliphatic diacid, diester or acid anhydrides; With
B) reaction product of the mixture of symmetry and asymmetric glycol.
2, additive as claimed in claim 1, wherein said asymmetric glycol is the 2-methyl isophthalic acid, ammediol.
3, additive as claimed in claim 1, wherein said aliphatic cpd are selected from one group that is made up of oxalic acid, propanedioic acid, succsinic acid, hexanodioic acid, pentanedioic acid, sebacic acid, nonane diacid and cyclohexane diacid.
4, additive as claimed in claim 1, its end group is mainly acid end group, and this acid end group is the polyester of 6000-16000 with multi-functional epoxy compound reaction to form the number-average molecular weight that is connected with described epoxy compounds further.
5, additive as claimed in claim 4, wherein said epoxide are the diglycidyl ether of dihydroxyphenyl propane.
6, additive as claimed in claim 1, its end group is mainly terminal hydroxy group, and this terminal hydroxy group is the polyester of 6000-16000 with a polyfunctional isocyanate compound reaction to form the number-average molecular weight (Mn) that is connected with described isocyanic ester further.
7, additive as claimed in claim 6, wherein said polyfunctional isocyanate's compound is toluene-2,4-diisocyanate or 4,4 '-two isocyanato-ditans.
8, additive as claimed in claim 1, wherein said symmetrical glycol is a Diethylene Glycol, described aromatic compound is a m-phthalic acid.
9, additive as claimed in claim 1 comprises reaction product and hexanodioic acid mixture and the ethylene glycol and the 2-methyl isophthalic acid of hexanodioic acid and terephthalic acid, the reaction product of the mixture of ammediol.
10, a kind of ashland index is less than 100, surface quality is the molded component of A level, comprise unsaturated polyester, the reaction product of unsaturated monomer and saturated thermoplastic polyester surface quality additive, this additive can be resisted and described unsaturated polyester generation transesterification, number-average molecular weight is 3,000-10,000, this additive comprises: the reaction product of the saturated difunctional's compound and the mixture of a kind of symmetry and asymmetric glycol, the major part of described saturated difunctional's compound is a kind of m-phthalic acid that is selected from, the aromatic compound of phthalic acid or terephthalic acid or ester or phthalic anhydride, its small portion are a kind of aliphatic diacids that is selected from, the aliphatic cpd of diester or acid anhydrides.
11, molded component as claimed in claim 10, wherein said additive comprise mixture and the ethylene glycol and the 2-methyl isophthalic acid of hexanodioic acid and terephthalic acid, the reaction product of the mixture of ammediol.
12, molded component as claimed in claim 10, wherein said two acid mixtures comprise that remaining is for to be less than 12 aliphatic diacid less than the carbonatoms of 20% (mole) greater than the aromatic diacid of 80% (mole).
13, a kind of thermoplasticity saturated resin surface quality additive that uses with unsaturated polyester resin and unsaturated monomer, it can be resisted and described unsaturated polyester generation transesterification, and number-average molecular weight is 3,000-10,000, this additive comprises:
The reaction product of the mixture of saturated difunctional's compound and the mixture of glycol, wherein said saturated difunctional's compound is selected from terephthalic acid and carbonatoms is less than 12 aliphatic acid esters and aliphatic anhydrides, and described glycol is selected from ethylene glycol and the glycol except that ethylene glycol.
14, additive as claimed in claim 13, wherein said glycol except that ethylene glycol are a kind of asymmetric glycol.
15, additive as claimed in claim 13, wherein said glycol except that ethylene glycol is a Diethylene Glycol.
16, additive as claimed in claim 13, wherein said asymmetric glycol is the 2-methyl isophthalic acid, ammediol.
17, additive as claimed in claim 13, wherein said aliphatic acid are a kind of compounds that is selected from a group that is made up of oxalic acid, propanedioic acid, succsinic acid, hexanodioic acid, pentanedioic acid, sebacic acid, nonane diacid and cyclohexane diacid.
18, additive as claimed in claim 13 comprises:
The reaction product of the mixture of the glycol except that ethylene glycol of the ethylene glycol of the mixture of the aliphatic acid of the terephthalic acid of 40-70% (mole) and 30-60% (mole) and 40-70% (mole) and 30-60% (mole).
19, further one that be connected with described epoxy compounds or isocyanate compound to form with the reaction of a multi-functional epoxy compound or polyfunctional isocyanate's compound, the number-average molecular weight of the described additive of claim 13 is the polyester of 6000-16000.
20, additive as claimed in claim 19, wherein said epoxy compounds are the diglycidyl ether of bisphenol-A epoxy compound, and described polyfunctional isocyanate is diethyl cyanic acid toluene ester or 4,4 '-two isocyanato-ditans.
21, a kind of with unsaturated polyester resin and unsaturated monomer use, number-average molecular weight is 3,000-10,000 saturated polyester surface quality additive comprises:
A) carbonatoms is less than 12 aliphatic diacid diester or acid anhydrides; With
B) oligomeric diol, this oligomeric diol contains the recovery component greater than 50% (quality), described recovery component be by in the polyethylene terephthalate that will the glycol except that ethylene glycol joins recovery and be heated to 150-250 ℃ so that described polyethylene terephthalate generation transesterification obtain; Reaction product.
22, additive as claimed in claim 21, wherein said diacid are hexanodioic acid.
23, additive as claimed in claim 22, further reaction is the polyester of 6000-16000 to form the number-average molecular weight that is connected with described epoxy compounds or isocyanate compound by adding polyfunctional epoxy compounds or isocyanate compound.
24, additive as claimed in claim 21, wherein said glycol except that ethylene glycol is asymmetric glycol.
25, additive as claimed in claim 24, wherein said asymmetric glycol is the 2-methyl isophthalic acid, ammediol.
26, additive as claimed in claim 21, wherein said glycol except that ethylene glycol is a Diethylene Glycol.
27, a kind ofly prepare the method that number-average molecular weight is the saturated polyester surface quality additive of 3000-10000, comprise that the ethylene glycol terephthalate polymkeric substance that will reclaim and the glycol except that ethylene glycol and first part's carbonatoms are less than 12 aliphatic diacid, diester or acid anhydrides and heat; Dissolve described polymkeric substance; Add heat extraction moisture to obtain uniform oligopolymer; Add the second section carbonatoms and be less than 12 aliphatic acid; Being heated to 230 ℃ makes number-average molecular weight reach 3000-10000.
28, method as claimed in claim 27 further comprises by adding polyfunctional epoxy compounds or isocyanate compound forming the polyester that number-average molecular weight is the connection of 6000-16000.
29, method as claimed in claim 27, wherein said glycol are ethylene glycol.
30, method as claimed in claim 27, wherein said glycol are asymmetric glycol.
31, method as claimed in claim 30, wherein said glycol are the 2-methyl isophthalic acid, ammediol.
32, method as claimed in claim 27, wherein said diacid are hexanodioic acid.
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/590,033 | 1996-02-02 | ||
| US08/595,538 US5756554A (en) | 1996-02-02 | 1996-02-02 | Low profile additives for polyester resin systems based on asymmetric glycols and aromatic diacids |
| US08/590033 | 1996-02-02 | ||
| US08/595,538 | 1996-02-02 | ||
| US08/595538 | 1996-02-02 | ||
| US08/590,033 US5552478A (en) | 1996-02-02 | 1996-02-02 | Low profile additives for polyester resin systems based on asymmetric glycols and aromatic diacids |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB011095687A Division CN1194039C (en) | 1996-02-02 | 1997-02-03 | Low-smoothness additive for saturated polyester resin and method for preparing same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1159457A true CN1159457A (en) | 1997-09-17 |
| CN1075825C CN1075825C (en) | 2001-12-05 |
Family
ID=27080728
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN97100595A Expired - Fee Related CN1075825C (en) | 1996-02-02 | 1997-02-03 | Low profile additives for polyester resin systems based on asymmetric glycols and aromatic diacids |
| CNB011095687A Expired - Fee Related CN1194039C (en) | 1996-02-02 | 1997-02-03 | Low-smoothness additive for saturated polyester resin and method for preparing same |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB011095687A Expired - Fee Related CN1194039C (en) | 1996-02-02 | 1997-02-03 | Low-smoothness additive for saturated polyester resin and method for preparing same |
Country Status (4)
| Country | Link |
|---|---|
| KR (1) | KR100201802B1 (en) |
| CN (2) | CN1075825C (en) |
| BR (1) | BR9700844A (en) |
| HK (1) | HK1003056A1 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102206311B (en) * | 2011-04-22 | 2013-01-30 | 常州华科树脂有限公司 | Saturated polyester for sheet moulding compound or bulk molding compound (SMC/BMC) low-shrinking agent and preparation method thereof |
| CN103874732B (en) * | 2012-01-30 | 2016-09-07 | 东丽株式会社 | Normal pressure dispersion dyeable polyester composition, its manufacture method and the fiber formed by it and the formed body formed by it |
| CN108264633B (en) * | 2018-01-26 | 2020-06-26 | 山东宏信化工股份有限公司 | High-stability quartz stone resin and preparation method thereof |
| KR102545381B1 (en) * | 2021-07-02 | 2023-06-20 | 주식회사 에코폴리머 | Process of Vinylester resins for eco-friendly corrosion resistance pultrusion using recycled polyethyleneterephthalate flake |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5296544A (en) * | 1992-07-14 | 1994-03-22 | Cook Composites And Polymers | Polyester-polyurethane hybrid resin systems containing low levels of unsaturation having improved low profiling behavior |
| US5470935A (en) * | 1992-12-15 | 1995-11-28 | Bayer Corporation | Preparation of cast elastomers using 2-methyl-1,3-propanediol as chain extender |
-
1997
- 1997-01-31 BR BR9700844A patent/BR9700844A/en not_active Application Discontinuation
- 1997-02-01 KR KR1019970003205A patent/KR100201802B1/en not_active IP Right Cessation
- 1997-02-03 CN CN97100595A patent/CN1075825C/en not_active Expired - Fee Related
- 1997-02-03 CN CNB011095687A patent/CN1194039C/en not_active Expired - Fee Related
-
1998
- 1998-03-17 HK HK98102233A patent/HK1003056A1/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| KR100201802B1 (en) | 1999-06-15 |
| CN1075825C (en) | 2001-12-05 |
| HK1003056A1 (en) | 1998-10-09 |
| CN1194039C (en) | 2005-03-23 |
| CN1346846A (en) | 2002-05-01 |
| KR970061958A (en) | 1997-09-12 |
| BR9700844A (en) | 1998-09-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Jankauskaite et al. | Polyethylene terephthalate waste recycling and application possibilities: a review | |
| US5756554A (en) | Low profile additives for polyester resin systems based on asymmetric glycols and aromatic diacids | |
| CN1094804C (en) | Resource recovery method of resin moulded rotary motor and resin for moulding | |
| US20080090954A1 (en) | Low shrinkage sheet molded composite formulations | |
| CN1012619B (en) | Phase stabilized polyester molding material | |
| EP0877771B1 (en) | Low profile additives for polyester resin systems based on asymmetric glycols and aromatic diacids | |
| CN1030713C (en) | Unsaturated polyester resin compositions containing compatible compounds | |
| CN104204869B (en) | Lamp reflector moulding material and products formed | |
| WO1997028204A9 (en) | Low profile additives for polyester resin systems based on asymmetric glycols and aromatic diacids | |
| US4421894A (en) | Polyurethane oligomer impact and shrinkage modifiers for thermoset polyesters | |
| CN1050854C (en) | Enhancers for thermoplastic low profile additives | |
| CN1072246C (en) | Polyethylene terephthalate resin composition | |
| EP0340019B1 (en) | Resin composition | |
| EP0383609B1 (en) | Resin composition and method of manufacturing the same | |
| CN1218484A (en) | Process for making high-performance polytherester resins and thermosets | |
| CN1194039C (en) | Low-smoothness additive for saturated polyester resin and method for preparing same | |
| JPH02185510A (en) | Castable resin blend containing terephthalic acid | |
| CN1787911B (en) | Polyester-based dimethacrylates designed for laminating applications. | |
| CN101200537A (en) | Thermoplastic composite material and preparation method thereof | |
| Kandelbauer et al. | Handbook of thermoset plastics: 6. Unsaturated polyesters and vinyl esters | |
| WO1995009202A1 (en) | Additives to improve surface characteristics of unsaturated polyester molding composition | |
| NL1002080C2 (en) | Low mol.wt. unsatd. polyester resin compsn. for a sheet moulding cpd. | |
| EP3814408A1 (en) | Aluminum organic thickeners for thermoset resins | |
| CN106832843A (en) | A kind of polyester 3D printing material of low melting point and preparation method thereof | |
| JPH06316611A (en) | Thermosetting resin composition and its curing method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| ASS | Succession or assignment of patent right |
Owner name: ASHLAND LICENSING AND INTELLECTUAL PROPERTY LTD. Free format text: FORMER OWNER: ASHLAND INC. Effective date: 20060818 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| C56 | Change in the name or address of the patentee | ||
| CP03 | Change of name, title or address |
Address after: Ohio, USA Patentee after: ASHLAND Inc. Address before: American Kentucky Patentee before: Ashland Inc. |
|
| TR01 | Transfer of patent right |
Effective date of registration: 20060818 Address after: Ohio, USA Patentee after: ASHLAND LICENSING AND INTELLECTUAL PROPERTY LLC Address before: American Ohio Patentee before: Ashland Inc. |
|
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20011205 Termination date: 20160203 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |