WO2008085397A1 - Processes for making elastomeric polyether esters and polyether esters made therefrom - Google Patents
Processes for making elastomeric polyether esters and polyether esters made therefrom Download PDFInfo
- Publication number
- WO2008085397A1 WO2008085397A1 PCT/US2007/026115 US2007026115W WO2008085397A1 WO 2008085397 A1 WO2008085397 A1 WO 2008085397A1 US 2007026115 W US2007026115 W US 2007026115W WO 2008085397 A1 WO2008085397 A1 WO 2008085397A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- polyester
- propanediol
- diol
- polyether ester
- glycol
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 63
- 229920000570 polyether Polymers 0.000 title claims abstract description 46
- 239000004721 Polyphenylene oxide Substances 0.000 title claims abstract description 45
- 150000002148 esters Chemical class 0.000 title claims abstract description 44
- 229920000728 polyester Polymers 0.000 claims abstract description 95
- 229920005862 polyol Polymers 0.000 claims abstract description 61
- 150000003077 polyols Chemical class 0.000 claims abstract description 59
- 238000004519 manufacturing process Methods 0.000 claims abstract description 11
- 150000002009 diols Chemical class 0.000 claims description 73
- -1 poly(ethylene terephthalate) Polymers 0.000 claims description 70
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 64
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 claims description 41
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 40
- 229940035437 1,3-propanediol Drugs 0.000 claims description 40
- 229920000166 polytrimethylene carbonate Polymers 0.000 claims description 40
- 239000003054 catalyst Substances 0.000 claims description 37
- 239000000203 mixture Substances 0.000 claims description 30
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 28
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 28
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 20
- 239000010936 titanium Substances 0.000 claims description 20
- 229910052719 titanium Inorganic materials 0.000 claims description 19
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 17
- 229920001707 polybutylene terephthalate Polymers 0.000 claims description 16
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 15
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (1R)-1,3-butanediol Natural products CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 13
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 11
- 229920001577 copolymer Polymers 0.000 claims description 11
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 10
- 235000013361 beverage Nutrition 0.000 claims description 8
- QWGRWMMWNDWRQN-UHFFFAOYSA-N 2-methylpropane-1,3-diol Chemical compound OCC(C)CO QWGRWMMWNDWRQN-UHFFFAOYSA-N 0.000 claims description 7
- 229960004063 propylene glycol Drugs 0.000 claims description 7
- 235000013772 propylene glycol Nutrition 0.000 claims description 7
- 238000004064 recycling Methods 0.000 claims description 6
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical class OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 6
- 125000003545 alkoxy group Chemical group 0.000 claims description 5
- 238000006116 polymerization reaction Methods 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims description 4
- QTCNKIZNNWURDV-UHFFFAOYSA-N 2,2-dimethylpropane-1,3-diol Chemical compound OCC(C)(C)CO.OCC(C)(C)CO QTCNKIZNNWURDV-UHFFFAOYSA-N 0.000 claims description 4
- 125000005037 alkyl phenyl group Chemical group 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 125000001475 halogen functional group Chemical group 0.000 claims description 4
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 150000002334 glycols Chemical class 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 3
- 238000004806 packaging method and process Methods 0.000 claims description 3
- 229920001281 polyalkylene Polymers 0.000 claims description 2
- 229920001451 polypropylene glycol Polymers 0.000 claims description 2
- 229920002215 polytrimethylene terephthalate Polymers 0.000 claims description 2
- 229940083957 1,2-butanediol Drugs 0.000 claims 1
- BMRWNKZVCUKKSR-UHFFFAOYSA-N butane-1,2-diol Chemical compound CCC(O)CO BMRWNKZVCUKKSR-UHFFFAOYSA-N 0.000 claims 1
- 235000019437 butane-1,3-diol Nutrition 0.000 claims 1
- 229940093476 ethylene glycol Drugs 0.000 claims 1
- 239000007858 starting material Substances 0.000 abstract description 11
- 230000007613 environmental effect Effects 0.000 abstract description 4
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical compound CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 28
- 229920000642 polymer Polymers 0.000 description 21
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 18
- 239000002253 acid Substances 0.000 description 18
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 14
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 11
- 230000032050 esterification Effects 0.000 description 11
- 238000005886 esterification reaction Methods 0.000 description 11
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 10
- 238000005809 transesterification reaction Methods 0.000 description 9
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 8
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 8
- 239000000376 reactant Substances 0.000 description 8
- 150000003606 tin compounds Chemical class 0.000 description 8
- 150000003609 titanium compounds Chemical class 0.000 description 7
- 239000002699 waste material Substances 0.000 description 7
- GHLKSLMMWAKNBM-UHFFFAOYSA-N dodecane-1,12-diol Chemical compound OCCCCCCCCCCCCO GHLKSLMMWAKNBM-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 229920002725 thermoplastic elastomer Polymers 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 5
- 150000007513 acids Chemical class 0.000 description 5
- 239000006085 branching agent Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000002609 medium Substances 0.000 description 5
- 238000006068 polycondensation reaction Methods 0.000 description 5
- 229940043375 1,5-pentanediol Drugs 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 150000005690 diesters Chemical class 0.000 description 4
- 229920001971 elastomer Polymers 0.000 description 4
- 239000000806 elastomer Substances 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 241000894007 species Species 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- 229920001169 thermoplastic Polymers 0.000 description 4
- 239000004416 thermosoftening plastic Substances 0.000 description 4
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 4
- 229920001634 Copolyester Polymers 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- PMMYEEVYMWASQN-IMJSIDKUSA-N cis-4-Hydroxy-L-proline Chemical compound O[C@@H]1CN[C@H](C(O)=O)C1 PMMYEEVYMWASQN-IMJSIDKUSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- FOTKYAAJKYLFFN-UHFFFAOYSA-N decane-1,10-diol Chemical compound OCCCCCCCCCCO FOTKYAAJKYLFFN-UHFFFAOYSA-N 0.000 description 3
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- OEIJHBUUFURJLI-UHFFFAOYSA-N octane-1,8-diol Chemical compound OCCCCCCCCO OEIJHBUUFURJLI-UHFFFAOYSA-N 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
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- 229920000909 polytetrahydrofuran Polymers 0.000 description 3
- XRVCFZPJAHWYTB-UHFFFAOYSA-N prenderol Chemical compound CCC(CC)(CO)CO XRVCFZPJAHWYTB-UHFFFAOYSA-N 0.000 description 3
- 229950006800 prenderol Drugs 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 239000013638 trimer Substances 0.000 description 3
- ALVZNPYWJMLXKV-UHFFFAOYSA-N 1,9-Nonanediol Chemical compound OCCCCCCCCCO ALVZNPYWJMLXKV-UHFFFAOYSA-N 0.000 description 2
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 2
- NHEKBXPLFJSSBZ-UHFFFAOYSA-N 2,2,3,3,4,4,5,5-octafluorohexane-1,6-diol Chemical compound OCC(F)(F)C(F)(F)C(F)(F)C(F)(F)CO NHEKBXPLFJSSBZ-UHFFFAOYSA-N 0.000 description 2
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 description 2
- CUCYNAXISGIFIS-UHFFFAOYSA-N 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10-hexadecafluorododecane-1,12-diol Chemical compound OCCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)CCO CUCYNAXISGIFIS-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
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- 238000005481 NMR spectroscopy Methods 0.000 description 2
- QVHMSMOUDQXMRS-UHFFFAOYSA-N PPG n4 Chemical compound CC(O)COC(C)COC(C)COC(C)CO QVHMSMOUDQXMRS-UHFFFAOYSA-N 0.000 description 2
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- UWHCKJMYHZGTIT-UHFFFAOYSA-N Tetraethylene glycol, Natural products OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 125000005907 alkyl ester group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 2
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- 239000007789 gas Substances 0.000 description 2
- SXCBDZAEHILGLM-UHFFFAOYSA-N heptane-1,7-diol Chemical compound OCCCCCCCO SXCBDZAEHILGLM-UHFFFAOYSA-N 0.000 description 2
- 239000002815 homogeneous catalyst Substances 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
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- 239000003960 organic solvent Substances 0.000 description 2
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- 229920000573 polyethylene Polymers 0.000 description 2
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- 238000000746 purification Methods 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
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- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
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- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- NYENCOMLZDQKNH-UHFFFAOYSA-K bis(trifluoromethylsulfonyloxy)bismuthanyl trifluoromethanesulfonate Chemical compound [Bi+3].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F NYENCOMLZDQKNH-UHFFFAOYSA-K 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- FAMUPMBATZGWOV-UHFFFAOYSA-M bromo(triphenyl)stannane Chemical compound C=1C=CC=CC=1[Sn](C=1C=CC=CC=1)(Br)C1=CC=CC=C1 FAMUPMBATZGWOV-UHFFFAOYSA-M 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 235000014633 carbohydrates Nutrition 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- PIMYDFDXAUVLON-UHFFFAOYSA-M chloro(triethyl)stannane Chemical compound CC[Sn](Cl)(CC)CC PIMYDFDXAUVLON-UHFFFAOYSA-M 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- WOSVXXBNNCUXMT-UHFFFAOYSA-N cyclopentane-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1CC(C(O)=O)C(C(O)=O)C1C(O)=O WOSVXXBNNCUXMT-UHFFFAOYSA-N 0.000 description 1
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- WNVQCJNZEDLILP-UHFFFAOYSA-N dimethyl(oxo)tin Chemical compound C[Sn](C)=O WNVQCJNZEDLILP-UHFFFAOYSA-N 0.000 description 1
- 235000021158 dinner Nutrition 0.000 description 1
- LQRUPWUPINJLMU-UHFFFAOYSA-N dioctyl(oxo)tin Chemical compound CCCCCCCC[Sn](=O)CCCCCCCC LQRUPWUPINJLMU-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- XWENCHGJOCJZQO-UHFFFAOYSA-N ethane-1,1,2,2-tetracarboxylic acid Chemical compound OC(=O)C(C(O)=O)C(C(O)=O)C(O)=O XWENCHGJOCJZQO-UHFFFAOYSA-N 0.000 description 1
- RWLDAJMGAVDXSH-UHFFFAOYSA-N ethane-1,1,2-tricarboxylic acid Chemical compound OC(=O)CC(C(O)=O)C(O)=O RWLDAJMGAVDXSH-UHFFFAOYSA-N 0.000 description 1
- HGVSZIWPYBQNOR-UHFFFAOYSA-N ethane-1,2-diol;propane-1,3-diol Chemical compound OCCO.OCCCO HGVSZIWPYBQNOR-UHFFFAOYSA-N 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- WDQNIWFZKXZFAY-UHFFFAOYSA-M fentin acetate Chemical compound CC([O-])=O.C1=CC=CC=C1[Sn+](C=1C=CC=CC=1)C1=CC=CC=C1 WDQNIWFZKXZFAY-UHFFFAOYSA-M 0.000 description 1
- NJVOZLGKTAPUTQ-UHFFFAOYSA-M fentin chloride Chemical compound C=1C=CC=CC=1[Sn](C=1C=CC=CC=1)(Cl)C1=CC=CC=C1 NJVOZLGKTAPUTQ-UHFFFAOYSA-M 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 1
- 239000013538 functional additive Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 239000001963 growth medium Substances 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 150000001261 hydroxy acids Chemical class 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 229940039696 lactobacillus Drugs 0.000 description 1
- WGJJZRVGLPOKQT-UHFFFAOYSA-K lanthanum(3+);trifluoromethanesulfonate Chemical compound [La+3].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F WGJJZRVGLPOKQT-UHFFFAOYSA-K 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- TVIDDXQYHWJXFK-UHFFFAOYSA-N n-Dodecanedioic acid Natural products OC(=O)CCCCCCCCCCC(O)=O TVIDDXQYHWJXFK-UHFFFAOYSA-N 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- DFFZOPXDTCDZDP-UHFFFAOYSA-N naphthalene-1,5-dicarboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=CC2=C1C(O)=O DFFZOPXDTCDZDP-UHFFFAOYSA-N 0.000 description 1
- HRRDCWDFRIJIQZ-UHFFFAOYSA-N naphthalene-1,8-dicarboxylic acid Chemical compound C1=CC(C(O)=O)=C2C(C(=O)O)=CC=CC2=C1 HRRDCWDFRIJIQZ-UHFFFAOYSA-N 0.000 description 1
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 1
- WPUMVKJOWWJPRK-UHFFFAOYSA-N naphthalene-2,7-dicarboxylic acid Chemical compound C1=CC(C(O)=O)=CC2=CC(C(=O)O)=CC=C21 WPUMVKJOWWJPRK-UHFFFAOYSA-N 0.000 description 1
- WYRSPTDNOIZOGA-UHFFFAOYSA-K neodymium(3+);trifluoromethanesulfonate Chemical compound [Nd+3].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F WYRSPTDNOIZOGA-UHFFFAOYSA-K 0.000 description 1
- KSCKTBJJRVPGKM-UHFFFAOYSA-N octan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCCCCCC[O-].CCCCCCCC[O-].CCCCCCCC[O-].CCCCCCCC[O-] KSCKTBJJRVPGKM-UHFFFAOYSA-N 0.000 description 1
- 238000006384 oligomerization reaction Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- VPPWQRIBARKZNY-UHFFFAOYSA-N oxo(diphenyl)tin Chemical compound C=1C=CC=CC=1[Sn](=O)C1=CC=CC=C1 VPPWQRIBARKZNY-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- ROTJZTYLACIJIG-UHFFFAOYSA-N pentane-1,3,5-tricarboxylic acid Chemical compound OC(=O)CCC(C(O)=O)CCC(O)=O ROTJZTYLACIJIG-UHFFFAOYSA-N 0.000 description 1
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 description 1
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 150000007519 polyprotic acids Polymers 0.000 description 1
- HKJYVRJHDIPMQB-UHFFFAOYSA-N propan-1-olate;titanium(4+) Chemical compound CCCO[Ti](OCCC)(OCCC)OCCC HKJYVRJHDIPMQB-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- HZXJVDYQRYYYOR-UHFFFAOYSA-K scandium(iii) trifluoromethanesulfonate Chemical compound [Sc+3].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F HZXJVDYQRYYYOR-UHFFFAOYSA-K 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 239000003930 superacid Substances 0.000 description 1
- HQHCYKULIHKCEB-UHFFFAOYSA-N tetradecanedioic acid Natural products OC(=O)CCCCCCCCCCCCC(O)=O HQHCYKULIHKCEB-UHFFFAOYSA-N 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- KQPIFPBKXYBDGV-UHFFFAOYSA-M triethylstannanylium;bromide Chemical compound CC[Sn](Br)(CC)CC KQPIFPBKXYBDGV-UHFFFAOYSA-M 0.000 description 1
- WOUNUBHOYKWRNA-UHFFFAOYSA-M triethylstannyl acetate Chemical compound CC[Sn](CC)(CC)OC(C)=O WOUNUBHOYKWRNA-UHFFFAOYSA-M 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- AHZJKOKFZJYCLG-UHFFFAOYSA-K trifluoromethanesulfonate;ytterbium(3+) Chemical compound [Yb+3].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F AHZJKOKFZJYCLG-UHFFFAOYSA-K 0.000 description 1
- JPJIEXKLJOWQQK-UHFFFAOYSA-K trifluoromethanesulfonate;yttrium(3+) Chemical compound [Y+3].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F JPJIEXKLJOWQQK-UHFFFAOYSA-K 0.000 description 1
- WJPWYVWFKYPSJS-UHFFFAOYSA-J trifluoromethanesulfonate;zirconium(4+) Chemical compound [Zr+4].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F WJPWYVWFKYPSJS-UHFFFAOYSA-J 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/91—Polymers modified by chemical after-treatment
- C08G63/914—Polymers modified by chemical after-treatment derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/916—Dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/52—Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
- C08G63/56—Polyesters derived from ester-forming derivatives of polycarboxylic acids or of polyhydroxy compounds other than from esters thereof
- C08G63/58—Cyclic ethers; Cyclic carbonates; Cyclic sulfites ; Cyclic orthoesters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/672—Dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J11/00—Recovery or working-up of waste materials
- C08J11/04—Recovery or working-up of waste materials of polymers
- C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
- C08J11/18—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material
- C08J11/22—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material by treatment with organic oxygen-containing compounds
- C08J11/24—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material by treatment with organic oxygen-containing compounds containing hydroxyl groups
Definitions
- the present invention relates to processes for manufacturing elastomeric polyether esters.
- the processes can use post-consumer polyesters as starting material, and such polyether esters can have attributes and functionality substantially similar to neat or virgin polyether esters.
- Polyesters such as polyethylene terephthalate (PET) and polybutylene terephthalate (PBT) are used in a wide variety of application markets, including fibers, films, and engineering components. Tremendous amount of waste is generated each year from the use of these polyesters that has to be disposed off. Clearly, the disposal creates environmental problems. It would be desirable to re-use these wasted and post-consumed polyesters.
- PET polyethylene terephthalate
- PBT polybutylene terephthalate
- One aspect of the present invention is a process for manufacturing polyether esters from a polyester, comprising contacting said polyester with at least one diol, and at least one polyol, at a temperature in the range of from about room temperature to about
- Another aspect of the present invention is a polyether ester prepared by a process comprising contacting a polyester with at least one diol, and at least one polyol, at a temperature in the range of from about room temperature to about 300°C in the presence of a catalyst.
- the TPA or DMT separation and purification steps used in conventional processes are eliminated, even when post-consumer polyesters are used as starting materials, lowering the cost of manufacturing.
- Polymers produced using these processes provide attributes and functionality similar to the virgin polyesters and in preferred embodiments, offer an overall reduction in cost of manufacturing and energy use, lower emissions of greenhouse gases, and therefore, lower environmental footprint.
- the diol and/or the polyol, used for transesterification of the hard segment and the soft segment in the polyether ester are derived from bio-based sources.
- the terms “comprises,” “comprising,” “includes,” “including,” “has,” “having” or any other variation thereof, are intended to cover a non-exclusive inclusion.
- a process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
- a process according to the present invention comprises contacting a polyester with at least one diol and at least one polyol at an elevated temperature in presence of a catalyst,
- the process can offer an overall reduction in manufacturing cost, energy use and can thus offer a reduction in global warming gases and a lower environmental footprint.
- the polyester starting material comprises polyester selected from the group consisting of polyethylene terephthalate, polybutylene terephthalate, mixtures thereof, blends thereof and copolymers thereof.
- one polyol is used. In other embodiments, at least two polyols are used.
- the present invention provides a process for manufacturing polyether esters from post-consumer polyester, comprising contacting the post-consumer polyester with at least one diol, and at least one oligomeric or polymeric diol ("polyol”), at a temperature in the range of from about room temperature to about
- the reaction is carried out in the presence of a catalyst comprising tin or titanium.
- the process provides polyether ester comprising polyethylene terephthalate-based hard segments and polytrimethylene ether glycol (PO3G)-based soft segments from post- consumer polyesters comprising PET, including beverage bottles such as, for example, soda bottles or water bottles, by transesterification reaction of the PET with 1 ,3-propanediol, preferably a biologically derived 1 ,3-propanediol (biologically-derived PDO), and PO3G, preferably a biologically derived PO3G.
- the post-consumer polyester comprises beverage bottles made from polyester having a recycling code 1 , or polyester derived from beverage bottles.
- the post-consumer polyester comprises polymeric species selected from the group consisting of polyesters, polyether esters, mixtures thereof, blends thereof, and copolymers thereof.
- a process for manufacturing polyether esters from post-consumer polyester comprises contacting said post- consumer polyester with at least one diol, and at least one polyol, wherein the diol is biologically-derived PDO, and wherein the polyol is PO3G and/or PO4G in the molecular weight range of up to about 5000 Da, at a temperature in the range of from about 200 0 C to about 300 0 C in the presence of a catalyst comprising tin or titanium, wherein said process utilizes energy less than energy required to make polyester from esterification of diacid or diester with a diol using a polycondensation catalyst.
- polyester used in the process is also referred to herein as
- polyester starting material include, by way of example, thermoplastics commonly known as 2GT, 3GT 1 4GT, 5GT, 6GT, 7GT, mixtures thereof, blends thereof, and copolymers thereof.
- the polyester starting material comprises polyester selected from the group consisting of polyethylene terephthalate, polybutylene terephthalate, mixtures thereof, blends thereof and copolymers thereof.
- the diol is selected from the group consisting of monomeric, dimeric, or trimeric, C2-C20 alkanediols, alkoxy C2-C20 alkanediol, alkenoxy C2-C20 alkanediol, C2-C20 alkenediol, phenoxy C2-C20 alkanediol, alkylphenoxy C2-C20 alkanediol, phenyl C2-C20 alkanediol, alkylphenyl C2-C20 alkanediol, halo C2-C20 alkanediol, and chemical mixtures thereof; and the polyol is selected from the group consisting of polyols resulting from monomeric, dimeric or trimeric C2-C20 alkanediols, polyalkylene diols, alkoxyalkanediol, alkenoxyalkanediol, alkenediol, glycols, polyether glycol,
- diols selected from the group consisting of monomeric, dimeric, or trimeric ethylene glycol 1 ,3-propanediol, n-butane-1 ,3-diol, 2-methyl-1 ,3-propanediol, neopentyl glycol (2,2-dimethyl- 1 ,3- propanediol), 1 ,4-butanediol, triethylene glycol, isomers thereof and mixtures thereof.
- the 1 ,3-propanediol comprises biologically-derived PDO.
- Biologically-derived PDO is available from E.I. DuPont de Nemours Company under the tradename Bio-PDOTM.
- a polyether ester prepared by a process comprising contacting a post-consumer polyester with at least one diol, and at least one polyol, at a temperature in the range of from about room temperature to about 300 0 C in the presence of a catalyst comprising tin or titanium.
- the catalyst is an organo titanate.
- the polyther ester is prepared by a process comprising contacting post-consumer polyether ester comprising polyethylene terephthalate with a diol, and at least one polyol, wherein the diol is biologically-derived PDO, and wherein the polyol is poly(trimethylene glycol) (PO3G) and/or poly(tetramethylene glycol) and/or polypropylene glycol, the diol having a molecular weight of up to about 5000 Da, at a temperature in the range of from about 200° to about 300 0 C in the presence of a catalyst comprising tin or titanium, wherein the polyester is at least 80% poly(trimethylene terephthalate) by weight and at most 20% and PET by weight.
- PO3G poly(trimethylene glycol)
- poly(tetramethylene glycol) and/or polypropylene glycol the diol having a molecular weight of up to about 5000 Da, at a temperature in the range of from about 200
- the polyether ester can be used to make finished products. Examples include products selected from the group consisting of molded products, monofilaments, and packaging applications, particularly packaging of products for medical applications.
- the polyether ester has an intrinsic viscosity in the range of from about 0.2 to about 2.0.
- Polyester starting material includes polyesters as well as thermoplastic elastomers based on polyesters, and including post- consumer polyester.
- polyesters polymeric or oligomeric species resulting from condensation reaction (polymerization or oligomerization) of dihydroxy compounds with polybasic acids.
- examples are organic dibasic acids having the formula of HOOCACOOH in which A is an alkylene group, an arylene group, alkenylene group.
- a single type of acid, or combinations of two or more thereof, can be used.
- Each A has about 2 to about 30, preferably about 3 to about 25, more preferably about 4 to about 20, and most preferably 4 to 15 carbon atoms per group.
- acids include, but are not limited to, terephthalic acid, isophthalic acid, phthalic acid, 4,4'-diphenylene dicarboxylic acids, succinic acid, adipic acid, glutaric acid, bibenzoic acid, naphthalic acid, bis(p- carboxyphenyl)methane, 1 ,5-naphthalene dicarboxylic acid, 2,6- naphthalene dicarboxylic acid, 2,7-naphthalene dicarboxylic acid, 4,4'- sulfonyl dibenzoic acid, p-(hydroxyethoxy)benzoic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, 1 ,12-dodecane dioic acid.
- the diacid or diester can be aliphatic (including cycloaliphatic) or aromatic, or a combination thereof, and is preferably selected from the group consisting of aromatic dicarboxylic acids and esters (preferably short chain alkyl esters, and more preferably methyl esters), and combinations thereof.
- aromatic dicarboxylic acids and esters preferably short chain alkyl esters, and more preferably methyl esters
- Preferred are aliphatic or aromatic diacids, and most preferred are aromatic dicarboxylic acids and combinations thereof.
- the aliphatic or aromatic diacid is an aromatic diacid selected from the group consisting of terephthalic acid, isophthalic acid. Of these, terephthalic acid and isophthalic acid, and mixtures thereof are preferred, with terephthalic acid being most preferred.
- polyesters are those resulting from esterification of dimethyl terephthalate, terephthalic acid, or isophthalic acid with diols. Polyesters also include copolyesters having either at least one type of the acid component of the repeat unit and/or at least one type of the diol component in the repeat unit.
- Thermoplastic elastomers can be used as starting materials if they are present in post-consumer polyester.
- Post Consumer Polyester
- post-consumer polyester polyester resulting after consumer or industrial use of the polyester.
- Post-consumer plastic frequently contains suitable polyester starting material for the processes disclosed herein.
- Exemplary post-consumer polyesters include poly(ethylene terephthalate) (2GT or PET, or PETE), poly(trimethylene terephthalate (PTT), poly(butylene terephthalate) (PBT or 4GT), poly(pentylene terephthalate) (5GT), poly(hexylene terephthalate) (6GT), and poly(heptylene terephthalate) (7GT), and polyether esters such as Hytrel® polymers, mixtures thereof, blends thereof, and copolymers thereof.
- the bulk of post-consumer polyester or polyester plastic waste consists of poly(ethylene terephthalate) identified by the recycling code 1.
- polyester plastic waste useful for the present processes include recyclable products having a polyester component such as bottles, cups, containers, packaging materials, carpets, textiles, fiber waste, films, engineering components, molded and extruded articles, laminates, coatings, adhesives, etc.
- Preferred post- consumer polyester includes polyester in the form of beverage bottles such as soda bottles and water bottles.
- Post-consumer polyester that can be used in the present processes also includes waste that contains thermoplastic elastomers (TPE) such as segmented copolyesters.
- TPE thermoplastic elastomers
- Thermoplastic elastomers are a class of polymers which combine the properties of two other classes of polymers, namely thermoplastics, which may be reformed upon heating, and elastomers which are rubber-like polymers.
- One form of TPE is a block copolymer, usually containing some blocks whose polymer properties usually resemble those of thermoplastics, and some blocks whose properties usually resemble those of elastomers.
- Post-consumer polyester starting materials useful in the processes disclosed herein can be made from additional aromatic dicarboxylic acids or diesters such as those disclosed in US6562457, US6599625, and US7144972.
- the post-consumer polyester comprises polyester selected from PET, PBT, 3GT, mixtures thereof, blends thereof and copolymers thereof;
- the diol is selected from ethylene glycol, propylene glycol, butylene glycol, isomers thereof and combinations thereof;
- the polyol is selected from the group consisting of polyols of ethylene glycol, polyols of propylene glycol, polyols of butylene glycol, polyols of isomers thereof, and combinations thereof.
- the post-consumer polyester waste comprises PET, the diol is bio-derived 1 ,3-propanediol, and the polyol is polytrimethylene glycol.
- the post-consumer polyester is PET the diol is bio-derived 1 ,3-propanediol, and the polyol is polytetramethylene glycol.
- the post- consumer polyester is PBT the diol is bio-derived 1 ,3-propanediol, and the polyol is polytrimethylene glycol.
- the post- consumer polyester is PBT the diol is bio-derived 1 ,3-propanediol, and the polyol is polytetramethylene glycol.
- the post-consumer polyester is PET and PBT
- the diol is bio-derived 1 ,3- propanediol
- the polyol is polytrimethylene glycol.
- the post-consumer polyester is PET and PBT
- the diol is bio-derived 1 ,3-propanediol
- the polyol is polytetramethylene glycol. Diols
- polyester is contacted with one or more diols to effect a transesterification reaction.
- at least one diol is used. In other embodiments, at least two diols are used.
- Exemplary diols useful for the present processes include C2- C20 alkanediols, alkoxy C2-C20 alkanediol, alkenoxy C2-C20 alkanediol, C2-C20 alkenediol, phenoxy C2-C20 alkanediol, alkylphenoxy C2-C20 alkanediol, phenyl C2-C20 alkanediol, alkylphenyl C2-C20 alkanediol, and halo C2-C20 alkanediol.
- Preferred diols include linear or branched chain C2-C20 alkanediol, for example, ethylene glycol, diethylene glycol, di-, tri- or tetraethylene glycol, di.-, tri- or tetrapropylene glycol and di-, tri- or tetrabutylene glycol, 1 , 2- propanediol, isopropylene glycol, 1 -methyl propylene glycol, 1 ,3- propanediol, n-butane-1 ,3-diol, 2-methyl-1 ,3-propanediol, neopentyl glycol (2,2-dimethyl- 1 ,3-propanediol), 2-methyl-1 ,3-propanediol, 2,2- diethyl-1 ,3-propanediol, 2-ethyl-2-(hydroxymethyl)-1 ,3-propanediol, 1 ,4-butanediol
- cycloaliphatic diols for example 1 ,4- cyclohexanediol, 1 ,4-cyclohexanedimethanol and isosorbitol.
- a highly preferred diol is 1 ,3-propanediol (PDO).
- 1 ,3-propanediol is meant a reactant comprising at least one of 1 ,3-propanediol, 1 ,3-propanediol dimer and 1 ,3-propanediol trimer, and includes mixtures thereof.
- the 1 ,3-propanediol can be obtained by any of various chemical routes or by biochemical transformation routes known to those skilled in the art.
- the PDO has a purity of greater than about 99% by weight as determined by gas chromatographic analysis. Although any combination of PDO, and dinners or trimers of PDO, can be used, it is preferred that the reactant comprise about 90% or more by weight of PDO. More preferably, the PDO reactant comprises 99% or more by weight of PDO.
- bio-derived PDO biologically-derived 1 ,3-propanediol
- Biochemical routes to PDO have been described that utilize feedstocks produced from biological and renewable resources such as corn feed stock.
- PDO is referred to herein as "biologically-derived PDO” or “bio-derived PDO”.
- biologically-derived PDO or “bio-derived PDO”.
- bacterial strains able to convert glycerol into 1 ,3-propanediol are found in e.g., in the species Klebsiella, Citrobacter, Clostridium, and Lactobacillus.
- the technique is disclosed in several patents, including, US5633362, US5686276, and, US5821092. In US5821092, Nagarajan, et al.
- the process incorporates E. CoIi bacteria, transformed with a heterologous pdu diol dehydratase gene, having specificity for 1 ,2-propanediol.
- the transformed E. CoIi is grown in the presence of glycerol as a carbon source and 1 ,3- propanediol is isolated from the growth media.
- the process of the invention provided a rapid, inexpensive and environmentally responsible source of 1 ,3-propanediol monomer useful in the production of polyesters, polyethers, and other polymers.
- the 1 , 3-propanediol may also contain small amounts, preferably no more than about 30%, more preferably no more than about 10%, by weight, based on the total weight of the diols,, of comonomer diols in addition to the reactant 1 ,3-propanediol or its dimers and trimers without detracting from the efficacy of the process.
- Examples of preferred comonomer diols include ethylene glycol, 2-methyl-1 ,3-propanediol, 2,2-dimethyM ,3 propanediol, and C6-C12 diols such as 2,2-diethyl-1 ,3-propanediol, 2-ethyl-2-hydroxymethyl-1 ,3-propanediol, 1 ,6-hexanediol, 1 ,8- octanediol, 1 ,10-decanediol, 1 ,12-dodecanediol, 1 ,4-cyclohexanediol and 1 ,4-cyclohexanedimethanol.
- a more preferred comonomer diol is ethylene glycol.
- the processes can be used for converting post-consumer polyester plastic, by reacting such plastic with 1 ,3- propanediol (PDO such as biologically-derived PDO) and a polyol, in presence of a catalyst under a nitrogen atmosphere at temperatures in the range of about 200 0 C to about 300 0 C.
- PDO 1 ,3- propanediol
- Organo titanate such as Tyzor® TPT can be used as a catalyst for this process.
- the process can be used to convert post-consumer polyester (waste) based on PET, by reacting such polyester with 1 ,3-propanediol (PDO or biologically-derived PDO) and a polyol, in presence of a catalyst under a nitrogen atmosphere at temperatures in the range of about 200 0 C to about 300°C.
- Organo titanate such as Tyzor® TPT is used as a catalyst for this process.
- the resulting polymer is a copolyester comprising ethoxy and butoxy repeat units.
- polyols oligomeric diols or polymeric diols.
- oligomeric diol is generally meant a species having more than three and up to about twenty repeat units of the same monomeric diol or a combination of comonomeric diols.
- polymeric diol is generally meant a species having more than twenty repeat units of the same monomeric diol or a combination of comonomeric diols in the backbone.
- polyester is contacted with at least one diol and at least one polyol in the presence of a catalyst, at elevated temperature, to produce an elastomeric polyether ester.
- a catalyst at elevated temperature
- the diol in the reaction mixture will contribute to the transesterification for the hard segment of the resulting elastomeric polyether ester and the polyol will contribute to the transesterification for the soft segment of the resulting elastomeric polyether ester.
- Diols can be converted to polyols in a polycondensation reaction in the presence of polycondensation catalysts.
- One or more diols can be used to produce such polyols having comonomeric diol-based repeat units.
- US6905765 describes condensation catalysts that can be used to produce the polyols. They include homogeneous catalysts such as Lewis Acids, Bronsted Acids, super acids, and mixtures thereof. Examples include inorganic acids, organic sulfonic acids, heteropolyacids, and metal salts thereof.
- Heterogeneous catalysts such as zeolites, fluorinated alumina, acid-treated silica, acid-treated silica- alumina, heteropolyacids and heteropolyacids supported on zirconia, titania, alumina and/or silica, can also be used.
- Diols from which such polyols can be produced include monomeric, dimeric, trimeric, or oligomeric C2-C20 alkanediols, alkoxy C2-C20 alkanediol, alkenoxy C2-C20 alkanediol, C2-C20 alkenediol, phenoxy C2-C20 alkanediol, alkylphenoxy C2-C20 alkanediol, phenyl C2-C20 alkanediol, alkylphenyl C2-C20 alkanediol, and halo C2-C20 alkanediol.
- diols from which such polyols can be produced include linear and branched chain monomeric, dimeric, trimeric, or oligomeric C2-C20 alkanediol, for example, ethylene glycol, diethylene glycol, di-, tri- or tetraethylene glycol, di.-, tri- or tetrapropylene glycol and di-, tri- or tetrabutylene glycol, 1 , 2-propanediol, isopropylene glycol, 1-methyl propylene glycol, 1 ,3-propanediol, n-butane-1 ,3-diol, 2-methyl-1 ,3- propanediol, neopentyl glycol (2,2-dimethyl- 1 ,3-propanediol), 2- methyl-1 ,3-propanediol, 2,2-diethyl-1 ,3-propanediol, 2-ethyl-2- (hydroxymethyl)-1
- cycloaliphatic diols for example 1 ,4- cyclohexanediol, 1 ,4-cyclohexanedimethanol and isosorbitol.
- Preferred diols for producing such polyols include monomeric, dimeric, trimeric, or oligomeric ethylene glycol, propylene glycol, and butylene glycol and their isomeric forms.
- a preferred diol is 1 ,3- propanediol (PDO).
- a further preferred diol is a bio-derived 1 ,3- propanediol (biologically-derived PDO).
- Preferred polyols are PDO and biologically-derived PDO based- polyols which are oligomeric or polymeric. Such polyols are alternatively called polytrimethylene ether glycols (PO3G).
- the soft segment when PO3G is used to form the soft segment of the resulting poly ether ester, the soft segment can be represented as comprising units represented by the following structure:
- the PO3G has a number average molecular weight (Mn) of at least about 1 ,000, more preferably at least about 1 ,500, and most preferably at least about 2,000.
- Mn is preferably less than about 5000, more preferably less than about 4,000, and most preferably less than about 3,500.
- x in the above formula is at least about 17, more preferably at least about 25 and most preferably at least about 34, and is less than about 86, more preferably less than about 67 and most preferably less than about 60.
- PO3G's useful for this invention are described in U.S. Patent Application Publication Nos. 2002/0007043 A1 and 2002/0010374 A1 ), and their PCT counterparts WO 01/44348 and 01/44150.
- up to 60 weight % of the soft segment can comprise polymeric ether glycol other than PO3G.
- polymeric ether glycol other than PO3G Preferred are those selected from the group consisting of polyethylene ether glycol (PEG), polypropylene ether glycol (PPG), polytetramethylene ether glycol (PO4G), polyhexamethylene ether glycol, and copolymers of tetrahydrofuran and 3-alkyl tetrahydrofuran (THF/3MeTHF).
- the other polymeric ether glycols preferably have a number average molecular weight of at least about 1 ,000, more preferably at least about 1 ,500, and preferably up to about 5,000, more preferably up to about 3,500.
- An especially important copolymer is the copolymer of tetrahydrofuran and 3-methyl tetrahydrofuran (THF/3MeTHF).
- THF/3MeTHF 3-methyl tetrahydrofuran
- Preferably up to 55 weight %, more preferably up to 50 weight %, and most preferably up to 15 weight %, of the polyethylene ether glycol used to form the soft segment is PO3G.
- substituted glycols such as, for example, tetrahydrofuran based polyols are included and methyl-substituted tetrahydrofuran-based polyols.
- polyether ester polymer or copolymer is produced by polycondensation of plastic waste based on PET, by reacting such waste with a mixture of 1 ,3-propanediol and polytrimethylene glycol in a molecular weight range of about 500 to about 5000.
- the soft segment content of the resulting polyether ester can also be controlled.
- the processes disclosed herein comprise contacting the post- consumer polyester with at least one diol, for example, 1 ,3- propanediol, bio-derived, or otherwise, in the presence of a catalyst comprising tin and/or titanium.
- a catalyst comprising tin and/or titanium.
- Any tin-containing compounds that can be used as an esterification catalyst can be used.
- the catalyst can be an inorganic tin compound or an organic tin compound.
- Suitable tin compounds include: n-butylstannoic acid, octylstannoic acid, dimethyltin oxide, dibutyltin oxide, dioctyltin oxide, diphenyltin oxide, tri-n-butyltin acetate, tri-n-butyltin chloride, tri-n- butyltin fluoride, triethyltin chloride, triethyltin bromide, triethyltin acetate, trimethyltin hydroxide, triphenyltin chloride, triphenyltin bromide, triphenyltin acetate, or combinations of two or more thereof.
- Tin oxide catalysts are preferred.
- Suitable tin compounds are generally commercially available.
- n-butylstannoic acid can be obtained from the Witco Chemical Corp., Greenwich, Conn.
- titanium compounds are organic titanium compounds, in particular, titanium tetrahydrocarbyloxides, also referred to as tetraalkyl titanates.
- suitable titanium tetrahydrocarbyloxide compounds include those expressed by the general formula Ti(OR)4 where each R is individually selected from an alkyl or aryl radical containing from 1 to about 30, preferably 2 to about 18, and most preferably 2 to 12 carbon atoms per radical and each R can be the same or different.
- Titanium tetrahydrocarbyloxides in which the hydrocarboxyl group contains from 2 to about 12 carbon atoms per radical which is a linear or branched alkyl radical are most preferred because they are relatively inexpensive, more readily available, and effective in forming the solution.
- Suitable titanium tetrahydrocarbyloxides include, but are not limited to, titanium tetraethoxide, titanium tetrapropoxide, titanium tetraisopropoxide, titanium tetra-n-butoxide, titanium tetrahexoxide, titanium tetra 2- ethylhexoxide, titanium tetraoctoxide, and combinations of two or more thereof.
- the titanium tetrahydrocarbyloxides can be produced by, for example, mixing titanium tetrachloride and an alcohol in the presence of a base, such as ammonia, to form the titanium tetracarbyloxide or tetraalkyl titanate.
- the alcohol can be ethanol, n-propanol, isopropanol, n-butanol, or isobutanol.
- Titanium tetrahydrocarbyloxides thus produced can be recovered by first removing by-product ammonium chloride by any means known to one skilled in the art such as filtration followed by distilling the titanium tetrahydrocarbyloxides from the reaction mixture. This process can be carried out at a temperature in the range of from about 0 to about 150 0 C. Titanates having longer alkyl groups can also be produced by transesterification of those having R groups up to C4 with alcohols having more than 4 carbon atoms per molecule.
- organic titanium compounds examples include TYZOR®TPT and TYZOR®TBT (tetra isopropyl titanate and tetra n-butyl titanate, respectively) available from E. I. du Pont de Nemours and Company, Wilmington, Del., U.S.A.
- the weight ratio of the tin compound to the titanium compound can be any ratio provided that the ratio can catalyze the esterification of an acid and 1 ,3-propanediol. Generally, the ratio can be about 0.01 :1 to about 100:1 and preferably about 0.1 :1 to about 10:1.
- the catalyst can be prepared by any method known to one skilled in the art.
- the catalyst can be produced by separately combining the tin compound or titanium compound with the acid or 1 ,3-propanediol in an esterification medium, or in situ in an esterification medium by combining the tin compound or titanium compound with the acid, 1 ,3-propanediol, or both.
- the catalyst is produced before the contacting with the esterification medium.
- a premixed catalyst comprising, consisting essentially of, or consisting of the tin compound and the titanium compound be produced before being contacted with the esterification medium.
- the tin and/or titanium catalysts are mixed in an organic solvent before adding to the reactants. Any solvent that can substantially dissolve or disperse the catalyst and does not interfere with polymerization can be used.
- the organic solvent can be 1 ,3-propanediol.
- the amount of tin used as catalyst is between about 2 and 400 ppm and the amount of titanium used as catalyst is between about 2 and 400 ppm, each elemental amount based on the weight of reactants in the esterification medium.
- the process can allow control of the ratio of the acid repeat units to the alkoxy repeat units and the ratio of soft segments to hard segments in the elastomeric polyether ester made by the process, by controlling the initial molar ratio of the diol, polyol, and the polyester.
- the mole ratio is in the range of from about 100:1 to about 1 :1 of (diol + polyol) to polyester (or to the amount of polyester in the post-consumer polyester when other components such as waste are present).
- the molar ratio of diol to polyol is from about 100:1 to about 1 :100.
- a preferred mole ratio of (diol+polyol) to polyester is in the range of 5:1 to about 1 :1.
- the transesterification can be affected in a preferred temperature range of from about 200 0 C to about 300 0 C.
- the temperature can, if desired, be maintained at one point for the entire reaction. Alternatively, the temperature can be maintained for different or same periods of time at more than one temperature points, and the temperature varied once or more than once.
- branching agents In preparing the polyether ester elastomers, it is sometimes desirable to incorporate known branching agents to increase melt strength. Such agents are incorporated added to the reaction mixture before transesterification. In such instances, a branching agent is typically used in a concentration of 0.00015 to 0.005 equivalents per 100 grams of polymer.
- the branching agent can be a polyol having 3- 6 hydroxyl groups, a polycarboxylic acid having 3 or 4 carboxyl groups, or a hydroxy acid having a total of 3-6 hydroxyl and carboxyl groups.
- Representative polyol branching agents include glycerol, sorbitol, pentaerythritol, 1 ,1 ,4,4-tetrakis(hydroxymethyl)cyclohexane, trimethylol propane, and 1 ,2,6-hexane triol.
- Suitable polycarboxylic acid branching agents include hemimellitic, trimellitic, trimesic pyromellitic, 1 ,1 ,2,2-ethanetetracarboxylic, 1 ,1 ,2-ethanetricarboxylic, 1 ,3,5- pentanetricarboxylic, 1 ,2,3,4-cyclopentanetetracarboxylic and like acids. Although the acids can be used as is, it is preferred to use them in the form of their lower alkyl esters.
- additives can be incorporated into the polyester product by addition during esterification.
- the additives include delusterants (e.g., TiO2, zinc sulfide or zinc oxide), colorants (e.g., dyes), stabilizers (e.g., antioxidants, ultraviolet light stabilizers, heat stabilizers, etc.), fillers, flame retardants, pigments, antimicrobial agents, antistatic agents, optical brightners, extenders, processing aids, viscosity boosters, and other functional additives.
- delusterants e.g., TiO2, zinc sulfide or zinc oxide
- colorants e.g., dyes
- stabilizers e.g., antioxidants, ultraviolet light stabilizers, heat stabilizers, etc.
- fillers flame retardants, pigments, antimicrobial agents, antistatic agents, optical brightners, extenders, processing aids, viscosity boosters, and other functional additives.
- the polyesters made by the processes disclosed herein can be used in all applications in which polyester
- the polyester made by the processes can be used as fibers in all fiber applications such as apparels, textiles, carpets, cords, tire components, woven materials, nonwoven materials, packaging materials, engineering applications such as molded parts, extruded parts, laminated parts, insulation, electrical insulation, automotive parts, exterior and interior building components, bottles, and containers.
- the temperature of the reactant mixture in the flask was raised gradually to 240 0 C with the reaction mixture under a nitrogen environment. The temperature was held at 240 0 C for about 1 hour. Temperature was further raised to 250 0 C and held at 250 0 C under a vacuum of 0.2 mm (2.66X10-5 MPa) for 2 hrs. At the end of the reaction, the flask was cooled and polymer was collected.
- the resulting polymer had a melting point of 190.4 0 C, and IV of
- PET+PBT poly(trimethylene glycol) with a MW of 500 Da (for an estimated polyol soft segment content of
- Tyzor® TPT (36 mg) was added as catalyst to the polymerization mixture.
- the temperature of the reactant mixture in the flask was raised gradually to 230 0 C under a nitrogen environment. The temperature was held at 230°C for 1 hour. The temperature was further raised to 250 0 C and held at 250 0 C under a vacuum of 0.2 mm (2.66X10-5 MPa) for 2 hrs. At the end of the reaction, the flask was cooled and polymer was collected.
- the resulting polymer had a melting point of 120°C, and IV of 0.6 dL/g.
- the PET content was 8.6% by weight and PBT content was 4.9% by weight by NMR analysis.
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Abstract
Description
Claims
Priority Applications (3)
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EP07863190A EP2121819A1 (en) | 2006-12-27 | 2007-12-20 | Processes for making elastomeric polyether esters and polyether esters made therefrom |
KR1020097015602A KR20090108047A (en) | 2006-12-27 | 2007-12-20 | Processes for making elastomeric polyether esters and polyether esters made therefrom |
JP2009544048A JP2010514895A (en) | 2006-12-27 | 2007-12-20 | Process for producing rubber elastic polyetheresters |
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US88207406P | 2006-12-27 | 2006-12-27 | |
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US11/944,276 | 2007-11-21 | ||
US11/944,276 US20090131625A1 (en) | 2007-11-21 | 2007-11-21 | Processes for making elastomeric polyester esters from post-consumer polyester |
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WO2015171631A1 (en) * | 2014-05-05 | 2015-11-12 | Invista North America S.A R.L. | Bio-derived polyurethane fiber |
US9580546B2 (en) | 2014-10-29 | 2017-02-28 | Resinate Materials Group, Inc. | Polymeric plasticizer compositions |
US9714334B2 (en) | 2015-01-30 | 2017-07-25 | Resinate Materials Group, Inc. | Integrated process for treating recycled PET and PTT materials |
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US9890243B2 (en) | 2014-10-29 | 2018-02-13 | Resinate Materials Group, Inc. | Polymeric plasticizer compositions |
US9896540B2 (en) | 2014-08-20 | 2018-02-20 | Resinate Materials Group, Inc. | Polyester polyols from recycled polymers and waste streams |
US9951171B2 (en) | 2014-08-20 | 2018-04-24 | Resinate Materials Group, Inc. | Polyester polyols from recycled polymers and waste streams |
EP4116366A1 (en) * | 2021-07-06 | 2023-01-11 | SHPP Global Technologies B.V. | Sustainable copolyester elastomer compositions with improved color capability |
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KR101433898B1 (en) * | 2012-08-22 | 2014-08-27 | 주식회사 휴비스 | Polyether Ester Elastomer with Excellent Thermal Stability and Method of Preparing Same |
EP3744804A1 (en) | 2013-06-10 | 2020-12-02 | DSM IP Assets B.V. | Thermoplastic polyester hot melt adhesive |
ITTO20130711A1 (en) * | 2013-09-02 | 2015-03-03 | Biochemtex Spa | COMPOSITIONS OF BIODERIVATED ETHYLENE GLYCOL FOR POLYESTER BOTTLES |
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- 2007-12-20 JP JP2009544048A patent/JP2010514895A/en active Pending
- 2007-12-20 EP EP07863190A patent/EP2121819A1/en not_active Withdrawn
- 2007-12-20 KR KR1020097015602A patent/KR20090108047A/en not_active Application Discontinuation
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KR20090108047A (en) | 2009-10-14 |
EP2121819A1 (en) | 2009-11-25 |
JP2010514895A (en) | 2010-05-06 |
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