CN102093673A - Polyester having thermal ageing resistant performance and production method thereof - Google Patents
Polyester having thermal ageing resistant performance and production method thereof Download PDFInfo
- Publication number
- CN102093673A CN102093673A CN2011100200856A CN201110020085A CN102093673A CN 102093673 A CN102093673 A CN 102093673A CN 2011100200856 A CN2011100200856 A CN 2011100200856A CN 201110020085 A CN201110020085 A CN 201110020085A CN 102093673 A CN102093673 A CN 102093673A
- Authority
- CN
- China
- Prior art keywords
- polyester
- resistant
- oxidation inhibitor
- toughner
- thermal aging
- 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
- 229920000728 polyester Polymers 0.000 title claims abstract description 43
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 230000032683 aging Effects 0.000 title abstract description 14
- 229920001169 thermoplastic Polymers 0.000 claims abstract description 10
- 239000004416 thermosoftening plastic Substances 0.000 claims abstract description 10
- -1 polyethylene terephthalate Polymers 0.000 claims description 43
- 239000003112 inhibitor Substances 0.000 claims description 34
- 230000003647 oxidation Effects 0.000 claims description 30
- 238000007254 oxidation reaction Methods 0.000 claims description 30
- 239000000463 material Substances 0.000 claims description 27
- 239000003063 flame retardant Substances 0.000 claims description 22
- 239000003963 antioxidant agent Substances 0.000 claims description 20
- 230000003078 antioxidant effect Effects 0.000 claims description 20
- 239000003381 stabilizer Substances 0.000 claims description 20
- 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 description 17
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 17
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 17
- 238000003878 thermal aging Methods 0.000 claims description 17
- 230000000979 retarding effect Effects 0.000 claims description 14
- 239000012752 auxiliary agent Substances 0.000 claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000005893 bromination reaction Methods 0.000 claims description 12
- 239000003365 glass fiber Substances 0.000 claims description 12
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 10
- 239000011521 glass Substances 0.000 claims description 10
- 230000031709 bromination Effects 0.000 claims description 9
- 229920001707 polybutylene terephthalate Polymers 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 9
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 7
- 229920000092 linear low density polyethylene Polymers 0.000 claims description 7
- 239000004707 linear low-density polyethylene Substances 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 239000004793 Polystyrene Substances 0.000 claims description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 6
- 229910052787 antimony Inorganic materials 0.000 claims description 6
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 150000002148 esters Chemical class 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 229920002223 polystyrene Polymers 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 125000002252 acyl group Chemical group 0.000 claims description 4
- 239000000314 lubricant Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 229920002215 polytrimethylene terephthalate Polymers 0.000 claims description 4
- 230000003068 static effect Effects 0.000 claims description 4
- ZITDOJMAOFWSQI-UHFFFAOYSA-N 4-(2,3,4-tribromophenoxy)triazine Chemical compound BrC1=C(Br)C(Br)=CC=C1OC1=CC=NN=N1 ZITDOJMAOFWSQI-UHFFFAOYSA-N 0.000 claims description 3
- 239000005995 Aluminium silicate Substances 0.000 claims description 3
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 3
- 239000004593 Epoxy Substances 0.000 claims description 3
- 239000005977 Ethylene Substances 0.000 claims description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 3
- 229920000265 Polyparaphenylene Polymers 0.000 claims description 3
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 3
- 229910021536 Zeolite Inorganic materials 0.000 claims description 3
- 239000005083 Zinc sulfide Substances 0.000 claims description 3
- 235000012211 aluminium silicate Nutrition 0.000 claims description 3
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 3
- 239000004917 carbon fiber Substances 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- 239000004927 clay Substances 0.000 claims description 3
- 229910052570 clay Inorganic materials 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 229920001577 copolymer Polymers 0.000 claims description 3
- 238000013461 design Methods 0.000 claims description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 3
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 230000036571 hydration Effects 0.000 claims description 3
- 238000006703 hydration reaction Methods 0.000 claims description 3
- 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 3
- 235000012204 lemonade/lime carbonate Nutrition 0.000 claims description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 3
- 239000010445 mica Substances 0.000 claims description 3
- 229910052618 mica group Inorganic materials 0.000 claims description 3
- 238000012856 packing Methods 0.000 claims description 3
- 238000005453 pelletization Methods 0.000 claims description 3
- 239000002530 phenolic antioxidant Substances 0.000 claims description 3
- 150000008301 phosphite esters Chemical group 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 239000010453 quartz Substances 0.000 claims description 3
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 3
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 3
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 3
- 150000007970 thio esters Chemical class 0.000 claims description 3
- NSBGJRFJIJFMGW-UHFFFAOYSA-N trisodium;stiborate Chemical compound [Na+].[Na+].[Na+].[O-][Sb]([O-])([O-])=O NSBGJRFJIJFMGW-UHFFFAOYSA-N 0.000 claims description 3
- 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 claims description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 3
- 229920002554 vinyl polymer Polymers 0.000 claims description 3
- 239000010456 wollastonite Substances 0.000 claims description 3
- 229910052882 wollastonite Inorganic materials 0.000 claims description 3
- 239000010457 zeolite Substances 0.000 claims description 3
- 239000011787 zinc oxide Substances 0.000 claims description 3
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 claims description 3
- 125000005543 phthalimide group Chemical class 0.000 claims description 2
- 239000000945 filler Substances 0.000 abstract 1
- 239000012760 heat stabilizer Substances 0.000 abstract 1
- 239000000126 substance Substances 0.000 description 16
- 229920003023 plastic Polymers 0.000 description 6
- 239000004033 plastic Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 5
- 230000015556 catabolic process Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 230000003245 working effect Effects 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- PWWSSIYVTQUJQQ-UHFFFAOYSA-N distearyl thiodipropionate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCCCCCCC PWWSSIYVTQUJQQ-UHFFFAOYSA-N 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- GXURZKWLMYOCDX-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol;dihydroxyphosphanyl dihydrogen phosphite Chemical class OP(O)OP(O)O.OCC(CO)(CO)CO GXURZKWLMYOCDX-UHFFFAOYSA-N 0.000 description 2
- QLZJUIZVJLSNDD-UHFFFAOYSA-N 2-(2-methylidenebutanoyloxy)ethyl 2-methylidenebutanoate Chemical compound CCC(=C)C(=O)OCCOC(=O)C(=C)CC QLZJUIZVJLSNDD-UHFFFAOYSA-N 0.000 description 2
- QYMGIIIPAFAFRX-UHFFFAOYSA-N butyl prop-2-enoate;ethene Chemical compound C=C.CCCCOC(=O)C=C QYMGIIIPAFAFRX-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 229920006245 ethylene-butyl acrylate Polymers 0.000 description 2
- 229920006244 ethylene-ethyl acrylate Polymers 0.000 description 2
- 239000005042 ethylene-ethyl acrylate Substances 0.000 description 2
- 229920006225 ethylene-methyl acrylate Polymers 0.000 description 2
- 239000005043 ethylene-methyl acrylate Substances 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 2
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 1
- NYTIGAIUQKZUHK-UHFFFAOYSA-N 2,6-ditert-butylphenol;propanamide Chemical compound CCC(N)=O.CC(C)(C)C1=CC=CC(C(C)(C)C)=C1O NYTIGAIUQKZUHK-UHFFFAOYSA-N 0.000 description 1
- QRFTXHFUNIFHST-UHFFFAOYSA-N 4,5,6,7-tetrabromoisoindole-1,3-dione Chemical compound BrC1=C(Br)C(Br)=C2C(=O)NC(=O)C2=C1Br QRFTXHFUNIFHST-UHFFFAOYSA-N 0.000 description 1
- VSAWBBYYMBQKIK-UHFFFAOYSA-N 4-[[3,5-bis[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]-2,4,6-trimethylphenyl]methyl]-2,6-ditert-butylphenol Chemical compound CC1=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C1CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 VSAWBBYYMBQKIK-UHFFFAOYSA-N 0.000 description 1
- ZAAQJFLUOUQAOG-UHFFFAOYSA-N 4-benzyl-2,6-ditert-butylphenol Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CC=2C=CC=CC=2)=C1 ZAAQJFLUOUQAOG-UHFFFAOYSA-N 0.000 description 1
- 206010009866 Cold sweat Diseases 0.000 description 1
- GHKOFFNLGXMVNJ-UHFFFAOYSA-N Didodecyl thiobispropanoate Chemical compound CCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCC GHKOFFNLGXMVNJ-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 241001075561 Fioria Species 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229920000426 Microplastic Polymers 0.000 description 1
- GQJDFTIOKVGUOF-UHFFFAOYSA-N OP(O)OP(O)O.C(C)(C)(C)C1=C(C=CC(=C1)C(C)(C)C)C(O)C(CO)(CO)CO Chemical class OP(O)OP(O)O.C(C)(C)(C)C1=C(C=CC(=C1)C(C)(C)C)C(O)C(CO)(CO)CO GQJDFTIOKVGUOF-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000004378 air conditioning Methods 0.000 description 1
- 239000002216 antistatic agent Substances 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
- 230000008859 change Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000006253 efflorescence Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- KWUZCAVKPCRJPO-UHFFFAOYSA-N n-ethyl-4-(6-methyl-1,3-benzothiazol-2-yl)aniline Chemical compound C1=CC(NCC)=CC=C1C1=NC2=CC=C(C)C=C2S1 KWUZCAVKPCRJPO-UHFFFAOYSA-N 0.000 description 1
- UTOPWMOLSKOLTQ-UHFFFAOYSA-M octacosanoate Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCC([O-])=O UTOPWMOLSKOLTQ-UHFFFAOYSA-M 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 125000001501 propionyl group Chemical group O=C([*])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000001012 protector Effects 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 206010037844 rash Diseases 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000035807 sensation Effects 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- LVEOKSIILWWVEO-UHFFFAOYSA-N tetradecyl 3-(3-oxo-3-tetradecoxypropyl)sulfanylpropanoate Chemical compound CCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCCC LVEOKSIILWWVEO-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
- B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/9258—Velocity
- B29C2948/9259—Angular velocity
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
- B29C2948/92885—Screw or gear
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses polyester having thermal ageing resistant performance, which comprises a thermoplastic polyester, a flexibilizer, antioxygen, a heat stabilizer, a filler and other assistant. The product has high thermal ageing resistant performance and high flame-retarding performance.
Description
Technical field
The present invention relates to a kind of polyester and production method thereof.
Background technology
Strengthening fire-retardant (not fire-retardant) polyester and be widely used in electronics, electrical equipment and automobile industry because of its favorable mechanical performance and electric property, is the employed ideal material of component of these industries.As everyone knows, plastics are that a kind of ratio is easier to the aged material, and in use, the quality of plastic part and work-ing life and plastic ageing have confidential relation, and in the time of aging the generation, its performance can degenerate gradually, until final forfeiture use value.Plastic ageing mainly shows as following several form, as chap, be clamminess, harden, soften, efflorescence, variable color, mildew etc.In the middle of daily life, strengthen fire-retardant (not fire-retardant) polyester material because the heat and the effect of oxygen to work-ing life of material playing critical effect, so prevent that plastic degradation that heat, oxygen association response are caused from just becoming and are even more important.
Strengthen flame retardant polyester at electronics; electrical apparatus industry and automobile industry can be used for electronic connector; the air-conditioning terminal strip; breaker protector; rly.; electrical condenser; coil rack; telephone socket; safety box; contactor; potentiometer; the tuner shell; junctor; transmitter; automobile ignition coil; the fan leaf; the electric iron parts; micromachine case etc.; reinforced polyester can be used for collision bumper in automobile industry; wiper; automobile handle; car light framework or the like; these fields are to all there being working life of material certain requirement; the aging resistance of material is good more; the working life that means material is long more; in the middle of U.S. UL product certification system, the RTI index has been proposed; being the relatively hot ageing index, is that the simulation material is at a certain temperature through the degradation degree of the action material of overheated and oxygen.Its index default value of polyester (PBT) is 75 ℃, reaches as high as 140 ℃ through the RTI value that promotes back polyester (PBT).Its method is that the plastic material high temperature (150 ℃-200 ℃) with different temperature points in the middle of the baking oven of fixed temperature and humidity after the sample preparation toasts experiment, in for some time, take out the variation of its intensity of test, experiment can be at short notice as was inferred the changing value of material property after 10 years in 1 year with interior method with mathematics, the RTI value is high more, the ageing resistance of illustrative material is good more, and every performance index of material descend slowly more.
Summary of the invention
The object of the present invention is to provide a kind of resistance to thermooxidation good, the polyester with resistant to thermal aging performance and the production method thereof that can prolong the work-ing life of material.
Technical solution of the present invention is:
A kind of polyester with resistant to thermal aging performance is characterized in that: in parts by weight, comprise following component:
130 parts of thermoplastic polyesters
Toughner 0-60 part
Oxidation inhibitor 0.05-3.0 part
Thermo-stabilizer 0.05-6.0 part
Weighting agent 0-300 part
Other auxiliary agent 0-12 part.
Spendable in the present invention exemplary polyester comprises, but be not limited in the middle of the polyethylene terephthalate (PET), poly terephthalic acid 1,4 butanediol ester (PBT), PEN (PEN), PBN (PBN), polytrimethylene terephthalate (PPT) one or more.
Spendable in the present invention toughner is that ethene and ethene copolymer (include but not limited to LLDPE, LDPE, HDPE, POE, ethylene-methyl acrylate (EMA), ethylene-ethyl acrylate (EEA), ethylene-butyl acrylate (EBA), ethylene-vinyl acetate (EVA)), vinyl grafting body (maleic anhydride graft or acrylic acid-grafted, include but not limited to POE-g-MAH, PE-g-MAH, ethylene-propylene maleic anhydride grafts or the like), ethylene-acrylate-glycidyl methacrylate (includes but not limited to EMA-GMA, EEA-GMA, one or more among the EBA-GMA).
Spendable in the present invention primary antioxidant is a phenolic antioxidant, includes but not limited to that the antioxidant 1010 chemical name is four (β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester, oxidation inhibitor 245 chemical names are the two β of triglycol-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic ester, oxidation inhibitor 1098 chemical names are N, N '-hexa-methylene two (3,5-di-t-butyl-4-hydroxybenzene propionic acid amide), oxidation inhibitor 1790 chemical names are 1,3,5-(three (the 4-tertiary butyls-3-hydroxyl-2,6-dimethyl benzene methyl)-1,3,5-triazine-2,4,6-(1H, 3H, 5H)-triketone, the antioxidant 3114 chemical name is 1,3,5-(three (3, the 5-di-tert-butyl-4-hydroxyl benzyl)-1,3,5-triazine-2,4,6-(1H, 3H, 5H)-triketone, the antioxidant 330 chemical name is 1.3.5-trimethylammonium-2.4.6-three (3.5-di-tert-butyl-4-hydroxyl benzyl) benzene, and oxidation inhibitor 1024 chemical names are 1, and 2-two (3, the 5-di-tert-butyl-hydroxy phenyl) propionyl, oxidation inhibitor BRUGGOLEN H12.
Spendable in the present invention assisted class oxidation inhibitor is phosphite ester kind antioxidant.Oxidation inhibitor 626 chemical names are two (3, the 5-di-tert-butyl-phenyl) pentaerythritol diphosphites, oxidation inhibitor 627/627A is two (2.4-di-tert-butyl-phenyl) pentaerythritol diphosphites, and oxidation inhibitor P-EPQ chemical name is four (2, the 4-di-tert-butyl-phenyl) 4,4 '-the xenyl bis-phosphite, oxidation inhibitor 168 chemical names are three (2,4 di-t-butyl) phosphorous acid ester, oxidation inhibitor S9228 chemical name two (2,4-two cruel bases) pentaerythritol diphosphites, oxidation inhibitor BRUGGOLEN H12.。
Spendable in the present invention thermo-stabilizer is thioesters type thermal stabilizing agent such as DLTDP chemical name 3,3 '-Tyox B, DSTDP chemical name 3,3 '-thio-2 acid ester in February acyl, two 14 esters of DMTDP chemical name thio-2 acid.
Spendable in the present invention filling modifying agent includes but not limited to one or more in glass fibre, glass microballon, carbon fiber, wollastonite, clay, zeolite, quartz, diatomite, silicon carbide, silicon oxide, mica, kaolin, calcium sulfate, barium sulfate, lime carbonate, talcum powder, Calucium Silicate powder, zinc oxide, zinc sulphide, the whisker etc.
Spendable in the present invention other auxiliary agent includes but not limited to one or more in lubricant, anti-dripping agent (tetrafluoroethylene, i.e. 4F), static inhibitor, the tinting material etc.
Described polyester with resistant to thermal aging performance also comprises following components in part by weight:
Main flame retardant 12-65 part
Fire retarding synergist 4-22 part;
Spendable in the present invention main flame retardant is that bromination epoxy, TDE (are called for short DBDPE, molecular formula C
14H
4Br
10), the poly-carbon of bromination, brominated polyphenylene, brominated polystyrene, three (tribromophenoxy) triazine (molecular formula C
21H
6Br
9N
3O
3), two tetrabromo phthalimide (the molecular formula C of ethylene
18H
4O
4N
2Br
8), in the poly-bromination pentabromobenzyl ester one or more.
Spendable in the present invention fire retarding synergist is the compound of antimonous oxide, sodium antimonate, antimony peroxide, antimony organic class, in the hydration zinc borate one or more.
Described polyester with resistant to thermal aging performance in parts by weight, comprises following component:
100 parts of polybutylene terephthalates
Polyethylene terephthalate 0-20 part
Main flame retardant 14-48 part
Fire retarding synergist 5-17 part
Toughner 1-16 part
Oxidation inhibitor 0.05-1.0 part
Thermo-stabilizer 0.05-2.0 part
Weighting agent 0-115 part
Other auxiliary agent 0.05-4.0 part;
Spendable in the present invention exemplary polyester comprises polybutylene terephthalate, is called for short PBT, and its density is 1.31-1.35g/cm
3, viscosity is 0.7-1.2dl/g, melt temperature 220-230 ℃.Polyethylene terephthalate is called for short PET, and its relative density is 1.38g/cm
3
Spendable in the present invention main flame retardant is a kind of in poly-carbon (as the BC-58 of U.S. Chemtura Corporation) of bromination and the brominated polystyrene (as the FR621 of U.S. Albemarle Corporation) or two kinds.
Spendable in the present invention fire retarding synergist is an antimonous oxide.
Spendable in the present invention toughner is LLDPE (linear low density polyethylene) or DUPONT company 4170 (EBA-GMA).。
Spendable in the present invention oxidation inhibitor is the blend of primary antioxidant and assisted class oxidation inhibitor, and trade name is the oxidation inhibitor BRUGGOLENH12 that BRUGGEMANN CHEMICAL company produces.
Spendable in the present invention thermo-stabilizer is a DSTDP chemical name 3,3 '-thio-2 acid ester in February acyl.
Spendable in the present invention glass fiber diameter is the 5-20 micron, and the glass through compound silane coupling agent is handled only refers to short glass fiber, as U.S. PPG company 3786 short fibers.
Toughner can be to use DUPONT company 4170 or PT862 separately, or with LLDPE and DUPONT company 4170 or the composite use of PT862.
Spendable in the present invention other auxiliary agent includes but not limited to lubricant (calcium stearate, montanate, illiteracy dawn ester, pentaerythritol ester, oxidized polyethlene wax etc.) anti-dripping agent (tetrafluoroethylene, be 4F), in static inhibitor (polyvalent alcohol, polyol ester such as Zerol, non-ionic antistatic agents such as sorbitan mono fatty acid ester), tinting material (pigment, dyestuff, white dyes etc.) etc. one or more.
A kind of production method with polyester of resistant to thermal aging performance, it is characterized in that: with thermoplastic polyester, toughner, oxidation inhibitor, thermo-stabilizer, other auxiliary agent set of dispense ratio by weight, after in the high speed blender, mixing, send in the main feeding in the twin screw extruder, the glass/glass fiber adds in the side direction feeding subsequently, through extrude, cooling, pelletizing, drying, packing and make.
When in the high speed blender, mixing, also add main flame retardant and fire retarding synergist is mixed together.
The length-to-diameter ratio of twin screw extruder screw rod is 25-50: 1, and the screw rod design temperature is 180-245 ℃, screw speed is set at 200-600 rev/min.
The present invention has following several characteristics
1, has excellent resistant to thermal aging performance.
Can still keep later the over half of starting material mechanical property and electrical property, long service life, ageing-resistant performance excellence the work-ing life of the utilization polyester material that the present invention produced in 10 years.Realize that in the present invention this function mainly is to pass through the following aspects:
(I) synergy of primary antioxidant, auxiliary antioxidant and thermo-stabilizer.Primary antioxidant and auxiliary antioxidant provide the ageing-resistant performance of material under normal temps, can eliminate the free radical that material is in use produced rapidly, long-acting good stability, and material thermostable effect has at high temperature been strengthened in the utilization of thermo-stabilizer DSTP.
(II) selection of resin and glass.The present invention has selected to have the vibrin than low terminal carboxy content≤20meq/kg, has alleviated because of the too high Degradation to material of content of carboxyl end group, has protected matrix resin.Selected the short fiber product based on PPG3786, the content for the treatment of compound and long fibre have significantly differently in the short fiber, and the bonding properties of itself and base resin is better, is difficult for taking place aging in the middle of the life-time service process.
(III) interpolation of a small amount of polyethylene terephthalate (PET) and barium sulfate.Add a spot of polyethylene terephthalate (PET) and barium sulfate the ageing resistance of material body has been played strengthening effect.
2, has good flame retardancy.The flame retardant rating of the utilization enhancing flame-retardant polyester material that the present invention produced is a 0.4mm UL94V-0 level.Can make the thick product of 0.4mm reach fire-retardant requirement, use this material can prepare aging-resistant electronics thin-walled, high temperature resistant, electric equipment products.
The invention will be further described below in conjunction with embodiment.
Embodiment
With thermoplastic polyester, toughner, oxidation inhibitor, thermo-stabilizer, other auxiliary agent set of dispense ratio by weight, after in the high speed blender, mixing, send in the main feeding in the twin screw extruder, the glass/glass fiber adds in the side direction feeding subsequently, through extrude, cooling, pelletizing, drying, packing and make.
When in the high speed blender, mixing, also main flame retardant can be added and fire retarding synergist is mixed together.
The length-to-diameter ratio of twin screw extruder screw rod is 25-50: 1, and the screw rod design temperature is 180-245 ℃, screw speed is set at 200-600 rev/min.
Each amounts of components of specific embodiment 1-6 and comparative example sees Table (consumption is a weight part in the table).
Experimental technique:
Plastic pellet is made the batten that to survey tensile strength, electric breakdown strength, simply supported beam unnotched impact strength, every six roots of sensation batten is one group, measure initial value earlier, then with all battens in the baking oven of fixed temperature and humidity, the consistence of all temperature in the maintenance baking oven, under being 200 ℃ condition, oven temperature carries out the relatively hot weathering test then, regularly the changing value of (about about 15 days) every performance index of test material.
The product test performance is as shown in the table:
The product test performance is as shown in the table:
Consumption of the foregoing description and component can change, as:
In parts by weight, comprise following component:
130 parts of thermoplastic polyesters
Toughner 0-60 part (example 1,30,60)
Oxidation inhibitor 0.05-3.0 part (example 0.1,2,3)
Thermo-stabilizer 0.05-6.0 part (example 0.1,3,6)
Weighting agent 0-300 part (example 1,150,300)
Other auxiliary agent 0-12 part (example 1,6,12).
Described thermoplastic polyester is one or more in polyethylene terephthalate, poly terephthalic acid 1,4 butanediol ester, PEN, PBN, the polytrimethylene terephthalate;
Described toughner is one or more in ethene, ethene copolymer, vinyl grafting body, the ethylene-acrylate-glycidyl methacrylate;
Described oxidation inhibitor comprises primary antioxidant, auxiliary antioxidant; Primary antioxidant is a phenolic antioxidant; Auxiliary antioxidant is a phosphite ester kind antioxidant;
Described thermo-stabilizer is the thioesters type thermal stabilizing agent.
Filling modifying agent is one or more in glass fibre, glass microballon, carbon fiber, wollastonite, clay, zeolite, quartz, diatomite, silicon carbide, silicon oxide, mica, kaolin, calcium sulfate, barium sulfate, lime carbonate, talcum powder, Calucium Silicate powder, zinc oxide, zinc sulphide, the whisker;
Other auxiliary agent is one or more in lubricant, anti-dripping agent, static inhibitor, the tinting material.
Also can comprise following components in part by weight:
Main flame retardant 12-65 part (example 15,30,60)
Fire retarding synergist 4-22 part (example 5,15,22);
Described main flame retardant is one or more in bromination epoxy, TDE, the poly-carbon of bromination, brominated polyphenylene, brominated polystyrene, three (tribromophenoxy) triazine, the two tetrabromo phthalimides of ethylene, the poly-bromination pentabromobenzyl ester.
Fire retarding synergist is the compound of antimonous oxide, sodium antimonate, antimony peroxide, antimony organic class, in the hydration zinc borate one or more.
Claims (10)
1. polyester with resistant to thermal aging performance is characterized in that: in parts by weight, comprise following component:
130 parts of thermoplastic polyesters
Toughner 0-60 part
Oxidation inhibitor 0.05-3.0 part
Thermo-stabilizer 0.05-6.0 part
Weighting agent 0-300 part
Other auxiliary agent 0-12 part.
2. the polyester with resistant to thermal aging performance according to claim 1, it is characterized in that: described thermoplastic polyester is one or more in polyethylene terephthalate, poly terephthalic acid 1,4 butanediol ester, PEN, PBN, the polytrimethylene terephthalate;
Described toughner is one or more in ethene, ethene copolymer, vinyl grafting body, the ethylene-acrylate-glycidyl methacrylate;
Described oxidation inhibitor comprises primary antioxidant, auxiliary antioxidant; Primary antioxidant is a phenolic antioxidant; Auxiliary antioxidant is a phosphite ester kind antioxidant;
Described thermo-stabilizer is the thioesters type thermal stabilizing agent;
Filling modifying agent is one or more in glass fibre, glass microballon, carbon fiber, wollastonite, clay, zeolite, quartz, diatomite, silicon carbide, silicon oxide, mica, kaolin, calcium sulfate, barium sulfate, lime carbonate, talcum powder, Calucium Silicate powder, zinc oxide, zinc sulphide, the whisker;
Other auxiliary agent is one or more in lubricant, anti-dripping agent, static inhibitor, the tinting material.
3. the polyester with resistant to thermal aging performance according to claim 1 and 2 is characterized in that: also comprise following components in part by weight:
Main flame retardant 12-65 part
Fire retarding synergist 4-22 part;
Described main flame retardant is one or more in bromination epoxy, TDE, the poly-carbon of bromination, brominated polyphenylene, brominated polystyrene, three (tribromophenoxy) triazine, the two tetrabromo phthalimides of ethylene, the poly-bromination pentabromobenzyl ester;
Fire retarding synergist is the compound of antimonous oxide, sodium antimonate, antimony peroxide, antimony organic class, in the hydration zinc borate one or more.
4. the polyester with resistant to thermal aging performance according to claim 1 and 2 is characterized in that: in parts by weight, comprise following component:
100 parts of polybutylene terephthalates
Polyethylene terephthalate 0-20 part
Main flame retardant 14-48 part
Fire retarding synergist 5-17 part
Toughner 1-16 part
Oxidation inhibitor 0.05-1.0 part
Thermo-stabilizer 0.05-2.0 part
Weighting agent 0-115 part
Other auxiliary agent 0.05-4.0 part;
Polyester is polybutylene terephthalate or polyethylene terephthalate; Polybutylene terephthalate density is 1.31-1.35g/cm
3, viscosity is 0.7-1.2dl/g, melt temperature 220-230 ℃; The relative density of polyester polyethylene terephthalate is 1.38g/cm
3
Main flame retardant is a kind of in the poly-carbon of bromination, the brominated polystyrene or two kinds;
Fire retarding synergist is an antimonous oxide;
Toughner is 4170 of LLDPE or DUPONT company;
Oxidation inhibitor is the blend of primary antioxidant and assisted class oxidation inhibitor;
Thermo-stabilizer is 3,3
,-thio-2 acid ester in February acyl;
Glass fiber diameter is the 5-20 micron, is the glass of handling through compound silane coupling agent, is short glass fiber.
5. the polyester with resistant to thermal aging performance according to claim 1 and 2 is characterized in that: in parts by weight, comprise following component:
100 parts of polybutylene terephthalates
Polyethylene terephthalate) 0-20 part
Toughner 0-11 part
Oxidation inhibitor 0.05-1.0 part
Thermo-stabilizer 0.05-2.0 part
Weighting agent 0-75 part
Other auxiliary agent 0-1.7 part;
Polyester is polybutylene terephthalate or polyethylene terephthalate; Polybutylene terephthalate density is 1.31-1.35g/cm
3, viscosity is 0.7-1.2dl/g, melt temperature 220-230 ℃; The relative density of polyester polyethylene terephthalate is 1.38g/cm
3
Main flame retardant is a kind of in the poly-carbon of bromination, the brominated polystyrene or two kinds;
Fire retarding synergist is an antimonous oxide;
Toughner is 4170 of LLDPE or DUPONT company;
Oxidation inhibitor is the blend of primary antioxidant and assisted class oxidation inhibitor;
Thermo-stabilizer is 3,3
,-thio-2 acid ester in February acyl;
Glass fiber diameter is the 5-20 micron, is the glass of handling through compound silane coupling agent, is short glass fiber.
6. the polyester with resistant to thermal aging performance according to claim 1 and 2 is characterized in that: described thermoplastic polyester is a polybutylene terephthalate, and its viscosity is 0.90-1.1dl/g, content of carboxyl end group≤20 meq/kg.
7. the polyester with resistant to thermal aging performance according to claim 1 and 2 is characterized in that: toughner is DUPONT company 4170, or the mixture of LLDPE and DUPONT company 4170.
8. described production method of claim 1 with polyester of resistant to thermal aging performance, it is characterized in that: with thermoplastic polyester, toughner, oxidation inhibitor, thermo-stabilizer, other auxiliary agent set of dispense ratio by weight, after in the high speed blender, mixing, send in the main feeding in the twin screw extruder, the glass/glass fiber adds in the side direction feeding subsequently, through extrude, cooling, pelletizing, drying, packing and make.
9. the production method with polyester of resistant to thermal aging performance according to claim 8 is characterized in that: when mixing in the high speed blender, also add main flame retardant and fire retarding synergist is mixed together.
10. according to Claim 8 or 9 described production methods with polyester of resistant to thermal aging performance, it is characterized in that: the length-to-diameter ratio of twin screw extruder screw rod is 25-50:1, and the screw rod design temperature is 180-245 ℃, and screw speed is set at 200-600 rev/min.
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Effective date of registration: 20170523 Address after: 523000 Guangdong Province, Dongguan City Dongcheng Street Xiakou Road No. 9 Patentee after: DONGGUAN DONGXIANG PLASTIC Co.,Ltd. Address before: 226000, No. 2, long shore road, Gangzha District, Nantong, Jiangsu, Dongxiang Patentee before: NANTONG DONGFANG PLASTIC Co.,Ltd. |
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