US20010016642A1 - Esterification process - Google Patents
Esterification process Download PDFInfo
- Publication number
- US20010016642A1 US20010016642A1 US09/793,832 US79383201A US2001016642A1 US 20010016642 A1 US20010016642 A1 US 20010016642A1 US 79383201 A US79383201 A US 79383201A US 2001016642 A1 US2001016642 A1 US 2001016642A1
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- United States
- Prior art keywords
- composition
- acid
- titanium
- esterification
- tin
- Prior art date
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- Granted
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- 238000000034 method Methods 0.000 title claims abstract description 39
- 238000005886 esterification reaction Methods 0.000 title abstract description 69
- 230000032050 esterification Effects 0.000 title abstract description 57
- 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 104
- 239000003054 catalyst Substances 0.000 claims abstract description 66
- -1 for example Polymers 0.000 claims abstract description 46
- 239000010936 titanium Substances 0.000 claims abstract description 44
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 38
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 37
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 36
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 claims abstract description 34
- 229920000166 polytrimethylene carbonate Polymers 0.000 claims abstract description 34
- 239000000203 mixture Substances 0.000 claims abstract description 33
- 239000002253 acid Substances 0.000 claims abstract description 24
- 229920000642 polymer Polymers 0.000 claims abstract description 21
- 229920002215 polytrimethylene terephthalate Polymers 0.000 claims abstract description 16
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 29
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 13
- 230000000873 masking effect Effects 0.000 claims description 3
- 239000000049 pigment Substances 0.000 claims description 3
- 102000018361 Contactin Human genes 0.000 claims 1
- 108060003955 Contactin Proteins 0.000 claims 1
- 238000006068 polycondensation reaction Methods 0.000 abstract description 12
- 229920000728 polyester Polymers 0.000 abstract description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 8
- ZHVZTRUUPYIJTQ-UHFFFAOYSA-N bis(3-hydroxypropyl) benzene-1,4-dicarboxylate Chemical compound OCCCOC(=O)C1=CC=C(C(=O)OCCCO)C=C1 ZHVZTRUUPYIJTQ-UHFFFAOYSA-N 0.000 abstract description 5
- 229920001577 copolymer Polymers 0.000 abstract description 2
- 229940035437 1,3-propanediol Drugs 0.000 description 29
- 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 20
- 230000000052 comparative effect Effects 0.000 description 17
- 239000000243 solution Substances 0.000 description 12
- 150000003606 tin compounds Chemical class 0.000 description 12
- 150000003609 titanium compounds Chemical class 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 6
- 229920001283 Polyalkylene terephthalate Polymers 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 239000012974 tin catalyst Substances 0.000 description 4
- 238000010923 batch production Methods 0.000 description 3
- 238000010924 continuous production Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 229920001707 polybutylene terephthalate Polymers 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000005809 transesterification reaction Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- MXDMYNUUAZTRHL-UHFFFAOYSA-N 2-hydroxyacetic acid;terephthalic acid Chemical compound OCC(O)=O.OCC(O)=O.OC(=O)C1=CC=C(C(O)=O)C=C1 MXDMYNUUAZTRHL-UHFFFAOYSA-N 0.000 description 2
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-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
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- 229940043375 1,5-pentanediol Drugs 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- CWESERWNUIUBJU-UHFFFAOYSA-N 2-(2-chlorophenyl)-5-methyl-4h-pyrazol-3-one Chemical compound O=C1CC(C)=NN1C1=CC=CC=C1Cl CWESERWNUIUBJU-UHFFFAOYSA-N 0.000 description 1
- NQEZDDPEJMKMOS-UHFFFAOYSA-N 4-trimethylsilylbut-3-yn-2-one Chemical compound CC(=O)C#C[Si](C)(C)C NQEZDDPEJMKMOS-UHFFFAOYSA-N 0.000 description 1
- HVGAPIUWXUVICC-UHFFFAOYSA-N 6-methylheptan-1-olate;titanium(4+) Chemical compound [Ti+4].CC(C)CCCCC[O-].CC(C)CCCCC[O-].CC(C)CCCCC[O-].CC(C)CCCCC[O-] HVGAPIUWXUVICC-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- GCTFWCDSFPMHHS-UHFFFAOYSA-M Tributyltin chloride Chemical compound CCCC[Sn](Cl)(CCCC)CCCC GCTFWCDSFPMHHS-UHFFFAOYSA-M 0.000 description 1
- TUEIURIZJQRMQE-UHFFFAOYSA-N [2-(tert-butylsulfamoyl)phenyl]boronic acid Chemical compound CC(C)(C)NS(=O)(=O)C1=CC=CC=C1B(O)O TUEIURIZJQRMQE-UHFFFAOYSA-N 0.000 description 1
- BLOIXGFLXPCOGW-UHFFFAOYSA-N [Ti].[Sn] Chemical class [Ti].[Sn] BLOIXGFLXPCOGW-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000004450 alkenylene group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 150000005840 aryl radicals Chemical class 0.000 description 1
- 125000000732 arylene group Chemical group 0.000 description 1
- 239000001055 blue pigment Substances 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
- OWBTYPJTUOEWEK-UHFFFAOYSA-N butane-2,3-diol Chemical compound CC(O)C(C)O OWBTYPJTUOEWEK-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- PIMYDFDXAUVLON-UHFFFAOYSA-M chloro(triethyl)stannane Chemical compound CC[Sn](Cl)(CC)CC PIMYDFDXAUVLON-UHFFFAOYSA-M 0.000 description 1
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 1
- WNVQCJNZEDLILP-UHFFFAOYSA-N dimethyl(oxo)tin Chemical compound C[Sn](C)=O WNVQCJNZEDLILP-UHFFFAOYSA-N 0.000 description 1
- LQRUPWUPINJLMU-UHFFFAOYSA-N dioctyl(oxo)tin Chemical compound CCCCCCCC[Sn](=O)CCCCCCCC LQRUPWUPINJLMU-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 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
- 238000001914 filtration Methods 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 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
- 229910052757 nitrogen Inorganic materials 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
- 235000005985 organic acids Nutrition 0.000 description 1
- 125000000962 organic group Chemical group 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
- WCVRQHFDJLLWFE-UHFFFAOYSA-N pentane-1,2-diol Chemical compound CCCC(O)CO WCVRQHFDJLLWFE-UHFFFAOYSA-N 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 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
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000003134 recirculating effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- UOULCEYHQNCFFH-UHFFFAOYSA-M sodium;hydroxymethanesulfonate Chemical compound [Na+].OCS([O-])(=O)=O UOULCEYHQNCFFH-UHFFFAOYSA-M 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 229910052718 tin 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
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 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
- 229910052726 zirconium Inorganic materials 0.000 description 1
- 150000003755 zirconium compounds Chemical class 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
- 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
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
Definitions
- This invention relates to a process for producing a prepolymer and polyester from 1,3-propanediol by direct esterification in the presence of a catalyst comprising tin and titanium.
- PET Polyethylene terephthalate
- PBT polybutylene terephthalate
- polyalkylene terephthalates are common commercial polyesters.
- PTT poly(trimethylene terephthalate), also called polypropylene terephthalate
- 2GT 2GT
- 4GT 3GT
- Polyalkylene terephthalates commonly are produced by one of two routes: (1) by transesterification of a dialkyl terephthalate diester, typically dimethyl terephthalate, with a glycol to form an intermediate bis-glycolate terephthalate, followed by polycondensation to form the polyalkylene terephthalate; or (2) by direct esterification of terephthalic acid (TPA) with a glycol to form a bis-glycolate terephthalate, followed by polycondensation to form the polyalkylene terephthalate.
- TPA terephthalic acid
- terephthalic acid and an alkylene glycol are reacted in the presence of a catalyst to form a monomer and water.
- the water is removed as formed during the reaction.
- Oligomers having a degree of polymerization of about 4 or less can also be formed.
- a mixture of monomer and oligomer is produced.
- This mixture also referred to as a prepolymer, can then be polycondensed or polymerized at higher temperatures under reduced pressure in the presence of a polycondensation catalyst to form a desired polyester resin that is suitable for carpets, textiles, films and many other end-uses.
- Esterification catalysts known in the art include titanium, tin and zirconium compounds.
- Organo titanium and organo zirconium compounds are disclosed in U.S. Pat. No. 3,056,818 for use as esterification catalysts.
- the combination of organo tin and organo titanium compounds for the esterification of terephthalic acid and 1,4-butanediol is disclosed in U.S. Pat. No. 3,936,421.
- the use of tin-titanium complexes as esterification catalysts for 2GT and 4GT is disclosed in U.S. Pat. No. 4,018,708 and U.S. Pat. No. 4,020,010.
- DuPont discloses a process for faster direct esterification of a diacid to make 2GT or 4GT using relatively high amounts of an organo titanium, organo tin or organo zirconium catalyst. None of these references discloses or suggest that any of these catalysts can be used to produce 3GT.
- U.S. Pat. No. 4,611,049 discloses a process for producing 3GT or 4GT using a sulfonic acid promoter to increase the rate of polymerization when using an organo titanium or organo tin catalyst.
- U.S. Pat. No. 5,340,909 discloses the use of an effective catalytic amount of tin for the polycondensation step to make 3GT, wherein about 100 to 650 ppm of tin based on the terephthalic acid is given as the permissible range.
- a blue pigment may be added prior to the polycondensation step.
- a titanium catalyst (0-125 ppm) or a portion of the above tin catalyst (0-650 ppm) may be used during this step. No examples show the use or benefit of either titanium or tin catalysts or both for direct esterification.
- the invention is directed to a process comprising contacting an acid with 1,3-propanediol in the presence of a catalyst comprising tin and titanium.
- the invention is directed to a composition of, or comprising, a bis(3-hydroxypropyl) terephthalate prepolymer that can contain 10 to 100 ppm tin and 10 to 200 ppm titanium relative to the terephthalic acid content.
- the invention is directed to a composition of, or comprising, a poly(trimethylene terephthalate) polymer that can contain 10 to 100 ppm tin and 10 to 200 ppm titanium relative to the terephthalic acid content.
- tin and “titanium” used herein, unless otherwise indicated, are interchangeable with “tin compound” or “titanium compound”.
- a prepolymer such as, for example, 3GT prepolymer is prepared by the catalytic esterification of terephthalic acid with 1,3-propanediol.
- the prepolymer can be then polymerized at a higher temperature, using the same or additional catalysts, to make the 3GT polymer.
- the process of the invention comprises contacting an acid, preferably an organic diacid, with 1,3-propanediol in the presence of a catalyst comprising tin and titanium. Any acids that can produce an ester or polyester, when contacted with a glycol, can be used.
- the presently preferred organic diacid is an organic acid having the formula of HO 2 CACO 2 H in which A is an alkylene group, an arylene group, alkenylene group, or combinations of two or more thereof. 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.
- suitable organic acids include, but are not limited to, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, succinic acid, adipic acid, phthalic acid, glutaric acid, and combinations of two or more thereof.
- the presently preferred organic diacid is terephthalic acid or naphthalenedicarboxylic acid because the polyesters such as, for example, 3GT, produced therefrom have a wide range of industrial applications.
- Any tin-containing compounds that can be used as an esterificatin catalyst can be used. Generally, it can be an inorganic tin compound or an organic tin compound.
- suitable tin compounds include, but are not limited to, 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.
- n-butylstannoic acid octylstannoic acid
- the preferred titanium compounds are organic titanium compounds. Titanium tetrahydrocarbyloxides, also referred to as tetraalkyl titanates herein, are presently most preferred organic titanium compounds because they are readily available and effective. Examples of 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 suitable for use in the present invention 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.
- Titanates having longer alkyl groups can also be produced by transesterification of those having R groups up to C 4 with alcohols having more than 4 carbon atoms per molecule.
- Examples of commercially available organic titanium compounds include, but are not limited to, 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 so long as 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 invention process can also comprise contacting an acid with 1,3 propanediol in the presence of a second glycol.
- the amount of the second glycol incorporated into the final polyester can be up to about 20 mole percent of the polyester.
- the present invention process can also produce a copolymer in which the majority of repeat units are derived from terephthalic acid and 1,3-propanediol and up to 20 mole percent of the repeat units are derived from another acid or the second glycol or both.
- the presently preferred second glycol has the formula of R(OH) n , an alkylene glycol of the formula (HO) n A(OH) n , or combinations thereof in which R and A are the same as those disclosed above and n is 1 to about 10, preferably 1 to about 7, and most preferably 1 to 5.
- suitable second glycols include, but are not limited to, ethylene glycol, propylene glycol, isopropylene glycol, butylene glycol, 1-methyl propylene glycol, pentylene glycol, diethylene glycol, triethylene glycol, and combinations of two or more thereof.
- the presently most preferred second glycol is an alkylene glycol such as ethylene glycol.
- the esterification catalyst can be present in any concentration in the esterification medium so long as the amount can catalyze the esterification of an acid.
- the weight of the catalyst can be in the range of about 1 to about 1,000 and preferably about 5 to about 500 mg of the catalyst per kg of the acid.
- the catalyst can be produced by any method known to one skilled in the art. For example, it can be produced by separately combining the tin compound or titanium compound with the acid or 1,3-propanediol in an esterification medium. It can also be produced in situ in an esterification medium by combining the tin compound or titanium compound with the acid, 1,3-propanediol, or both. Preferably, it is produced by combining the tin compound or titanium compound before the contacting with the acid or 1,3-propanediol in an esterification medium. In other words, it is preferred that a premixed catalyst comprising, consisting essentially of, or consisting of the tin compound and the titanium compound be produced before being contacted with the acid or 1,3-propanediol.
- the tin and titanium catalysts are mixed in an organic solvent before adding to the reaction mass.
- organic solvent can be 1,3-propanediol.
- the amount of tin used as catalyst is between about 10 and 100 ppm and the amount of titanium used as catalyst is between about 10 and 200 ppm, each elemental amount based on the weight of acid present in the esterification medium.
- the molar ratio of 1,3-propanediol to the acid can be any ratio so long as the esterification can take place. Presently it is preferred that the ratio be in the range of about 0.1:1 to about 10:1, preferably about 0.5:1 to about 5:1, and most preferably 1.1:1 to about 2.2:1.
- the esterification can be carried out under any condition known to one skilled in the art. The condition can include a temperature from about 100° C. to about 300° C., preferably about 155° C. to about 250° C. The esterification can be carried out under any pressure that can accommodate the temperature.
- a composition of, or comprising, a bis(3-hydroxypropyl) terephthalate prepolymer is provided.
- the prepolymer can be produced by the process or other processes.
- the composition can contain about 10 to 100 ppm tin and 0 to 200 ppm titanium relative to the terephthalic acid content.
- ppm refers to mg of elemental tin or titanium per kg terephthalic acid.
- the prepolymer can be produced by either batch or continuous processes.
- a batch process the terephthalic acid is contacted with 1,3-propanediol in the presence of a catalyst.
- a continuous process the terephthalic acid and 1,3-propanediol are combined with a recirculating stream of prepolymer in the presence of a catalyst. Variations of these processes can also be used, as will be apparent to one skilled in the art.
- the reaction temperature can range from about 100 to about 300° C., and at a pressure that can accommodate the temperature range. The preferred temperature ranges from about 155 to 250° C.
- 1,3-propanediol be present in a slight molar excess compared to the terephthalic acid as disclosed above.
- Terephthalic acid is commercially available from E. I. duPont de Nemours and Company and 1,3-propanediol is commercially available from the Degussa Corporation.
- a composition of, or comprising, a poly(trimethylene terephthalate) polymer is provided.
- the poly(trimethylene terephthalate) polymer can have an intrinsic viscosity (IV) in the range from about 0.3 to about 2.0 and a b value in the range of from less than about 10, preferably less than 8, more preferably less than about 6, and most preferably less than about 5.
- the composition can be produced from the prepolymer disclosed above and can contain 10 to 100 ppm tin and 10 to 200 ppm titanium relative to the terephthalic acid content.
- ppm refers to mg of elemental tin or titanium per kg terephthalic acid.
- the composition can be produced by a polymerization process, which is also known as polycondensation in which a prepolymer is polycondensed to form a polyester such as, for example, poly(trimethylene terephthalate) or 3GT, with the elimination of alcohol, as is known in the art. Typically, the alcohol can be removed by distillation under reduced pressure.
- the catalyst disclosed above can be used in the polycondensation step alone or with an additional catalyst. Polymerization can be continued until the resulting polymer has the desired degree of polycondensation, as measured by its IV. Intrinsic viscosity is determined by measuring the flow time of a solution of known polymer concentration and the flow time of the polymer solvent in a capillary viscometer, as set forth in ASTM D2857.95
- the color of the resulting polymer is measured in terms of the L-value and b-value, using an instrument such as the SP-78 Spectrophotometer.
- the L-value shows brightness, with the greater the numerical value showing higher (desirable) brightness and the b-value shows the degree of yellowness, with a higher numerical value showing a higher (undesirable) degree of yellowness.
- This example demonstrates the esterification reaction of terephthalic acid with 1,3-propanediol using only n-butylstannoic acid as the esterification catalyst to form bis(3-hydroxypropyl) terephthalate.
- This example demonstrates the esterification reaction of terephthalic acid with 1,3-propanediol using n-butylstannoic acid (149 ppm tin based on TPA) as the esterification catalyst.
- n-butylstannoic acid 149 ppm tin based on TPA
- the procedure of Comparative Example 1 was followed except that 17.4 mg of n-butylstannoic acid was used as the esterification catalyst. It took 4.5 hours to reach a clear solution.
- This example demonstrates the esterification reaction of terephthalic acid with 1,3-propanediol using n-butylstannoic acid (99 ppm of tin based on TPA) as the esterification catalyst.
- n-butylstannoic acid 99 ppm of tin based on TPA
- the procedure of Comparative Example 1 was followed except that 11.6 mg of n-butylstannoic acid was used as the esterification catalyst. It took 5.5 hours at 210° C. to reach a clear solution.
- This example demonstrates the esterification reaction of terephthalic acid with 1,3-propanediol using n-butylstannoic acid (62 ppm of tin based on TPA) as the esterification catalyst.
- n-butylstannoic acid 62 ppm of tin based on TPA
- the procedure of Comparative Example 1 was followed except that 7.2 mg of n-butylstannoic acid was used as the esterification catalyst. It took 9 hours at 210° C. to reach a clear solution.
- This example demonstrates the esterification reaction of terephthalic acid with 1,3-propanediol in the absence of a catalyst.
- the procedure of Comparative Example 1 was followed except that no catalyst was used. It took more than 16 hours at 210° C. to reach a clear solution.
- This example demonstrates the esterification reaction of terephthalic acid with 1,3-propanediol using tetraisopropyl titanate (62 ppm of Ti based on TPA) as the esterification catalyst.
- tetraisopropyl titanate 62 ppm of Ti based on TPA
- the procedure of Comparative Example 1 was followed except that 24.4 mg of tetraisopropyl titanate was used as the esterification catalyst. It took 7.5 hours at 210° C. to reach a clear solution.
- This example demonstrates the esterification reaction of terephthalic acid with 1,3-propanediol using a combination of n-butylstannoic acid (31 ppm of tin based on TPA) and tetraisopropyl titanate (62 ppm of Ti based on TPA) as the esterification catalyst.
- n-butylstannoic acid 31 ppm of tin based on TPA
- tetraisopropyl titanate 62 ppm of Ti based on TPA
- This example demonstrates the esterification reaction of terephthalic acid with 1,3-propanediol using combination of n-butylstannoic acid (99 ppm of tin based on TPA) and tetraisopropyl titanate (62 ppm of Ti based on TPA) as the esterification catalyst.
- the procedure of Comparative Example 1 was followed except that 11.6 mg of n-butylstannoic acid and 24.4 mg of tetraisopropyl titanate was added separately as the esterification catalyst. It took 4 hours 15 minutes at 210° C. to reach a clear solution. Thereafter, the resulting monomer was polymerized in the same reaction vessel at a temperature of 250° C. and a pressure of 0.2 mm Hg without any additional catalyst.
- the poly(trimethylene terephthalate) resin color and IV are given in Table 1.
- This example demonstrates the esterification reaction of terephthalic acid with 1,3-propanediol using a pre-mixed solution of n-butylstannoic acid (99 ppm of tin based on TPA) and tetraisopropyl titanate (62 ppm of Ti based on TPA) as the esterification catalyst.
- n-butylstannoic acid 99 ppm of tin based on TPA
- tetraisopropyl titanate 62 ppm of Ti based on TPA
- the resulting monomer bis(3-hydroxypropyl)terephthalate
- the poly(trimethylene terephthalate) resin obtained had an IV of 0.78 dl/g and melting point of 230° C. (measured as the peak on the endotherm of differential scanning calorimeter, DSC).
- Table 1 summarizes the results of the above examples.
- the catalyst concentration used during the esterification reaction is given in the table as the parts per million (ppm) relative to the weight of TPA or as mg catalyst per kg TPA.
- Example 3A and 3B in comparison to Example 2, show that premixing the tin and titanium catalysts had the shortest the reaction time and produced a polymer having the highest L value, lowest b value, and highest IV among those tested.
- the invention catalyst a combination of tin and titanium catalysts, completes esterification faster than the individual catalyst components thereby minimizing the time and temperature required for esterification.
- the invention product is a polyester such as 3GT of high quality having low tin concentration.
- a high concentration of tin compounds causes discoloration and degradation of polymer as well as the formation of large amounts of by-products.
- the invention catalyst can be used for both esterification and polycondensation thereby eliminating the need for a separate catalyst during the polycondensation step.
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Abstract
Description
- This application is a Divisional of application Ser. No. 09/500,340 filed on Feb. 8, 2000, which is incorporated herein by reference.
- This invention relates to a process for producing a prepolymer and polyester from 1,3-propanediol by direct esterification in the presence of a catalyst comprising tin and titanium.
- Polyethylene terephthalate (PET) and polybutylene terephthalate (PBT), generally referred to as “polyalkylene terephthalates”, are common commercial polyesters. Recently, poly(trimethylene terephthalate), (PTT), also called polypropylene terephthalate, has achieved commercial importance because of its elasticity, as measured by its elastic recovery and resilience. Based on the numbers of carbon atoms in the glycol used, the above PET, PBT and PTT are also referred to as 2GT, 4GT and 3GT, respectively.
- Polyalkylene terephthalates commonly are produced by one of two routes: (1) by transesterification of a dialkyl terephthalate diester, typically dimethyl terephthalate, with a glycol to form an intermediate bis-glycolate terephthalate, followed by polycondensation to form the polyalkylene terephthalate; or (2) by direct esterification of terephthalic acid (TPA) with a glycol to form a bis-glycolate terephthalate, followed by polycondensation to form the polyalkylene terephthalate.
- In producing polyalkylene terephthalates by direct esterification, terephthalic acid and an alkylene glycol are reacted in the presence of a catalyst to form a monomer and water. The water is removed as formed during the reaction. Oligomers having a degree of polymerization of about 4 or less can also be formed. Generally, during an esterification a mixture of monomer and oligomer is produced. This mixture, also referred to as a prepolymer, can then be polycondensed or polymerized at higher temperatures under reduced pressure in the presence of a polycondensation catalyst to form a desired polyester resin that is suitable for carpets, textiles, films and many other end-uses.
- These reactions can be carried out in a batch or continuous process. The same or different catalysts can be used for the esterification and polycondensation steps.
- Esterification catalysts known in the art include titanium, tin and zirconium compounds. Organo titanium and organo zirconium compounds are disclosed in U.S. Pat. No. 3,056,818 for use as esterification catalysts. The combination of organo tin and organo titanium compounds for the esterification of terephthalic acid and 1,4-butanediol is disclosed in U.S. Pat. No. 3,936,421. The use of tin-titanium complexes as esterification catalysts for 2GT and 4GT is disclosed in U.S. Pat. No. 4,018,708 and U.S. Pat. No. 4,020,010. U.S. Pat. No. 5,015,759 (DuPont) discloses a process for faster direct esterification of a diacid to make 2GT or 4GT using relatively high amounts of an organo titanium, organo tin or organo zirconium catalyst. None of these references discloses or suggest that any of these catalysts can be used to produce 3GT.
- The use of 3GT is handicapped by various difficulties in its preparation. Surprisingly, using direct analogs of the processes developed for preparation of 2GT and 4GT do not necessarily give 3GT with satisfactory properties.
- For example, relatively high temperature (about 290° C.) esterification is considered commercially acceptable for 2GT made from TPA. However, esterification to produce 3GT under similar process conditions appeared to result in the significant liberation of undesirable by-products, including acrolein and allyl alcohol. In addition, the intermediate 3GT prepolymer was found to be highly discolored under these conditions, an indication of poor 3GT polymer quality. Similar esterification difficulties in processes for the production of 4GT prepolymer by direct esterification have led to a preference for the transesterification route using dimethylterephthalate instead of terephthalic acid. For 3GT, because of the greater availability of terephthalic acid in many countries, it is important to develop a low temperature esterification process for the commercial production of good quality 3GT prepolymer.
- U.S. Pat. No. 4,611,049 discloses a process for producing 3GT or 4GT using a sulfonic acid promoter to increase the rate of polymerization when using an organo titanium or organo tin catalyst.
- U.S. Pat. No. 5,340,909 discloses the use of an effective catalytic amount of tin for the polycondensation step to make 3GT, wherein about 100 to 650 ppm of tin based on the terephthalic acid is given as the permissible range. To mask the resulting polymer yellowness, a blue pigment may be added prior to the polycondensation step. When the prepolymer is made by direct esterification, a titanium catalyst (0-125 ppm) or a portion of the above tin catalyst (0-650 ppm) may be used during this step. No examples show the use or benefit of either titanium or tin catalysts or both for direct esterification.
- In the above processes for 3GT, too high an amount of catalyst results in a color problem, while too low an amount results in an unacceptably slow reaction. In particular, using a high concentration of tin catalyst is inadvisable since it causes discoloration and degradation of polymer as well as the formation of large amounts of undesirable by-products. In addition, a high amount of tin compounds remaining in the final polymer may be undesirable in certain end-use applications. None of the above references specifically disclose a combination of tin and titanium catalysts for the direct esterification of terephthalic acid with 1,3-propylene glycol, nor is there any information to suggest that there would be any advantage in using a combination of these two catalysts for this process.
- There is a need for an improved process for the direct esterification of an acid such as, for example, terephthalic acid with 1,3-propylene glycol. There is also a need to reduce the reaction time for esterification, carry out the esterification at relatively lower temperatures, reduce the concentration of tin in the resulting polymer, and produce a product with improved color without the need of a masking pigment.
- In a first embodiment, the invention is directed to a process comprising contacting an acid with 1,3-propanediol in the presence of a catalyst comprising tin and titanium.
- In a second embodiment, the invention is directed to a composition of, or comprising, a bis(3-hydroxypropyl) terephthalate prepolymer that can contain 10 to 100 ppm tin and 10 to 200 ppm titanium relative to the terephthalic acid content.
- In a third embodiment, the invention is directed to a composition of, or comprising, a poly(trimethylene terephthalate) polymer that can contain 10 to 100 ppm tin and 10 to 200 ppm titanium relative to the terephthalic acid content.
- The term “tin” and “titanium” used herein, unless otherwise indicated, are interchangeable with “tin compound” or “titanium compound”.
- A prepolymer such as, for example, 3GT prepolymer is prepared by the catalytic esterification of terephthalic acid with 1,3-propanediol. The prepolymer can be then polymerized at a higher temperature, using the same or additional catalysts, to make the 3GT polymer.
- The process of the invention comprises contacting an acid, preferably an organic diacid, with 1,3-propanediol in the presence of a catalyst comprising tin and titanium. Any acids that can produce an ester or polyester, when contacted with a glycol, can be used.
- The presently preferred organic diacid is an organic acid having the formula of HO2CACO2H in which A is an alkylene group, an arylene group, alkenylene group, or combinations of two or more thereof. 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. Examples of suitable organic acids include, but are not limited to, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, succinic acid, adipic acid, phthalic acid, glutaric acid, and combinations of two or more thereof. The presently preferred organic diacid is terephthalic acid or naphthalenedicarboxylic acid because the polyesters such as, for example, 3GT, produced therefrom have a wide range of industrial applications.
- Any tin-containing compounds that can be used as an esterificatin catalyst can be used. Generally, it can be an inorganic tin compound or an organic tin compound. Examples of suitable tin compounds include, but are not limited to, 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. These tin compounds are believed commercially available. For example, n-butylstannoic acid can be obtained from the Witco Chemical Company.
- According to the invention, the preferred titanium compounds are organic titanium compounds. Titanium tetrahydrocarbyloxides, also referred to as tetraalkyl titanates herein, are presently most preferred organic titanium compounds because they are readily available and effective. Examples of 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 suitable for use in the present invention 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° 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.
- Examples of commercially available organic titanium compounds include, but are not limited to, 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 so long as 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.
- According to the invention, the invention process can also comprise contacting an acid with 1,3 propanediol in the presence of a second glycol. The amount of the second glycol incorporated into the final polyester can be up to about 20 mole percent of the polyester. The present invention process can also produce a copolymer in which the majority of repeat units are derived from terephthalic acid and 1,3-propanediol and up to 20 mole percent of the repeat units are derived from another acid or the second glycol or both.
- The presently preferred second glycol has the formula of R(OH)n, an alkylene glycol of the formula (HO)nA(OH)n, or combinations thereof in which R and A are the same as those disclosed above and n is 1 to about 10, preferably 1 to about 7, and most preferably 1 to 5. Examples of suitable second glycols include, but are not limited to, ethylene glycol, propylene glycol, isopropylene glycol, butylene glycol, 1-methyl propylene glycol, pentylene glycol, diethylene glycol, triethylene glycol, and combinations of two or more thereof. The presently most preferred second glycol is an alkylene glycol such as ethylene glycol.
- According to the invention, the esterification catalyst can be present in any concentration in the esterification medium so long as the amount can catalyze the esterification of an acid. Generally, the weight of the catalyst can be in the range of about 1 to about 1,000 and preferably about 5 to about 500 mg of the catalyst per kg of the acid.
- The catalyst can be produced by any method known to one skilled in the art. For example, it can be produced by separately combining the tin compound or titanium compound with the acid or 1,3-propanediol in an esterification medium. It can also be produced in situ in an esterification medium by combining the tin compound or titanium compound with the acid, 1,3-propanediol, or both. Preferably, it is produced by combining the tin compound or titanium compound before the contacting with the acid or 1,3-propanediol in an esterification medium. In other words, it is preferred that a premixed catalyst comprising, consisting essentially of, or consisting of the tin compound and the titanium compound be produced before being contacted with the acid or 1,3-propanediol.
- More preferably, the tin and titanium catalysts are mixed in an organic solvent before adding to the reaction mass. Any solvent that can substantially dissolve or disperse the catalyst and does not interfere with polymerization can be used. For convenience, the organic solvent can be 1,3-propanediol.
- Preferably, the amount of tin used as catalyst is between about 10 and 100 ppm and the amount of titanium used as catalyst is between about 10 and 200 ppm, each elemental amount based on the weight of acid present in the esterification medium.
- The molar ratio of 1,3-propanediol to the acid can be any ratio so long as the esterification can take place. Presently it is preferred that the ratio be in the range of about 0.1:1 to about 10:1, preferably about 0.5:1 to about 5:1, and most preferably 1.1:1 to about 2.2:1. The esterification can be carried out under any condition known to one skilled in the art. The condition can include a temperature from about 100° C. to about 300° C., preferably about 155° C. to about 250° C. The esterification can be carried out under any pressure that can accommodate the temperature.
- In the second embodiment, a composition of, or comprising, a bis(3-hydroxypropyl) terephthalate prepolymer is provided. The prepolymer can be produced by the process or other processes. The composition can contain about 10 to 100 ppm tin and 0 to 200 ppm titanium relative to the terephthalic acid content. The term “ppm” used herein refers to mg of elemental tin or titanium per kg terephthalic acid.
- The prepolymer can be produced by either batch or continuous processes. In a batch process, the terephthalic acid is contacted with 1,3-propanediol in the presence of a catalyst. In a continuous process, the terephthalic acid and 1,3-propanediol are combined with a recirculating stream of prepolymer in the presence of a catalyst. Variations of these processes can also be used, as will be apparent to one skilled in the art. The reaction temperature can range from about 100 to about 300° C., and at a pressure that can accommodate the temperature range. The preferred temperature ranges from about 155 to 250° C. It is also preferred that 1,3-propanediol be present in a slight molar excess compared to the terephthalic acid as disclosed above. Terephthalic acid is commercially available from E. I. duPont de Nemours and Company and 1,3-propanediol is commercially available from the Degussa Corporation.
- In the third embodiment, a composition of, or comprising, a poly(trimethylene terephthalate) polymer is provided. The poly(trimethylene terephthalate) polymer can have an intrinsic viscosity (IV) in the range from about 0.3 to about 2.0 and a b value in the range of from less than about 10, preferably less than 8, more preferably less than about 6, and most preferably less than about 5.
- The composition can be produced from the prepolymer disclosed above and can contain 10 to 100 ppm tin and 10 to 200 ppm titanium relative to the terephthalic acid content. The term “ppm” used herein refers to mg of elemental tin or titanium per kg terephthalic acid.
- The composition can be produced by a polymerization process, which is also known as polycondensation in which a prepolymer is polycondensed to form a polyester such as, for example, poly(trimethylene terephthalate) or 3GT, with the elimination of alcohol, as is known in the art. Typically, the alcohol can be removed by distillation under reduced pressure. The catalyst disclosed above can be used in the polycondensation step alone or with an additional catalyst. Polymerization can be continued until the resulting polymer has the desired degree of polycondensation, as measured by its IV. Intrinsic viscosity is determined by measuring the flow time of a solution of known polymer concentration and the flow time of the polymer solvent in a capillary viscometer, as set forth in ASTM D2857.95
- The color of the resulting polymer is measured in terms of the L-value and b-value, using an instrument such as the SP-78 Spectrophotometer. The L-value shows brightness, with the greater the numerical value showing higher (desirable) brightness and the b-value shows the degree of yellowness, with a higher numerical value showing a higher (undesirable) degree of yellowness.
- The following examples further illustrate the invention and are not to be construed to unduly limit the scope of the invention. The comparative examples show the use of tin or titanium catalysts without the other being present. These results are summarized and compared with the examples using the inventive combinations of tin and titanium catalysts in subsequent Table 1.
- This example demonstrates the esterification reaction of terephthalic acid with 1,3-propanediol using only n-butylstannoic acid as the esterification catalyst to form bis(3-hydroxypropyl) terephthalate.
- A 250 ml flask equipped with a stirrer was charged with 66.5 g of terephthalic acid (TPA), 48.7 g of 1,3-propanediol and 35 mg of n-butylstannoic acid (298 ppm tin based on TPA) for a molar ratio of 1,3-propanediol:TPA of 1.6:1. The flask was then purged with nitrogen and the contents of the flask were heated with stirring. When the temperature reached about 210° C., water started to evolve. The temperature was held at 210° C., and it took 3 hours to reach a clear solution indicating the end of esterification reaction.
- This example demonstrates the esterification reaction of terephthalic acid with 1,3-propanediol using n-butylstannoic acid (149 ppm tin based on TPA) as the esterification catalyst. The procedure of Comparative Example 1 was followed except that 17.4 mg of n-butylstannoic acid was used as the esterification catalyst. It took 4.5 hours to reach a clear solution.
- Upon the completion of esterification, the resulting monomer was polymerized in the same reaction vessel at a temperature of 250° C. and a pressure of 0.2 mm Hg in presence of an additional 62 ppm titanium based on TPA. The poly(trimethylene terephthalate) resin color and intrinsic viscosity (IV) are given in Table 1.
- This example demonstrates the esterification reaction of terephthalic acid with 1,3-propanediol using n-butylstannoic acid (99 ppm of tin based on TPA) as the esterification catalyst. The procedure of Comparative Example 1 was followed except that 11.6 mg of n-butylstannoic acid was used as the esterification catalyst. It took 5.5 hours at 210° C. to reach a clear solution.
- This example demonstrates the esterification reaction of terephthalic acid with 1,3-propanediol using n-butylstannoic acid (62 ppm of tin based on TPA) as the esterification catalyst. The procedure of Comparative Example 1 was followed except that 7.2 mg of n-butylstannoic acid was used as the esterification catalyst. It took 9 hours at 210° C. to reach a clear solution.
- This example demonstrates the esterification reaction of terephthalic acid with 1,3-propanediol in the absence of a catalyst. The procedure of Comparative Example 1 was followed except that no catalyst was used. It took more than 16 hours at 210° C. to reach a clear solution.
- This example demonstrates the esterification reaction of terephthalic acid with 1,3-propanediol using tetraisopropyl titanate (62 ppm of Ti based on TPA) as the esterification catalyst. The procedure of Comparative Example 1 was followed except that 24.4 mg of tetraisopropyl titanate was used as the esterification catalyst. It took 7.5 hours at 210° C. to reach a clear solution.
- This example demonstrates the esterification reaction of terephthalic acid with 1,3-propanediol using a combination of n-butylstannoic acid (31 ppm of tin based on TPA) and tetraisopropyl titanate (62 ppm of Ti based on TPA) as the esterification catalyst. The procedure of Comparative Example 1 was followed except that 3.6 mg of n-butylstannoic acid and 24.4 mg of tetraisopropyl titanate were used as the esterification catalyst. It took 6 hours 45 minutes at 210° C. to reach a clear solution indicating the end of the esterification reaction.
- This example demonstrates the esterification reaction of terephthalic acid with 1,3-propanediol using combination of n-butylstannoic acid (99 ppm of tin based on TPA) and tetraisopropyl titanate (62 ppm of Ti based on TPA) as the esterification catalyst. The procedure of Comparative Example 1 was followed except that 11.6 mg of n-butylstannoic acid and 24.4 mg of tetraisopropyl titanate was added separately as the esterification catalyst. It took 4 hours 15 minutes at 210° C. to reach a clear solution. Thereafter, the resulting monomer was polymerized in the same reaction vessel at a temperature of 250° C. and a pressure of 0.2 mm Hg without any additional catalyst. The poly(trimethylene terephthalate) resin color and IV are given in Table 1.
- This example demonstrates the esterification reaction of terephthalic acid with 1,3-propanediol using a pre-mixed solution of n-butylstannoic acid (99 ppm of tin based on TPA) and tetraisopropyl titanate (62 ppm of Ti based on TPA) as the esterification catalyst. The procedure of Comparative Example 1 was followed except that 11.6 mg of n-butylstannoic acid and 24.4 mg of tetraisopropyl titanate were used as the esterification catalyst, which were pre-mixed in 1,3-propanediol at room temperature. It took 3 hours 10 minutes at 210° C. to reach a clear solution.
- Upon the completion of esterification, the resulting monomer, bis(3-hydroxypropyl)terephthalate, was polymerized in the same vessel at a temperature of 250° C. and a pressure of 0.2 mm Hg without additional catalyst. The poly(trimethylene terephthalate) resin obtained had an IV of 0.78 dl/g and melting point of 230° C. (measured as the peak on the endotherm of differential scanning calorimeter, DSC).
- The procedure of example 3A was repeated. It took 3 hours 15 minutes at 210° C. to reach a clear solution. After polymerization, the poly(trimethylene terephthalate) resin obtained had an intrinsic viscosity of 0.89 dl/g.
- Table 1 summarizes the results of the above examples. The catalyst concentration used during the esterification reaction is given in the table as the parts per million (ppm) relative to the weight of TPA or as mg catalyst per kg TPA.
TABLE 1 Direct Esterification Time and Polymer Ouality Ester- Esterification ification Polymer Catalyst Time Viscosity Example ppm (Sn/Ti) (hour) Polymer Color (IV) Comp. Ex. 1 298/0 3.0 Comp. Ex. 2 149/0 4.5 L = 74.8; b = 4.2 0.74 Comp. Ex. 3 99/0 5.5 Comp. Ex. 4 62/0 9 Comp. Ex. 5 0/0 16 Comp. Ex. 6 0/62 7.5 Example 1 31/62 6.75 Example 2 99/62 4.25 L = 75; b = 4.06 0.74 Ex. 3A 99/62 3.17 L = 76.1; b = 2.77 0.78 (premix) Ex. 3B 99/62 3.25 L = 76.1; b = 2.98 0.89 (premix) - The results show that the tin content of the prepolymer of the invention process (Example 1), in comparison to Comparative Example 4, decreased by 50% while the reaction time is cut by 25%. It demonstrated that the invention process increased the reaction rate at lower tin content.
- The results also show that the tin content of the prepolymer (Example 2), in comparison to Comparative Example 2, decreased by a third while the reaction rate and product color were also improved.
- The results further show that the invention process greatly improved over the known process when the invention catalyst was premixed. Example 3A and 3B, in comparison to Example 2, show that premixing the tin and titanium catalysts had the shortest the reaction time and produced a polymer having the highest L value, lowest b value, and highest IV among those tested.
- In summary, the invention catalyst, a combination of tin and titanium catalysts, completes esterification faster than the individual catalyst components thereby minimizing the time and temperature required for esterification. The invention product is a polyester such as 3GT of high quality having low tin concentration. A high concentration of tin compounds causes discoloration and degradation of polymer as well as the formation of large amounts of by-products. Furthermore, the invention catalyst can be used for both esterification and polycondensation thereby eliminating the need for a separate catalyst during the polycondensation step.
Claims (20)
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US09/793,832 US6426398B2 (en) | 2000-02-08 | 2001-02-27 | Poly (trimethylene terephthalate) polymer composition |
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US09/500,340 US6255442B1 (en) | 2000-02-08 | 2000-02-08 | Esterification process |
US09/793,832 US6426398B2 (en) | 2000-02-08 | 2001-02-27 | Poly (trimethylene terephthalate) polymer composition |
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US09/500,340 Division US6255442B1 (en) | 2000-02-08 | 2000-02-08 | Esterification process |
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US09/793,832 Expired - Lifetime US6426398B2 (en) | 2000-02-08 | 2001-02-27 | Poly (trimethylene terephthalate) polymer composition |
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EP (1) | EP1165651A1 (en) |
JP (1) | JP4928698B2 (en) |
KR (1) | KR100800955B1 (en) |
CN (1) | CN1162458C (en) |
AR (1) | AR025862A1 (en) |
BR (1) | BR0011155A (en) |
CA (1) | CA2366515C (en) |
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EP1491569A1 (en) * | 2002-06-13 | 2004-12-29 | Asahi Kasei Kabushiki Kaisha | Polytrimethylene terephthalate resin |
WO2006007067A1 (en) * | 2004-06-18 | 2006-01-19 | Stepan Company | Manufacture of esters using a multiple catalyst approach |
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1491569A1 (en) * | 2002-06-13 | 2004-12-29 | Asahi Kasei Kabushiki Kaisha | Polytrimethylene terephthalate resin |
EP1491569A4 (en) * | 2002-06-13 | 2006-03-29 | Asahi Chemical Ind | Polytrimethylene terephthalate resin |
CN1308368C (en) * | 2002-06-13 | 2007-04-04 | 旭化成株式会社 | Polytrimethylene terephthalate resin |
WO2006007067A1 (en) * | 2004-06-18 | 2006-01-19 | Stepan Company | Manufacture of esters using a multiple catalyst approach |
US20080132714A1 (en) * | 2004-06-18 | 2008-06-05 | Hillshafer D Kip | Manufacture of Esters Using a Multiple Catalyst Approach |
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CN1353730A (en) | 2002-06-12 |
CA2366515A1 (en) | 2001-08-16 |
TR200102882T1 (en) | 2002-08-21 |
JP4928698B2 (en) | 2012-05-09 |
CA2366515C (en) | 2011-01-11 |
WO2001058983A1 (en) | 2001-08-16 |
EP1165651A1 (en) | 2002-01-02 |
US6426398B2 (en) | 2002-07-30 |
CN1162458C (en) | 2004-08-18 |
US6255442B1 (en) | 2001-07-03 |
BR0011155A (en) | 2002-09-17 |
KR20010112407A (en) | 2001-12-20 |
AR025862A1 (en) | 2002-12-18 |
MXPA01010155A (en) | 2002-04-24 |
KR100800955B1 (en) | 2008-02-04 |
JP2003522264A (en) | 2003-07-22 |
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