TW592811B - Titanium-containing catalyst composition and processes therefor and therewith - Google Patents
Titanium-containing catalyst composition and processes therefor and therewith Download PDFInfo
- Publication number
- TW592811B TW592811B TW088106251A TW88106251A TW592811B TW 592811 B TW592811 B TW 592811B TW 088106251 A TW088106251 A TW 088106251A TW 88106251 A TW88106251 A TW 88106251A TW 592811 B TW592811 B TW 592811B
- Authority
- TW
- Taiwan
- Prior art keywords
- acid
- group
- item
- composition
- patent application
- Prior art date
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 112
- 239000003054 catalyst Substances 0.000 title claims abstract description 98
- 238000000034 method Methods 0.000 title claims abstract description 32
- 239000010936 titanium Substances 0.000 title claims description 33
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims description 31
- 229910052719 titanium Inorganic materials 0.000 title claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 44
- 150000003609 titanium compounds Chemical class 0.000 claims abstract description 34
- 239000002904 solvent Substances 0.000 claims abstract description 33
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 23
- 239000011574 phosphorus Substances 0.000 claims abstract description 21
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 18
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims abstract description 16
- 150000001728 carbonyl compounds Chemical class 0.000 claims abstract description 13
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 9
- 239000010941 cobalt Substances 0.000 claims abstract description 9
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 91
- 125000004432 carbon atom Chemical group C* 0.000 claims description 31
- -1 phosphinate compound Chemical class 0.000 claims description 28
- 239000002253 acid Substances 0.000 claims description 26
- 238000004090 dissolution Methods 0.000 claims description 23
- 238000004519 manufacturing process Methods 0.000 claims description 22
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 18
- 229910052787 antimony Inorganic materials 0.000 claims description 15
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 14
- 229920000728 polyester Polymers 0.000 claims description 14
- 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 claims description 14
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 13
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 12
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 12
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 claims description 11
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 11
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 11
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical group [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 10
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 10
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 8
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 8
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 239000003426 co-catalyst Substances 0.000 claims description 7
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 6
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 claims description 6
- 150000007513 acids Chemical class 0.000 claims description 5
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 5
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 5
- HCGFUIQPSOCUHI-UHFFFAOYSA-N 2-propan-2-yloxyethanol Chemical compound CC(C)OCCO HCGFUIQPSOCUHI-UHFFFAOYSA-N 0.000 claims description 4
- NGSWKAQJJWESNS-UHFFFAOYSA-N 4-coumaric acid Chemical compound OC(=O)C=CC1=CC=C(O)C=C1 NGSWKAQJJWESNS-UHFFFAOYSA-N 0.000 claims description 4
- XQXPVVBIMDBYFF-UHFFFAOYSA-N 4-hydroxyphenylacetic acid Chemical compound OC(=O)CC1=CC=C(O)C=C1 XQXPVVBIMDBYFF-UHFFFAOYSA-N 0.000 claims description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 4
- 125000003342 alkenyl group Chemical group 0.000 claims description 4
- 150000008064 anhydrides Chemical class 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 4
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 claims description 4
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 claims description 4
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 claims description 4
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 claims description 4
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 claims description 4
- 235000019260 propionic acid Nutrition 0.000 claims description 4
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 4
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 4
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000005711 Benzoic acid Substances 0.000 claims description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 3
- 125000002947 alkylene group Chemical group 0.000 claims description 3
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 3
- 239000011976 maleic acid Substances 0.000 claims description 3
- FUZZWVXGSFPDMH-UHFFFAOYSA-N n-hexanoic acid Natural products CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 3
- PVACDNXAICDVIC-UHFFFAOYSA-N (4-hydroxyphenyl)arsinic acid Chemical compound OC1=CC=C(C=C1)[AsH](O)=O PVACDNXAICDVIC-UHFFFAOYSA-N 0.000 claims description 2
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 claims description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- IWHLYPDWHHPVAA-UHFFFAOYSA-N 6-hydroxyhexanoic acid Chemical compound OCCCCCC(O)=O IWHLYPDWHHPVAA-UHFFFAOYSA-N 0.000 claims description 2
- 235000021314 Palmitic acid Nutrition 0.000 claims description 2
- 235000021355 Stearic acid Nutrition 0.000 claims description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 2
- 239000001361 adipic acid Substances 0.000 claims description 2
- 235000011037 adipic acid Nutrition 0.000 claims description 2
- 125000003158 alcohol group Chemical group 0.000 claims description 2
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 2
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 claims description 2
- 125000000732 arylene group Chemical group 0.000 claims description 2
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 claims description 2
- 229940092714 benzenesulfonic acid Drugs 0.000 claims description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 239000001530 fumaric acid Substances 0.000 claims description 2
- 235000011087 fumaric acid Nutrition 0.000 claims description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 2
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 claims description 2
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 claims 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 claims description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- WLJNZVDCPSBLRP-UHFFFAOYSA-N pamoic acid Chemical compound C1=CC=C2C(CC=3C4=CC=CC=C4C=C(C=3O)C(=O)O)=C(O)C(C(O)=O)=CC2=C1 WLJNZVDCPSBLRP-UHFFFAOYSA-N 0.000 claims description 2
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 2
- WAJUCMNAGKFHLB-UHFFFAOYSA-N phenylarsinic acid Chemical compound O[AsH](=O)C1=CC=CC=C1 WAJUCMNAGKFHLB-UHFFFAOYSA-N 0.000 claims description 2
- 229960004889 salicylic acid Drugs 0.000 claims description 2
- 239000008117 stearic acid Substances 0.000 claims description 2
- GZSSFSARCMSPPW-UHFFFAOYSA-N butane-2,2-diol Chemical compound CCC(C)(O)O GZSSFSARCMSPPW-UHFFFAOYSA-N 0.000 claims 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims 2
- 229940043375 1,5-pentanediol Drugs 0.000 claims 1
- UGDSDVUYLMTPIF-UHFFFAOYSA-N C1C2=CC=CC=C2C3=C(C=CC(=C31)C4=CC=CC=C4)O Chemical compound C1C2=CC=CC=C2C3=C(C=CC(=C31)C4=CC=CC=C4)O UGDSDVUYLMTPIF-UHFFFAOYSA-N 0.000 claims 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-N Caprylic acid Natural products CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 claims 1
- 150000008065 acid anhydrides Chemical class 0.000 claims 1
- 239000000654 additive Substances 0.000 claims 1
- 230000000996 additive effect Effects 0.000 claims 1
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 1
- 150000001336 alkenes Chemical class 0.000 claims 1
- 229910052786 argon Inorganic materials 0.000 claims 1
- 230000003796 beauty Effects 0.000 claims 1
- 235000010233 benzoic acid Nutrition 0.000 claims 1
- GONOPSZTUGRENK-UHFFFAOYSA-N benzyl(trichloro)silane Chemical compound Cl[Si](Cl)(Cl)CC1=CC=CC=C1 GONOPSZTUGRENK-UHFFFAOYSA-N 0.000 claims 1
- 125000003636 chemical group Chemical group 0.000 claims 1
- CBBCGMXHLPFKJY-UHFFFAOYSA-N oxane-2-sulfonic acid Chemical compound OS(=O)(=O)C1CCCCO1 CBBCGMXHLPFKJY-UHFFFAOYSA-N 0.000 claims 1
- WCVRQHFDJLLWFE-UHFFFAOYSA-N pentane-1,2-diol Chemical compound CCCC(O)CO WCVRQHFDJLLWFE-UHFFFAOYSA-N 0.000 claims 1
- 239000001294 propane Substances 0.000 claims 1
- 238000005886 esterification reaction Methods 0.000 abstract description 11
- 230000032050 esterification Effects 0.000 abstract description 10
- 238000005809 transesterification reaction Methods 0.000 abstract description 9
- 150000001463 antimony compounds Chemical class 0.000 abstract description 6
- 238000006116 polymerization reaction Methods 0.000 abstract description 6
- 238000006243 chemical reaction Methods 0.000 description 23
- 150000002148 esters Chemical class 0.000 description 22
- 229920000642 polymer Polymers 0.000 description 20
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 16
- 239000007787 solid Substances 0.000 description 16
- 150000007524 organic acids Chemical class 0.000 description 11
- MLCHBQKMVKNBOV-UHFFFAOYSA-N phenylphosphinic acid Chemical compound OP(=O)C1=CC=CC=C1 MLCHBQKMVKNBOV-UHFFFAOYSA-N 0.000 description 11
- 229920000139 polyethylene terephthalate Polymers 0.000 description 11
- 239000005020 polyethylene terephthalate Substances 0.000 description 11
- 229920001283 Polyalkylene terephthalate Polymers 0.000 description 9
- 150000001298 alcohols Chemical class 0.000 description 9
- 238000002474 experimental method Methods 0.000 description 8
- 235000005985 organic acids Nutrition 0.000 description 8
- 238000013019 agitation Methods 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 6
- 150000002430 hydrocarbons Chemical group 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 239000012429 reaction media Substances 0.000 description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 238000006068 polycondensation reaction Methods 0.000 description 4
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 3
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910000410 antimony oxide Inorganic materials 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 3
- 229920001707 polybutylene terephthalate Polymers 0.000 description 3
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- GHPVDCPCKSNJDR-UHFFFAOYSA-N 2-hydroxydecanoic acid Chemical compound CCCCCCCCC(O)C(O)=O GHPVDCPCKSNJDR-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 229940058905 antimony compound for treatment of leishmaniasis and trypanosomiasis Drugs 0.000 description 2
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 2
- OEIWPNWSDYFMIL-UHFFFAOYSA-N dioctyl benzene-1,4-dicarboxylate Chemical compound CCCCCCCCOC(=O)C1=CC=C(C(=O)OCCCCCCCC)C=C1 OEIWPNWSDYFMIL-UHFFFAOYSA-N 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- QFMZQPDHXULLKC-UHFFFAOYSA-N 1,2-bis(diphenylphosphino)ethane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CCP(C=1C=CC=CC=1)C1=CC=CC=C1 QFMZQPDHXULLKC-UHFFFAOYSA-N 0.000 description 1
- LVEYOSJUKRVCCF-UHFFFAOYSA-N 1,3-bis(diphenylphosphino)propane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CCCP(C=1C=CC=CC=1)C1=CC=CC=C1 LVEYOSJUKRVCCF-UHFFFAOYSA-N 0.000 description 1
- YIWGJFPJRAEKMK-UHFFFAOYSA-N 1-(2H-benzotriazol-5-yl)-3-methyl-8-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carbonyl]-1,3,8-triazaspiro[4.5]decane-2,4-dione Chemical group CN1C(=O)N(c2ccc3n[nH]nc3c2)C2(CCN(CC2)C(=O)c2cnc(NCc3cccc(OC(F)(F)F)c3)nc2)C1=O YIWGJFPJRAEKMK-UHFFFAOYSA-N 0.000 description 1
- ONSRFWYJJIOQSQ-UHFFFAOYSA-N 1-(9H-fluoren-1-yl)propane-1,2-diol Chemical compound C1C2=CC=CC=C2C2=C1C(C(O)C(O)C)=CC=C2 ONSRFWYJJIOQSQ-UHFFFAOYSA-N 0.000 description 1
- GCUWBTGMXUIKOB-UHFFFAOYSA-N 1-methyl-4-(4-methylphenyl)phosphonoylbenzene Chemical compound C1=CC(C)=CC=C1P(=O)C1=CC=C(C)C=C1 GCUWBTGMXUIKOB-UHFFFAOYSA-N 0.000 description 1
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 1
- IUVCFHHAEHNCFT-INIZCTEOSA-N 2-[(1s)-1-[4-amino-3-(3-fluoro-4-propan-2-yloxyphenyl)pyrazolo[3,4-d]pyrimidin-1-yl]ethyl]-6-fluoro-3-(3-fluorophenyl)chromen-4-one Chemical compound C1=C(F)C(OC(C)C)=CC=C1C(C1=C(N)N=CN=C11)=NN1[C@@H](C)C1=C(C=2C=C(F)C=CC=2)C(=O)C2=CC(F)=CC=C2O1 IUVCFHHAEHNCFT-INIZCTEOSA-N 0.000 description 1
- FYELSNVLZVIGTI-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-5-ethylpyrazol-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C=NN(C=1CC)CC(=O)N1CC2=C(CC1)NN=N2 FYELSNVLZVIGTI-UHFFFAOYSA-N 0.000 description 1
- WEHZNZTWKUYVIY-UHFFFAOYSA-N 3-oxabicyclo[3.2.2]nona-1(7),5,8-triene-2,4-dione Chemical compound O=C1OC(=O)C2=CC=C1C=C2 WEHZNZTWKUYVIY-UHFFFAOYSA-N 0.000 description 1
- BCJVBDBJSMFBRW-UHFFFAOYSA-N 4-diphenylphosphanylbutyl(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CCCCP(C=1C=CC=CC=1)C1=CC=CC=C1 BCJVBDBJSMFBRW-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- RWPICVVBGZBXNA-BGYRXZFFSA-N Bis(2-ethylhexyl) terephthalate Natural products CCCC[C@H](CC)COC(=O)C1=CC=C(C(=O)OC[C@H](CC)CCCC)C=C1 RWPICVVBGZBXNA-BGYRXZFFSA-N 0.000 description 1
- QHAVBYDYCMEMTA-UHFFFAOYSA-N C(CCCCC)[Ti](CCCCCC)(CCCCCC)CCCCCC Chemical compound C(CCCCC)[Ti](CCCCCC)(CCCCCC)CCCCCC QHAVBYDYCMEMTA-UHFFFAOYSA-N 0.000 description 1
- DVHZXMUCUMGEDP-UHFFFAOYSA-N C(CCCCCCC)[Ti](CCCCCCCC)(CCCCCCCC)CCCCCCCC Chemical compound C(CCCCCCC)[Ti](CCCCCCCC)(CCCCCCCC)CCCCCCCC DVHZXMUCUMGEDP-UHFFFAOYSA-N 0.000 description 1
- WKSQLPKPHUAMEX-UHFFFAOYSA-N C1C2=CC=CC=C2C3=C(C=CC(=C31)C4=CC=CC=C4C(=O)O)O Chemical compound C1C2=CC=CC=C2C3=C(C=CC(=C31)C4=CC=CC=C4C(=O)O)O WKSQLPKPHUAMEX-UHFFFAOYSA-N 0.000 description 1
- NDSXSCFKIAPKJG-UHFFFAOYSA-N CC(C)O[Ti] Chemical compound CC(C)O[Ti] NDSXSCFKIAPKJG-UHFFFAOYSA-N 0.000 description 1
- RCZPHVPIOWNERS-UHFFFAOYSA-N CCCO[Ti] Chemical compound CCCO[Ti] RCZPHVPIOWNERS-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- UDSFAEKRVUSQDD-UHFFFAOYSA-N Dimethyl adipate Chemical compound COC(=O)CCCCC(=O)OC UDSFAEKRVUSQDD-UHFFFAOYSA-N 0.000 description 1
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- NPWGWQRXHVJJRD-UHFFFAOYSA-N N-hydroxyglycine Chemical compound ONCC(O)=O NPWGWQRXHVJJRD-UHFFFAOYSA-N 0.000 description 1
- QLZHNIAADXEJJP-UHFFFAOYSA-N Phenylphosphonic acid Chemical compound OP(O)(=O)C1=CC=CC=C1 QLZHNIAADXEJJP-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 229910052775 Thulium Inorganic materials 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- WYOFTXWVYIGTCT-UHFFFAOYSA-K [OH-].[Sb+3].OCC([O-])=O.OCC([O-])=O Chemical compound [OH-].[Sb+3].OCC([O-])=O.OCC([O-])=O WYOFTXWVYIGTCT-UHFFFAOYSA-K 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 150000001409 amidines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- SZOADBKOANDULT-UHFFFAOYSA-K antimonous acid Chemical compound O[Sb](O)O SZOADBKOANDULT-UHFFFAOYSA-K 0.000 description 1
- 150000001462 antimony Chemical class 0.000 description 1
- 229910000379 antimony sulfate Inorganic materials 0.000 description 1
- KIQKNTIOWITBBA-UHFFFAOYSA-K antimony(3+);phosphate Chemical compound [Sb+3].[O-]P([O-])([O-])=O KIQKNTIOWITBBA-UHFFFAOYSA-K 0.000 description 1
- JRLDUDBQNVFTCA-UHFFFAOYSA-N antimony(3+);trinitrate Chemical compound [Sb+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JRLDUDBQNVFTCA-UHFFFAOYSA-N 0.000 description 1
- MVMLTMBYNXHXFI-UHFFFAOYSA-H antimony(3+);trisulfate Chemical compound [Sb+3].[Sb+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O MVMLTMBYNXHXFI-UHFFFAOYSA-H 0.000 description 1
- PHIBEYMUALDAQI-UHFFFAOYSA-N benzylphosphinic acid Chemical group OP(=O)CC1=CC=CC=C1 PHIBEYMUALDAQI-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- RWPICVVBGZBXNA-UHFFFAOYSA-N bis(2-ethylhexyl) benzene-1,4-dicarboxylate Chemical compound CCCCC(CC)COC(=O)C1=CC=C(C(=O)OCC(CC)CCCC)C=C1 RWPICVVBGZBXNA-UHFFFAOYSA-N 0.000 description 1
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 1
- QDHFHIQKOVNCNC-UHFFFAOYSA-N butane-1-sulfonic acid Chemical compound CCCCS(O)(=O)=O QDHFHIQKOVNCNC-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910001919 chlorite Inorganic materials 0.000 description 1
- 229910052619 chlorite group Inorganic materials 0.000 description 1
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical compound OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000010960 commercial process Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- XTDYIOOONNVFMA-UHFFFAOYSA-N dimethyl pentanedioate Chemical compound COC(=O)CCCC(=O)OC XTDYIOOONNVFMA-UHFFFAOYSA-N 0.000 description 1
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 description 1
- 229960001826 dimethylphthalate Drugs 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- BEQVQKJCLJBTKZ-UHFFFAOYSA-N diphenylphosphinic acid Chemical compound C=1C=CC=CC=1P(=O)(O)C1=CC=CC=C1 BEQVQKJCLJBTKZ-UHFFFAOYSA-N 0.000 description 1
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- CCIVGXIOQKPBKL-UHFFFAOYSA-M ethanesulfonate Chemical compound CCS([O-])(=O)=O CCIVGXIOQKPBKL-UHFFFAOYSA-M 0.000 description 1
- 150000002168 ethanoic acid esters Chemical class 0.000 description 1
- XGZNHFPFJRZBBT-UHFFFAOYSA-N ethanol;titanium Chemical compound [Ti].CCO.CCO.CCO.CCO XGZNHFPFJRZBBT-UHFFFAOYSA-N 0.000 description 1
- VGASFSFONALGLS-UHFFFAOYSA-N ethene;terephthalic acid Chemical compound C=C.C=C.OC(=O)C1=CC=C(C(O)=O)C=C1 VGASFSFONALGLS-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- LNTHITQWFMADLM-UHFFFAOYSA-M gallate Chemical compound OC1=CC(C([O-])=O)=CC(O)=C1O LNTHITQWFMADLM-UHFFFAOYSA-M 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000004021 humic acid Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- ITNVWQNWHXEMNS-UHFFFAOYSA-N methanolate;titanium(4+) Chemical compound [Ti+4].[O-]C.[O-]C.[O-]C.[O-]C ITNVWQNWHXEMNS-UHFFFAOYSA-N 0.000 description 1
- 229940095102 methyl benzoate Drugs 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002905 orthoesters Chemical class 0.000 description 1
- 125000005489 p-toluenesulfonic acid group Chemical group 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- RPGWZZNNEUHDAQ-UHFFFAOYSA-N phenylphosphine Chemical compound PC1=CC=CC=C1 RPGWZZNNEUHDAQ-UHFFFAOYSA-N 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 230000003389 potentiating effect Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- KCXFHTAICRTXLI-UHFFFAOYSA-N propane-1-sulfonic acid Chemical compound CCCS(O)(=O)=O KCXFHTAICRTXLI-UHFFFAOYSA-N 0.000 description 1
- CIBMHJPPKCXONB-UHFFFAOYSA-N propane-2,2-diol Chemical compound CC(C)(O)O CIBMHJPPKCXONB-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- YPMOSINXXHVZIL-UHFFFAOYSA-N sulfanylideneantimony Chemical compound [Sb]=S YPMOSINXXHVZIL-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
- B01J31/128—Mixtures of organometallic compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0201—Oxygen-containing compounds
- B01J31/0211—Oxygen-containing compounds with a metal-oxygen link
- B01J31/0212—Alkoxylates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0215—Sulfur-containing compounds
- B01J31/0225—Sulfur-containing compounds comprising sulfonic acid groups or the corresponding salts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0255—Phosphorus containing compounds
- B01J31/0257—Phosphorus acids or phosphorus acid esters
- B01J31/0259—Phosphorus acids or phosphorus acid esters comprising phosphorous acid (-ester) groups ((RO)P(OR')2) or the isomeric phosphonic acid (-ester) groups (R(R'O)2P=O), i.e. R= C, R'= C, H
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0255—Phosphorus containing compounds
- B01J31/0257—Phosphorus acids or phosphorus acid esters
- B01J31/0261—Phosphorus acids or phosphorus acid esters comprising phosphonous acid (-ester) groups (RP(OR')2) or the isomeric phosphinic acid (-ester) groups (R2(R'O)P=O), i.e. R= C, R'= C, H
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0255—Phosphorus containing compounds
- B01J31/0257—Phosphorus acids or phosphorus acid esters
- B01J31/0262—Phosphorus acids or phosphorus acid esters comprising phosphinous acid (-ester) groups (R2P(OR')) or the isomeric phosphine oxide groups (R3P=O), i.e. R= C, R'= C, H
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0272—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255
- B01J31/0274—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255 containing silicon
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/10—Polymerisation reactions involving at least dual use catalysts, e.g. for both oligomerisation and polymerisation
- B01J2231/14—Other (co) polymerisation, e.g. of lactides or epoxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/49—Esterification or transesterification
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
Description
592811 修正 案號 88106251 五、發明說明(1) 發明範圍 本發明係關於一種含有鈦化合物之催化劑組成物,製造 組成物之方法及在例如羰基化合物的酯化作用、酯基轉移 作用或聚合作用中使用組成物之方法。 發明背景 通常稱為π聚伸烷基對苯二酸酯π之聚酯類,如舉例的聚 對苯二甲酸乙二酯(PET)及聚對苯二曱酸丁二酯(ΡΒΤ)是重 要的工業聚合物分類。其在熱塑性纖維、膜及模製應用中 受到廣泛地使用。592811 Amendment No. 88106251 V. Description of the invention (1) Scope of the invention The present invention relates to a catalyst composition containing a titanium compound, a method for manufacturing the composition, and in, for example, esterification, transesterification, or polymerization of a carbonyl compound Method of using composition. BACKGROUND OF THE INVENTION Polyesters commonly referred to as π-polyalkylene terephthalate, such as polyethylene terephthalate (PET) and polybutylene terephthalate (PBT) are important Industrial Polymer Classification. It is widely used in thermoplastic fibers, films, and molding applications.
以對笨二酸二烷酯與乙二醇之酯基轉移作用或在聚濃縮 作用之後以對苯二酸與經選擇之乙二醇的直接酯化作用可 製造聚伸烷基對二酸酯。利用催化劑催化酯化作用、酯基 轉移作用或聚濃縮作用。 許多商業法利用鎂或鋅鹽當成酯基轉移步驟之催化劑。 典型係將銻以化銻的乙二醇形式當成或在酯基轉移作用, 或在以上指出的直接酯化作用中的聚濃縮作用催化劑。但 是,銻會形成堵塞纖維喷絲嘴之不溶性銻錯合物。而且, 使用銻催化劑通常被視為環境不利,與爭議有關重金屬可 能出現在食物接觸應用中。 已知有機鈦酸酯,如酖酸四異丙醋及鈦酸四正丁酷是一 般製備聚伸烷基對苯二酸酯有效的聚縮合催化劑,並常常 是被選上的催化劑。但是,通常不在PET的製造中使用有 機鈦酸酯,因為殘留的鈦酸酯傾於在聚濃縮作用及PET處 理期間形成的少量雜質反應,如醛,因此形成不希望的黃 褪色。此外,許多有機鈦酸酯催化劑實質上也不溶於聚合Polyalkylene terephthalate can be produced by transesterification of dialkyl p-dimonate with ethylene glycol or by direct esterification of terephthalic acid with selected ethylene glycol after polyconcentration . A catalyst is used to catalyze esterification, transesterification or polyconcentration. Many commercial processes use magnesium or zinc salts as catalysts for the transesterification step. Typically, antimony is used as the antimonylated ethylene glycol as a polycondensation catalyst in transesterification or in the direct esterification indicated above. However, antimony can form insoluble antimony complexes that block fiber spinnerets. Moreover, the use of antimony catalysts is generally considered to be environmentally unfavorable, and controversial heavy metals may appear in food contact applications. Organic titanates, such as tetraisopropylacetate and tetra-n-butyltitanate, are known to be effective polycondensation catalysts for the preparation of polyalkylene terephthalates, and are often the catalysts of choice. However, organic titanates are generally not used in the manufacture of PET because the residual titanates are reacted with small amounts of impurities formed during polyconcentration and PET processing, such as aldehydes, and thus form undesired yellow discoloration. In addition, many organic titanate catalysts are essentially insoluble in polymerization
O:\58\58096-910820.ptc 第6頁 592811 _案號88106251 Θ丨年P月日 修正_ 五、發明說明(2) 混合物中,因此在混合物中形成不均勻分布的催化劑。 。 因此,有增加對發展具有實質上可溶性、有效力及製造 具有還原色之聚合物的新催化劑需求。 本發明催化劑組成物的一個優點是在用於製造特殊的聚 伸烷基對苯二酸酯時,其具有高反應性及以其製造的聚合-物已改良光學特性(例如,較不受期望的色彩),與利用先 ’ 前已知的有機鈦酸酯催化劑製造聚合物比較時。由以下更 - 完整的揭示,使得本發明其它的優點將變得更顯而易見。 # 本發明的概述 · 根據本發明的第一個具體實施例,其提供一種可當成酯 化作用或酯基轉移作用催化劑,或當成製造聚伸烷基對苯參 二酸酯之聚濃縮作用催化劑使用之催化劑組成物。組成物 包含有機鈦化合物、溶解促進劑及磷來源。組成物進一步 包含磺酸及視需要之催化劑,其中溶劑促進劑係選自由原 矽酸酯、原锆酸酯及其組合物組成的各物。 根據本發明的第二具體實施例,其係提供一種製造催化 劑組成物之方法。該方法包含結合溶劑、有機鈦化合物、 磷來源、溶解促進劑及視需要之磺酸、共催化劑或其組合 物,其中溶解促進劑係選自由原矽酸酯、原鍅酸酯及其組 合物等組成的各物。 根據本發明的第三個具體實施例,其係提供一種可在例 φ 如聚酯的製造中使用的方法。該方法包含在催化劑組成物 的存在下將羰基化合物與醇接觸。催化劑組成物與以上揭 示的組成物一樣。 本發明的詳細說明O: \ 58 \ 58096-910820.ptc Page 6 592811 _Case No. 88106251 Θ 丨 Year P Month Day Amendment_ V. Description of the invention (2) In the mixture, an unevenly distributed catalyst is formed in the mixture. . Therefore, there is an increasing demand for new catalysts for the development of polymers that are substantially soluble, potent, and that produce polymers with reduced colors. One advantage of the catalyst composition of the present invention is that it has high reactivity when used in the manufacture of special polyalkylene terephthalates, and the polymers made therefrom have improved optical properties (e.g., less desirable) Color) when compared to polymers made using previously known organic titanate catalysts. Other advantages of the present invention will become more apparent from the following more complete disclosure. # SUMMARY OF THE INVENTION · According to the first embodiment of the present invention, it provides a catalyst that can be used as an esterification or transesterification catalyst, or as a polyconcentration catalyst for the production of polyalkylene terephthalate. Catalyst composition used. The composition contains an organic titanium compound, a dissolution promoter, and a phosphorus source. The composition further includes a sulfonic acid and an optional catalyst, wherein the solvent accelerator is selected from the group consisting of orthosilicate, orthozirconate, and combinations thereof. According to a second embodiment of the present invention, a method for manufacturing a catalyst composition is provided. The method comprises combining a solvent, an organic titanium compound, a source of phosphorus, a dissolution promoter, and optionally a sulfonic acid, a cocatalyst, or a combination thereof, wherein the dissolution promoter is selected from the group consisting of orthosilicate, orthophosphonate, and a combination thereof And so on. According to a third embodiment of the present invention, it is provided a method which can be used in the production of, for example, polyester. The method includes contacting a carbonyl compound with an alcohol in the presence of a catalyst composition. The catalyst composition is the same as the composition disclosed above. Detailed description of the invention
O:\58\58096-910820.ptc 第7頁 592811 修正 案號 88106251 五、發明說明(3) 根據本發明的第一具體實施例,其係提供一種催化劑組 成物。組成物可以包含有機鈦化合物、溶解促進劑、磷來 源及視需要之磺酸、共催化劑或其組合物。組成物基本上 也是由或由有機鈦化合物、溶解促進劑、磷來源及磺酸等 組成的。溶解促進劑可選自由原矽酸酯、原錘酸酯及其組 合物等組成的各物,並且共催化劑可自由根據美國專利申 請案第5,6 7 4,8 0 1號說明的鈷/鋁催化劑、銻化合物及其組 合物等組成的各物。 本發明的催化劑組成物實質上可溶於溶劑中。以π實質 上π術語代表更微不足道。組成物以完全可溶於溶劑中較 佳。但是,實質上有部份的組成物也可以懸浮或分散在溶 劑中。根據本發明,目前較佳的鈦化合物是有機鈦化合 物。四烴基氧化鈦是目前最佳的有機鈦化合物,因為其可 輕易取得及具有效力。適合的四烴基氧化鈦化合物實例包 括那些以通式T i ( OR )4表示的化合物,在此一個R單獨係選 自由烷基、環烷基、芳烷烴基及二或數個其3組合物等組 成的各物。每一個基可以包括從1至約3 0個碳原子,以每 一個基具有2至約1 8個碳原子較佳,並以2至1 2個碳原子最 佳,並且每一個R可以相同或不同。其中以每一個烴基含2 至約1 2個碳原子及其是線型或支化烷基之四烴基氧化鈦最 理想,因為其比較不貴、更容易取得及有效形成溶液。適 合的四烴基氧化鈦包括四乙氧鈦、丙氧鈦、異丙氧鈦、四 正丁氧鈦、四己氧鈦、四2-乙基己氧鈦、四辛氧鈦及任何 二或數個其組合物,但不限於此。 通常在R基中避免鹵化物或其它活性取代物的存在,因O: \ 58 \ 58096-910820.ptc Page 7 592811 Amendment No. 88106251 V. Description of the Invention (3) According to a first embodiment of the present invention, a catalyst composition is provided. The composition may include an organic titanium compound, a dissolution promoter, a source of phosphorus, and optionally a sulfonic acid, a cocatalyst, or a combination thereof. The composition basically consists of or consists of an organic titanium compound, a dissolution accelerator, a source of phosphorus, and a sulfonic acid. The dissolution accelerator may be selected from the group consisting of orthosilicate, orthorammate, and a combination thereof, and the co-catalyst may be free of cobalt as described in U.S. Patent Application No. 5,6 7 4,8 01. Each is composed of an aluminum catalyst, an antimony compound, and a composition thereof. The catalyst composition of the present invention is substantially soluble in a solvent. In terms of π, the term π is more trivial. The composition is preferably completely soluble in a solvent. However, a substantial part of the composition may be suspended or dispersed in a solvent. According to the present invention, the currently preferred titanium compound is an organic titanium compound. Tetrahydrocarbyl titanium oxide is currently the best organic titanium compound because it is easily available and effective. Examples of suitable tetrahydrocarbyl titanium oxide compounds include those represented by the general formula T i (OR) 4, where one R is independently selected from the group consisting of alkyl, cycloalkyl, aralkyl, and two or more of them. And so on. Each radical may include from 1 to about 30 carbon atoms, preferably each radical has from 2 to about 18 carbon atoms, and most preferably from 2 to 12 carbon atoms, and each R may be the same or different. Among them, tetrahydrocarbyl titanium oxide containing 2 to about 12 carbon atoms per hydrocarbon group and a linear or branched alkyl group is most preferable because it is relatively inexpensive, easier to obtain, and effectively forms a solution. Suitable tetrahydrocarbon-based titanium oxides include tetraethoxytitanium, propoxytitanium, isopropoxytitanium, tetra-n-butoxytitanium, tetrahexyltitanium, tetra2-ethylhexyltitanium, tetraoctyltitanium and any two or more Its composition, but not limited to this. The presence of halides or other reactive substituents is usually avoided in the R group, because
O:\58\58096-910820.ptc 第8頁 592811 修正 案號 88106251 五、發明說明(4) 為這些取代物可能會干擾催化劑的反應或形成不預期的副 產物,在利用鈦化物製造聚合物時,其可能會污染聚合 物。目前使每一個R基相同也較理想,有助於有機鈦酸酯 的合成。在一些實例中,二或數個R基可來自不是在鈦原 子上以化學鍵結在一起的常見化合物(即多配位基,如三 乙醇胺、檸檬酸、乳酸、馬來酸、酒石酸、羥基甘氨酸、 酸的鹽類及二或數個其混合物)。 以例如四氯化鈦與醇在鹼的存在下(如氨)混合,形成鈦 酸四烷酯,也可以製造適用於本發明的四烴基氧化鈦。醇 典型係乙醇、正丙醇、異丙醇、正丁醇或異丁醇。通常不 使用曱醇,因為生成的鈦酸四曱酯不溶於反應混合物中, 使其分離複雜化。以任何本技藝的熟練者已知的方式(如 過濾)先除去氣化銨副產物及接著自反應混合物蒸餾出鈦 酸四院S旨,可以回收因此製造的鈦酸四烧S旨。本方法可以 在從約0至約1 5 0 °C為範圍的溫度下進行。以那些具有至多 C4之1?基與具有每分子超過4個碳原子之醇的酯基轉移作用 有可以製造具有高碳烷基之鈦酸酯。 在商業上可取得的有機鈦化合物實例包括取自美國德拉 威州Wilmington 之E.I. du Pont de Nemours 公司之 TYZOR® TPT及TYZOR® TBT(分別是鈦酸四異丙酯及鈦酸四 正丁酯),但不限於此。 磷來源目前以選自膦酸、次膦酸、膦或其組合物較佳。 不想受到理論的限制,顯然磷化合物會在催化劑組成物製 備期間與有機鈦化合物鍵結,藉以改良鈦化合物之溶解度 及有助於控制利用這些化合物製造的聚酯之光學特性。O: \ 58 \ 58096-910820.ptc Page 8 592811 Amendment No. 88106251 V. Description of the invention (4) Because these substitutions may interfere with the reaction of the catalyst or form unexpected by-products, polymers are produced using titanium compounds As a result, it may contaminate the polymer. At present, it is also ideal to make each R group the same, which is helpful for the synthesis of organic titanates. In some examples, two or more R groups may be derived from common compounds that are not chemically bonded together on the titanium atom (i.e. multi-ligands, such as triethanolamine, citric acid, lactic acid, maleic acid, tartaric acid, hydroxyglycine , Acid salts and two or more of them). For example, titanium tetrachloride is mixed with an alcohol in the presence of a base (such as ammonia) to form a tetraalkyl titanate, and a tetrahydrocarbyl titanium oxide suitable for use in the present invention can also be produced. Alcohols are typically ethanol, n-propanol, isopropanol, n-butanol or isobutanol. Methanol is generally not used because the tetramethyl titanate produced is insoluble in the reaction mixture and complicates the separation. In any manner known to those skilled in the art (e.g., filtration), first removing the gasified ammonium by-product and then distilling out the titanate titanate from the reaction mixture, the titanate titanate can be recovered. The method can be carried out at a temperature ranging from about 0 to about 150 ° C. It is possible to produce titanates having a high-carbon alkyl group by transesterification of 1? Groups with at most C4 and alcohols having more than 4 carbon atoms per molecule. Examples of commercially available organic titanium compounds include TYZOR® TPT and TYZOR® TBT (tetraisopropyl titanate and tetra-n-butyl titanate, respectively) from EI du Pont de Nemours, Wilmington, Delaware, USA ), But not limited to this. The phosphorus source is currently preferably selected from phosphonic acid, phosphinic acid, phosphine, or a combination thereof. Without wishing to be bound by theory, it is clear that phosphorus compounds will bond with organic titanium compounds during the preparation of the catalyst composition, thereby improving the solubility of the titanium compounds and helping to control the optical characteristics of polyesters made from these compounds.
O:\58\58096-910820.ptc 第9頁 592811 _案號88106251 5丨年P月M7日 修正_ 五、發明說明(5) 膦酸、次膦酸或膦可以具有直接鍵結至磷原子之烷基、 烯基、芳烷基或芳基。每一個基典型係可以包括1至約25 個碳原子,以1至約2 0個碳原子較佳,並以1至約1 5個碳原 子最佳。例如,可以出現曱基、乙基、苯基或萘基。這些 基可以進一步被完全不干擾催化劑組成物製備作用或接著 利用催化劑之反應的基取代。而且,也可以取代酸的羥 基。例如,可將一或兩個鍵結至膦酸的磷原子之OH基酯 化。 有機膦酸具有比次膦酸更強的螯合劑之傾向,並可用希 望在磷化合物與有機鈦化合物之間有強鍵結之應用。已發 現苯基次膦酸、二苯基次膦酸及3 -(羥基苯基次膦基)丙酸 會在反應速度之間提供極佳的平衡及避免在其中將催化劑 系統當成通常製備聚伸烷基對苯二酸酯及尤其是PET之聚 濃縮催化劑使用的應用中產生色彩。適合的膦實例包括 1,2 -雙-二苯基膦基乙烷、1,3-雙-二苯基膦基丙烷、1,4-雙-二苯基膦基丁烷、雙-4-甲苯基膦氧化物、雙-3,5 -二 曱苯基膦氧化物或二或數個其組合物,但不限於此。 在本發明可以使用實質上可溶解以上揭示的催化劑組成 物之任何溶劑。目前較佳的溶劑是具有化學式RKOH),的 醇、化學式伸烷基乙二醇、具有化學式 RiOCCI^CiURDOLH的烷氧基化醇或二或數個其組合物,其 中每一個R1可以相同或不相同,其是每一個基具有1至約 1 0個碳原子之烴基,以1至約8個碳原子較佳,並以1至約5 個碳原子最佳。目前較佳的是R1或支化,或直鏈烷基。A 可以每分子具有2至約1 0個碳原子,以2至約7個碳原子較O: \ 58 \ 58096-910820.ptc Page 9 592811 _Case No. 88106251 5 Rev. P7 M7_ V. Description of the invention (5) Phosphonic acid, phosphinic acid or phosphine may have a direct bond to a phosphorus atom Alkyl, alkenyl, aralkyl or aryl. Each radical may typically include from 1 to about 25 carbon atoms, preferably from 1 to about 20 carbon atoms, and most preferably from 1 to about 15 carbon atoms. For example, fluorenyl, ethyl, phenyl or naphthyl can occur. These groups may be further substituted with a group which does not interfere with the preparation of the catalyst composition at all or which is followed by a reaction using the catalyst. Moreover, it is also possible to replace the hydroxyl group of the acid. For example, one or two OH groups of a phosphorus atom bonded to a phosphonic acid can be esterified. Organic phosphonic acid has a tendency to be a stronger chelating agent than phosphinic acid, and can be used in applications where a strong bond between a phosphorus compound and an organic titanium compound is desired. It has been found that phenylphosphinic acid, diphenylphosphinic acid, and 3- (hydroxyphenylphosphiphosino) propionic acid provide an excellent balance between reaction speeds and avoid using the catalyst system as a conventionally-produced polymer Alkyl terephthalates and polyconcentrate catalysts, especially PET, are used to produce color. Examples of suitable phosphines include 1,2-bis-diphenylphosphinoethane, 1,3-bis-diphenylphosphinopropane, 1,4-bis-diphenylphosphinobutane, bis-4- Tolylphosphine oxide, bis-3,5-bisfluorenylphenylphosphine oxide, or two or more thereof, but is not limited thereto. Any solvent that can dissolve the catalyst composition disclosed above can be used in the present invention. The currently preferred solvents are alcohols with the chemical formula RKOH), alkylene glycols with the chemical formula, alkoxylated alcohols with the formula RiOCCI ^ CiURDOLH, or two or more of their compositions, where each R1 may be the same or not Similarly, it is a hydrocarbon group having 1 to about 10 carbon atoms per group, preferably 1 to about 8 carbon atoms, and most preferably 1 to about 5 carbon atoms. Currently preferred are R1 or branched, or linear alkyl. A may have 2 to about 10 carbon atoms per molecule, with 2 to about 7 carbon atoms compared
O:\58\58096-910820.ptc 第10頁 592811 案號 88106251 修正 五、發明說明(6) 佳,並以2至約4個碳原子 同,其是單獨以從1至約1 佳,並1至5最佳。適合的 醇、丁醇、乙二醇、丙二 丙二醇、戊二醇、二乙二 醚、三乙二醇 但不限於此。 造之聚S旨的乙 目前較佳的 或其組合物。 催化劑組成物 濃度在室溫下 引入利用催化 化劑組成物之 公克催化劑的 溶解促進劑是 但不限於此。 酸醋具有化學 樣。這些溶解 氯化石夕或四氣 R1取代氯化物 酸四乙酯、原 正丁酯及二或 基及原矽酸四 及四正丁基原 單乙醚、2-目前較佳的 二醇。 溶解促進劑 目前最佳的 中出現的鈦 (2 5 °C )溶解 劑的方法中 組份會使得 濃度溶解, 有機原矽酸 有機原矽酸 式 ZKOR1)* 促進劑通常 化锆引入以 的方式製造 石夕酸四正丙 數個其組合 正丙酯可自 鍅酸酯係在 最佳。每一個η可以相同或不相 0為範圍之數字,以1至約7較 溶劑實例包括乙醇、丙醇、異丙 醇、異丙二醇、丁二醇、1-曱基 醇、三乙二醇、二乙二醇單乙 乙基己醇及二或數個其組合物, 溶劑是用於自廣泛的工業應用製 可以是有機矽酸酯、有機锆酸酯 溶解促進劑可幫助基本上在所有 以特殊應用預期的催化劑組成物 在用於製備組成物中。為了減少 之溶劑量,典型係選擇使形成催 該組成物以每1 0 0公克溶劑至少3 以至少5公克較佳。目前最佳的 酉旨、有機原錯酸酯或其組合物, 酯具有學式Si (OR1 )4及有機原鍅 ,其中每一個R1與以上的揭示一 可自商業上取得或可以例如將四 上揭示的溶劑中,以在溶劑中的 。適合的溶解促進劑實例包括矽 酯、原鍅酸四正丙酯、原锆酸四 物,但不限於此。原矽酸酯四乙 商業上取得。四正丙基原錘酸酯 商業上取自Ε·Ι. du Pont deO: \ 58 \ 58096-910820.ptc Page 10 592811 Case No. 88106251 Amendment V. Description of the Invention (6) is good, and it is the same with 2 to about 4 carbon atoms, which is alone to be from 1 to about 1, and 1 to 5 is best. Suitable alcohols, butanol, ethylene glycol, propylene glycol, pentanediol, diethylene glycol, triethylene glycol are not limited thereto. The B of the purpose of making S is currently preferred or a combination thereof. Catalyst composition Concentration The dissolution promoter introduced into the gram catalyst using the catalyst composition at room temperature is, but is not limited to. Sour vinegar is chemical. These dissolved chlorite or tetrakis R1 substituted tetraethyl chloride, tetra-n-butyl chloride and di- ortho- and tetra- and tetra-n-butyl orthosilicate monoethyl ether, 2-the currently preferred diols. Dissolving Accelerator Currently the best method of titanium (2 5 ° C) dissolving agent is to make the components dissolve in concentration. Organic ortho-silicic acid Organic-ortho-silicic acid type ZKOR1) * Tetra-n-propyl oxalate is produced in several combinations, and the combination of n-propyl ester can be the best from the acetic acid esters. Each η may be a number in the same or different range from 0 to 1 and more. Examples of solvents include ethanol, propanol, isopropanol, isopropanediol, butanediol, 1-fluorenyl alcohol, triethylene glycol, Diethylene glycol monoethylethylhexanol and two or more of its compositions. The solvent is used in a wide range of industrial applications. It can be an organic silicate, organic zirconate dissolution promoter that can help The catalyst composition intended for a particular application is used in the preparation of the composition. In order to reduce the amount of the solvent, it is typically selected to form the composition at least 3 and at least 5 g per 100 g of the solvent. Currently the best formula, organic orthoester or combination thereof, the ester has the chemical formula Si (OR1) 4 and organic orthocyanin, each of which R1 and the above disclosure can be obtained commercially or can, for example, be Among the solvents disclosed above, to the solvent. Examples of suitable dissolution accelerators include, but are not limited to, silicon ester, tetra-n-propyl orthoacetate, and tetra-ortho-zirconate. Tetraethyl orthosilicate was obtained commercially. Tetra-n-propyl orthanoic acid ester is commercially obtained from E.I. du Pont de
O:\58\58096-910820.ptc 第11頁 592811 _案號 88106251_q I 年 P 月 曰__ 五、發明說明(7)O: \ 58 \ 58096-910820.ptc Page 11 592811 _Case No. 88106251_q I Year P Month __ V. Description of the Invention (7)
Nemours公司以TYZOR® 為商標之有機锆酸酯。選擇特殊的 原矽酸酯及原錘酸酯將會改變經促進的特殊反應。例如, 在製備PET時,以原矽酸酯比原錘酸酯理想,因為其在濃 縮速度上具有的影響比較小。 可視需要在本發明中使用磺酸或其鹽類。目前較佳的磺 酸可以是任何實質上可溶解在以上揭示的溶劑中之芳基或 烧基續酸。適合的續酸實例包括對-曱苯續酸、苯磺酸、 曱烷磺酸、乙烷磺酸、丙烷磺酸、丁烷磺酸及二或數個其 組合物,但不限於此。磺酸的鹽類可以是鹼金屬鹽、鹼土 金屬鹽、銨鹽或二或數個其組合物。 催化劑組成物可以進一步包含共催化劑。共催化劑實例 包括鈷/鋁催化劑、銻化合物及其組合物,但不限於此。 鈷/鋁催化劑包含鈷鹽與鋁鹽,其中鋁對鈷之莫耳比例是 以從0 . 2 5 : 1至1 6 : 1為範圍。在美國專利申請案第 5,6 7 4,8 0 1號中揭示鈷/鋁催化劑,將其併入本文以供參 考。 目前較佳的銻化合物可以是任何實質上溶解在以上揭示 的溶劑中之銻化合物。適合的銻化合物實例包括氧化銻、 氫氧化銻、鹵化銻、硫化銻、羧酸銻、銻醚、乙醇酸銻、 醇酸銻、硝酸銻、硫酸銻、磷酸銻及二或數個其組合物, 但不限於此。 根據本發明的第一個較佳的具體實施例,根據P : T i的測 量,磷來源對鈦化合物之莫耳比例可以在從約0. 1 : 1至約 1 0 : 1的範圍内,以約0 . 5 : 1至約7 : 1較佳,並以從約1 : 1至 約4 : 1最佳。溶解促進劑對鈦化合物之莫耳比例(S i : T i或Nemours is an organic zirconate under the trademark TYZOR®. The choice of special ortho- ortho- ortho-amarconic esters will alter the special reactions that are promoted. For example, in the preparation of PET, ortho-silicate is preferred over ortho-humic acid ester because it has a smaller effect on the concentration rate. If necessary, a sulfonic acid or a salt thereof may be used in the present invention. The currently preferred sulfonic acid can be any aryl or alkanoic acid that is substantially soluble in the solvents disclosed above. Examples of suitable dicarboxylic acids include, but are not limited to, p-benzoic acid, benzenesulfonic acid, pinanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, and two or more thereof. The salts of the sulfonic acid may be an alkali metal salt, an alkaline earth metal salt, an ammonium salt, or two or more combinations thereof. The catalyst composition may further include a co-catalyst. Examples of co-catalysts include, but are not limited to, cobalt / aluminum catalysts, antimony compounds, and combinations thereof. The cobalt / aluminum catalyst comprises a cobalt salt and an aluminum salt, wherein the molar ratio of aluminum to cobalt ranges from 0.25: 1 to 16: 1. A cobalt / aluminum catalyst is disclosed in U.S. Patent Application No. 5,6 7,4,801, which is incorporated herein by reference. The presently preferred antimony compound may be any antimony compound that is substantially soluble in the solvents disclosed above. Examples of suitable antimony compounds include antimony oxide, antimony hydroxide, antimony halide, antimony sulfide, antimony carboxylic acid, antimony ether, antimony glycolate, antimony alkyd, antimony nitrate, antimony sulfate, antimony phosphate, and two or more combinations thereof , But not limited to this. According to the first preferred embodiment of the present invention, according to the measurement of P: T i, the molar ratio of the phosphorus source to the titanium compound may be in a range from about 0.1: 1 to about 10: 1, It is preferably from about 0.5: 1 to about 7: 1, and most preferably from about 1: 1 to about 4: 1. Molar ratio of dissolution accelerator to titanium compound (S i: T i or
O:\58\58096-910820.ptc 第12頁 592811 _案號88106251_今/年β月曰_^_ 五、發明說明(8) Z r : T i )可以在從約0 . 1 : 1至約1 0 : 1的範圍内,以約0 · 5 : 1至 約7 : 1較佳,並以從約1 : 1至約4 : 1最佳。磺酸對鈦化合物 之莫耳比例(S i 03: T i )通常以小於或等於2 ·· 1較佳。但是, 比例也可以在從約0 · 1 : 1至約4 : 1的範圍内,以約0 · 5 : 1至 約3 : 1的範圍内較佳,並以約1 : 1至約2 : 1最佳。共催化劑 對鈦化合物之莫耳比例,如S b : T i或C 〇 : T i可以在從約 0 . 0 1 : 1至約1 0 : 1的範圍内。如果在製造聚伸烷基對苯二酸 酯時使用催化劑組成物時,則磷來源對溶解促進劑之莫耳 比例(S i : P或Z r : P )通常大於或等於約0 . 5 : 1,因為較低的 比例可能引起聚伸烷基對苯二酸酯的褪色作用。鈦化合物 可選擇以組成物總重量當成1 0 0 %為基礎計從約0 · 0 1 0至約 1 5 %為範圍存在催化劑組成物中,以約0 . 1至約1 0 %較佳, 並以0 . 5至5 %最佳。 根據本發明,催化劑組成物可進一步含有水,尤其是含 有磺酸之組成物。含水之組成物具有高活性及有助於控制 利用組成物製造的聚酯之光學特性。當有水存在時,則水 對鈦化合物之莫耳比例可以在從約0. 0 1 : 1至約6 : 1的範圍 内,以約0 . 1 : 1至約4 : 1較佳,並以從約1 : 1至約2 : 1最佳。 雖然已以其較佳的應用詳細說明當成製造聚伸烷基對苯 二酸酯之聚濃縮催化劑的催化劑組成物,但是組成物也具 有當成在要求高活性催化劑的熟知方法中的酯化或酯基轉 移催化劑之一般用途。例如,可在苯二酸酐與辛醇的反應 中使用催化劑組成物,以形成對苯二酸二辛酯,聚氯乙烯 之增塑劑,且有低霧性。可調整催化劑組成物之相對比 例,以符合特殊應用的要求。O: \ 58 \ 58096-910820.ptc Page 12 592811 _ Case No. 88106251_ Today / Year β Month _ ^ _ V. Description of the invention (8) Z r: T i) can be from about 0.1: 1 In the range from about 10: 1, about 0.5: 1 to about 7: 1 is preferred, and most preferably from about 1: 1 to about 4: 1. The molar ratio (S i 03: T i) of the sulfonic acid to the titanium compound is usually preferably less than or equal to 2 ·· 1. However, the ratio may also be in a range from about 0.1: 1 to about 4: 1, preferably in a range of about 0.5: 1 to about 3: 1, and about 1: 1 to about 2: 1 is the best. The molar ratio of the co-catalyst to the titanium compound, such as Sb: Ti or C0: Ti, can be in a range from about 0.01: 1 to about 10: 1. If the catalyst composition is used in the production of polyalkylene terephthalate, the molar ratio (S i: P or Z r: P) of the phosphorus source to the dissolution promoter is usually greater than or equal to about 0.5: 1, because lower proportions may cause the discoloration of polyalkylene terephthalates. The titanium compound may optionally be present in the catalyst composition in a range from about 0. 0 1 0 to about 15% based on the total weight of the composition as 100%, preferably about 0.1 to about 10%, And the best is 0.5 to 5%. According to the present invention, the catalyst composition may further contain water, especially a composition containing sulfonic acid. Water-containing compositions have high activity and help control the optical characteristics of polyesters made from the compositions. When water is present, the molar ratio of water to titanium compound may range from about 0.01: 1 to about 6: 1, preferably about 0.1: 1 to about 4: 1, and It is preferably from about 1: 1 to about 2: 1. Although it has been described in detail as a catalyst composition for a polycondensation catalyst for producing a polyalkylene terephthalate with its preferred application, the composition also has an esterification or an ester as a well-known method requiring a highly active catalyst General purpose of base transfer catalyst. For example, a catalyst composition can be used in the reaction of phthalic anhydride and octanol to form dioctyl terephthalate, a plasticizer of polyvinyl chloride, and have low haze. The relative proportions of the catalyst composition can be adjusted to meet the requirements of special applications.
O:\58\58096-910820.ptc 第13頁 592811 _案號88106251 91年2月乂曰 修正_ 五、發明說明(9) 可以本技藝的熟練者已知的任何方式製造催化劑組成 物。但是,以在本發明的第二個具體實施例中揭示的方法 製造較佳。 可在與酯化或酯基轉移或聚濃縮反應相容或不干擾的溶 劑中製造催化劑組成物。例如,如果將催化劑組成物當成 製造PET的聚濃縮催化劑使用時,則以在乙二醇中製造組 成物較佳;如果利用催化劑組成物製造PBT時,則以在 1,4 - 丁二醇中製造組成物較佳;如果利用催化劑組成物製 造聚丙二醇對苯二酸酯(PPT)時,則以在1,3-丙二醇中製 造組成物較佳。關於二辛基對苯二酸酯之製造,以2 _乙基 己醇是較佳的醇。 雖然可將各個組份以任何順序結合,但是以先結合溶解 促進劑與溶劑,以產生第一個混合物較佳。接著將第一個 混合物與磷來源結合,以產生第二個混合物,因為溶解促 進劑有助於磷來源溶解。通常可將產生第一或第二個混合 物之結合攪拌,並可以在從約0 °C至約1 0 0 °c為範圍之溫度 下進行,以約3 0 °C至約5 0 °C較佳。通常可以使用任何溶劑 量,只要實質上可溶解組成物的量即可,並可以組成物中 使用的鈦化合物以每莫耳計從約5至約5 0莫耳為範圍,以 約1 0至約3 0較佳,並以約1 0至約2 0最佳。 接著可將鈦化合物與第二個混合物結合,以產生本發明 的催化劑組合物。該步驟以在惰性氣體下進行較佳,氮 氣、二氧化碳、氦或二或數個其組合物,以避免產生可燃 性醇,因為該步驟會放熱,造成溫度會上昇10至30 °C。該 步驟以攪拌一段足以使鈦化合物幾乎溶解的時間進行,通O: \ 58 \ 58096-910820.ptc Page 13 592811 _Case No. 88106251 Issued February 1991 Modified_ V. Description of the invention (9) The catalyst composition can be produced in any manner known to those skilled in the art. However, it is preferable to manufacture it by the method disclosed in the second embodiment of the present invention. The catalyst composition can be produced in a solvent compatible or non-interfering with the esterification or transesterification or polyconcentration reaction. For example, if the catalyst composition is used as a polyconcentrated catalyst for manufacturing PET, it is better to manufacture the composition in ethylene glycol; if the catalyst composition is used to manufacture PBT, it is used in 1,4-butanediol It is preferable to produce a composition; when a polypropylene glycol terephthalate (PPT) is produced using a catalyst composition, it is preferable to produce the composition in 1,3-propanediol. Regarding the production of dioctyl terephthalate, 2-ethylhexanol is the preferred alcohol. Although the components can be combined in any order, it is preferred to combine the dissolution accelerator and solvent first to produce the first mixture. The first mixture is then combined with the phosphorus source to produce a second mixture because the dissolution promoter helps dissolve the phosphorus source. The combination that produces the first or second mixture can usually be stirred and can be performed at a temperature ranging from about 0 ° C to about 100 ° C, with a temperature of about 30 ° C to about 50 ° C. good. Generally, any amount of solvent may be used as long as the composition is substantially soluble, and the titanium compound used in the composition may range from about 5 to about 50 moles per mole, and from about 10 to About 30 is preferred, and most preferably about 10 to about 20. The titanium compound can then be combined with a second mixture to produce the catalyst composition of the present invention. This step is preferably performed under an inert gas, such as nitrogen, carbon dioxide, helium, or two or more of them, to avoid the generation of flammable alcohols, as this step will exotherm and cause a temperature increase of 10 to 30 ° C. This step is performed by stirring for a time sufficient to allow the titanium compound to be almost dissolved.
O:\58\58096-910820.ptc 第14頁 592811 _案號88106251 9丨年只月日 修正_ 五、發明說明(10) 常約5分鐘至約2 0小時或更長,接著以冷卻至室溫。 接著可將催化劑組成物與磺酸、共催化劑或兩者結合, 以產生視需要之催化劑組成物。也可同時結合磺酸與磷來 源及第一個混合物,以產生第二個混合物。 可選擇將磷來源與溶劑及鈦化合物結合,以形成複合 物。可以任何熟知的方式(如過濾)自溶劑分離出複合物, 以產生分離的複合物。接著可將分離的複合物與含有溶 劑、溶解促進劑、續酸或共催化劑或二或數個其組合物之 混合物結合,以產生本發明的催化劑組成物。 各個組份量可隨選擇的化合物改變,並且通常可使每一 個組份對在製得的催化劑化合物中的鈦之莫耳比例是在以 上揭示的範圍内。 未建立過催化劑系統的結構。但是,以經^發現的放熱為 基礎,咸信組份已以一些方式反應或複合,以形成二元或 三元組成物(等),以至少某種程度使催化劑組成物尤其適 合當成通常在製造聚伸烷氧基對苯二酸酯之聚濃縮催化 劑,特別是聚對苯二曱酸乙二酯(PET )。 根據本發明的第三個具體實施例,其係提供例如可在製 造酯或聚酯時使用的方法。本方法包含在催化劑組成物的 存在下將羰基化合物與醇接觸。組成物與以上本發明的第 一個具體實施例揭示之組成物相同。 根據本發明的第三個具體實施例,可以使用任何可與醇 反應產生酯的羰基化合物。通常這些羰基化合物與醇接 觸。組成物與以上本發明的第一個具體實施例揭示之組成 物相同。O: \ 58 \ 58096-910820.ptc Page 14 592811 _Case No. 88106251 9 丨 Only Month and Day Amendment_ V. Description of the invention (10) Often about 5 minutes to about 20 hours or longer, and then cooled to Room temperature. The catalyst composition may then be combined with a sulfonic acid, a cocatalyst, or both to produce a catalyst composition as desired. It is also possible to combine the sulfonic acid with the phosphorus source and the first mixture simultaneously to produce a second mixture. Optionally, the phosphorus source can be combined with a solvent and a titanium compound to form a complex. The complex can be separated from the solvent in any well-known manner (e.g., filtration) to produce an isolated complex. The separated complex can then be combined with a mixture containing a solvent, a dissolution promoter, a continuous acid or co-catalyst, or a mixture of two or more of its compositions to produce the catalyst composition of the present invention. The amount of each component may vary depending on the selected compound, and the molar ratio of each component to titanium in the prepared catalyst compound is usually within the range disclosed above. The structure of the catalyst system has not been established. However, on the basis of the exothermicity discovered by ^, the Xianxin components have reacted or compounded in some ways to form a binary or ternary composition (etc.), making the catalyst composition particularly suitable as at least to some extent in the manufacture Polycondensation catalyst for polyalkylene terephthalate, especially polyethylene terephthalate (PET). According to a third embodiment of the present invention, it provides a method which can be used, for example, in the manufacture of esters or polyesters. The method includes contacting a carbonyl compound with an alcohol in the presence of a catalyst composition. The composition is the same as that disclosed in the first embodiment of the present invention. According to a third embodiment of the present invention, any carbonyl compound which can react with an alcohol to produce an ester can be used. These carbonyl compounds are usually in contact with alcohols. The composition is the same as that disclosed in the first embodiment of the present invention.
O:\58\58096-910820.ptc 第15頁 592811 _案號88106251 f年分月^日 修正_ 五、發明說明(11) 根據本發明第三個具體實施例,可以使用任何可與醇反 應產生酯的羰基化合物。通常這些幾基化合物包括酸、 酯、醯胺、酸酐、酸鹵化物、具有衍生自酸之重覆單元的 募聚物或聚合物或二或數個其組合物,但不限於此。目前 較佳的酸是有機酸。目前較佳的方法是(1 )從苯二酸酐與 2-乙基己醇之酯製造,如舉例的雙(2-乙基己基)對苯二酸 酯及(2 )酸或酯與醇之聚合作用,以製造聚酯。 一個製造酯或聚酯較佳的方法包含或基本上由將反應介 質與在以上本發明的第一個具體實施例揭示之組成物接觸 構成。反應介質可以包含或基本上由(1)或有機酸,或其 酯與醇,或(2)醇與具有衍生自有機酸或酯之重覆單元的 募聚物等構成的。 羰基化合物、有機酸或其酯可以具有化學式 (HO)mR2(COOR, )p,其中m是從0至約10之數字,以從0至約5 較佳,並以從0至3最佳,每一個R2及R’可以單獨是(1 ) 氫,(2)在末端具有羧基之烴基,(3)烴基,或(4)二或數 個其組合物,其中每一個基可被取代或不被取代;每一個 基具有1至約3 0個碳原子,以約3至1 5個碳原子較佳,其可 以是烷基、烯基、芳基、烷芳基、芳烷基或二或數個其組 合物;並且p可以是從1至等於R2碳原子數之整數。也可以 使用任何有機酸之酐。目前較佳的有機酸是具有化學式 HOJAiCOd,其中A1是伸烷基、伸芳基、伸烯基或二或數個 其組合物。每一個A1具有約2至約3 0個碳原子,以約3至約 2 5個碳原子較佳,以約4至約2 0個碳原子更佳,並以約4至 約1 5個碳原子最佳。適合的有機酸實例包括對.苯二酸、異O: \ 58 \ 58096-910820.ptc Page 15 592811 _Case No. 88106251 F Year Minute ^ Day Amendment_ V. Description of the Invention (11) According to the third embodiment of the present invention, any reaction with alcohol can be used An ester carbonyl compound is produced. Generally these several base compounds include, but are not limited to, acids, esters, amidines, anhydrides, acid halides, agglomerates or polymers having repeat units derived from an acid, or two or more of them. The currently preferred acids are organic acids. The presently preferred method is (1) Manufactured from esters of phthalic anhydride and 2-ethylhexanol, such as exemplified bis (2-ethylhexyl) terephthalate and (2) acids or esters and alcohols. Polymerization to make polyester. A preferred method for making an ester or polyester comprises or consists essentially of contacting a reaction medium with the composition disclosed in the first embodiment of the invention above. The reaction medium may contain or consist essentially of (1) or an organic acid, or an ester and an alcohol thereof, or (2) an alcohol and a polymer having a repeating unit derived from an organic acid or an ester, and the like. A carbonyl compound, an organic acid or an ester thereof may have a chemical formula (HO) mR2 (COOR,) p, where m is a number from 0 to about 10, preferably from 0 to about 5, and most preferably from 0 to 3, Each of R2 and R 'may be (1) hydrogen, (2) a hydrocarbon group having a carboxyl group at the terminal, (3) a hydrocarbon group, or (4) two or more combinations thereof, each of which may be substituted or not Substituted; each group has 1 to about 30 carbon atoms, preferably about 3 to 15 carbon atoms, which may be alkyl, alkenyl, aryl, alkaryl, aralkyl, or two or Several of its compositions; and p may be an integer from 1 to equal to the number of carbon atoms in R2. Any anhydride of organic acids can also be used. The currently preferred organic acids are those having the chemical formula HOJAiCOd, where A1 is an alkylene, an arylene, an alkenyl or two or more of them. Each A1 has about 2 to about 30 carbon atoms, preferably about 3 to about 25 carbon atoms, more preferably about 4 to about 20 carbon atoms, and about 4 to about 15 carbon atoms. Atomic best. Examples of suitable organic acids include terephthalic acid,
O:\58\58096-910820.ptc 第16頁 592811 修正 案號 88106251 五、發明說明(12) 苯二酸、萘二甲酸、丁二酸、己二酸、苯二酸、戊二酸、 丙烯酸、草酸、苯曱酸、馬來酸、丙酸、4 -羥基苯曱酸、 1 2 -羥基癸酸、6 -羥基已酸、4 -羥基肉桂酸、4 -羥基曱基 苯曱酸、4 -羥基苯基醋酸、壬二酸、水楊酸、已酸、硬脂 酸、棕櫚酸、富馬酸、萘烷二羧酸、檸檬酸、苯均三酸、 雙羥萘酸、癸二酸、這些酸的任何酐及二或數個其組合 物,但不限於此。目前較佳的有機二酸是苯二酸,因為以 其製造的聚酯具有廣泛的工業應用性。適合的酯實例包括 已二酸二甲酯、苯二酸二甲酯、對苯二酸二曱酯、苯曱酸 甲酯、戊二酸二曱酯及二或數個其組合物,但不限於此。 本發明可以使用任何可將酸酯化成酯或聚酯之醇。目前 較佳的醇具有化學式R3(〇H)n之醇、化學式(HO)nA(OH)n或其 組合物,其中每一個R3可以相同或不相同,並且是每一個 基具有1至約1 0個碳原子之烴基,以1至約8個碳原子較 佳,並以1至5個碳原子最佳。目前較佳的R3是或支化,或 直鏈烷基。A可每分子具有2至約1 0個碳原子,以2至約7個 碳原子較佳,並以2至約4個碳原子最佳。每一個η可以相 同或不相同,其是單獨以從1至約1 0為範圍之數字,以1至 約7較佳,並以1至5最佳,適合的醇實例包括乙醇、丙 醇、異丙醇、丁醇、乙二醇、丙二醇、異丙二醇、丁二 醇、1-曱基丙二醇、戊二醇、二乙二醇、三乙二醇、2-乙 基己醇、硬脂醇、1,6 -己二醇、丙三醇、異戊四醇及二或 數個其組合物,但不限於此。目前最佳的醇是伸烷基乙二 醇,如以其製得的聚酯之乙二醇具有廣泛的工業應用性。 可以任何適合的方式進行反應介質與催化劑的接觸。例O: \ 58 \ 58096-910820.ptc Page 16 592811 Amendment No. 88106251 V. Description of the invention (12) Phthalic acid, naphthalenedicarboxylic acid, succinic acid, adipic acid, phthalic acid, glutaric acid, acrylic acid , Oxalic acid, phenylarsinic acid, maleic acid, propionic acid, 4-hydroxyphenylarsinic acid, 1 2-hydroxydecanoic acid, 6-hydroxyhexanoic acid, 4-hydroxycinnamic acid, 4-hydroxyfluorenylbenzoic acid, 4 -Hydroxyphenylacetic acid, azelaic acid, salicylic acid, caproic acid, stearic acid, palmitic acid, fumaric acid, decalinic acid, citric acid, trimesic acid, pamoic acid, sebacic acid Any anhydride of these acids and two or more of its compositions, but are not limited thereto. The currently preferred organic diacid is phthalic acid because the polyesters made from it have a wide range of industrial applicability. Examples of suitable esters include dimethyl adipate, dimethyl phthalate, dimethyl terephthalate, methyl benzoate, dimethyl glutarate, and two or more of their compositions, but not Limited to this. The present invention can use any alcohol that can be esterified into an ester or polyester. The currently preferred alcohol has an alcohol of the formula R3 (OH) n, a formula of the formula (HO) nA (OH) n, or a combination thereof, wherein each R3 may be the same or different, and each group has 1 to about 1 A hydrocarbon group of 0 carbon atoms is preferably 1 to about 8 carbon atoms, and most preferably 1 to 5 carbon atoms. Currently preferred R3 is either branched or linear alkyl. A may have 2 to about 10 carbon atoms per molecule, preferably 2 to about 7 carbon atoms, and most preferably 2 to about 4 carbon atoms. Each η may be the same or different, it is a number ranging from 1 to about 10 alone, preferably from 1 to about 7, and most preferably from 1 to 5. Examples of suitable alcohols include ethanol, propanol, Isopropanol, butanol, ethylene glycol, propylene glycol, isopropyl glycol, butylene glycol, 1-fluorenyl propylene glycol, pentanediol, diethylene glycol, triethylene glycol, 2-ethylhexanol, stearyl alcohol , 1,6-hexanediol, glycerol, isopentaerythritol, and two or more thereof, but not limited thereto. At present, the best alcohol is alkylene glycol, such as the ethylene glycol of the polyester prepared therefrom, which has wide industrial applicability. The contacting of the reaction medium with the catalyst can be carried out in any suitable manner. example
O:\58\58096-910820.ptc 第17頁 592811 _案號88106251_年2月义曰 修正_ 五、發明說明(13) 如,在與催化劑接觸之前,先將反應介質的各個組成物結 合。但是,目前以先將催化劑以任何適合的方式溶解或分 散在溶劑中,如機械混合或攪拌,以產溶液或分散液,接 著將溶液或分散液與(1 )有機酸、酯、有機酸募聚物或二 或數個其組合物及(2 )醇在足以完成製造酯或聚酯之條件 下結合。 根據本發明,如果在催化劑組成物中含有磺酸時,則反 應介質也可以包含水。如果有水的存在,則水量與以上揭 示的量一樣。 二酸的募聚物與伸烷基乙二醇通常具有總共約1至約1 0 0 個自二酸及伸烷基氧化物衍生之重覆單元,以從約2至約 1 0個較佳。 適合於完成製造聚酯之條件包括以從約1 5 0 °C至約3 5 0 °C 為範圍之溫度下,以約2 0 0 °C至3 0 0 °C較佳,並以約2 5 0 °C 至約3 0 0 °C最佳及在從約0 . 0 0 1至約1 0大氣壓為範圍之壓力 下經從約1至約2 0小時的時間範圍,以從約1至約1 5小時較 佳,並以從1至1 0小時最佳。 醇(或伸烷基乙二醇)對羰基化合物之莫耳比例可以是任 何比例,只要是可以完成製造酯之比例即可。通常該比例 以從約0 . 1 : 1至約1 0 : 1為範圍,以從約0 · 5 : 1至約5 : 1較 佳,並以從約1 : 1至約3 : 1最佳。關於衍生自醇羰基化合物 (或有機酸或酯)之募聚物對醇(或伸烷基乙二醇)之莫耳比 例,醇(或伸烷基乙二醇)對羰基化合物(或有機酸或酯)之 莫耳比例可以具有相同的q : ( q- 1 )比例,其中q可以從約2 至約2 0為範圍,以約2至1 0較佳,並以2至5最隹。O: \ 58 \ 58096-910820.ptc P.17 592811 _Case No. 88106251_Year February Amendment_ V. Description of the invention (13) For example, before contacting the catalyst, first combine the various components of the reaction medium . However, at present, the catalyst is first dissolved or dispersed in a solvent in any suitable manner, such as mechanical mixing or stirring to produce a solution or dispersion, and then the solution or dispersion is mixed with (1) organic acids, esters, and organic acids. The polymer or two or more of its composition and (2) the alcohol are combined under conditions sufficient to complete the manufacture of the ester or polyester. According to the present invention, when a sulfonic acid is contained in the catalyst composition, the reaction medium may contain water. If water is present, the amount of water is the same as disclosed above. The diacid polymer and alkylene glycol generally have a total of about 1 to about 100 repeat units derived from the diacid and alkylene oxide, preferably from about 2 to about 10 . Suitable conditions for completing the manufacture of polyester include temperatures ranging from about 150 ° C to about 350 ° C, preferably about 200 ° C to 300 ° C, and about 2 50 ° C to about 300 ° C is optimal and at a pressure ranging from about 0.01 to about 10 atmospheres over a time range from about 1 to about 20 hours, to from about 1 to It is preferably about 15 hours, and most preferably from 1 to 10 hours. The molar ratio of the alcohol (or alkylene glycol) to the carbonyl compound may be any ratio as long as it is a ratio that can complete the production of an ester. Usually the ratio ranges from about 0.1: 1 to about 10: 1, preferably from about 0.5: 1 to about 5: 1, and most preferably from about 1: 1 to about 3: 1 . Regarding the molar ratio of the polymer to alcohol (or alkylene glycol) derived from alcohol carbonyl compounds (or organic acids or esters), alcohol (or alkylene glycol) to carbonyl compounds (or organic acids) The molar ratios of the esters or esters can have the same q: (q-1) ratio, where q can range from about 2 to about 20, preferably about 2 to 10, and most preferably 2 to 5.
O:\58\58096-910820.ptc 第18頁 592811 案號 88106251 五、發明說明(14) - 催化劑可以每百萬聚合介暂&曰4 了 雨水口 ,丨貝的重篁计約0.0001至30, 000 = Ϊ(ΡΡ=)為範圍的量存,以約0 0 0 1至約 匕判二:°〇?mw最佳。也可以存在其它會增加催 ϊ i ϊ彳ϋ 之成份。雖然通常以聚伸炫•基對苯二酸 画曰可獲付催化㈣的優點,但是在製造ΡΕΤ時,以取 會Λ得優Λ等別明顯,因為色彩純度是典型係以 PET衣k之商。〇物件的重要標準。 田:ί Γ:ϊ ί熟知的熔融或固態技術之酯或聚酯製造作O: \ 58 \ 58096-910820.ptc Page 18 592811 Case No. 88106251 V. Description of the invention (14)-The catalyst can be used per million polymerizations, and the rainwater outlet is 4 times, the weight of the shell is about 0.0001 to 30, 000 = Ϊ (PP =) is the stock of the range, from about 0.001 to about 2: ° 0? Mw is the best. There may also be other components that increase the reminder ϊ i ϊ 彳 ϋ. Although the advantages of polyisocyanate and terephthalic acid are usually used to obtain catalytic dysprosium, it is obvious that when producing PET, it will be better than Λ, because color purity is typically based on PET clothing. Business. 〇 Important criteria for objects. Tian: ί Γ: ϊ ί well-known melting or solid state technology for the manufacture of esters or polyesters
Hit! Ϊ :卜,]組成物。催化劑組成物可與熟知的酯化或 画曰基轉移催化劑相容(例如,鎂,鈷及/或鋅越),並可盥 醋化催化劑同時或之後引入製造方法中。也:經發現催化 劑組成物具有促進酯化反應的效用,並可以當成部份或全 部la化催化劑與聚濃縮催化劑之取代物使用。 提供以下的實施例進一步例證本發明,並不是將其解釋 成對本發明範圍的不當限制。 實施例 根據實施例A 1,利用醋酸鋅催化使對苯二酸二曱酯以乙 二醇自旨化’以形成龍T募聚物。將根據實施例2至1 5合成的 本發明新穎催化劑當成根據實施例丨A及接著根據實施例i B 步驟之DMT的聚濃縮催化劑使用。將結果與四個控制實驗 一起記錄在表1中。 利用如SP-分光光度計之類的儀器,以l-值及b—值的角 度測量生成的聚合物之色彩。L -值表示明亮度,以數值越 大表示越高的明亮度(受期望的)。1-值將以等於或大於利 用録催化劑製備之聚合物較佳。b -值表示黃色度,以數值Hit! Ϊ: Bu,] composition. The catalyst composition may be compatible with well-known esterification or picotransfer catalysts (e.g., magnesium, cobalt, and / or zinc oxide), and the acetification catalyst may be introduced into the manufacturing process simultaneously or later. Also: It has been found that the catalyst composition has the effect of promoting the esterification reaction, and can be used as a substitute for part or all of the lamination catalyst and polyconcentration catalyst. The following examples are provided to further illustrate the present invention and are not to be construed as improperly limiting the scope of the invention. EXAMPLES According to Example A1, zinc acetate was catalyzed with ethylene glycol to purify diethylene terephthalate 'to form Dragon T polymer. The novel catalyst of the present invention synthesized according to Examples 2 to 15 was used as a polyconcentrated catalyst for DMT according to Example 丨 A and subsequent to step IB of Example IB. The results are recorded in Table 1 along with the four control experiments. The color of the resulting polymer is measured using an instrument such as an SP-spectrophotometer at l-value and b-value angles. The L-value represents brightness, with larger values indicating higher brightness (desired). The 1-value will preferably be equal to or greater than the polymer prepared using the catalyst. b-value represents yellowness, as a value
O:\58\58096-910820.ptc 第19頁 592811O: \ 58 \ 58096-910820.ptc Page 19 592811
O:\58\58096-910820.ptc 第20頁 592811 修正O: \ 58 \ 58096-910820.ptc Page 20 592811 Fix
案號 88106251 五、發明說明(16) 攪動下維持一段足以達到1 5盎司-英吋扭力之時間(根據 Electro-Craft Motomatic扭力控制器的測量)。將^步 的時間記錄成最終時間’並隨使用的催化劑改變。將著將 溶融的聚合物倒至水浴中,使熔融物固化,並將生成的固 體在150 t下以12小時退火,並以通過2毫米的過渡器研古 磨’供利用先前說明的分光光度計測量色彩。在以下的表 1中提供與以分鐘計的最終時間比較的結果及根據分光光 度方式測量的色彩。 實施例2 將2 40公克(3.87莫耳)之乙二醇裝至5 0 0毫升的燒杯中, 其配備一個攪動器、濃縮器、滴液漏斗及N 2沖洗。開始授 動,並加入2 5公克(0 · 1 7 6莫耳)之苯基次膦酸。將泥聚加見 熱至3 5-4 5 °C ,直到固體溶解為止,接著在35 °C下以]^小% 逐滴加入5 0公克(0 · 1 7 6莫耳)之鈦酸四異丙酯(取自E . j du Pont de Nemours 公司之TYZ OR® TPT)。當加入完成 時,將反應塊攪拌30分鐘,並接著以30分鐘加入36. 6公克 (0.176莫耳)之原石夕酸四乙醋(TE0S)。將獲得含有2·4%欽 之澄清溶液。 實施例3 重覆實施例2,除了加入73· 2公克之TE0S之外。將獲得 含有2 · 1 7 %鈦之澄清溶液。Case No. 88106251 V. Description of the invention (16) Maintain a period of time sufficient to achieve 15 ounce-inch torque under agitation (as measured by the Electro-Craft Motomatic torque controller). The time of ^ step is recorded as the final time 'and varies with the catalyst used. The molten polymer is poured into a water bath, the melt is solidified, and the resulting solid is annealed at 150 t for 12 hours, and the mill is passed through a 2 millimeter transition device to use the spectrophotometer previously described Meter to measure color. The results compared with the final time in minutes and the color measured spectrophotometrically are provided in Table 1 below. Example 2 A 40 ml beaker of 2.40 g (3.87 mol) of ethylene glycol was equipped with a stirrer, a concentrator, a dropping funnel and a N 2 rinse. Initiation was initiated and 25 grams (0.176 mol) of phenylphosphinic acid was added. Heat the mud to 3 5-4 5 ° C until the solids dissolve, and then add 50 g (0.116 mol) of titanium titanate dropwise at 35 ° C in a small amount. Isopropyl ester (from TYZ OR® TPT by E. j du Pont de Nemours). When the addition was complete, the reaction mass was stirred for 30 minutes, and then 36.6 g (0.176 mol) of tetraethylorthoacetate (TEOS) was added over 30 minutes. A clear solution containing 2.4% Chin will be obtained. Example 3 Example 2 was repeated, except that 73.2 g of TEOS was added. A clear solution containing 2.17% titanium will be obtained.
實施例4 將240.2公克(3.87莫耳)之乙二醇裝至具有酉己備如實施 例2之1公升燒杯中。開始攪動,並裝入5 0公克(〇 · 3 5 2莫 耳)之苯基次鱗酸。將泥衆加熱3 0至3 5 C ’直到固體溶解Example 4 240.2 g (3.87 moles) of ethylene glycol was charged into a 1 liter beaker prepared as described in Example 2. Stirring was started and charged with 50 grams (0.352 mol) of phenyl hypopic acid. The mud is heated for 30 to 3 5 C ′ until the solid is dissolved
O:\58\58096-910820.ptc 第21頁 592811 修正 _案號 88106251 五、發明說明(17) 為止,並接著在4 5 °C下以1小時逐滴加入5 0公克(〇 · 1 7 6莫 耳)之TYZOR® TPT。將獲得含有2· 48%鈦之澄清溶液。 實施例5 將240公克(3.87莫耳)之乙二醇裝至具有配備如實施例2 之5 00毫升燒杯中。開始攪動,並加入50公克(0.352莫耳) 之苯基次膦酸。將泥漿加熱3 0至3 5 °C ,直到固體溶解為 止。接著在冷卻至4 0。(:或更低之溫度下以1小時逐滴加入 50公克(0.176 莫耳)之TYZOR® TPT。當加入完成時,將 反應塊攪拌1小時。 在室溫下將5 · 4公克之原矽酸四乙酯加至5 0公克以上的 反應塊中。在混合之後,將獲得含有2 . 2 4 %鈦之澄清溶 液,其具有T i : P : S i以1 : 2 : 1之莫耳比例。 實施例6 將35.3公克(0.569莫耳)之乙二醇裝至具有配備如實施 例2之1 0 〇毫升燒杯中。開始攪動,並加入7 . 3公克(0 . 0 5 2 莫耳)之苯基次膦酸。將反應塊加熱至3 5 °C,直到固體溶 解為止,並接著在45 °C下以1 5分鐘逐滴加入7. 4公克 (0· 0 2 6莫耳)之TYZOR® TPT。當加入完成時,則加入1〇. 77 公克(0.052莫耳)之TE0S。生成之澄清溶液含有2. 04%鈦。 實施例7O: \ 58 \ 58096-910820.ptc Page 21 592811 Amendment_Case No. 88106251 V. To the description of the invention (17), and then add 50 grams (0 · 17) dropwise at 1 hour at 45 ° C 6 mol) of TYZOR® TPT. A clear solution containing 2.48% titanium will be obtained. Example 5 240 g (3.87 moles) of ethylene glycol were charged into a 500 ml beaker equipped with the same as in Example 2. Start agitation and add 50 grams (0.352 moles) of phenylphosphinic acid. Heat the mud at 30 to 35 ° C until the solids are dissolved. It is then cooled to 40. (: 50 grams (0.176 mol) of TYZOR® TPT is added dropwise at 1 hour or lower at 1 hour. When the addition is complete, the reaction block is stirred for 1 hour. At room temperature, 5 · 4 grams of raw silicon Tetraethyl acid is added to the reaction block above 50 grams. After mixing, a clear solution containing 2.24% titanium will be obtained, which has a molar ratio of T i: P: S i of 1: 2: 1 Example 6 35.3 grams (0.569 moles) of ethylene glycol was charged into a 100 ml beaker equipped as in Example 2. Agitation was started and 7.3 grams (0.052 moles) was added. ) 的 phenyl phosphinic acid. The reaction block was heated to 3 5 ° C until the solids were dissolved, and then 7.4 grams (0 · 0 2 6 mole) was added dropwise at 45 ° C over 15 minutes. TYZOR® TPT. When the addition was complete, 10.77 grams (0.052 moles) of TEOS was added. The resulting clear solution contained 2.04% titanium. Example 7
將35.3公克(〇·569莫耳)之乙二醇裝至具有配備如實施 例2之100毫升燒杯中。開始攪動,並加入7· 3公克(〇. 〇52 莫耳)之苯基次膦酸。將反應塊加熱至4 5 °C,直到固體溶 解為止,並接著以15分鐘逐滴加入7.4公克(0.026莫耳)之 TYZOR® TPT。然後加入16.2公克(0.078莫耳)之T EOS。生35.3 grams (0.569 mol) of ethylene glycol was charged into a 100 ml beaker equipped with the same as in Example 2. Begin agitation and add 7.3 g (0.052 mol) of phenylphosphinic acid. The reaction block was heated to 45 ° C until the solids were dissolved, and then 7.4 grams (0.026 moles) of TYZOR® TPT was added dropwise over 15 minutes. Then add 16.2 grams (0.078 moles) of T EOS. Raw
O:\58\58096-910820.ptc 第22頁 592811 -------#1¾ 88106251_I 年 9 月 M 曰_修正 五、發明說明(18) 成之澄清溶液含有1 · 8 7 %鈦。 實施例8 將240.2公克(3.869莫耳)之乙二醇裝至具有配備如實施 例2之5 0 0毫升燒杯中。開始攪動,並加入75公克(〇· 5 28莫 耳)之苯基次膦酸。將反應塊加熱至4 5 °c,直到固體溶解 為止’並接著在45°C以1小時逐滴加入50公克(〇·ΐ76莫耳) 之TYZOR® ΤΡΤ。然後加入36.6公克(0.176莫耳)之TEOS, 以得到含有2 · 1 %鈦之澄清溶液。 實施例9 重覆實施例8,除了使用73· 2公克(〇· 3 5 2莫耳)之丁EOS之 外’以獲得含有1 · 9 2 %鈦之澄清溶液。 實施例1 0 重覆實施例8,除了加入99.8公克(0.528莫耳)之τ E〇s之 外’以獲得含有1 . 7 7 %鈦之澄清溶液。 實施例1 1 將2 40· 2公克(3· 8 6 9莫耳)之乙二醇裝至具有配備如實施 例2之5 0 0毫升燒杯中。開始攪動,並加入1 〇 〇公克(〇 · 7 〇 3 莫耳)之本基次鱗酸。將反應塊加熱至3 5 °C,直到固體溶 解為止,接著以1小時逐滴加入5 0公克(〇 · 1 7 6莫耳)之 TYZOR® TPT,以得到含有2· 16%鈦之澄清溶液。 實施例1 2 重覆實施例11,只是在TYZOR® TPT之後將36.6公克 (0 · 1 7 6莫耳)之T E 0 S加至反應混合物中,以得到含有1 8 2 % 鈦之澄清溶液。 實施例1 3O: \ 58 \ 58096-910820.ptc Page 22 592811 ------- # 1¾ 88106251_September I M_Revision V. Description of the invention (18) The resulting clear solution contains 1.87% titanium. Example 8 240.2 g (3.869 mol) of ethylene glycol was charged into a 500 ml beaker equipped with the same as in Example 2. Agitation was started and 75 grams (0.528 mol) of phenylphosphinic acid was added. The reaction block was heated to 45 ° C until the solids were dissolved 'and then 50 grams (0 · 76 mole) of TYZOR® TPT was added dropwise over 1 hour at 45 ° C. Then 36.6 grams (0.176 moles) of TEOS was added to obtain a clear solution containing 2.1% titanium. Example 9 Example 8 was repeated, except that 73.2 g (0.352 mol) of Ding EOS was used 'to obtain a clear solution containing 1.92% titanium. Example 10 Example 8 was repeated, except that 99.8 g (0.528 mol) of τ E0s was added 'to obtain a clear solution containing 1.77% titanium. Example 11 1 2 40 · 2 g (3.89 mol) of ethylene glycol was charged into a 500 ml beaker equipped with the same as in Example 2. Begin agitation and add 100 g (0.707 mol) of Benzoylpic acid. The reaction block was heated to 35 ° C until the solid was dissolved, and then 50 grams (0.176 mol) of TYZOR® TPT was added dropwise over 1 hour to obtain a clear solution containing 2.16% titanium . Example 1 2 Example 11 was repeated, except that 36.6 grams (0.176 mol) of TEOS was added to the reaction mixture after TYZOR® TPT to obtain a clear solution containing 182% titanium. Example 1 3
O:\58\58096-910820.ptc 第23頁 592811 _88106251_9 i 年 S 月 曰_修正 五、發明說明(19) 重覆實施例11,除了在TYZOR® TPT之後加入53. 2公克 (〇_ 3 5 2莫耳)<TE〇s之外,以得到含有l 82%鈦之澄清溶 液。 實施例1 4 將2 40· 2公克(3· 8 6 9莫耳)之乙二醇裝至具有配備如實施 命J2之5 0 0毫升燒杯中。開始攪動,並加〇〇公克(〇 · 7〇3 莫耳)之本基次膦酸。將反應塊加熱至4 5 °C,直到固體溶 解為止,並接著加入109·9公克(〇·528莫耳)之TEOS。接著 在38 C下以1小時逐滴加入5〇公克(〇· 176莫耳)之TYZOR® Τ Ρ Τ,以得到含有丨· 6 8 %鈦之澄清溶液。 實施例1 5 將40公克(〇·〇135莫耳)在乙二醇/乙醇溶液中的鈦四苯 基次膦酸溶液裝至具有配備如實施例2之1 〇 〇毫升燒杯中。 開始攪動,並逐滴加入11 · 2 7公克(〇 · 〇 5 4 1莫耳)之原石夕酸 四乙酯。將生成之溶液在室溫下攪拌1小時,並倒出,得 到5 1 · 3公克之淡黃色液體,其含有1 · 2 6 %鈦。 在以下的表中,T i組份是鈦酸四異丙酯,ρ組份是笨基 次膦酸及A組份是原矽酸四乙酯。鈦量是以募聚物重量為 基礎每百萬計2 5份(p p m )。最終時間是在既定壓力及溫度 下維持的時間’直到達成預定的濃縮度為止。根據實施例 1 A的說明製備預濃縮組成物募聚物及根據實施例丨β測試催 化劑。除了以註解以外,在這些試驗中所有的催化劑可溶 於乙二醇中。O: \ 58 \ 58096-910820.ptc Page 23 592811 _88106251_9 Year S_Revision V. Description of Invention (19) Example 11 was repeated except that 53.2 grams (〇_ 3 was added after TYZOR® TPT 5 2 moles) < TE0s to obtain a clear solution containing 182% titanium. Example 1 4 2 40 · 2 g (3.89 mol) of ethylene glycol was charged into a 500 ml beaker equipped with the same J2. Stirring was started, and 0.00 g (0.703 mol) of this basic phosphinic acid was added. The reaction block was heated to 45 ° C until the solids were dissolved, and then 109.9 g (0.528 mol) of TEOS was added. Then, 50 g (0.176 mol) of TYZOR® TP Τ was added dropwise at 38 C for 1 hour to obtain a clear solution containing 丨 68% titanium. Example 15 A 40-gram (0.0135 mole) titanium tetraphenylphosphinic acid solution in an ethylene glycol / ethanol solution was charged into a 100 ml beaker equipped with the same as in Example 2. Stirring was started, and 11.27 g (0.051 mol) of tetraethyl ortholate were added dropwise. The resulting solution was stirred at room temperature for 1 hour and decanted to obtain 5 1 · 3 g of a pale yellow liquid containing 1.26% of titanium. In the following table, the T i component is tetraisopropyl titanate, the p component is benzyl phosphinic acid and the A component is tetraethyl orthosilicate. The amount of titanium is 25 parts per million (p p m) based on the weight of the agglomerates. The final time is the time maintained at a given pressure and temperature 'until a predetermined concentration is achieved. A pre-concentrated composition polymer was prepared according to the instructions of Example 1A and a β-test catalyst was used according to Examples 丨. Except as noted, all catalysts were soluble in ethylene glycol in these tests.
O:\58\58096-910820.ptc 第24頁 592811O: \ 58 \ 58096-910820.ptc Page 24 592811
表1 以最終時間與色彩比較催化劑 係本成份之寡聚物,1薹尖汞柱,285。〇,225ppmTi 莫 耳比 例 色彩 實施例 Ti P Si \ 在乙二#中的溶解f生 最終時間(分鐘) L b 註解 銻 不明的溶解性 110 71.98 7.78 1 1.0 0.0 0.0 不可溶 75 68.80 11.57 2 1.0 0.0 3.0 可溶 ----------- · 90 75.32 12.00 3 — 1.0 1.0 0.0 不可溶 — 4 2 1.0 1.0 1.0 可溶 120 73.05 13.01 5 3 1.0 1.0 2.0 可溶 65 73.86 11.20 5 4 1.0 2.0 0.0 可溶 145 73.99 12.44 5 5 1.0 2.0 1.0 可溶 80 76.40 10.69 5 6 1.0 2.0 2.0 可溶 80 77.04 9.87 5 7 1.0 2.0 3.0 可溶 100 76.01 11.33 6 8 1.0 3.0 1.0 70 74.11 10.82 5 9 1.0 3.0 2.0 可溶 ------ 175 70.18 8.71 5 10 1.0 3.0 3.0 _ 可溶 125 70.57 11.94 6 11 1.0 4.0 0.0 可溶 -------- 80 74.01 11.35 6 12 1.0 4.0 1.0 — 145 75.29 10.37 5 13 1.0 4.0 2.0 可溶 95 76.30 9.86 5 14 1.0 4.0 3.0 _. 可溶 .120 79.77 7.98 5 15 1.0 4:0 4.0 可溶 130 74.38 10.94 6 註解:1 ·這是控制實驗,使用 3 0 0 ppm 銻 〇 在乙二醇中的氧化銻溶液Table 1 Comparison of catalyst and oligomers based on final time. Oligomers of this component, 1 Hg, 285. 〇, 225ppmTi Mohr proportion color Example Ti P Si \ Dissolution in Ethylene ## Final time (minutes) L b Note Antimony Unknown solubility 110 71.98 7.78 1 1.0 0.0 0.0 Insoluble 75 68.80 11.57 2 1.0 0.0 3.0 soluble ----------- · 90 75.32 12.00 3 — 1.0 1.0 0.0 insoluble — 4 2 1.0 1.0 1.0 soluble 120 73.05 13.01 5 3 1.0 1.0 2.0 soluble 65 73.86 11.20 5 4 1.0 2.0 0.0 soluble 145 73.99 12.44 5 5 1.0 2.0 1.0 soluble 80 76.40 10.69 5 6 1.0 2.0 2.0 soluble 80 77.04 9.87 5 7 1.0 2.0 3.0 soluble 100 76.01 11.33 6 8 1.0 3.0 1.0 70 74.11 10.82 5 9 1.0 3.0 2.0 soluble Soluble -------- 175 70.18 8.71 5 10 1.0 3.0 3.0 _ soluble 125 70.57 11.94 6 11 1.0 4.0 0.0 soluble -------- 80 74.01 11.35 6 12 1.0 4.0 1.0 — 145 75.29 10.37 5 13 1.0 4.0 2.0 Soluble 95 76.30 9.86 5 14 1.0 4.0 3.0 _. Soluble. 120 79.77 7.98 5 15 1.0 4: 0 4.0 Soluble 130 74.38 10.94 6 Notes: 1 This is a control experiment using 3 0 0 ppm antimony. Antimony oxide solution in ethylene glycol
第25頁 ^«11 ^«11 修正 五、發明說明(21) ^ =是控制實驗,只使用鈦酸四異丙酯,2 5 ρριη T i。 例·這是不用苯基次鱗酸之控制實驗,使用以1 : 3莫耳比 之敎酸四異丙g日與原石夕酸四乙g旨之混合物,2 & p p m T i。 t這是一個試驗品,不使用矽酸酯(無任何期限),生成 + >容於乙二醇之副產物。 在這些實驗中,Ti代表鈦四異丙基鈦酸酯(τρτ),p代 基次膦酸(ΡΡΑ)及Si代表原矽酸四乙酯(TE〇s)。除了 η主解之外’將teos(當存在時)加至ppA與τρΑ之乙二醇溶 液中,以製備催化劑。在2 5Ppm Ti下評估催化劑。 6.在這些實驗中,si:p之比例=或〉1 ,其造成在聚合物 宁較低的L色彩及/或較高的b色彩。 以上的表顯示在利用鈦酸四異丙g旨(τ ρ τ)本身時,其會 ^生不滿意的聚合物,具有比銻更低的L及較高的b色彩。 等原矽酸四乙酯加至TPT中,則會改良[值,但是對b色彩 1〜響很少。當使用以TPT與TE 0S組合之pp A時,則會明顯 ^,良L及b兩者。Si/Ti比例越高,則重點是乙及/或]^色彩 顧^二當S 1 /T 1比例等於或大於1 · 0,貝扎及/或b色彩會明 顯變差。 A其,用實施例14之催化劑(3. 69% Τι )催化苯二酸針與2_ 乙^ =之醋化作用。將1 52.8 8公克之 杯配備n2氣體噴霧、stark接收器及 t暴己 溫和的授動加熱。反應溫度緩慢地爬為。t f =以 止。在此時,溫度會突然下降至137\升’4直到 f c ’接著溫度會開始Page 25 ^ «11 ^« 11 Amendment V. Description of the invention (21) ^ = Control experiment, using only tetraisopropyl titanate, 2 5 ρριη Ti. Example: This is a control experiment without using phenylphosphinoic acid, using a mixture of tetraisopropylglycate gallate and tetraethylglycolate 1: 1 at a molar ratio of 1: 3, 2 & p p m T i. This is a test product. It does not use silicate (without any deadline) and produces + > by-products that are contained in ethylene glycol. In these experiments, Ti represents titanium tetraisopropyl titanate (τρτ), p-substituted phosphinic acid (PPA), and Si represents tetraethyl orthosilicate (TEOs). In addition to the main solution of η ', teos (when present) is added to a glycol solution of ppA and τρA to prepare a catalyst. The catalyst was evaluated at 25 Ppm Ti. 6. In these experiments, the ratio of si: p = or> 1, which results in lower L color and / or higher b color in the polymer. The above table shows that when using tetraisopropyl titanate (τ ρ τ) itself, it will produce unsatisfactory polymers with lower L and higher b color than antimony. When tetraethyl orthosilicate is added to TPT, the value will be improved, but it has little effect on b color 1 ~. When using pp A combined with TPT and TE 0S, ^, good L and b will be obvious. The higher the Si / Ti ratio, the more important is the B and / or color. When the S 1 / T 1 ratio is equal to or greater than 1.0, the color of Beza and / or b will be significantly worsened. A: The catalyst of Example 14 (3.69% Tm) was used to catalyze the acetic acid reaction of phthalic acid needle and 2-ethyl ^ =. The 1 52.8 8 gram cup is equipped with n2 gas spray, stark receiver, and t-bomb. The reaction temperature climbed slowly. t f = up. At this point, the temperature will suddenly drop to 137 \ L’ 4 until f c ’and then the temperature will start
592811 修正 案號 88106251 五、發明說明(22) 再穩定增加,並開始在接收器中收集蒸餾液。在1 4 3 °C 時,自反應燒瓶中取出3毫升樣品。在取出第一個樣品之 後1 5分鐘時,在1 5 1 °C下立即加入1 · 3 0公克之催化劑之後 取出2毫升樣品。1 · 3 0公克之催化劑對應於3 1 3 · 8 p pm T i對 苯二酸酐。該反應的最終產物是無色的及具有非常有限的 霧性。未顯示任何造成霧狀之沉澱信號。 B.當成控制品,利用TYZOR® TBT當成在苯二酸針與2-乙 基己醇之酯作用中的催化劑。將反應以類似於上述的實施 例1 6 A酯化用的方式進行。使用3 1 3 · 3公克之T B T。該反應 的最終產物是無色的,但是其具有以懸浮狀沉澱物顯現的 輕微霧性。 實施例1 7 將75公克(0.528莫耳)之苯基次膦酸及218.6公克之乙二 醇裝至具有配備如實施例2之5 0 0毫升燒杯中。開始攪動, 並將混合物加熱至4 5 °C ,使固體溶解。一旦固體溶解時, 則在溫度維持在45 + /-2。(:下以30分鐘逐滴加入50公克 (0 · 1 7 6莫耳)之TYZOR® TPT。當加入完成時,則在溫度維 持在45 + /2 °C下以30分鐘逐滴加入11〇公克(〇·534莫耳)之 原矽酸四乙酯(TEOS)。當TEOS加入完成時,則加入33· 5公 克(0 · 1 7 6莫耳)之對-甲苯磺酸及持續攪動,直到固體溶 解為止,得到含有1 · 7 4 % T i之淡黃色溶液。 實施例1 8 重覆實施例1 7,除了以使用5 0公克(〇 · 3 5 2莫耳)之苯基 次膦酸取代7 5公克之外。生成之淡黃色溶液含有1 · 8 3 %592811 Amendment No. 88106251 V. Description of the invention (22) Increased steadily, and began to collect distillate in the receiver. Remove 3 ml of sample from the reaction flask at 14 ° C. 15 minutes after the first sample was taken, immediately after the addition of 1.30 g of catalyst at 15 1 ° C, a 2 ml sample was taken. 1.3 g of catalyst corresponds to 3 1 3 · 8 p pm T i terephthalic anhydride. The end product of this reaction is colorless and has very limited haze. No signs of precipitation were observed. B. As a control product, use TYZOR® TBT as a catalyst in the action of phthalic acid needle and 2-ethylhexanol ester. The reaction was carried out in a manner similar to that used for the esterification of Example 16A described above. Use 3 1 3 · 3 grams of T B T. The final product of this reaction is colorless, but it has a slight haze that appears as a suspended precipitate. Example 17 75 grams (0.528 moles) of phenylphosphinic acid and 218.6 grams of ethylene glycol were charged into a 500 ml beaker equipped with the same as in Example 2. Begin agitation and heat the mixture to 4 5 ° C to dissolve the solid. Once the solids are dissolved, the temperature is maintained at 45 + / -2. (: 50 g (0.176 mol) of TYZOR® TPT is added dropwise over 30 minutes. When the addition is complete, the temperature is maintained at 45 + / 2 ° C and added dropwise for 30 minutes. Grams (0.534 moles) of tetraethyl orthosilicate (TEOS). When TEOS addition is complete, add 33.5 grams (0.176 moles) of p-toluenesulfonic acid and keep stirring, Until the solids were dissolved, a light yellow solution containing 1.74% T i was obtained. Example 18 8 Example 7 was repeated except that 50 grams (0.352 mol) of phenylphosphine was used. Acid substitutions other than 7 5 g. The resulting pale yellow solution contains 1.83%
Ti 〇Ti 〇
O:\58\58096-910820.ptcO: \ 58 \ 58096-910820.ptc
第27頁Page 27
592811 __^塞號88106251 斤丨午c月^^ 修正_ 五、發明說明(23) 例1 9 重覆實施例1 7 ’除了以使用5 〇公克(〇 . 3 5 2莫耳)之苯基 次膦酸取代7 5公克及以6 7公克(〇 · 3 5 2莫耳)之對-曱苯磺酸 取代3 3 · 5公克之外。生成之淡黃色溶液含有丨· 7 〇 % τ i。 列 2 0 重覆實施例1 7 ’除了以使用2 5公克(〇 ·丨7 6莫耳)之苯基 次膦酸取代7 5公克之外。生成之淡黃色溶液含有丨· 9 3 Ti ° 將以上貫施例的結果總結在以下的表2中。 L·!592811 __ ^ Plug No. 88106251 kg 丨 afternoon c month ^ amendment _ V. Description of the invention (23) Example 1 9 Repeat Example 17 7 'Except to use 50 grams (0.32 2 Moore) of phenyl The phosphinic acid was replaced by 75 g and 67 g (0.352 mol) of p-toluenesulfonic acid was replaced by 3 3.5 g. The resulting light yellow solution contained 丨 · 70% τ i. Column 20 repeats Example 17 'except that 75 grams are replaced with 25 grams (0. 76 moles) of phenylphosphinic acid. The resulting light yellow solution contained 丨 · 9 3 Ti ° The results of the previous examples are summarized in Table 2 below. L ·!
以最終時間與色彩比較催化劑 丨毫米汞柱,285〇c,225ppmTi 莫 耳比 例 色彩 實施例 Ti P SA Si 最終時間(分鐘) L b 許解1 銻 95、 75.52 7.07 1 17 1.0 3.0 1.0 3.0 90 ^ 73.65 7 ^;Q 2 18 1.0 2.0 1.0 — /•〇y 3.0 85 75.18 7.13 2 19 1.0 2.0 2.0 75 74.99 8.21 2 20 1.0 1.0 1.0 3.0 ------ 50 74.64 8.31 2Comparison of catalyst with final time 丨 mmHg, 285 ° C, 225ppmTi molar ratio Example Ti P SA Si Final time (minutes) L b Xu Xie 1 Antimony 95, 75.52 7.07 1 17 1.0 3.0 1.0 3.0 90 ^ 73.65 7 ^; Q 2 18 1.0 2.0 1.0 — / • 〇y 3.0 85 75.18 7.13 2 19 1.0 2.0 2.0 75 74.99 8.21 2 20 1.0 1.0 1.0 3.0 ------ 50 74.64 8.31 2
乙二醇上的氧化鈦,300ppm録c p=苯基次膦酸;Si=TEOS ;及SA 對 2 · T =欽酸四異兩酉旨 -甲苯磺酸 表2顯不經改良之聚合速度,與利用録當成催化劑比 幸交。 實施例2 1 - 2 8Titanium oxide on ethylene glycol, 300 ppm recorded cp = phenylphosphinic acid; Si = TEOS; and SA p 2 · T = tetrakis (2-ethylhexyl) -toluenesulfonic acid Table 2 shows the polymerization rate without improvement Compared with the use of video as a catalyst than fortunate. Example 2 1-2 8
O:\58\58096-910820.ptc 第28頁 592811 修正 案號 88106251 五、發明說明(24) 在實施例2 1 - 2 8中,利用2毫米汞柱再測試在表1中展示 的許多組合物。將結果展示在表3中。 表3 以最終時間與色彩比較銻催化劑 DMT係主成份之寡聚物,2毫米汞柱 莫耳比例 色彩 實施例 Ti P SA ppm金屬催傭J Ti Sb 最終時間(分鐘) L b 註解a 銻 0 375 98 72.9 -5.7 1 21 1.0 4.0 3.0 20 100 90 62.8 -5.1 2,4 錄 0 375 92 70.5 -4.0 3 22 1.0 4.0 3.0 20 100 81 64.7 -4.4 2,4 23 1.0 4.0 3.0 20 50 95.5 74.2 1.2 2,4 24 1.0 4.0 3.0 20 0 93 77.5 3.2 2,4 25 1.0 2.0 2.0 20 100 81.5 72.8 0.2 2,5 26 1.0 2.0 2.0 15 188 94.5 74.1 0.7 235 27 1.0 2.0 2.0 20 375 105 ' 64.2 -2.3 2,5 28 1.0 2.0 2.0 12.5 0 101.5 77.7 1.8 2,5 a.控制實驗,使用氧化銻 2.參考表2中的註腳2 3 ·第二個控制實驗 4 .對應於表1的實施例1 4 5 ·對應於表1的實施例6 原矽酸酯與銻 表3的結果顯示使用鈦化合物、次膦酸 之組合物(等)獲得的最終時間明顯縮短了 實施例2 9O: \ 58 \ 58096-910820.ptc Page 28 592811 Amendment No. 88106251 V. Description of the Invention (24) In Examples 2 1-28, many combinations shown in Table 1 were retested with 2 mm Hg Thing. The results are shown in Table 3. Table 3 Comparison of the final time and color of the antimony catalyst DMT-based oligomers, 2 mm Hg mole ratio color Example Ti P SA ppm Metal urging J Ti Sb Final time (minutes) L b Note a Antimony 0 375 98 72.9 -5.7 1 21 1.0 4.0 3.0 20 100 90 62.8 -5.1 2,4 Record 0 375 92 70.5 -4.0 3 22 1.0 4.0 3.0 20 100 81 64.7 -4.4 2,4 23 1.0 4.0 3.0 20 50 95.5 74.2 1.2 2 , 4 24 1.0 4.0 3.0 20 0 93 77.5 3.2 2,4 25 1.0 2.0 2.0 20 100 81.5 72.8 0.2 2,5 26 1.0 2.0 2.0 15 188 94.5 74.1 0.7 235 27 1.0 2.0 2.0 20 375 105 '64.2 -2.3 2,5 28 1.0 2.0 2.0 12.5 0 101.5 77.7 1.8 2,5 a. Control experiment using antimony oxide 2. Refer to footnote 2 in Table 2 3 · Second control experiment 4. Example 1 corresponding to Table 1 4 5 · Correspondence Example 6 in Table 1 Orthosilicate and antimony The results in Table 3 show that the final time obtained using the titanium compound, phosphinic acid composition (etc.) is significantly shortened in Example 2 9
O:\58\58096-910820.ptc 第29頁 592811 _ 案號 88106251_βΐ年p 月>1?曰_修正__ 五、發明說明(25) 將50公克(〇·352莫耳)之苯基次膦酸及218.6公克之1,3- 丙二醇裝至具有配備如實施例2之5 0 0毫升燒杯中。開始授 動’並將混合物加熱至4 5 °C,使固體溶解。當所有酶固體 溶解時,則以3 0分鐘逐滴加入1 1 〇公克(〇 · 5 2 8莫耳)之原^ 酸四乙酯。接著以30分鐘逐滴加入50公克(〇· 176莫耳^之 TYZOR® TPT。最後加入33.5公克之對-曱苯石黃酸,並允許 反應塊攪拌,直到其溶解為止。最終的黃色溶液含有° K 8 % T 卜 實施例3 0 將100公克(0.704莫耳)之苯基次膦酸及ι〇9·4公克之 1,3-丙二醇裝至具有配備如實施例2之5 〇〇毫升燒杯中。開 始授動’並將混合物加熱至4 5 °C,並維持,直到所有的固 體溶解為止。接著以類似於實施例29之方式逐滴加入丨〇 〇 公克(0.528莫耳)之原矽酸四乙酯及5〇公克(〇176莫 TYZOR® TPT。最終產物是含有2· 3% Ti之淡黃色溶液。 實施例3 1 、 將40公克(〇· 28 2莫耳)之苯基次膦酸及174· 7公克之i 3一 丙二醇裝至具有配備如實施例2之5〇〇毫升燒杯中。接著加 入53· 5公克之對-曱苯磺酸(PTSA)。將溶液攪拌,直到σ PTSA溶解為止,並接著在低於4〇 t下逐滴加入4〇公 (0· 141莫耳)之TYZOR® TPT。將反應塊維持在4〇 t 小 時,並接著在低於4〇 〇c下逐滴加入40公克(〇 ι41莫耳、 TYZOR® TPT。將反應塊維持在小時,並接著 卻,以得到含有2 · 2 % T i之淡黃色溶液。 7 實施例3 2O: \ 58 \ 58096-910820.ptc page 29 592811 _ case number 88106251_β leap year p month > 1? _ Revision __ 5. Description of the invention (25) 50 grams (0.352 mole) of phenyl Phosphonic acid and 218.6 grams of 1,3-propanediol were placed in a 500 ml beaker equipped with the same as in Example 2. Initiate induction 'and heat the mixture to 45 ° C to dissolve the solid. When all the enzyme solids were dissolved, 110 g (0.528 mol) of tetraethyl orthoacetate was added dropwise over 30 minutes. Then, 50 grams (0.176 moles of TYZOR® TPT) was added dropwise over 30 minutes. Finally, 33.5 grams of p-xanthoxyflavonic acid was added and the reaction block was allowed to stir until it dissolved. The final yellow solution contained ° K 8% T Example 30 0 100 g (0.704 mol) of phenylphosphinic acid and ι0.9 · 4 g of 1,3-propanediol were charged to 500 ml equipped with the same as in Example 2. In the beaker. Start to infuse and heat the mixture to 45 ° C and maintain until all solids are dissolved. Then, in a similar manner as in Example 29, 100 g (0.528 mol) of raw material is added dropwise. Tetraethyl silicate and 50 grams (0176 Mo TYZOR® TPT. The final product is a light yellow solution containing 2.3% Ti. Example 31. 40 grams (0.22 Mole) of phenyl Put phosphinic acid and 174.7 grams of i 3 propylene glycol into a 500 ml beaker equipped as in Example 2. Then 53.5 grams of p-toluenesulfonic acid (PTSA) was added. The solution was stirred, Until the σ PTSA is dissolved, and then 40 g (0.141 mol) of TY is added dropwise below 40 t. ZOR® TPT. The reaction block was maintained at 40 t hours, and then 40 grams (41 mol, TYZOR® TPT) was added dropwise below 400 c. The reaction block was maintained at hours, and then, To obtain a pale yellow solution containing 2.2% T i. Example 3 2
592811 _案號88106251 4丨年P月^^日 修正_ 五、發明說明(26) ^ 在相同的方式中,將在實施例1 4及1 8中的乙二醇以相同 , 量的1,4- 丁二醇或線型或支化醇取代,如乙醇或異丙醇, 以得到淡黃色溶液,其以類似於其乙二醇的份量進行實 驗0592811 _ Case No. 88106251 Rev. P ^^^ 4 of the year _ V. Description of the invention (26) ^ In the same way, the ethylene glycol in Examples 14 and 18 will be the same, the amount of 1, 4-butanediol or linear or branched alcohol substitution, such as ethanol or isopropanol, to give a pale yellow solution, which was tested in an amount similar to its ethylene glycol.
O:\58\58096-910820.ptc 第31頁 592811 _案號88106251 β丨年$月>€7日 修正 圖式簡單說明 第32頁 O:\58\58096-910820.ptcO: \ 58 \ 58096-910820.ptc Page 31 592811 _Case No. 88106251 β 丨 year $ month > € 7th Amendment Simple diagram description Page 32 O: \ 58 \ 58096-910820.ptc
Claims (1)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US6234898A | 1998-04-17 | 1998-04-17 |
Publications (1)
Publication Number | Publication Date |
---|---|
TW592811B true TW592811B (en) | 2004-06-21 |
Family
ID=22041888
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
TW088106251A TW592811B (en) | 1998-04-17 | 1999-06-09 | Titanium-containing catalyst composition and processes therefor and therewith |
Country Status (3)
Country | Link |
---|---|
TW (1) | TW592811B (en) |
WO (1) | WO1999054039A1 (en) |
ZA (1) | ZA200004287B (en) |
Families Citing this family (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TW548291B (en) | 1999-06-24 | 2003-08-21 | Teijin Ltd | Catalyst for producing a polyester and process for producing the polyester by using same |
US6166170A (en) * | 1999-12-02 | 2000-12-26 | E. I. Du Pont De Nemours And Company | Esterification catalysts and processes therefor and therewith |
JP5152608B2 (en) * | 2000-01-26 | 2013-02-27 | 東洋紡株式会社 | Polyester polymerization catalyst, polyester produced using the same, and method for producing polyester |
JP2001323055A (en) * | 2000-03-09 | 2001-11-20 | Toyobo Co Ltd | Polyester polymerization catalyst and polyester produced using the catalyst and method for producing polyester |
JP5044870B2 (en) * | 2001-02-22 | 2012-10-10 | 東洋紡績株式会社 | Method for producing polyester film and polyester film |
JP5028713B2 (en) * | 2001-02-23 | 2012-09-19 | 東洋紡績株式会社 | Oriented polyester film |
JP5028712B2 (en) * | 2001-02-23 | 2012-09-19 | 東洋紡績株式会社 | White oriented polyester film |
TWI302154B (en) | 2001-07-05 | 2008-10-21 | Teijin Ltd | |
CN100526364C (en) | 2001-07-16 | 2009-08-12 | 帝人株式会社 | Catalyst for polyester production and process for producing polyester with the same |
JP2003160656A (en) * | 2001-11-28 | 2003-06-03 | Teijin Ltd | Method of manufacturing polyester and fiber |
CN102050942A (en) | 2009-11-02 | 2011-05-11 | 远东新世纪股份有限公司 | Titaniferous composition and method for catalyzing polyesterification reaction by same |
CN101927182B (en) * | 2010-07-05 | 2012-11-07 | 北京林业大学 | Biodiesel catalyst and method for preparing biodiesel by using same |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0102115B1 (en) * | 1982-08-17 | 1987-06-10 | Akzo N.V. | Polyester-ester urethane |
FR2653036B1 (en) * | 1989-10-17 | 1992-01-10 | Inst Francais Du Petrole | CATALYTIC COMPOSITION COMPRISING TITANIUM AND PHOSPHORUS, ITS PREPARATION AND ITS USE FOR THE CONDENSATION OF AN EPOXIDE ON A CARBOXYLIC ACID ANHYDRIDE. |
US5453479A (en) * | 1993-07-12 | 1995-09-26 | General Electric Company | Polyesterification catalyst |
-
1999
- 1999-04-16 WO PCT/US1999/008337 patent/WO1999054039A1/en not_active Application Discontinuation
- 1999-06-09 TW TW088106251A patent/TW592811B/en not_active IP Right Cessation
-
2000
- 2000-08-21 ZA ZA200004287A patent/ZA200004287B/en unknown
Also Published As
Publication number | Publication date |
---|---|
ZA200004287B (en) | 2001-08-21 |
WO1999054039A1 (en) | 1999-10-28 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US6080834A (en) | Titanium-containing catalyst composition and processes therefor and therewith | |
CN1179790C (en) | Esterification catalyst compositions and use thereof | |
JP4504197B2 (en) | Catalysts and processes | |
KR20010052255A (en) | Catalytic Composition Comprising a Titanium Compound, an Amine and a Phosphorus Compound, Preparation and Use Thereof | |
TW592811B (en) | Titanium-containing catalyst composition and processes therefor and therewith | |
JP2003026789A (en) | Polyester polycondensation by catalyst and catalyst improver | |
CA2538913A1 (en) | Catalyst for manufacture of esters | |
US6255441B1 (en) | Titanium-containing catalyst composition and processes therefor and therewith | |
JP2002512267A (en) | Catalyst composition comprising titanium compound, amine and phosphorus compound, production and use thereof | |
TWI651338B (en) | Catalyst for esterification reaction and method for catalyzing esterification reaction | |
EP1771247A1 (en) | Composition comprising titanium and aluminum and polyester production | |
JP2541792B2 (en) | Method for producing polyester | |
TW200305457A (en) | Stable aqueous solutions comprising titanium and zinc and process therewith | |
KR0122004B1 (en) | Method for manufacturing polyester | |
JP2007002093A (en) | Polyester polymerization catalyst and method for producing polyester with the same | |
MXPA00010105A (en) | Catalyst composition comprising a titanium compound, a phosphorus compound and a solubility promoter;preparation and use thereof | |
JP2004256719A (en) | Polyester polymerization catalyst and manufacturing process of polyester using it | |
KR20010052254A (en) | Catalyst Composition Comprising a Titanium Compound, a Phosphorus Compound and a Solubility Promoter, Preparation and Use Thereof | |
TW200422317A (en) | Mixed catalytic composition | |
JP2003252976A (en) | Method for manufacturing polyester, and catalyst for manufacturing polyester | |
JP2005162925A (en) | Catalyst for polyester polymerization and method for producing polyester by using the same | |
JP2005139247A (en) | Catalyst for polymerizing polyester and method for producing polyester with the same | |
JP2006265435A (en) | Polyester polymerization catalyst and method for producing polyester using the same | |
JPH10195087A (en) | Phosphonic acid derivative and its production | |
JP2006299222A (en) | Catalyst for producing polyester and production method for polyester using the same |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
MM4A | Annulment or lapse of patent due to non-payment of fees |