CN1402653A - 酯化催化剂组合物及其应用 - Google Patents
酯化催化剂组合物及其应用 Download PDFInfo
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- CN1402653A CN1402653A CN00816585A CN00816585A CN1402653A CN 1402653 A CN1402653 A CN 1402653A CN 00816585 A CN00816585 A CN 00816585A CN 00816585 A CN00816585 A CN 00816585A CN 1402653 A CN1402653 A CN 1402653A
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- acid
- composition
- alcohol
- complexing agent
- solvent
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- 239000000203 mixture Substances 0.000 title claims abstract description 73
- 239000003054 catalyst Substances 0.000 title claims abstract description 42
- 230000032050 esterification Effects 0.000 title abstract description 14
- 238000005886 esterification reaction Methods 0.000 title abstract description 14
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 68
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 46
- 150000002148 esters Chemical class 0.000 claims abstract description 42
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000002904 solvent Substances 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 23
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000008139 complexing agent Substances 0.000 claims abstract description 18
- 150000003609 titanium compounds Chemical class 0.000 claims abstract description 18
- 150000003839 salts Chemical class 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims abstract description 12
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims abstract description 11
- 150000003755 zirconium compounds Chemical class 0.000 claims abstract description 6
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical class NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 claims abstract description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims abstract description 4
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- 229910052719 titanium Inorganic materials 0.000 claims description 34
- -1 zirconium iso-propoxides Chemical class 0.000 claims description 33
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 32
- 229910052799 carbon Inorganic materials 0.000 claims description 25
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 19
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 18
- 239000002253 acid Substances 0.000 claims description 14
- 125000000217 alkyl group Chemical group 0.000 claims description 13
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical group CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 12
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 claims description 10
- 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 9
- 150000001875 compounds Chemical class 0.000 claims description 8
- 229910052726 zirconium Inorganic materials 0.000 claims description 7
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 6
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 claims description 6
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-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
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 claims description 6
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- 235000014655 lactic acid Nutrition 0.000 claims description 6
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 5
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 claims description 5
- GZSSFSARCMSPPW-UHFFFAOYSA-N butane-2,2-diol Chemical compound CCC(C)(O)O GZSSFSARCMSPPW-UHFFFAOYSA-N 0.000 claims description 5
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 claims description 5
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical class CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 claims description 5
- CIBMHJPPKCXONB-UHFFFAOYSA-N propane-2,2-diol Chemical compound CC(C)(O)O CIBMHJPPKCXONB-UHFFFAOYSA-N 0.000 claims description 5
- 239000004471 Glycine Substances 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-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
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 4
- 235000015165 citric acid Nutrition 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 4
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 3
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 3
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 2
- LQVVVEHMZPWBOQ-UHFFFAOYSA-N 1-amino-2-(propan-2-ylamino)ethane-1,1,2,2-tetrol Chemical compound OC(C(N)(O)O)(NC(C)C)O LQVVVEHMZPWBOQ-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
- 239000005711 Benzoic acid Substances 0.000 claims description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 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
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-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
- 125000003342 alkenyl group Chemical group 0.000 claims description 2
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 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
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 235000010233 benzoic acid Nutrition 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
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 2
- 229940043237 diethanolamine Drugs 0.000 claims description 2
- 150000001261 hydroxy acids Chemical group 0.000 claims description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 2
- 239000011976 maleic acid Substances 0.000 claims description 2
- 239000001630 malic acid Substances 0.000 claims description 2
- 235000011090 malic acid Nutrition 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
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 239000011975 tartaric acid Substances 0.000 claims description 2
- 235000002906 tartaric acid Nutrition 0.000 claims description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-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 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims 2
- XSISQURPIRTMAY-UHFFFAOYSA-N Hydroxyethyl glycine Chemical compound NCC(=O)OCCO XSISQURPIRTMAY-UHFFFAOYSA-N 0.000 claims 1
- FOUZISDNESEYLX-UHFFFAOYSA-N N-hydroxyethyl glycine Natural products OCCNCC(O)=O FOUZISDNESEYLX-UHFFFAOYSA-N 0.000 claims 1
- 229920000728 polyester Polymers 0.000 abstract description 22
- 238000006116 polymerization reaction Methods 0.000 abstract description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 abstract 4
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 abstract 1
- 229940043375 1,5-pentanediol Drugs 0.000 abstract 1
- OWBTYPJTUOEWEK-UHFFFAOYSA-N butane-2,3-diol Chemical compound CC(O)C(C)O OWBTYPJTUOEWEK-UHFFFAOYSA-N 0.000 abstract 1
- 150000001728 carbonyl compounds Chemical class 0.000 abstract 1
- 229910052751 metal Inorganic materials 0.000 abstract 1
- 239000002184 metal Substances 0.000 abstract 1
- WCVRQHFDJLLWFE-UHFFFAOYSA-N pentane-1,2-diol Chemical compound CCCC(O)CO WCVRQHFDJLLWFE-UHFFFAOYSA-N 0.000 abstract 1
- 238000005809 transesterification reaction Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 23
- 238000004519 manufacturing process Methods 0.000 description 22
- 239000007864 aqueous solution Substances 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 229920000642 polymer Polymers 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 8
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- 150000001298 alcohols Chemical class 0.000 description 7
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- 229920001283 Polyalkylene terephthalate Polymers 0.000 description 5
- 229910052787 antimony Inorganic materials 0.000 description 5
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- 239000000835 fiber Substances 0.000 description 5
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- 238000002360 preparation method Methods 0.000 description 5
- 159000000000 sodium salts Chemical class 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
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- IAGCDJZAYOZMCS-UHFFFAOYSA-N 2-hydroxypropanoic acid;titanium Chemical compound [Ti].CC(O)C(O)=O IAGCDJZAYOZMCS-UHFFFAOYSA-N 0.000 description 4
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- 229910021645 metal ion Inorganic materials 0.000 description 4
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- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 3
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- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
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- UXFQFBNBSPQBJW-UHFFFAOYSA-N 2-amino-2-methylpropane-1,3-diol Chemical compound OCC(N)(C)CO UXFQFBNBSPQBJW-UHFFFAOYSA-N 0.000 description 1
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- XTDYIOOONNVFMA-UHFFFAOYSA-N dimethyl pentanedioate Chemical compound COC(=O)CCCC(=O)OC XTDYIOOONNVFMA-UHFFFAOYSA-N 0.000 description 1
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- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
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Abstract
公开了一种催化剂组合物。该组合物含有钛化合物、络合剂、次磷酸或其金属盐、水和任选的溶剂。所述络合剂可以是羟基羧酸、链烷醇胺、氨基羧酸或它们的两种或多种的混合物。所述溶剂可以是水、乙醇、丙醇、异丙醇、丁醇、乙二醇、丙二醇、异丙二醇、丁二醇、1-甲基丙二醇、戊二醇或它们的两种或多种的混合物。所述钛化合物可以与锆化合物混合。还公开了一种使用所述组合物生产酯或聚酯的方法。该方法包括在所述组合物的存在下,在适合于酯化、酯交换、聚合或这些反应的两种或多种的结合的条件下,使羰基化合物与醇接触。
Description
发明领域
本发明涉及含有次磷酸的催化剂组合物以及将该组合物用于例如酯化、酯交换或羰基化合物的聚合反应的方法。
发明背景
聚酯例如通常被称作“聚对苯二甲酸亚烷基酯”的聚对苯二甲酸乙二醇酯、聚对苯二甲酸亚丙基酯和聚对苯二甲酸丁二醇酯是一类重要的工业用聚合物。它们被广泛用于热塑性纤维、薄膜和模塑领域。
聚对苯二甲酸亚烷基酯的制备可以通过对苯二甲酸二烷基酯与二元醇进行酯交换,并随后进行缩聚反应来进行;或者通过对苯二甲酸与经选择的二醇直接酯化,并随后进行缩聚反应来进行。使用催化剂来催化酯化、酯交换或缩聚。
常常将处于氧化锑的二元醇溶液形式的锑用作酯交换或酯化过程中的催化剂。但是,锑会形成不可溶的锑络合物,堵塞纤维喷丝板,从而导致纤维纺丝中频繁停机以清除喷丝板上沉积的锑化合物。所述锑基催化剂也受到增加的环境压力和调节控制的影响,特别是在与食品接触的领域尤其如此。
已知有机钛酸酯如四异丙基和四正丁基钛酸酯是通常生产聚对苯二甲酸亚烷基酯的有效的缩聚催化剂,经常被选为催化剂使用。但是,这些催化剂与水接触后趋向于水解形成失去催化活性的不溶于二元醇的低聚物类。当这些有机钛酸酯被用作聚酯催化剂时,也会产生大量的黄变。此外,许多有机钛酸酯催化剂也基本上不溶于聚合混合物,从而使得混合物中产生非均匀分布的催化剂。
当与水相容的钛酸盐,如EP 812818中公开的乳酸钛双铵、二(三乙醇胺)钛酸盐或柠檬酸钛钠催化剂被用作聚酯化催化剂时,在最后得到的聚合物中将产生明显的泛黄。同样,WO 99/28033公开了一种用于生产酯的有机金属化合物。所述有机金属化合物包含钛、锆或铝的邻位酯的反应产物、含至少两个羟基的醇、有机磷化合物和碱。但是,当被用作聚酯化催化剂时,发现所述有机金属化合物也在最终产品中产生不希望的明显的泛黄。
因此,越来越需要开发出一种新的催化剂,要求该催化剂基本上溶于二元醇,是有效的催化剂,并且产生减轻了颜色的聚合物,显示出良好的催化活性,不会引起纤维喷丝板堵塞,并且对环境无害。
本发明催化剂组合物的一个优点在于:与只用有机钛酸盐催化剂生产的聚合物相比,用本发明催化剂生产的聚合物具有改进的光学性能(例如减轻了不希望的变色)。本发明的另一优点在于本发明催化剂在用于生产聚酯的醇中是可溶的,不会在聚酯中产生沉淀而堵塞纤维喷丝板,并且对环境无害。随着下面对本发明的更全面的公开,本发明的其它优点将变得显而易见。
发明简述
根据本发明的第一实施方案,提供了一种催化剂组合物,该组合物可被用作酯化或酯交换催化剂,或者用作缩聚催化剂以生产聚对苯二甲酸亚烷基酯。所述组合物包含钛或钛化合物、络合剂、次磷酸或其盐和任选的溶剂。所述络合剂选自羟基羧酸、链烷醇胺、氨基羧酸以及它们的混合物。
根据本发明的第二实施方案,提供了一种可被用于例如酯或聚酯生产的方法。该方法包括在催化剂组合物的存在下,使羰基化合物与醇接触。所述催化剂组合物可以与上述相同。
发明详述
本发明的催化剂组合物基本上可溶于溶剂。术语“基本上”意指比普通的多。优选所述组合物完全溶于溶剂。但是,所述组合物的大部分也可以是悬浮或分散在溶剂中。
根据本发明的第一实施方案,提供了一种催化剂组合物。所述组合物可以包含、基本上由或由钛化合物、络合剂、次磷酸或其盐组成。所述组合物可进一步包含溶剂。
根据本发明,优选的钛化合物为有机钛化合物。四烃氧基钛(在本文中也称为四烷基钛酸酯)是目前最优选的有机钛化合物,这是因为它们易于获得并且有效。适当的四烃氧基钛化合物的例子包括以通式Ti(OR)4表示的物质,其中各R独立选自每个基团中含有1至约30,优选2至约18,最优选2至12个碳原子的烷基、环烷基、烷芳基、烃基;并且各R可以相同或不同。其中每个烃氧基(hydrocarboxyl)中含有2至约12个碳原子(为线性或支化烷基)的四烃氧基钛是最优选的,因为它们相对不贵,更易于获得,并且在形成溶液时是有效的。适当的四烃氧基钛包括(但不限于)四乙醇钛、四丙醇钛、四异丙醇钛、四正丁醇钛、四己醇钛、四(2-乙基己醇)钛、四辛醇钛和它们的两种或多种的混合。
通常需要避免卤化物或其它活性取代基在R基团中的存在,因为这些取代基会干扰催化反应或者形成不需要的副产物,而它们会在用钛化合物生产聚合物时污染聚合物。目前还优选各R基团相同以促进有机钛酸酯的合成。在一些情况下,两个或多个R基团可以来自一个在钛原子以外的位置化学结合在一起的共同的化合物(即多齿配体如三乙醇胺、柠檬酸或乳酸)。
根据本发明,四烃氧基钛也可以与锆化合物结合以产生含四烃氧基钛和四烃氧基锆的混合物。目前优选的四烃氧基锆包括(但不限于)四乙醇锆、四丙醇锆、四异丙醇锆、四正丁醇锆、四己醇锆、四(2-乙基己醇)锆、四辛醇锆和它们的两种或多种的混合。Ti/Zr的摩尔比可以在约0.001∶1-约10∶1的范围内。
适用于本发明的四烃氧基钛可以通过例如在碱如氨的存在下,将四氯化钛和醇混合以形成四烃氧基钛或四烷基钛酸酯来进行制备。所述醇可以是乙醇、正丙醇、异丙醇、正丁醇或异丁醇。通常不使用甲醇,因为形成的四甲醇钛不溶于反应混合物,从而使它的分离变得复杂。由此产生的四烃氧基钛可以通过如下操作进行回收:首先通过本领域技术人员已知的任何方法如过滤除去副产物氯化铵,然后从反应混合物中蒸馏四烃氧基钛。该方法可以在约0℃至约150℃的温度下进行。具有较长烷基基团的钛酸酯也可以通过具有最多C4的R基团的化合物与每个分子中碳原子超过4的醇的酯交换来进行制备。
可买到的有机钛化合物的例子包括(但不限于)从美国特拉华州威尔明顿市的E.I.du Pont de Nemours and Company买到的TYZORTPT和TYZORTBT(四异丙基钛酸酯和四正丁基钛酸酯)。
适用于本发明的络合剂通常为羟基羧酸、链烷醇胺、氨基羧酸或它们的两种或多种的混合物。目前优选所述络合剂为其中烃基或烷基的每个基团具有1至约15,优选1-10个碳原子的α-羟基羧酸、链烷醇胺或α-氨基羧酸以及它们的两种或多种的混合物。适当的络合剂的例子包括(但不限于)乳酸、乙醇酸、柠檬酸、酒石酸、苹果酸、二乙醇胺、三乙醇胺、四羟基异丙基乙二胺、甘氨酸、二羟乙基甘氨酸、羟乙基甘氨酸以及它们的两种或多种的混合物。
根据本发明,次磷酸为具有式H2P(O)OM的无机酸,其中M为氢、铵离子、金属离子或它们的两种或多种的混合,并且磷原子与两个氢原子连接。所述金属离子可以是任何金属离子。目前优选所述金属离子为碱金属离子。次磷酸或其金属盐可以以水溶液形式买到,并且在本文中通常以水溶液的形式使用。
任何可基本上溶解以上公开的催化剂组合物的溶剂都可用于本发明。目前优选的溶剂为水或具有式R1(OH)n的醇、具有式(OH)nA(OH)n的烷撑二醇、具有式R1O[CH2CH(R1)O]nH的聚(亚烷基)二醇或烷氧基化醇或者它们的两种或多种的混合物,其中各R1可以相同或不同,为每个基团具有1至约10,优选1至约8,最优选1-5个碳原子的烃基。目前优选的R1为支链或直链烷基。A为每个分子具有2至约10,优选2至约7,最优选2-4个碳原子的亚烷基。各n可以相同或不同,独立为1至约10,优选1至约7,最优选1-5的数字。适当的溶剂的例子包括(但不限于)乙醇、丙醇、异丙醇、丁醇、乙二醇、丙二醇、异丙二醇、丁二醇、1-甲基丙二醇、戊二醇、二甘醇、三甘醇、2-乙基己醇以及它们的两种或多种的混合物。目前优选的溶剂为水、乙二醇或它们的混合物。目前最优选的溶剂为水。
或者,所述溶剂可以是在四烷基钛酸酯与络合剂的反应中形成的,例如从四异丙基钛酸酯得到的异丙醇或者从四正丁基钛酸酯得到的正丁醇。
根据本发明的第一实施方案,络合剂与钛化合物的摩尔比可以是任何有效的比例,该比例可以在溶剂的存在下基本上防止钛化合物沉淀。通常所述比例可以为约1∶1-约10∶1,优选约1∶1-约7∶1,最优选1∶1-4∶1。次磷酸或其盐与钛化合物的摩尔比(P∶Ti)可以是任何比例,当将所述组合物用作催化剂生产聚酯时,该比例可以减轻聚酯的黄色。优选的比例可以为约0.1∶1-约10∶1,优选约0.5∶1-约7∶1,最优选1∶1-4∶1。溶剂可存在于所述组合物中以产生可溶或基本上可溶的组合物。或者,所述钛化合物可以以下述量存在于所述催化剂组合物中:以所述组合物的总重为100%计,钛化合物的量为约0.01%至约30%,优选约0.1%至约15%,最优选0.5%-10%。
所述催化剂组合物可以通过本领域技术人员已知的任何方法进行制备。
所述催化剂组合物也可以在水以外的第二溶剂中进行制备,所述第二溶剂与酯化或酯交换或缩聚反应相容或对其没有干扰。例如,如果将所述催化剂组合物用作生产聚对苯二甲酸乙二醇酯的缩聚催化剂,则优选在乙二醇中制备所述组合物;如果将所述催化剂组合物用于生产聚对苯二甲酸丁二醇酯,则优选在1,4-丁二醇中制备所述组合物;如果将所述催化剂组合物用于生产聚对苯二甲酸丙二醇酯,则优选在1,3-丙二醇中制备所述组合物。对于邻苯二甲酸二辛酯的生产来说,2-乙基己基醇是优选的。
虽然各组分可以以任何顺序混合,但是优选通常在溶剂中首先将络合剂与钛化合物混合,以产生第一混合物。然后可以将所述第一混合物与第二络合剂(如果存在)混合,以产生第二混合物。通常来说,产生第一或第二混合物的混合操作可以进行搅拌,并且可以在约0℃至约100℃,优选约20℃至约50℃的温度范围内进行。只要所使用的溶剂量能够基本上溶解所述组合物,则通常可以使用任何量的溶剂,溶剂的使用量相对于组合物中所使用的每摩尔钛化合物可以为约5至约50摩尔,优选约10至约30摩尔,最优选10-20摩尔。然后将第一或第二混合物与次磷酸或其盐混合,以制备本发明的组合物。
所述组合物的制备优选在惰性气氛如氮气、二氧化碳、氦或它们的两种或多种的混合物下进行,以避免在存在醇时释放出易燃醇,因为该反应为放热反应。
各个组分的量通常可以为使所制备的催化剂化合物中各个组分与钛的摩尔比在以上公开范围内的量。
根据本发明的第二实施方案,提供了一种可以用于例如酯或聚酯生产的方法。所述方法包括在催化剂组合物的存在下,使羰基化合物与醇接触。所述组合物与以上本发明第一实施方案所公开的相同。
根据本发明的第二实施方案,可以使用任何与醇混合时能够产生酯或聚酯的羰基化合物。通常,这样的羰基化合物包括(但不限于)酸、酯、酰胺、酸酐、酰基卤、具有来自酸的重复单元的羧酸低聚物或聚合物的盐,或者它们的两种或多种的混合物。目前优选的酸为有机酸如羧酸或其盐。目前优选的方法为用以生产聚酯的(1)酸或酯与(2)醇或二醇的聚合。
生产酯或聚酯的的优选方法包括、基本上由或者由下述步骤组成:使反应介质与在本发明的第一实施方案中公开的组合物接触。所述反应介质可以包括、基本上由或者由醇和(1)有机酸、它的盐、它的酯或它们的混合物或者(2)具有来自有机酸或酯的重复单元的低聚物组成。
有机酸或其酯可以具有式R2COOR2,其中各R2可独立为(1)氢、(2)末端具有羧酸基团的烃氧基或者(3)可以是烷基、链烯基、芳基、烷芳基、芳烷基或它们的两种或多种的混合的烃基,其中各基团的每个基团具有1至约30,优选约3至约15个碳原子。目前优选的有机酸为具有式HO2CA1CO2H的有机酸,其中A1为亚烷基、亚芳基、亚链烯基(alkenylene)或(4)它们的两种或多种的混合物。各A1的每个基团具有约2至约30,优选约3至约25,更优选约4至约20,最优选4-15个碳原子。适当的有机酸的例子包括(但不限于)对苯二甲酸、间苯二甲酸、萘二甲酸(napthalic acid)、丁二酸、己二酸、邻苯二甲酸、戊二酸、丙烯酸(acrylic acid)、草酸、苯甲酸、马来酸、丙烯酸(propenoic acid)和它们的两种或多种的混合物。目前优选的有机二酸为对苯二甲酸,因为由其生产的聚酯具有大范围的工业应用性。适当的酯的例子包括(但不限于)己二酸二甲酯、邻苯二甲酸二甲酯、对苯二甲酸二甲酯、苯甲酸甲酯、戊二酸二甲酯和它们的两种或多种的混合物。
羧酸金属盐或其酯的例子包括具有式(R3O2C)2ArS(O)2OM1的5-硫代间苯二甲酸金属盐及其酯,其中各R3可以相同或不同,为氢或含1至约6,优选2个碳原子的烷基。Ar为亚苯基。M1可以为碱金属离子如钠。酯的一个例子为5-硫代间苯二甲酸钠盐的双乙醇酸酯。
可以酯化酸以生产酯或聚酯的任何醇都可用于本发明。目前优选的醇具有式R1(OH)n、式(HO)nA(OH)n的烷撑二醇或者它们的混合物,其中R1、A和n与前述相同。适当的醇的例子包括(但不限于)乙醇、丙醇、异丙醇、丁醇、乙二醇、丙二醇、异丙二醇、丁二醇、1-甲基丙二醇、戊二醇、二甘醇、三甘醇、2-乙基己醇和它们的两种或多种的混合物。目前最优选的醇为烷撑二醇如乙二醇,因为由其生产的聚酯具有广泛的工业用途。
当所述羰基化合物包括如上所述5-硫代间苯二甲酸金属盐或其酯时,所述醇优选为二元醇如乙二醇、丙二醇、异丙二醇、丁二醇、1-甲基丙二醇、戊二醇、二甘醇、三甘醇、1,6-己二醇、环己基-1,4-双甲醇和它们的两种或多种的混合物。目前最优选的醇为烷撑二醇如乙二醇。
5-硫代间苯二甲酸金属盐或其酯与二元醇的接触产生5-硫代间苯二甲酸金属盐的双乙醇酸酯。
所述羰基化合物与醇在催化剂存在下的接触可以以任何适当的方式进行。例如,可以将羰基化合物和醇在与催化剂接触之前先进行混合。但是,目前优选通过适当的方式如机械混合或搅拌首先将催化剂分散在醇中以得到分散体,然后在足以进行酯或聚酯生产的条件下,将所得分散体与(1)羰基化合物和(2)醇混合。
羰基化合物与醇的低聚物通常具有总计约1至约100,优选约2至约10个来自羰基化合物和醇的重复单元。
生产酯或聚酯的任何适当的条件可以包括:在约0.001至约1大气压范围内的压力下的约150℃至约500℃,优选约200℃至约400℃,最优选约250℃至约300℃的温度;约0.2至约20,优选约0.3至约15,最优选0.5-10小时的时间。
只要醇与羰基化合物的摩尔比可以进行酯或聚酯的生产,则该比例可以为任何比例。通常该比例为约1∶1至约10∶1,优选约1∶1至约5∶1,最优选约1∶1-4∶1。
所述催化剂以Ti或Zr表示,其存在量可以为包括羰基化合物和醇在内的介质的约百万分之0.0001重量份至约百万分之30,000重量份(ppmw),优选为约0.001至约1,000ppmw,最优选为0.001-100ppmw。还可以存在其它组分以提高催化剂稳定性或性能。
进一步根据本发明的第二实施方案,提供了一种可以用于生产阳离子可染色聚对苯二甲酸亚烷基酯的方法。该方法包括在上述催化剂的存在下,使包含(i)对苯二甲酸或对苯二甲酸二烷基酯和(ii)5-硫代间苯二甲酸或酯、它的金属盐或上述生产的5-硫代间苯二甲酸金属盐的双乙醇酸酯的混合物与二元醇接触。所述5-硫代间苯二甲酸金属盐的双乙醇酸酯通常以占混合物约1%重量至约5%重量的量存在于混合物中。所述二元醇的范围和用量可以与上述相同。
可以将所述催化剂组合物用在通过使用任何常用熔体或固态技术进行的酯或聚酯的生产中。所述催化剂组合物与常规酯化和酯交换催化剂(例如镁、钴和/或锌盐)相容,可以将其在引进酯化催化剂的同时或之后引进生产工艺中。还发现所述催化剂组合物在促进酯化反应方面是有效的,可被用作酯化催化剂的部分或全部替代物以及缩聚催化剂。
提供下面的实施例以进一步说明本发明,而不应将其视为对本发明范围的不适当的限制。实施例中所提及的所有TYZOR产品都从DuPont,Wilmington,Delaware,USA获得。
实施例 对比实施例1
向装备有搅拌器、冷凝器、滴液漏斗和氮气排放口(nitrogen bleed)的100ml烧瓶内装入100g(0.17摩尔)TYZORLA和60g(0.34摩尔)苯膦酸钠,以得到含5.1%钛的透明无色溶液。TYZORLA为乳酸钛双铵的水溶液,它是通过将2摩尔乳酸加入到TYZORTPT中,然后加入水,除去副产物异丙醇,再用28%氢氧化铵水溶液中和而制得的。TYZORTPT为四异丙基钛酸酯。TYZORLA和TYZORTPT都是从美国特拉华州威尔明顿市E.I.du Pont de Nemours andCompany获得的。对比实施例2
向与对比实施例1一样装备的250ml烧瓶内装入61.3g(0.319摩尔)柠檬酸和46.4g水。开始搅拌,并向其中滴加36g(0.127摩尔)TYZORTPT,得到混合物。将该混合物加热回流并保持1小时,在此期间,通过迪安-斯达克榻分水器移出50g馏出液。将残余的混合物冷却至70℃,加入47.5g(0.38摩尔)32%的氢氧化铵水溶液。将所得溶液过滤,向滤液中加入63g乙二醇。在20mmHg真空下在旋转蒸发器上对含乙二醇的溶液进行汽提,得到137.5g粘性溶液,用63g乙二醇稀释该溶液,得到200gm含3%Ti的浅黄色液体。实施例1
向装备有搅拌器、N2入口、加热罩、滴液漏斗和冷凝器的250ml烧瓶中装入100g(0.17摩尔)TYZORLA。开始搅拌,并加入45g(0.34摩尔)50%的次磷酸水溶液。将所得反应物料在室温下搅拌2小时,得到145g含5.8%Ti的无色透明溶液。实施例2
用106.4g(0.17摩尔)TYZORLA钠盐和45gm(0.34摩尔)50%的次磷酸水溶液重复实施例1,得到151.4gm含5.4%Ti的无色透明溶液。通过将2摩尔乳酸加入到TYZORTPT中,然后加入水,除去副产物异丙醇,再用23.4%重量的氢氧化钠溶液进行中和,制得TYZORLA钠盐(乳酸钠钛)的溶液。实施例3
用100g(0.17摩尔)TYZORLA和72g(0.34摩尔)50%的次磷酸钠水溶液重复实施例1,得到含4.8%Ti的无色透明溶液。实施例4
用100g(0.17摩尔)TYZORLA和33.8g(0.26摩尔)50%的次磷酸水溶液重复实施例1,得到133.8g含6.1%Ti的无色透明溶液。实施例5
通过将106.4g(0.17摩尔)乳酸钛二钠水溶液加入到33.7g(0.26摩尔)50%的次磷酸水溶液中来重复实施例1,得到140.1g含6.2%Ti的无色透明溶液。通过将2摩尔乳酸加入到TYZORTPT中,然后加入水,除去副产物异丙醇,再用23.4%重量的氢氧化钠溶液进行中和,制得乳酸钛二钠的溶液。实施例6
用100g(0.17摩尔)TYZORLA和53.8g(0.26摩尔)50%的次磷酸钠水溶液重复实施例1,得到153.8g含5.3%Ti的无色透明溶液。实施例7
用100g(0.17摩尔)TYZORLA和22.5g(0.26摩尔)50%的次磷酸水溶液重复实施例1,得到122.5g含6.7%Ti的无色透明溶液。实施例8
用106.4g(0.17摩尔)乳酸钛二钠水溶液和22.5g(0.17摩尔)50%的次磷酸水溶液重复实施例1,得到128.9g含6.7%Ti的无色透明溶液。实施例9
用100g(0.17摩尔)TYZORLA和36g(0.17摩尔)50%的次磷酸钠水溶液重复实施例1,得到136g含6%Ti的无色透明溶液。实施例10
向如实施例1装备的100ml烧瓶中装入14.2g(0.05摩尔)TyzorTPT。开始搅拌,并向其中滴加14.9g(0.1摩尔)三乙醇胺。当滴加结束时,再向其中滴加13.2g(0.1摩尔)50%的次磷酸水溶液。将反应混合物搅拌2小时,得到42.3g含5.7%Ti的无色透明溶液。实施例11
下面对生产对苯二甲酸低聚物的方法进行说明。向高压釜中装入100磅(45.4Kg)对苯二甲酸和67磅(30.4Kg)乙二醇。将该批物料在15rpm的搅拌速度下加热至240℃,移出21.6磅(9.8Kg)水和14.3磅(6.5Kg)乙二醇。然后在90分钟内,将釜内物料加热至275℃,并在285℃、低于2mmHg的真空下除去剩余的乙二醇。一旦判定缩合物料用完,立刻将熔融物料挤进水浴中,以使产物固化。将所得低聚物干燥以在使用前除去残余的水分。
使用如SP-78分光光度计等设备测定所得低聚物和由其生产的任何聚合物的颜色,以L-值和b-值表示。L-值表示亮度,数据越大表明亮度越高(越理想)。b-值表示泛黄的程度,数据越大表明泛黄程度越高(越不理想)。
在1升树脂釜上装配以40rpm旋转的Jiffy Mixer搅拌器、热电偶、冷凝器和氮气吹扫口(nitrogen sweep)。向该釜内装入待测试的催化剂、115ml乙二醇和400g上述制备的对苯二甲酸低聚物。启动搅拌器,使温度在约2.5小时内升高至275℃。通过在搅拌、275℃、120mmHg压力条件下保持20分钟,在280℃、30mmHg的压力下再保持20分钟使釜内物质聚合。然后将釜内物质在搅拌、285℃、1-2mmHg压力下保持一个足以达到15盎司-英寸(0.106牛顿-米)扭矩的时间,该转矩通过Electro-Craft Motomatic扭矩调节器测定。将进行该步骤的时间记录为结束时间,该时间随所用催化剂的不同而不同。然后将所述聚合物熔体倒进水浴中,以使熔体固化,将所得固体在150℃退火12小时,并进行研磨以通过2mm过滤器,用于用前述分光光度计进行的颜色测定。由分光光度计测定的颜色的比较结果在下表1中给出。
表1
实施例 | ppm | L | b |
乙醇酸锑A | 300 Sb | 75.66 | 6.07 |
TYZORTPTB | 25 Ti | 70.68 | 10.54 |
TYZORLAC | 25 Ti | 72.39 | 10.96 |
1-TYZORLA/H3PO2(2/1)D | 25 Ti | 70.22 | 5.36 |
2-TYZORLA(钠盐)/H3PO2(2/1) | 25 Ti | 74.64 | 5.00 |
3-TYZORLA/NaH2PO2(2/1) | 25 Ti | 71.67 | 4.94 |
4-TYZORLA/H3PO2(1.5/1) | 25 Ti | 73.11 | 8.96 |
5-TYZORLA(钠盐)/H3PO2(1.5/1) | 25 Ti | 72.42 | 7.94 |
6-TYZORLA/NaH2PO2(1.5/1) | |||
7-TYZORLA/H3PO2(1/1) | 25 Ti | 72.38 | 8.73 |
8-TYZORLA(钠盐)/H3PO2(1/1) | 25 Ti | 72.41 | 8.48 |
9-TYZORLA/NaH2PO2(1/1) | 25 Ti | 75.02 | 8.40 |
10-三乙醇胺钛酸盐/H3PO2(2/1) | 25 Ti | 72.33 | 6.49 |
对比实施例1-TYZORLA/BPANa(2/1) | 25 Ti | 70.66 | 11.11 |
对比实施例2-柠檬酸钠钛 | 25 Ti | 68.40 | 11.46 |
A,B和C对照试验
D圆括号内的比例为钛络合物与磷化合物的摩尔比
表1表明用含钛和次磷酸或其盐(实施例1-10)的催化剂生产的聚酯具有明显较低的b值,即比用钛化合物但没用次磷酸或其盐生产的聚酯更少泛黄。表1还显示用含钛、苯膦酸、钠盐的催化剂(对照实施例1)和用有机磷化合物生产的聚酯分别具有不理想的11.11和11.46的高b值。使用TYZORLA的对照试验和对比实施例2显示有或没有碱的α-羟基羧酸钛络合物具有比含次磷酸或其盐的物质更高的b颜色值。
Claims (16)
1.一种组合物,该组合物含有钛化合物、络合剂、次磷酸或其盐以及任选的溶剂、锆化合物或两者,其中所述络合剂为羟基羧酸、链烷醇胺或氨基羧酸。
2.一种组合物,该组合物含有钛络合物、次磷酸或其盐以及任选的溶剂、锆化合物或两者,其中所述钛络合物为钛化合物与络合剂的络合物;并且所述络合剂为α-羟基羧酸、链烷醇胺或氨基羧酸。
3.权利要求1或2的组合物,其中所述钛化合物具有式Ti(OR)4,各R为烷基、环烷基或芳烷基,每个基团中含有1至约30个碳原子。
4.权利要求1、2或3的组合物,其中所述钛化合物为四异丙基钛酸酯或四正丁基钛酸酯。
5.权利要求1-4中任一项的组合物,其中所述溶剂为水、乙醇、丙醇、异丙醇、丁醇、乙二醇、丙二醇、异丙二醇、丁二醇、1-甲基丙二醇或戊二醇。
6.权利要求5的组合物,其中所述溶剂为水或乙醇。
7.权利要求1-6中任一项的组合物,其中所述锆化合物为四乙醇锆、四丙醇锆、四异丙醇锆、四正丁醇锆、四己醇锆、四(2-乙基己醇)锆或四辛醇锆。
8.权利要求1-7中任一项的组合物,其中所述络合剂为乳酸、乙醇酸、柠檬酸、酒石酸、苹果酸、二乙醇胺、三乙醇胺、四羟基异丙基乙二胺、甘氨酸、双羟乙基甘氨酸或羟乙基甘氨酸。
9.权利要求1-8中任一项的组合物,其中所述组合物是通过将所述有机钛化合物、所述络合剂、所述次磷酸或其盐以及任选的所述溶剂或所述锆化合物混合来制备的。
10.一种方法,该方法包括在催化剂组合物的存在下,使羰基化合物与醇接触,其中所述催化剂为权利要求1-9中任一项的催化剂。
11.权利要求10的方法,其中所述羰基化合物具有式R2COOR2;各R2独立选自(1)氢;(2)末端具有羧酸基团的烃氧基;或者(3)可以是烷基、链烯基、芳基、烷芳基、芳烷基的烃基,其中各基团的每个基团具有1至约30,优选约3至约15个碳原子;(4)5-硫代间苯二甲酸金属盐或其酯;以及(5)它们的两种或多种的混合物。
12.权利要求11的方法,其中所述醇为乙二醇、丙二醇、异丙二醇、丁二醇、1-甲基丙二醇或戊二醇。
13.权利要求12的方法,其中所述醇为乙二醇。
14.权利要求10-13中任一项的方法,其中所述羰基化合物为对苯二甲酸、对苯二甲酸二甲酯、间苯二甲酸、萘二甲酸、丁二酸、己二酸、邻苯二甲酸、戊二酸、丙烯酸、草酸、苯甲酸、马来酸、丙烯酸或5-硫代间苯二甲酸钠盐的双乙醇酸酯。
15.权利要求14的方法,其中所述羰基化合物为对苯二甲酸。
16.权利要求10-13和15中任一项的方法,其中所述羰基化合物包含对苯二甲酸和5-硫代间苯二甲酸钠盐的双乙醇酸酯的混合物。
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US09/453,100 | 1999-12-02 | ||
US09/453,100 US6166170A (en) | 1999-12-02 | 1999-12-02 | Esterification catalysts and processes therefor and therewith |
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EP (1) | EP1235647A1 (zh) |
JP (1) | JP2003515441A (zh) |
KR (1) | KR100613807B1 (zh) |
CN (1) | CN1179790C (zh) |
AR (1) | AR025709A1 (zh) |
BR (1) | BR0016102A (zh) |
MX (1) | MXPA02005397A (zh) |
TR (1) | TR200201461T2 (zh) |
TW (1) | TW591050B (zh) |
WO (1) | WO2001039885A1 (zh) |
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BR0016102A (pt) | 2002-08-20 |
WO2001039885A1 (en) | 2001-06-07 |
TW591050B (en) | 2004-06-11 |
EP1235647A1 (en) | 2002-09-04 |
US6166170A (en) | 2000-12-26 |
CN1179790C (zh) | 2004-12-15 |
KR20020059838A (ko) | 2002-07-13 |
JP2003515441A (ja) | 2003-05-07 |
TR200201461T2 (tr) | 2002-10-21 |
MXPA02005397A (es) | 2003-01-28 |
USRE39246E1 (en) | 2006-08-22 |
KR100613807B1 (ko) | 2006-08-18 |
AR025709A1 (es) | 2002-12-11 |
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