WO2000015717A1 - Compositions de polyester renfermant un agent antichoc - Google Patents
Compositions de polyester renfermant un agent antichoc Download PDFInfo
- Publication number
- WO2000015717A1 WO2000015717A1 PCT/US1999/021169 US9921169W WO0015717A1 WO 2000015717 A1 WO2000015717 A1 WO 2000015717A1 US 9921169 W US9921169 W US 9921169W WO 0015717 A1 WO0015717 A1 WO 0015717A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- residues
- weight percent
- polyester
- ethylene
- epoxy
- Prior art date
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- 229920000728 polyester Polymers 0.000 title claims abstract description 129
- 239000000203 mixture Substances 0.000 title claims abstract description 99
- 239000004609 Impact Modifier Substances 0.000 title abstract description 80
- -1 phosphorus compound Chemical class 0.000 claims abstract description 53
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 37
- 239000011574 phosphorus Substances 0.000 claims abstract description 37
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 35
- 239000004593 Epoxy Substances 0.000 claims abstract description 30
- KKEYFWRCBNTPAC-UHFFFAOYSA-N terephthalic acid group Chemical group C(C1=CC=C(C(=O)O)C=C1)(=O)O KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 16
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical group OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052751 metal Inorganic materials 0.000 claims abstract description 11
- 239000002184 metal Substances 0.000 claims abstract description 11
- 150000002009 diols Chemical group 0.000 claims abstract description 9
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical group C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 claims abstract description 9
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 32
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical group C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 28
- 239000005977 Ethylene Substances 0.000 claims description 28
- 229920001897 terpolymer Polymers 0.000 claims description 26
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 22
- 229920001577 copolymer Polymers 0.000 claims description 20
- 229920000642 polymer Polymers 0.000 claims description 20
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- 239000000178 monomer Substances 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 claims description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- GXBYFVGCMPJVJX-UHFFFAOYSA-N Epoxybutene Chemical compound C=CC1CO1 GXBYFVGCMPJVJX-UHFFFAOYSA-N 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229920001169 thermoplastic Polymers 0.000 claims description 6
- 239000004416 thermosoftening plastic Substances 0.000 claims description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 claims description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 3
- 101000623895 Bos taurus Mucin-15 Proteins 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 4
- LLLVZDVNHNWSDS-UHFFFAOYSA-N 4-methylidene-3,5-dioxabicyclo[5.2.2]undeca-1(9),7,10-triene-2,6-dione Chemical compound C1(C2=CC=C(C(=O)OC(=C)O1)C=C2)=O LLLVZDVNHNWSDS-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 238000001746 injection moulding Methods 0.000 abstract description 3
- 239000003054 catalyst Substances 0.000 description 30
- 229920000139 polyethylene terephthalate Polymers 0.000 description 25
- 239000005020 polyethylene terephthalate Substances 0.000 description 25
- 239000002245 particle Substances 0.000 description 19
- 238000006243 chemical reaction Methods 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 15
- 239000011159 matrix material Substances 0.000 description 14
- 238000004627 transmission electron microscopy Methods 0.000 description 12
- 150000003018 phosphorus compounds Chemical class 0.000 description 11
- 229920000573 polyethylene Polymers 0.000 description 10
- 125000000524 functional group Chemical group 0.000 description 9
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 8
- 238000013329 compounding Methods 0.000 description 8
- 229920001971 elastomer Polymers 0.000 description 8
- RGASRBUYZODJTG-UHFFFAOYSA-N 1,1-bis(2,4-ditert-butylphenyl)-2,2-bis(hydroxymethyl)propane-1,3-diol dihydroxyphosphanyl dihydrogen phosphite Chemical compound OP(O)OP(O)O.C(C)(C)(C)C1=C(C=CC(=C1)C(C)(C)C)C(O)(C(CO)(CO)CO)C1=C(C=C(C=C1)C(C)(C)C)C(C)(C)C RGASRBUYZODJTG-UHFFFAOYSA-N 0.000 description 7
- 239000011258 core-shell material Substances 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 6
- 125000005250 alkyl acrylate group Chemical group 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- AIBRSVLEQRWAEG-UHFFFAOYSA-N 3,9-bis(2,4-ditert-butylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP1OCC2(COP(OC=3C(=CC(=CC=3)C(C)(C)C)C(C)(C)C)OC2)CO1 AIBRSVLEQRWAEG-UHFFFAOYSA-N 0.000 description 5
- 239000004698 Polyethylene Substances 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 239000000806 elastomer Substances 0.000 description 5
- 229920001038 ethylene copolymer Polymers 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 238000004626 scanning electron microscopy Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 4
- 239000002174 Styrene-butadiene Substances 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- JVLRYPRBKSMEBF-UHFFFAOYSA-K diacetyloxystibanyl acetate Chemical compound [Sb+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JVLRYPRBKSMEBF-UHFFFAOYSA-K 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 4
- 239000000155 melt Substances 0.000 description 4
- 229920003048 styrene butadiene rubber Polymers 0.000 description 4
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical group OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 3
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- CGPRUXZTHGTMKW-UHFFFAOYSA-N ethene;ethyl prop-2-enoate Chemical compound C=C.CCOC(=O)C=C CGPRUXZTHGTMKW-UHFFFAOYSA-N 0.000 description 3
- 238000010128 melt processing Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 229920001778 nylon Polymers 0.000 description 3
- 229920000515 polycarbonate Polymers 0.000 description 3
- 239000004417 polycarbonate Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000005060 rubber Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229920002943 EPDM rubber Polymers 0.000 description 2
- 244000043261 Hevea brasiliensis Species 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- 229920000459 Nitrile rubber Polymers 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 229920000147 Styrene maleic anhydride Polymers 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 150000001463 antimony compounds Chemical class 0.000 description 2
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 230000001627 detrimental effect Effects 0.000 description 2
- YLFBFPXKTIQSSY-UHFFFAOYSA-N dimethoxy(oxo)phosphanium Chemical compound CO[P+](=O)OC YLFBFPXKTIQSSY-UHFFFAOYSA-N 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 230000002779 inactivation Effects 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229920003052 natural elastomer Polymers 0.000 description 2
- 229920001194 natural rubber Polymers 0.000 description 2
- 150000002903 organophosphorus compounds Chemical class 0.000 description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 150000003003 phosphines Chemical class 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 229920001195 polyisoprene Polymers 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- 229920002379 silicone rubber Polymers 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000011115 styrene butadiene Substances 0.000 description 2
- 238000003856 thermoforming Methods 0.000 description 2
- 238000005809 transesterification reaction Methods 0.000 description 2
- 229910000391 tricalcium phosphate Inorganic materials 0.000 description 2
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- 229940035437 1,3-propanediol Drugs 0.000 description 1
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 1
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 1
- FQXGHZNSUOHCLO-UHFFFAOYSA-N 2,2,4,4-tetramethyl-1,3-cyclobutanediol Chemical compound CC1(C)C(O)C(C)(C)C1O FQXGHZNSUOHCLO-UHFFFAOYSA-N 0.000 description 1
- OCSIKZYSDOXRPA-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)-3-octadecylhenicosane-1,3-diol dihydroxyphosphanyl dihydrogen phosphite Chemical compound OP(O)OP(O)O.C(CCCCCCCCCCCCCCCCC)C(O)(C(CO)(CO)CO)CCCCCCCCCCCCCCCCCC OCSIKZYSDOXRPA-UHFFFAOYSA-N 0.000 description 1
- GXURZKWLMYOCDX-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol;dihydroxyphosphanyl dihydrogen phosphite Chemical compound OP(O)OP(O)O.OCC(CO)(CO)CO GXURZKWLMYOCDX-UHFFFAOYSA-N 0.000 description 1
- JECYNCQXXKQDJN-UHFFFAOYSA-N 2-(2-methylhexan-2-yloxymethyl)oxirane Chemical class CCCCC(C)(C)OCC1CO1 JECYNCQXXKQDJN-UHFFFAOYSA-N 0.000 description 1
- PZRWFKGUFWPFID-UHFFFAOYSA-N 3,9-dioctadecoxy-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound C1OP(OCCCCCCCCCCCCCCCCCC)OCC21COP(OCCCCCCCCCCCCCCCCCC)OC2 PZRWFKGUFWPFID-UHFFFAOYSA-N 0.000 description 1
- 238000004435 EPR spectroscopy Methods 0.000 description 1
- RYECOJGRJDOGPP-UHFFFAOYSA-N Ethylurea Chemical compound CCNC(N)=O RYECOJGRJDOGPP-UHFFFAOYSA-N 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- BEIOEBMXPVYLRY-UHFFFAOYSA-N [4-[4-bis(2,4-ditert-butylphenoxy)phosphanylphenyl]phenyl]-bis(2,4-ditert-butylphenoxy)phosphane Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(C=1C=CC(=CC=1)C=1C=CC(=CC=1)P(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C BEIOEBMXPVYLRY-UHFFFAOYSA-N 0.000 description 1
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 229940058905 antimony compound for treatment of leishmaniasis and trypanosomiasis Drugs 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- 239000006085 branching agent Substances 0.000 description 1
- WWNGFHNQODFIEX-UHFFFAOYSA-N buta-1,3-diene;methyl 2-methylprop-2-enoate;styrene Chemical compound C=CC=C.COC(=O)C(C)=C.C=CC1=CC=CC=C1 WWNGFHNQODFIEX-UHFFFAOYSA-N 0.000 description 1
- NTXGQCSETZTARF-UHFFFAOYSA-N buta-1,3-diene;prop-2-enenitrile Chemical compound C=CC=C.C=CC#N NTXGQCSETZTARF-UHFFFAOYSA-N 0.000 description 1
- FACXGONDLDSNOE-UHFFFAOYSA-N buta-1,3-diene;styrene Chemical compound C=CC=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 FACXGONDLDSNOE-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
- AHVOFPQVUVXHNL-UHFFFAOYSA-N butyl prop-2-enoate;methyl 2-methylprop-2-enoate Chemical compound COC(=O)C(C)=C.CCCCOC(=O)C=C AHVOFPQVUVXHNL-UHFFFAOYSA-N 0.000 description 1
- FUFJGUQYACFECW-UHFFFAOYSA-L calcium hydrogenphosphate Chemical compound [Ca+2].OP([O-])([O-])=O FUFJGUQYACFECW-UHFFFAOYSA-L 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 150000001993 dienes Chemical group 0.000 description 1
- NAPSCFZYZVSQHF-UHFFFAOYSA-N dimantine Chemical compound CCCCCCCCCCCCCCCCCCN(C)C NAPSCFZYZVSQHF-UHFFFAOYSA-N 0.000 description 1
- 229950010007 dimantine Drugs 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 1
- 235000019820 disodium diphosphate Nutrition 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 229910000397 disodium phosphate Inorganic materials 0.000 description 1
- GYQBBRRVRKFJRG-UHFFFAOYSA-L disodium pyrophosphate Chemical compound [Na+].[Na+].OP([O-])(=O)OP(O)([O-])=O GYQBBRRVRKFJRG-UHFFFAOYSA-L 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229920003247 engineering thermoplastic Polymers 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229920006228 ethylene acrylate copolymer Polymers 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 150000002431 hydrogen Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 238000012886 linear function Methods 0.000 description 1
- 229920000092 linear low density polyethylene Polymers 0.000 description 1
- 239000004707 linear low-density polyethylene Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 1
- 235000019799 monosodium phosphate Nutrition 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- OEIJHBUUFURJLI-UHFFFAOYSA-N octane-1,8-diol Chemical compound OCCCCCCCCO OEIJHBUUFURJLI-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical class [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 description 1
- 150000002924 oxiranes Chemical group 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 150000008301 phosphite esters Chemical class 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 150000003017 phosphorus Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000010817 post-consumer waste Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 229940005657 pyrophosphoric acid Drugs 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000012748 slip agent Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229920006132 styrene block copolymer Polymers 0.000 description 1
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 239000012745 toughening agent Substances 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- MFXMOUUKFMDYLM-UHFFFAOYSA-L zinc;dihydrogen phosphate Chemical compound [Zn+2].OP(O)([O-])=O.OP(O)([O-])=O MFXMOUUKFMDYLM-UHFFFAOYSA-L 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
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
Definitions
- This invention pertains to certain, novel polyester compositions which exhibit improved toughness. More specifically, this invention pertains to novel polyester compositions comprising (i) at least one polyester containing diol residues comprising ethylene glycol residues and diacid residues comprising terephthalic acid residues, 2,6-naphthalenedicarboxylic acid resides or a mixture thereof, and containing antimony residues; (ii) certain epoxy-containing impact modifiers and (iii) at least one phosphorus compound or residues of at least one phosphorus compound.
- Polyesters such as poly(ethylene terephthalate) (PET) are engineering thermoplastics used in a wide variety of end use applications such as fibers, films, automotive parts, food and beverage containers and the like. They can be processed by a variety of techniques including injection molding, compression molding, extrusion, thermoforming, blow molding, and combinations thereof. Sometimes, it is desirable to add impact modifiers to improve the toughness of polyesters used in the manufacture of molded parts such as those used in automotive, appliance, cookware or food storage applications.
- PTT poly(ethylene terephthalate)
- Patent 4,172,859 discloses that polymeric materials that serve well as impact modifiers should (i) possess a modulus 1/10 that of the polyester matrix material, (ii) be well dispersed within the matrix material in discrete phases of 0.01 micron to 3.0 micron in size, and (iii) be well bonded to the matrix.
- Low modulus polymers commonly used as impact modifiers fall into several general classes.
- the first class comprises rubbers based on butadiene or isoprene, e.g., polybutadiene, polyisoprene, natural rubber, styrene-butadiene (SBR), acrylonytrile-butadiene (ABN or nitrile rubber), styrene-butatene-styrene (SBS) or hydrogenated SBS (styrene-ethylene- butene-styrene) block copolymers (SEBS), or acrylonytrile-butadiene- styrene (ABS) polymers containing high levels of butadiene.
- SBR styrene-butadiene
- ABS acrylonytrile-butadiene
- SEBS acrylonytrile-butadiene- styrene
- Butadiene- based rubbers generally have lower glass transition temperatures (Tg's) which help to improve low temperature toughness, but they may not be stable under the high temperatures at which polyesters are processed.
- the second major class of impact modifiers comprise elastomers based on polyethylene, e.g., ethylene-propylene rubbers (EPR) or EPRs with a small amount of side chain diene moiety (EPDM), ethylene-acrylate copolymers such as ethylene/methyl acrylate, ethylene/ethyl acrylate, ethylene/butyl acrylate and ethylene/methylacrylate/glycidyl methacrylate, or ethylene- vinyl acetate copolymers (EVA).
- EPR ethylene-propylene rubbers
- EPDM side chain diene moiety
- EVA ethylene-acrylate copolymers
- a third group of impact modifiers consists of core-shell impact modifiers such as those that contain a poly(methyl methacrylate) (PMMA) hard shell with either a butadiene methcrylate- butadiene-styrene (MBS) or butyl acrylate (acrylic) core, e.g., PARALOID manufactured by Rohm & Haas Company.
- Core-shell impact modifiers based on ABS (acrylonitrile-butadiene-styrene) also are commercially available, e.g., BLENDEX manufactured by GE Specialty Chemicals).
- Other elastomers that may serve as impact modifiers include polyesters, e.g., HYTRELI manufactured by E.I.
- a fine discrete impact modifier phase can be created by the shearing forces obtained during melt processing.
- a mixing screw must be designed properly to create the appropriate shear fields during a compounding/extrusion process.
- impact modifiers dispersed by purely mechanical action may re- coalesce during a later stage of processing where shear may be reduced.
- impact modifiers can be manufactured to an inherently small size using latex or other polymerization processes.
- Impact modifiers manufactured in this way often contain a stiff shell of harder polymer and are, therefore, often referred to as core-shell impact modifiers.
- These impact modifiers can be made in 0.2 - 0.5 micron sizes ideally suited for impact modification of nylons, polycarbonates and polyesters. Nonetheless, these core-shell impact modifiers also must be dispersed by shearing action during melt processing, and are prone to re-coalesce during later stages of molding or compounding.
- Impact modifiers can be functionalized with a variety of reactive or non- reactive monomers. These functional monomers can be incorporated into the impact modifier directly during preparation of the impact modifier or subsequently by means of a grafting polymerization step.
- Non-reactive impact modifiers for example an EPDM-grafted-SAN
- the reactive groups of reactive impact modifiers chemically bond to the matrix polymer but, to be effective, they must do so in the limited time available in the extruder during compounding.
- U.S. Patent 4,172,859 lists a variety of functional groups which can be grafted or copoiymerized onto ethylene-based elastomers for use with polyesters and nylons.
- maleic anhydride (MAH) functionalized impact modifiers work well for nylons, and there are many commercial products available, e.g., EPR-MAH, EVA-MAH, and SEBS-MAH.
- EPR-MAH EVA-MAH
- SEBS-MAH SEBS-MAH
- a functional group that reacts particularly well with polyesters is the monosubstituted oxirane, or epoxy, group such as is present in glycidyl methacrylate (GMA), glycidyl acrylate, allyl glycidyl ether, and 3,4-epoxy-1- butene (EpB).
- GMA glycidyl methacrylate
- EpB 3,4-epoxy-1- butene
- polyester compositions which contain epoxy-containing, ethylene-based polymeric materials.
- U.S. Patent 4,284,540 describes the use of ethylene/GMA copolymers as a toughening agent for polyesters when combined with 0.1 to 5 weight percent of an added barium catalyst.
- U.S. Patent 4,753,980 discloses that polyester compositions containing 3-40 weight percent of either ethylene/ethyl acrylate/GMA terpolymer or ethylene/butyl acrylate/GMA terpolymer superior possess low temperature toughness when compared to analogous polyester compositions which contain an ethylene/methyl acrylate/GMA terpolymer.
- Patents 5,098,953, 5,086,119, 5,086,118, 5,086,116, and 5,068,283 disclose that the toughness of polyester compositions containing ethylene/GMA copolymers or ethylene/alkyl acrylate/GMA terpolymers can be improved by adding a functional crosslinking agent in the compositions.
- the functional crosslinking agent contains, in one molecule, at least two functional groups having reactivity with epoxy group, carboxyl group or hydroxyl group.
- U.S. Patent 5,206,291 describes compositions comprising a polyester containing 1 ,4-cyclohexanedimethanol residues and an ethylene/GMA copolymer.
- U.S. Patent 5,436,296 discloses that an ethylene/GMA copolymer may be used to compatibilize blends of polyethylene and polyester.
- European Patent Publication EP 481 ,471 B1 and Penco et al., Journal of Applied Polymer Science, 57, 329 (1995) disclose compositions comprising a polyester, a linear low density polyethylene, an ethylene/ethyl acrylate/GMA terpolymer and 0.5% to 1 % of an amine for the opening of an epoxy ring.
- Patent 5,652,306 and European Patent Publication EP 737,715 A2 disclose polyester compositions containing MBS or acrylic-type core-shell impact modifiers and small amounts of ethylene/alkyl acrylate/GMA terpolymers. While several of the preceding patents discuss the use of added . catalysts to promote a reaction between epoxy-containing ethylene polymers and polyesters, in none of these patents is there any direct disclosure that the toughness of the blend is affected by the presence of residues of catalysts used in the preparation of the polyester. Polyesters typically are prepared using metal catalysts that remain in the polyester product. Examples of these catalysts include organic and inorganic compounds of arsenic, cobalt, tin, antimony, zinc, titanium, magnesium, gallium, germanium, sodium, lithium and the like. Antimony compounds frequently are used in the preparation of PET.
- torque rheometry provides a simple and straightforward method for monitoring the viscosity of polymer blends as a function of blending time.
- the rheometer continuously measures the torque required to turn the rotor blades that shear and mix the sample within the mixing bowl. For a given material and set of processing conditions, the torque measured is approximately a linear function of the viscosity of the sample.
- any change in viscosity with time is in turn related to such effects as changes in molecular weight of the sample (for example, an increase due to a reaction or a decrease due to degradation) or the formation of grafts, branches or crosslinks in the sample.
- the work by Stewart et al. shows that mixtures of E/GMA with PET containing antimony catalyst residues gave rise to significant increases in torque with mixing time. This led to the conclusion that PET containing antimony catalyst residues accelerated the reaction between the PET and the E/GMA. PET containing residual antimony catalyst was found to produce a more rapid increase in torque than PET containing other residual catalysts.
- U.S. Patent 4,845,169 describes a thermoplastic blend of PET, a polyester elastomer, and 2 to 6 weight percent of an alkyl-aryl phosphite to allow grafting between the two polyesters. We have found this amount of phosphite to be excessive and detrimental to the toughness of our systems.
- U.S. Patent 5,194,468 discloses the use of a mixture of two aromatic phosphites to transesterify a polyester elastomer to another polyester and improve compatibility to a high density polyethylene.
- U.S. Patent 5,411 ,999 discloses compositions comprising a polycarbonate, an epoxy-functionalized polyester, a rubbery impact modifier and a catalyst quencher such as sodium dihydrogen phosphate to inhibit transesterification between the polycarbonate and the polyester.
- a catalyst quencher such as sodium dihydrogen phosphate to inhibit transesterification between the polycarbonate and the polyester.
- Sodium acid pyrophosphate gave the best hydrolytic stability.
- An alkyl phosphite was found to give very poor hydrolytic stability.
- U.S. Patent 5,541 ,244 teaches that certain phosphates, in particular zinc dihydrogen phosphate, are good transesterification inhibitors that "do not negatively influence the impact strength" of a mixture of two polyesters. No impact modifiers containing an epoxide functionality are disclosed.
- compositions comprising certain polyesters containing antimony residues and certain epoxy-containing impact modifiers exhibit improved toughness when a phosphorus compound is included in the compositions.
- the polyester utilized typically contains up to about 400 parts per million by weight (ppmw) antimony metal, e.g., antimony residues resulting from the use of an antimony catalyst in the manufacture of the polyester.
- the polyester compositions provided by the present invention comprise: i. about 75 to 98 weight percent of a thermoplastic polyester comprised of:
- (A) diacid residues comprising at least 85 mole percent terephthalic acid residues, 2,6-napthalenedicarboxylic acid residues or a mixture of terephthalic acid and 2,6-naphthalenedicarboxylic acid residues;
- an impact modifying polymer comprised of about 0.5 to 15 weight percent of epoxy-containing residues derived from monomers selected from glycidyl methacrylate, glycidyl acrylate, allyl gycidyl ether, 3,4-epoxy-1- butene, or a mixture of any two or more of such monomers; and
- polyester component of our novel compositions are commercially available and/or may be prepared by batch or continuous processes using conventional melt phase or solid state condensation procedures well known in the art. Also, the polyester component may be obtained from post consumer waste, e.g., recycled polyester.
- Polyesters useful in the present invention are comprised of diacid residues comprising at least 85 mole percent terephthalic acid residues, 2,6-napthalenedicarboxylic acid residues or a mixture of terephthalic acid and 2,6-naphthalene- dicarboxylic acid residues; (B) diol residues comprising at least 85 mole percent ethylene glycol residues; and (C) at least 50 ppmw of antimony metal wherein the polyester is made up of 100 mole percent diacid residues and 100 mole percent diol residues.
- Up to 15 mole percent of the diacid component of the polyesters may be derived from diacids other than terephthalic and 2,6-napthalenedicarboxylic acid residues.
- diacid residues may be residues derived from dicarboxylic acids containing about 4 to about 40 carbon atoms such as succinic, glutaric, adipic, pimelic, suberic, azelic, sebacic, terephthalic, isophthalic, sulfodibenzoic, sulphoisophthalic, maleic, fumaric, 1 ,4-cyclo- hexanedicarboxylic (cis-, trans-, or cis/trans mixtures), and the like.
- the diacid residues may be derived from the dicaroxylic acids, esters and acid chlorides thereof, and, in some cases, anhydrides thereof.
- diol residues may be derived from diols other than ethylene glycol.
- diols which may be used in the preparation of the polyester component include those containing 3 to about 10 carbon atoms such as propylene glycol, 1 ,3-pro- panediol, 1 ,4-butanediol, 1,6-hexanediol, 1 ,8-octanediol, neopentyl glycol, 2,2,4, 4-tetramethyl-1 ,3-cyclobutanediol, diethylene glycol, 1 ,4-cyclohexane- dimethanol (cis, trans, or cis/trans mixtures) and the like.
- a branching agent such as trimellitic anhydride, pyromellitic dianhydride, glycerol, pentaerythritol, polyvinyl alcohol, styrene-maleic anhydride (SMA) and the like may be may be included in the polyester if desired.
- a branching agent such as trimellitic anhydride, pyromellitic dianhydride, glycerol, pentaerythritol, polyvinyl alcohol, styrene-maleic anhydride (SMA) and the like may be included in the polyester if desired.
- the polyester component of the compositions of the present invention should have an inherent viscosity (IV) in the range of about 0.4 to about 1.4 dL/g, preferably about 0.55 to 0.95 dL/g, measured at 25°C using 0.50 g of polyester per 100 mL of a solvent consisting of 60 weight percent phenol and 40 weight percent tetrachloroethane.
- the polyester component preferably is unmodified PET having an IV of about 0.55 to 0.95 dlJg.
- the polyester component of our novel compositions contains at least
- antimony metal typically about 50 to 400 ppmw Sb and preferably about 100 to 300 ppmw Sb.
- the antimony metal may be introduced to the polyester by using an antimony compound, e.g., antimony acetate or oxide, as a catalyst in the preparation of the polyester. It is also possible to introduce the antimony into the polyester subsequent to the preparation of the polyester.
- the second component of the compositions of the present invention is an impact modifying polymer comprised of about 0.5 to 20 weight percent of epoxy-containing residues derived from monomers selected from glycidyl methacrylate, glycidyl acrylate, allyl gycidyl ether, 3,4-epoxy-1 -butene, or a mixture of any two or more of such monomers.
- epoxy-containing monomers may be introduced into the impact modifier during polymerization, or they may be subsequently grafted onto the impact modifier.
- Such epoxy-containing, impact modifier polymers are well known in the art and are available from a plurality of manufactures.
- Impact modifiers that may be modified with a functional epoxy group include, but are not restricted to, polyethylene; polypropylene; polybutene; ethylene based copolymers and terpolymers containing vinyl acetate, alkyl acrylate, alkyl methacrylate where the alkyl group could be methyl, ethyl, butyl or ethylhexyl; ethylene-propylene copolymers (EPR); ethylene- propylene-diene (EPDM); natural rubber; polybutadiene; polyisoprene; acrylonitrile-butadiene (nitrile rubber); styrene-butadiene (SBR); styrene- butadiene-styrene (SBS); styrene-ethylene-butene-styrene (SEBS); acrylonitrile-butadiene-styrene (ABS); methyl methacrylate-butyl acrylate (acrylic core
- Preferred epoxy-containing impact modifiers include copolymers and terpolymers having the respective general formulas E/Y and E/X/Y wherein: X represents residues derived from R 2 O
- R 1 is alkyl of up to about 8 carbon atoms, preferably alkyl of
- R 2 is hydrogen, methyl or ethyl, preferably hydrogen or methyl
- X constitutes about 10 to 40 weight percent, preferably 15 to 35 weight percent, and most preferably 20 to 35 weight percent, of terpolymer E/X Y
- Y represents residues derived from glycidyl methacrylate, glycidyl acrylate, allyl glycidyl ether and 3,4-epoxy-1 -butene which constitute about 0.5 to 20 weight percent, preferably about 2 to 10 weight percent, of copolymer E/Y and terpolymer E/X/Y; and
- E represents ethylene residues that constitute the remainder of the composition.
- copolymers based on ethylene-GMA containing about 2 to 10 weight percent GMA residues
- terpolymers based on ethylene-methyl acrylate-GMA, ethylene-ethyl acrylate-GMA and ethylene- butyl acrylate-GMA containing about 20 to 35 weight percent alkyl acrylate residues and about 2 to 10 weight percent GMA residues are particularly preferred.
- the concentration of the epoxy-containing impact modifiers in the compositions of the present invention preferably is about 10 to 25 weight percent, based on the total weight of components I and II, for injection molding uses and about 2 to 15 weight percent, based on the total weight of components I and II, for compositions intended for extrusion into sheet or film or for use in thermoforming applications.
- the third component of our novel compositions is at least one phosphorus compound which is present in an amount which gives a P:Sb atomic ratio of at least 1 :1.
- the particular phosphorus compound is not critical and may be selected from a wide variety of phosphorus-containing compounds such as organo-phosphorus compounds, e.g., phosphite esters such as trihydrocarbyl phosphites, phosphonate esters such as dihydro- carbyl phosphonates, phosphate esters such as trihydrocarbyl phosphates, phosphines such as trihydrocarbyl phosphines, phosphine oxides such as trihydrocarbylphosphine oxides and and the like, wherein the hydrocarbyl groups may be selected from alkyl, cycloalkyl and aryl groups containing up to about 20 carbon atoms.
- a preferred phosphorus compound is bis(2,4-t-butylphenyl)pentaerythritol diphosphite available under the tradenames Ultranox 626 and Alkanox P-24. Additional examples of specifc organo-phosphorus compounds include distearylpentaerythritol diphosphite available under the tradenames Weston 618 and Mark 5060, tetrakis(2,4-di- t-butylphenyl)4,4'-biphenylenediphosphonite available under the trade- names Sandostab P-EPQ and Alkanox 24-44, triphenyl phosphate, triphenyl phosphite, and dimethylphosphonate available under the trade- names Antiblaze 1045 and Amgard P-45.
- Phosphorus acids such as phosphorous acid, phosphoric acid, pyrophosphoric acid, polyphosphoric acid and their respective salts also may be sued. All of these phosphorus compounds are believed to be effective in slowing the epoxy - epoxy reaction due to a phosphorus-induced inactivation of the residual antimony catalyst. Inactivation of the antimony permits a selective reaction between the epoxy portion of the impact modifying polymer and the polyester which results in a better dispersion and thus, better impact modification.
- the amount of phosphorus compound present in the polyester compositions of our invention normally should be an amount which gives a P:Sb atomic ratio of 1 :1 or greater, e.g., a P:Sb atomic ratio in the range of about 1 :1 to 5:1 , preferably in the range of 2:1 to 3:1.
- the inclusion of excessive amounts of phosphorus compounds in the polyester compositions can result in compositions having poor impact properties even though the impact modified is present as small dispersions.
- Excessive phosphorus compounds (of various oxidation states) can form strong acids by combination with trace amounts of water present in even the most thoroughly dried polyester. Such strong acids are detrimental to polyester molecular weight (Mw) upon which toughness depends directly. Strong acids also can catalyze epoxy-epoxy reactions which may lessen adhesion to the matrix.
- the phosphorus compound normally is added to the molten polyester simultaneously with or prior to the addition of the epoxy- containing impact modifier.
- the phosphorous compound also may be added to the polyester during its manufacture although adding the phosphorus compound during polyester preparation may have a negative effect on the rates of polymerization and/or solid stating.
- addition of a phosphorus compound during polymerization is a not a preferred method of addition.
- the impact modifier and polyester may be pellet blended before extrusion or they may be fed from separate streams. These reactive impact modifiers also may be combined with non-reactive impact modifiers of similar composition.
- the polyester compositions of this invention can be readily prepared by conventional compounding technology, such as the use of single or twin screw extruders. The resultant blends are readily extruded into film or sheeting and injection molded, compression molded or thermoformed into desired shapes or objects.
- polyesters such as stabilizers, antioxidants, pigments, colorants, plasticizers, flame retardants, mold release agents, slip agents and the like may be used as desired.
- Glass fibers or other inorganic fillers can also be included.
- nucleating agents such as polyethylene, polypropylene, talc and the like may be used.
- thermoplastic polyester comprising poly(ethylene terephthalate) having an inherent viscosity of about 0.55 to 0.95 dLJg, measured at 25°C using 0.50 g of polyester per 100 mL of a solvent consisting of 60 weight percent phenol and 40 weight percent tetrachloroethane, containing about 100 to 300ppmw [Sb];
- an impact modifying polymer selected from ethylene/methyl acrylate/ glycidyl methacrylate terpolymers containing about 20 to 35 weight percent methyl acrylate residues and about 2 to 10 weight percent glycidyl methacrylate residues; and III. a phosphorus compound; wherein the amount of phosphorus compound present gives a P:Sb atomic ratio of about 2:1 to 3:1 and the weight percentages are based on the total weight of components I and II.
- up to 50% of the amount of component II may consist of an ethylene/methyl acrylate copomlymer containing about 20 to 35 weight percent methyl acrylate residues.
- polyester A Poly(ethylene terephthalate) having an IV of 0.72 prepared from ethylene glycol and terephthalic acid using 200 ppmw antimony catalyst provided as antimony triacetate.
- Polyester B Poly(ethylene terephthalate) modified with 1 ,4-cyclohexane- dimethanol residues having an IV of 0.72 prepared from terephthalic acid and a mixture of 96.5 mole percent ethylene glycol with 3.5 mole percent cyclohexanedimenthanol using 200 ppmw antimony catalyst to an IV of
- Impact Modifier 1 An ethylene/methyl acrylate/glycidyl methacrylate terpolymer containing 24% methyl acrylate residues and 8% glycidyl methacrylate residues, available from Elf Atochem under the name "Lotader
- Impact Modifier 2 An ethylene/methyl acrylate copolymer containing 24% methyl acrylate residues, available from Elf Atochem under the name "Lotryl 24MA07" having a melt flow of 8 g/10 minutes measured by ASTM D1238 at 190°C using a 2.16 kg weight.
- IM-2 is similar to IM-1 but contains no epoxy functionality.
- Impact Modifier 3 An ethylene/glycidyl methacrylate copolymer containing
- polyester compositions of the examples were prepared by feeding the polyester, impact modifier and phosphorus compound through separate feeders into the main hopper of a 30 mm twin-screw, compounding extruder.
- the extruder barrel temperatures was set at 290°C (554°F), screw speed was 300 revolutions per minute and the throughput rate was 11.4 kg (25 pounds) per hour.
- Test bars 3.2mm thick by 12.8mm wide by 125mm long were molded on a ToyoA molding machine using a chilled -4°C (25°F) mold.
- the test bars thus prepared contained essentially amorphous polyester.
- the test bars then were crystallized in an air oven at
- Test bars were machined into notched Izod test coupons and tested in accordance with ASTM D256.
- Morphology was examined using either TEM (transmission electron microscopy) or SEM (scanning electron microscopy). Specimens for TEM examination were cut using a cryomicrotome. Specimens for SEM examination were freeze fractured in liquid nitrogen. The particle sizes listed represent the diameters of the most common large particles of the impact modifier phases present in the SEM or TEM photo.
- the polyester composition of Comparative Example 1 consisted of 80% Polyester A containing about 200 ppmw antimony and 20% Impact Modifier 1. This composition has a 23°C (72°F) Notched Izod value of 354 Joules per meter (6.62 foot-pounds per inch). The TEM particle size of the impact modifier was 2 microns.
- the polyester composition of Comparative Example 2 consisted of 80% Polyester B containing about 200 ppmw antimony and 20% Impact Modifier 1. This composition has a 23°C (72°F) Notched Izod value of 373 Joules per meter (6.98 foot-pounds per inch). The TEM particle size of the impact modifier was 2 microns.
- the polyester composition of Comparative Example 3 consisted of 80% Polyester A containing about 200 ppmw antimony and 20% Impact Modifier 2. This composition has a 23°C (72°F) Notched Izod value of 45 Joules per meter (1.12 foot-pounds per inch).
- the TEM particle size of the impact modifier was 0.84 microns. The particle size is good but there is no bonding.
- Polyester A containing about 200 ppmw antimony and 20% Impact Modifier 3. This composition has a 23°C (72°F) Notched Izod value of 243 Joules per meter (4.54 foot-pounds per inch). The TEM particle size of the impact modifier was 2 microns.
- the polyester composition of Example 1 consisted of 80% Polyester A containing about 200 ppmw antimony, 20% Impact Modifier 1 and 0.05% of bis(2,4-di-t-butylphenyl)pentaerythritol diphosphite (Ultranox 626, 50 ppmw phosphorus). This composition has a 23°C (72°F) Notched Izod value of "No Break”. A "No Break" result indicates that the material did not completely fracture under the indicated conditions with an Izod value of greater than 1000 Joules per meter (534.5 foot-pounds per inch). The TEM particle size of the impact modifier was 0.5 microns.
- the polyester composition of Example 2 consisted of 80% Polyester B containing about 200 ppmw antimony, 20% Impact Modifier 1 and 0.05% of bis(2,4-di-t-butylphenyl)pentaerythritol diphosphite (Ultranox 626, 50 ppmw phosphorus). This composition has a 23°C (72°F) Notched Izod value of No Break. The TEM particle size of the impact modifier was 0.5 microns.
- Example 3 The polyester composition of Example 3 consisted of 80% Polyester
- This composition has a 23°C (72°F) Notched Izod value of 501 Joules per meter (9.37 foot-pounds per inch).
- the TEM particle size of the impact modifier was 0.5 microns.
- the polyester composition of Example 4 consisted of 80% Polyester A containing about 200 ppmw antimony, 20% Impact Modifier 3 and 0.05% of bis(2,4-di-t-butylphenyl)pentaerythritol diphosphite (Ultranox 626, 50 ppmw phosphorus). This composition has a 23°C (72°F) Notched Izod value of "No Break”. A "No Break" result indicates that the material did not completely fracture under the indicated conditions with an Izod vajue of greater than 1000 Joules per meter (534.5 foot-pounds per inch). The TEM particle size of the impact modifier was 0.5 microns.
- Examples 5-15 show the effect that different types of organic and inorganic phosphorus compounds have on the 72°F (23°C) and 32°F (0°C) Notched Izod toughness of blends of comprising 80% Polyester A and 20% Impact Modifier 1.
- the concentration of each of the phosphorus compounds was 0.3%. All of the phosphorus compounds had a favorable effect on the 23°C (72°F) Notched Izod toughness.
- Example 13 shows that 0.3% Ca 3 (PO 4 ) 2 also improves the 32°F (0°C) notched Izod toughness of the blend.
- Example 5 Bis(2,4-di-t-butylphenyl)pentaerythritol diphosphite
- Example 6 Distearylpentaerythritol di phosphite
- Example 7 Tetrakis(2,4-di-t-butylphenyl)4,4"-biphenylenediphosphonite
- Example 8 Triphenyl phosphate
- Example 9 Triphenyl phosphite
- Example 10 Dimethylphosphonate
- Example 11 Na 2 H 2 P 2 0 7
- Example 12 CaHPO 4
- Example 13 Ca 3 (PO 4 )2
- Example 14 Na 2 HPO 4
- Example 15 NaH 2 P0 4
- Comparative Example 5 shows the 23°C (72F) and 0°C (32°F) Notched Izod toughness of a blend of comprising 80% Polyester A and 20% Impact Modifier 1 which contains no phosphorus compound.
- the 23°C (72°F) and 0°C (32°F) Notched Izod Values for the compositions of Examples 5-15 and Comparative Example 5 are set forth in Table I wherein the values given are joules per meter and (foot-pounds per inch).
- Examples 16-21 show the effect that varying concentrations of bis(2,4-di-t-butylphenyl)pentaerythritol diphosphite have on particle size and and 0°C (32°F) Notched Izod toughness of polyester compositions containing 80% Polyester A and 20% Impact Modifier 1.
- the 0°C (32°F) Notched Izod values are more sensitive to differing concentrations of phosphorus than are the 23°C (72°F) Notched Izod values.
- compositions of Comparative Examples C-6 and C-7 consist of 80% Polyester A and 20% Impact Modifier 1 and no phosphorus compound.
- the 0°C (32°F) Notched Izod Values for the compositions of Examples 16-21 and Comparative Examples C-6 and C-7 are set forth in
- Table II wherein the values given are joules per meter and (foot-pounds per inch). Table II also reports the particle sizes (microns) of the impact modifier phase determined by SEM for the compositions of Examples 16-21 and Comparatives Examples C-6 and C-7.
- the values given for Concentration of Phosphorus Compound are the weight/weight concentrations of bis(2,4-di-t-butylphenyl)pentaerythritol diphosphite based on the total weight of the polyester and the impact modifier.
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Abstract
La présente invention concerne de nouvelles compositions à base de polyester qui comprennent (i) au moins un polyester renfermant des résidus diol, lesquels renferment eux-mêmes des résidus d'éthylène glycol, des résidus diacides avec résidus d'acide téréphtalique des résidus d'acide dicarboxylique 2,6 naphtalène ou un mélange de ces substances, ainsi que de l'antimoine; (ii) certains agents antichoc renfermant une résine époxy; et (iii) un composé phosphoré. Ces compositions de polyester se caractérisent par une robustesse accrue et conviennent pour la fabrication d'articles moulés par injection ou de matériaux en film ou en feuille obtenus par extrusion.
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US15284298A | 1998-09-14 | 1998-09-14 | |
US152,842 | 1998-09-14 |
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WO2000015717A1 true WO2000015717A1 (fr) | 2000-03-23 |
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PCT/US1999/021169 WO2000015717A1 (fr) | 1998-09-14 | 1999-09-13 | Compositions de polyester renfermant un agent antichoc |
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7304107B2 (en) * | 2004-12-21 | 2007-12-04 | E.I. Du Pont De Nemours And Company | Toughened poly(ethylene terephthalate) compositions |
US8058360B2 (en) | 2007-06-01 | 2011-11-15 | Grupo Petrotemex, S.A. De C.V. | Polyester blends exhibiting low temperature toughness |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0017942A1 (fr) * | 1979-04-17 | 1980-10-29 | Toray Industries, Inc. | Compositions de moulage à base de polytéréphtalate d'éthylène |
JPS62146949A (ja) * | 1985-12-23 | 1987-06-30 | Toray Ind Inc | 成形用ポリエチレンテレフタレ−ト系組成物 |
JPS62146950A (ja) * | 1985-12-23 | 1987-06-30 | Toray Ind Inc | ポリエチレンテレフタレ−ト系成形用樹脂組成物 |
EP0268287A2 (fr) * | 1986-11-20 | 1988-05-25 | Kanegafuchi Kagaku Kogyo Kabushiki Kaisha | Composition de résine polyester |
US5194468A (en) * | 1992-06-19 | 1993-03-16 | General Motors Corporation | High density polyethylene polyblends |
EP0838501A2 (fr) * | 1996-10-23 | 1998-04-29 | Hoechst Celanese Corporation | Procédé et compositions pour modifier la tenacité de résines de polyester |
-
1999
- 1999-09-13 WO PCT/US1999/021169 patent/WO2000015717A1/fr active Application Filing
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0017942A1 (fr) * | 1979-04-17 | 1980-10-29 | Toray Industries, Inc. | Compositions de moulage à base de polytéréphtalate d'éthylène |
US4284540A (en) * | 1979-04-17 | 1981-08-18 | Toray Industries, Inc. | Polyethylene terephthalate molding compositions |
JPS62146949A (ja) * | 1985-12-23 | 1987-06-30 | Toray Ind Inc | 成形用ポリエチレンテレフタレ−ト系組成物 |
JPS62146950A (ja) * | 1985-12-23 | 1987-06-30 | Toray Ind Inc | ポリエチレンテレフタレ−ト系成形用樹脂組成物 |
EP0268287A2 (fr) * | 1986-11-20 | 1988-05-25 | Kanegafuchi Kagaku Kogyo Kabushiki Kaisha | Composition de résine polyester |
US5194468A (en) * | 1992-06-19 | 1993-03-16 | General Motors Corporation | High density polyethylene polyblends |
EP0838501A2 (fr) * | 1996-10-23 | 1998-04-29 | Hoechst Celanese Corporation | Procédé et compositions pour modifier la tenacité de résines de polyester |
Non-Patent Citations (2)
Title |
---|
CHEMICAL ABSTRACTS, vol. 107, no. 20, 16 November 1987, Columbus, Ohio, US; abstract no. 177300, XP002127737 * |
CHEMICAL ABSTRACTS, vol. 107, no. 20, 16 November 1987, Columbus, Ohio, US; abstract no. 177301, XP002127738 * |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7304107B2 (en) * | 2004-12-21 | 2007-12-04 | E.I. Du Pont De Nemours And Company | Toughened poly(ethylene terephthalate) compositions |
US8058360B2 (en) | 2007-06-01 | 2011-11-15 | Grupo Petrotemex, S.A. De C.V. | Polyester blends exhibiting low temperature toughness |
US8859681B2 (en) | 2007-06-01 | 2014-10-14 | Grupo Petrotemex, S.A. De C.V. | Polyester blends exhibiting low temperature toughness |
US9062200B2 (en) | 2007-06-01 | 2015-06-23 | Grupo Petrotemex, S.A. De C.V. | Polyester blends exhibiting low temperature toughness |
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