TWI596135B - Preparation of catalyst, catalyst obtained and and the preparation of polyester applications - Google Patents
Preparation of catalyst, catalyst obtained and and the preparation of polyester applications Download PDFInfo
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- TWI596135B TWI596135B TW105143613A TW105143613A TWI596135B TW I596135 B TWI596135 B TW I596135B TW 105143613 A TW105143613 A TW 105143613A TW 105143613 A TW105143613 A TW 105143613A TW I596135 B TWI596135 B TW I596135B
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- Prior art keywords
- acid
- catalyst
- polyester
- preparing
- organic
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- 229920000728 polyester Polymers 0.000 title claims description 68
- 239000003054 catalyst Substances 0.000 title claims description 57
- 238000002360 preparation method Methods 0.000 title claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 47
- 239000000203 mixture Substances 0.000 claims description 33
- 239000002253 acid Substances 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 25
- KKEYFWRCBNTPAC-UHFFFAOYSA-N terephthalic acid group Chemical group C(C1=CC=C(C(=O)O)C=C1)(=O)O KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 20
- -1 ruthenium (III) compound Chemical class 0.000 claims description 17
- 150000002148 esters Chemical class 0.000 claims description 12
- 238000006068 polycondensation reaction Methods 0.000 claims description 11
- 150000002009 diols Chemical class 0.000 claims description 9
- 125000003118 aryl group Chemical group 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 8
- 150000007519 polyprotic acids Polymers 0.000 claims description 8
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- 125000000962 organic group Chemical group 0.000 claims description 7
- QYMFNZIUDRQRSA-UHFFFAOYSA-N dimethyl butanedioate;dimethyl hexanedioate;dimethyl pentanedioate Chemical compound COC(=O)CCC(=O)OC.COC(=O)CCCC(=O)OC.COC(=O)CCCCC(=O)OC QYMFNZIUDRQRSA-UHFFFAOYSA-N 0.000 claims description 5
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 5
- BCBHDSLDGBIFIX-UHFFFAOYSA-N 4-[(2-hydroxyethoxy)carbonyl]benzoic acid Chemical compound OCCOC(=O)C1=CC=C(C(O)=O)C=C1 BCBHDSLDGBIFIX-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
- 150000008064 anhydrides Chemical class 0.000 claims description 4
- PFURGBBHAOXLIO-UHFFFAOYSA-N cyclohexane-1,2-diol Chemical compound OC1CCCCC1O PFURGBBHAOXLIO-UHFFFAOYSA-N 0.000 claims description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 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
- KQTIIICEAUMSDG-UHFFFAOYSA-N tricarballylic acid Chemical compound OC(=O)CC(C(O)=O)CC(O)=O KQTIIICEAUMSDG-UHFFFAOYSA-N 0.000 claims description 4
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 claims description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 2
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 claims description 2
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 claims description 2
- FQXGHZNSUOHCLO-UHFFFAOYSA-N 2,2,4,4-tetramethyl-1,3-cyclobutanediol Chemical compound CC1(C)C(O)C(C)(C)C1O FQXGHZNSUOHCLO-UHFFFAOYSA-N 0.000 claims description 2
- LFBALUPVVFCEPA-UHFFFAOYSA-N 4-(3,4-dicarboxyphenyl)phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C(C(O)=O)=C1 LFBALUPVVFCEPA-UHFFFAOYSA-N 0.000 claims description 2
- KLDXJTOLSGUMSJ-JGWLITMVSA-N Isosorbide Chemical compound O[C@@H]1CO[C@@H]2[C@@H](O)CO[C@@H]21 KLDXJTOLSGUMSJ-JGWLITMVSA-N 0.000 claims description 2
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-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
- XDODWINGEHBYRT-UHFFFAOYSA-N [2-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCCCC1CO XDODWINGEHBYRT-UHFFFAOYSA-N 0.000 claims description 2
- LUSFFPXRDZKBMF-UHFFFAOYSA-N [3-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCCC(CO)C1 LUSFFPXRDZKBMF-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
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 2
- PMMYEEVYMWASQN-IMJSIDKUSA-N cis-4-Hydroxy-L-proline Chemical compound O[C@@H]1CN[C@H](C(O)=O)C1 PMMYEEVYMWASQN-IMJSIDKUSA-N 0.000 claims description 2
- XBZSBBLNHFMTEB-UHFFFAOYSA-N cyclohexane-1,3-dicarboxylic acid Chemical compound OC(=O)C1CCCC(C(O)=O)C1 XBZSBBLNHFMTEB-UHFFFAOYSA-N 0.000 claims description 2
- RWLDAJMGAVDXSH-UHFFFAOYSA-N ethane-1,1,2-tricarboxylic acid Chemical compound OC(=O)CC(C(O)=O)C(O)=O RWLDAJMGAVDXSH-UHFFFAOYSA-N 0.000 claims description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 2
- 229960002479 isosorbide Drugs 0.000 claims description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 2
- XFBLPIPEFDRLTH-UHFFFAOYSA-N oxoruthenium(1+) Chemical compound [Ru+]=O XFBLPIPEFDRLTH-UHFFFAOYSA-N 0.000 claims description 2
- 229920000166 polytrimethylene carbonate Polymers 0.000 claims description 2
- 235000013772 propylene glycol Nutrition 0.000 claims description 2
- OJLCQGGSMYKWEK-UHFFFAOYSA-K ruthenium(3+);triacetate Chemical compound [Ru+3].CC([O-])=O.CC([O-])=O.CC([O-])=O OJLCQGGSMYKWEK-UHFFFAOYSA-K 0.000 claims description 2
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 claims 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims 1
- 239000001273 butane Substances 0.000 claims 1
- 235000019253 formic acid Nutrition 0.000 claims 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 34
- 239000005020 polyethylene terephthalate Substances 0.000 description 34
- 230000015572 biosynthetic process Effects 0.000 description 17
- 238000003786 synthesis reaction Methods 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 16
- 239000000843 powder Substances 0.000 description 11
- QPKOBORKPHRBPS-UHFFFAOYSA-N bis(2-hydroxyethyl) terephthalate Chemical group OCCOC(=O)C1=CC=C(C(=O)OCCO)C=C1 QPKOBORKPHRBPS-UHFFFAOYSA-N 0.000 description 10
- 239000000126 substance Substances 0.000 description 6
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical compound [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 0.000 description 5
- 229910052746 lanthanum Inorganic materials 0.000 description 4
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- 239000004135 Bone phosphate Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 229910000421 cerium(III) oxide Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000003426 co-catalyst Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 150000003304 ruthenium compounds Chemical class 0.000 description 2
- RLHGFJMGWQXPBW-UHFFFAOYSA-N 2-hydroxy-3-(1h-imidazol-5-ylmethyl)benzamide Chemical compound NC(=O)C1=CC=CC(CC=2NC=NC=2)=C1O RLHGFJMGWQXPBW-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 241000254158 Lampyridae Species 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- VQXHBHRWCQCXMN-UHFFFAOYSA-N [Ru].C(CO)O Chemical compound [Ru].C(CO)O VQXHBHRWCQCXMN-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000006136 alcoholysis reaction Methods 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 1
- 150000001785 cerium compounds Chemical class 0.000 description 1
- XQTIWNLDFPPCIU-UHFFFAOYSA-N cerium(3+) Chemical class [Ce+3] XQTIWNLDFPPCIU-UHFFFAOYSA-N 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
- C08G63/183—Terephthalic acids
-
- 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
- C08G63/86—Germanium, antimony, or compounds thereof
- C08G63/866—Antimony or compounds thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
Description
本發明是有關於一種觸媒的製法及其所製得的觸媒,該觸媒主要應用於製備聚酯。The present invention relates to a process for preparing a catalyst and a catalyst produced therefrom, which is mainly used for the preparation of polyester.
在聚酯產品[如:聚對苯二甲酸乙二酯(PET)]的現有製程中,多是以銻(III)化合物[如:醋酸銻(III)、氧化銻(III)或乙二醇銻(III)]作為縮聚反應的觸媒,然而,使用上述銻(III)化合物往往會導致觸媒溶液或聚酯產物的色相暗沉且偏黃,因而需要另外添加穩定劑或使用共觸媒(cocatalyst) (如US 3,844,976及US 8,648,166B2)。In the existing processes of polyester products [eg polyethylene terephthalate (PET)], most of them are cerium (III) compounds [eg cerium (III) acetate, cerium (III) oxide or ethylene glycol).锑(III)] as a catalyst for the polycondensation reaction, however, the use of the above ruthenium (III) compound tends to cause the hue of the catalyst solution or the polyester product to be dull and yellowish, thus requiring the addition of a stabilizer or the use of a co-catalyst. (cocatalyst) (eg US 3,844,976 and US 8,648,166 B2).
CN 1255478A公開一種聚酯催化劑(即乙二醇銻)的製備方法,是透過多段分離步驟除去雜質及未反應(或過量)之反應物(乙二醇及Sb 2O 3),但其所製備的聚酯產物的色相仍有改善空間。 CN 1255478A discloses a method for preparing a polyester catalyst (ie, ethylene glycol ruthenium) by removing impurities and unreacted (or excess) reactants (ethylene glycol and Sb 2 O 3 ) through a plurality of separation steps, but preparing the same. The hue of the polyester product still has room for improvement.
CN 103435793A公開一種常溫均相(homogeneous)液態聚酯催化劑,主要是將銻化合物與二元有機酸、乳酸及乙二醇混合,加熱溶解後生成一常溫均相溶液(在常溫下為均勻液態,不會結晶析出),該液態聚酯催化劑可於聚酯合成時,進料程序更為便利,然而,其僅是進行物理混摻,其銻化合物的化學結構並未改變,所以使用該觸媒進行聚合反應時,仍然會有聚酯產物色相不佳的問題。CN 103435793A discloses a normal temperature homogeneous liquid polyester catalyst, which mainly comprises mixing a cerium compound with a dibasic organic acid, lactic acid and ethylene glycol, and heating and dissolving to form a normal temperature homogeneous solution (a uniform liquid state at normal temperature, The liquid polyester catalyst can be more conveniently used in the synthesis of the polyester. However, it is only physically mixed, and the chemical structure of the ruthenium compound is not changed, so the catalyst is used. When the polymerization is carried out, there is still a problem that the polyester product has a poor hue.
因此,本發明之一目的,即在提供一種觸媒的製法,藉由該製法將銻化合物進行化學改質,以改善前述銻(III)化合物導致聚酯的色相不佳問題。Accordingly, it is an object of the present invention to provide a process for the preparation of a catalyst by chemically modifying a ruthenium compound to improve the hue of the polyester of the ruthenium (III) compound.
於是,本發明觸媒的製法,包含將一混合物加熱進行化學反應,以得到一含有 部分(moiety)之化合物的產物,其中, R表示二價有機基團(divalent organic group),該混合物實質上由有機二元酸雙二醇酯及銻(III)化合物所組成。 Thus, the process of the catalyst of the present invention comprises heating a mixture to carry out a chemical reaction to obtain a A product of a compound of the formula wherein R represents a divalent organic group consisting essentially of an organic dibasic acid dibasic ester and a ruthenium (III) compound.
因此,本發明之另一目的,即在提供一種觸媒,是由如上所述的製法所製得。Therefore, another object of the present invention, that is, to provide a catalyst, is produced by the above-described method.
因此,本發明之又一目的,即在提供一種用於製備聚酯的組成物,包含如上所述的觸媒;有機多元酸、其酸酐或其酯;及二元醇。Accordingly, it is still another object of the present invention to provide a composition for preparing a polyester comprising the catalyst as described above; an organic polybasic acid, an anhydride thereof or an ester thereof; and a glycol.
因此,本發明之又一目的,即在提供一種製備聚酯的方法,包含將一混合物加熱進行化學反應,以得到一含有 部分之化合物的觸媒,其中, R表示二價有機基團,該混合物實質上由有機二元酸雙二醇酯及銻(III)化合物所組成;及使有機多元酸、其酸酐或其酯及二元醇在與該觸媒接觸下進行縮聚反應,以得到該聚酯。 Accordingly, it is still another object of the present invention to provide a method of preparing a polyester comprising heating a mixture to carry out a chemical reaction to obtain a a catalyst for a part of a compound, wherein R represents a divalent organic group, the mixture consists essentially of an organic dibasic acid dibasic ester and a ruthenium (III) compound; and an organic polybasic acid, an anhydride thereof or an ester thereof And the diol is subjected to a polycondensation reaction in contact with the catalyst to obtain the polyester.
本發明之功效在於:透過本發明製法所製得的觸媒,無需另外添加穩定劑或使用共觸媒即可使用於製備聚酯的縮聚反應,並製得色相佳的聚酯產物。The effect of the present invention is that the catalyst prepared by the process of the present invention can be used for the polycondensation reaction of preparing a polyester without additionally adding a stabilizer or using a co-catalyst, and a polyester product having a good hue can be obtained.
以下將就本發明內容進行詳細說明:The contents of the present invention will be described in detail below:
本發明觸媒的製法,包含將一混合物加熱進行化學反應,以得到一含有 部分(moiety)之化合物的產物,其中, R表示二價有機基團(divalent organic group),該混合物實質上由有機二元酸雙二醇酯及銻(III)化合物所組成。 The method for preparing a catalyst according to the invention comprises heating a mixture to carry out a chemical reaction to obtain a A product of a compound of the formula wherein R represents a divalent organic group consisting essentially of an organic dibasic acid dibasic ester and a ruthenium (III) compound.
較佳地,在本發明觸媒的製法中,包含將該混合物加熱進行化學反應,以得到一含有 部分之化合物的產物,其中, Ar表示二價芳香族基團(divalent aromatic group), R表示二價有機基團。更佳地, Ar表示1,4-伸苯基, R表示–C 2H 4–。 Preferably, in the method of preparing the catalyst of the present invention, the mixture is heated to carry out a chemical reaction to obtain a A product of a partial compound, wherein Ar represents a divalent aromatic group and R represents a divalent organic group. More preferably, Ar represents 1,4-phenylene and R represents -C 2 H 4 -.
較佳地,該有機二元酸雙二醇酯是芳香二元酸雙二醇酯。更佳地,該芳香二元酸雙二醇酯是對苯二甲酸雙2-羥乙酯[bis(2-hydroxyethyl) terephthalate, BHET單體,結構如下化學式1所示]。在本發明中,對苯二甲酸雙2-羥乙酯可為市售試藥級化學品、由PET經乙二醇醇解而得的產物、由對苯二甲酸與環氧乙烷經反應而得的產物,但排除由對苯二甲酸與乙二醇經聚合反應而得的聚合物或寡聚物。 【化學式1】 Preferably, the organic dibasic acid didiol ester is an aromatic dibasic acid didiol ester. More preferably, the aromatic dibasic acid didiol ester is a bis(2-hydroxyethyl) terephthalate, BHET monomer having the structure shown in the following Chemical Formula 1. In the present invention, bis 2-hydroxyethyl terephthalate may be a commercially available reagent-grade chemical, a product obtained by alcoholysis of PET with ethylene glycol, and reacted with terephthalic acid and ethylene oxide. The resulting product, but excludes polymers or oligomers obtained by the polymerization of terephthalic acid and ethylene glycol. [Chemical Formula 1]
較佳地,在本發明的觸媒的製法中,該銻(III)化合物是選自於醋酸銻(III)或氧化銻(III)(即Sb 2O 3)。 Preferably, in the process of the catalyst of the present invention, the ruthenium (III) compound is selected from the group consisting of ruthenium (III) acetate or ruthenium (III) oxide (i.e., Sb 2 O 3 ).
在本發明的具體實施例中,該混合物是由有機二元酸雙二醇酯及銻(III)化合物所組成。In a particular embodiment of the invention, the mixture is comprised of an organic dibasic acid didiol ester and a ruthenium (III) compound.
較佳地,在本發明的觸媒的製法中,在該混合物中,該有機二元酸雙二醇酯相對於該銻(III)化合物的莫耳比值範圍為1.5~3.2,更佳地,該有機二元酸雙二醇酯相對於該銻(III)化合物的莫耳比值範圍為2.2~3.2。在本發明的具體實施例中,該有機二元酸雙二醇酯相對於該銻(III)化合物的莫耳比值為2.5。Preferably, in the process of the catalyst of the present invention, the molar ratio of the organic dibasic acid diglyceride to the ruthenium (III) compound in the mixture ranges from 1.5 to 3.2, more preferably, The molar ratio of the organic dibasic acid diglyceride to the ruthenium (III) compound ranges from 2.2 to 3.2. In a particular embodiment of the invention, the molar ratio of the organic dibasic acid diglyceride to the ruthenium (III) compound is 2.5.
較佳地,在本發明的觸媒的製法中,該混合物是在120~170℃中進行化學反應。更佳地,該混合物是在120~140℃中進行化學反應。在本發明的具體實施例中,該混合物是在120~130℃中進行化學反應。Preferably, in the process of the catalyst of the present invention, the mixture is subjected to a chemical reaction at 120 to 170 °C. More preferably, the mixture is subjected to a chemical reaction at 120 to 140 °C. In a particular embodiment of the invention, the mixture is subjected to a chemical reaction at 120 to 130 °C.
較佳地,在本發明觸媒的製法中,該混合物是在不含乙二醇的環境中加熱進行化學反應。Preferably, in the process of the catalyst of the present invention, the mixture is heated to carry out a chemical reaction in an environment free of ethylene glycol.
較佳地,在本發明用於製備聚酯的組成物中,該有機多元酸是選自於芳香族二元酸(例如對苯二甲酸或間苯二甲酸)、脂肪族二元酸(例如1,4-環己烷二甲酸、1,3-環己烷二甲酸、丁二酸、己二酸或癸二酸)、脂肪族三元酸或四元酸(例如1,1,2-乙烷三甲酸、1,2,3-丙烷三甲酸或1,2,3,4-丁烷四甲酸)、芳香族三元酸或四元酸(例如1,2,4,5-苯四酸、1,2,4-苯三酸、1,3,5-苯三酸或3,3',4,4'-聯苯四甲酸)或其組合。在本發明的具體實施例中,該有機多元酸是對苯二甲酸。Preferably, in the composition for preparing a polyester of the present invention, the organic polybasic acid is selected from an aromatic dibasic acid (for example, terephthalic acid or isophthalic acid) or an aliphatic dibasic acid (for example). 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, succinic acid, adipic acid or sebacic acid), an aliphatic tribasic acid or a tetrabasic acid (for example, 1,1,2- Ethane tricarboxylic acid, 1,2,3-propane tricarboxylic acid or 1,2,3,4-butane tetracarboxylic acid), an aromatic tribasic acid or a tetrabasic acid (for example, 1,2,4,5-benzene IV) Acid, trimellitic acid, trimellitic acid or 3,3',4,4'-biphenyltetracarboxylic acid) or a combination thereof. In a particular embodiment of the invention, the organic polyacid is terephthalic acid.
較佳地,在本發明用於製備聚酯的組成物中,該二元醇是選自於1,2-乙二醇、三甘醇、1,2-丙二醇、1,3-丙二醇、1,4-丁二醇、1,5-戊二醇、1,6-己二醇、新戊二醇、1,2-環己烷二醇、1,4-環己烷二醇、1,2-環己烷二甲醇、1,3-環己烷二甲醇、2,2,4,4-四甲基-1,3-環丁烷二醇、異山梨醇或其組合。在本發明的具體實施例中,該二元醇是1,2-乙二醇(ethylene glycol)。Preferably, in the composition for preparing a polyester of the present invention, the diol is selected from the group consisting of 1,2-ethanediol, triethylene glycol, 1,2-propanediol, 1,3-propanediol, and , 4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 1,2-cyclohexanediol, 1,4-cyclohexanediol, 1, 2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, isosorbide or a combination thereof. In a particular embodiment of the invention, the glycol is 1,2-ethylene glycol.
較佳地,在本發明用於製備聚酯的組成物中,該觸媒與該二元醇是呈兩相(two distinct phases)。Preferably, in the composition for preparing a polyester of the present invention, the catalyst and the diol are in two distinct phases.
較佳地,在本發明製備聚酯的方法中, R表示–C 2H 4–,該有機二元酸雙二醇酯是對苯二甲酸雙2-羥乙酯,該有機多元酸是對苯二甲酸,該二元醇是乙二醇。 Preferably, in the method for producing a polyester of the present invention, R represents -C 2 H 4 -, and the organic dibasic acid dibasic ester is bis 2-hydroxyethyl terephthalate, and the organic polybasic acid is Terephthalic acid, the glycol is ethylene glycol.
較佳地,在本發明製備聚酯的方法中,該混合物是在不含乙二醇的環境中加熱進行化學反應,該觸媒與該二元醇是呈兩相。Preferably, in the method of preparing a polyester of the present invention, the mixture is heated in a glycol-free environment for chemical reaction, and the catalyst is in two phases with the diol.
本發明的用於製備聚酯的組成物,進一步可含有其它任何已知的聚合物、穩定劑、抗氧化劑、抗靜電劑、防沫劑、染色助劑、染料、顏料、去光劑、螢光增白劑或其它添加劑。The composition for preparing a polyester of the present invention may further contain any other known polymer, stabilizer, antioxidant, antistatic agent, antifoaming agent, dyeing auxiliary, dye, pigment, delustering agent, firefly Light whitening agent or other additives.
本發明的用於製備聚酯的組成物,進一步可透過一般現有的方法進行縮聚反應,以得到聚酯產物。The composition for producing a polyester of the present invention can be further subjected to a polycondensation reaction by a generally existing method to obtain a polyester product.
本發明將就以下實施例來作進一步說明,但應瞭解的是,該等實施例僅為例示說明之用,而不應被解釋為本發明實施之限制。The invention is further described in the following examples, but it should be understood that these examples are for illustrative purposes only and are not to be construed as limiting.
<合成例>以<synthesis example> BHETBHET 單體合成觸媒Monomer synthesis catalyst C E C E
在250 mL玻璃瓶中置入106.22 g (0.42 mol)對苯二甲酸雙2-羥乙酯(BHET單體)並加熱至120℃,接著加入50 g (0.17 mol)醋酸銻(III),升溫至130℃進行化學反應4小時,最後進行減壓蒸餾後得到白色粉體產物(觸媒C E),由其HMBC (heteronuclear multiple-bond correlation)圖譜可以得知BHET單體與醋酸銻(III)反應產生具有H-6(δ=4.37)與C-4(δ=164.8)、C-7(δ=171.5)遠程偶合(long-range coupling)的產物(如下化學式2所示),其化合物確實含有 部分(在本合成例中, R表示–C 2H 4–)。 【化學式2】 106.22 g (0.42 mol) of bis 2-hydroxyethyl terephthalate (BHET monomer) was placed in a 250 mL glass vial and heated to 120 ° C, followed by 50 g (0.17 mol) of cerium (III) acetate. The chemical reaction was carried out at 130 ° C for 4 hours, and finally distilled under reduced pressure to obtain a white powder product (catalyst C E ). From the HMBC (heteronuclear multiple-bond correlation) spectrum, the BHET monomer and cerium (III) acetate were known. The reaction produces a product having a long-range coupling of H-6 (δ = 4.37) and C-4 (δ = 164.8) and C-7 (δ = 171.5) (shown in the following Chemical Formula 2), the compound of which is indeed contain Part (in the present synthesis, R represents -C 2 H 4 -). [Chemical Formula 2]
<比較合成例>以<Comparative Synthesis Example> BHETBHET 寡聚物合成觸媒Oligomer synthesis catalyst C C C C
[[ 製備preparation BHETBHET 寡聚物Oligomer ]]
首先,在1 L反應器中置入345.8 g對苯二甲酸與161.5 g乙二醇,在250℃及2 kg/cm 2N 2加壓下進行反應280 min,餾出水後得到平均聚合度為15.6的BHET寡聚物( M p =3016),其PDI=1.18 ( =4341, =5122),顯示該BHET寡聚物的分子量分布相當集中。 First, 345.8 g of terephthalic acid and 161.5 g of ethylene glycol were placed in a 1 L reactor, and the reaction was carried out under a pressure of 250 ° C and 2 kg/cm 2 N 2 for 280 min, and the average degree of polymerization was obtained after distilling off water. BHET oligomer of 15.6 ( M p = 3016) with PDI = 1.18 ( =4341, = 5122), showing that the molecular weight distribution of the BHET oligomer is quite concentrated.
[[ 合成觸媒Synthetic catalyst ]]
其次,在200 mL玻璃瓶中置入253.3 g (0.084 mol)上述BHET寡聚物並加熱至230℃,接著加入11.4 g (0.038 mol)醋酸銻(III),升溫至260℃進行反應4小時,最後進行減壓蒸餾後得到黃褐色粉體產物(觸媒C C)。 Next, 253.3 g (0.084 mol) of the above BHET oligomer was placed in a 200 mL glass vial and heated to 230 ° C, followed by the addition of 11.4 g (0.038 mol) of cerium (III) acetate, and the temperature was raised to 260 ° C for 4 hours. Finally, distillation under reduced pressure gave a yellow-brown powder product (catalyst C C ).
<色相測量><Hue measurement>
利用日本NIPPON DENSHOKU公司的色差儀(型號為NE4000)分別測量上述合成例及比較合成例之觸媒C E及C C的CIE L*值、a*值及b*值,結果如下表1所示。 【表1】 <TABLE border="1" borderColor="#000000" width="_0009"><TBODY><tr><td> </td><td> CIE L*值 </td><td> CIE a*值 </td><td> CIE b*值 </td></tr><tr><td> 觸媒C<sub>E</sub></td><td> 91.70 </td><td> -0.49 </td><td> 6.60 </td></tr><tr><td> 觸媒C<sub>C</sub></td><td> 65.11 </td><td> 4.70 </td><td> 16.73 </td></tr></TBODY></TABLE>The CIE L* value, a* value and b* value of the catalysts C E and C C of the above synthesis examples and comparative synthesis examples were respectively measured by a color difference meter (model NE4000) of Japan NIPPON DENSHOKU Co., Ltd., and the results are shown in Table 1 below. . [Table 1] <TABLE border="1"borderColor="#000000"width="_0009"><TBODY><tr><td></td><td> CIE L* value</td><td> CIE a* value</td><td> CIE b* value</td></tr><tr><td> Catalyst C<sub>E</sub></td><td> 91.70 </ Td><td> -0.49 </td><td> 6.60 </td></tr><tr><td> Catalyst C<sub>C</sub></td><td> 65.11 </ Td><td> 4.70 </td><td> 16.73 </td></tr></TBODY></TABLE>
由表1可以明顯看出,相較於合成例之觸媒C E,比較合成例之觸媒C C的CIE L*值較小且CIE a*值及CIE b*值大於0較多,顯示其明度較低(顏色較暗沉)且較偏黃褐色(顏色較偏離白色),故色相較差。此外,比較合成例的製程需要加熱至230~260℃才能反應得到其產物觸媒C C,而合成例的製程只需要加熱至120~130℃即可反應得到其產物觸媒C E。 It can be clearly seen from Table 1 that compared with the catalyst C E of the synthesis example, the CIE L* value of the catalyst C C of the comparative synthesis example is small and the CIE a* value and the CIE b* value are more than 0, showing Its brightness is lower (the color is darker) and it is more yellowish brown (the color is more deviated from white), so the hue is poor. In addition, the process of the comparative synthesis method needs to be heated to 230~260 °C to obtain the catalyst C C of the product, and the process of the synthesis example only needs to be heated to 120-130 ° C to obtain the catalyst C E of the product.
<實施例>聚酯<Examples> Polyester PET E PET E
[[ 配製用於製備聚酯的組成物Formulating a composition for preparing a polyester ]]
首先,在5 L反應器中置入2161.5 g對苯二甲酸與1009.1 g乙二醇,在250℃及2 kg/cm 2N 2加壓下進行預聚合反應285 min,接著加入磷酸(用量相對於對苯二甲酸的莫耳比為0.00015:1)以及上述合成例之觸媒C E粉體(用量相當於致使後續得到的每100 g聚酯產物中含有0.0133 g銻元素),此時觸媒C E與乙二醇是呈兩相。 First, 2161.5 g of terephthalic acid and 1009.1 g of ethylene glycol were placed in a 5 L reactor, and prepolymerization was carried out at 250 ° C under a pressure of 2 kg/cm 2 N 2 for 285 min, followed by the addition of phosphoric acid (amount relative to The molar ratio of terephthalic acid is 0.00015:1) and the catalyst C E powder of the above synthesis example (the amount equivalent to causing 0.0133 g of lanthanum element per 100 g of the polyester product obtained later) The medium C E and the ethylene glycol are in two phases.
[[ 合成聚酯Synthetic polyester ]]
隨後,使上述用於製備聚酯的組成物在270~275℃下進行縮聚反應,並於反應345 min後出料,得到聚酯產物(聚酯PET E)。 Subsequently, the above composition for preparing a polyester was subjected to a polycondensation reaction at 270 to 275 ° C, and discharged after 345 minutes of reaction to obtain a polyester product (polyester PET E ).
<比較例<Comparative example 11 >聚酯>polyester PET C1 PET C1
比較例1與上述實施例大致相同,不同之處在於將上述合成例之觸媒C E粉體改變為上述比較合成例之觸媒C C粉體(用量相當於致使後續得到的每100 g聚酯產物中含有0.0133 g銻元素)。隨後進行縮聚反應,並於反應350 min後出料,得到聚酯產物(聚酯PET C1)。 Comparative Example 1 is substantially the same as the above embodiment except that the catalyst C E powder of the above synthesis example is changed to the catalyst C C powder of the above comparative synthesis example (the amount is equivalent to each subsequent 100 g of poly The ester product contains 0.0133 g of lanthanum). Subsequently, a polycondensation reaction was carried out and discharged after 350 minutes of reaction to obtain a polyester product (polyester PET C1 ).
<比較例<Comparative example 22 >聚酯>polyester PET C2 PET C2
比較例2與上述實施例大致相同,不同之處在於將上述合成例之觸媒C E粉體改變為醋酸銻(III)粉體(用量相當於致使後續得到的每100 g聚酯產物中含有0.0133 g銻元素)。隨後進行縮聚反應,並於反應415 min後出料,得到聚酯產物(聚酯PET C2)。 Comparative Example 2 is substantially the same as the above embodiment except that the catalyst C E powder of the above synthesis example was changed to cerium (III) acetate powder (the amount corresponding to the subsequent obtained per 100 g of the polyester product) 0.0133 g锑 element). Subsequently, a polycondensation reaction was carried out, and after the reaction was carried out for 415 min, a polyester product (polyester PET C2 ) was obtained.
<比較例<Comparative example 33 、, 44 >聚酯>polyester PET C3 PET C3 、, PET C4 PET C4
比較例3、4分別與上述實施例大致相同,不同之處在於將上述合成例之觸媒C E粉體改變為氧化銻(III)粉體(用量相當於致使後續得到的每100 g聚酯產物中分別含有0.0133 g、0.0250 g銻元素)。隨後進行縮聚反應,並分別於反應380 min、305 min後出料,得到聚酯產物(聚酯PET C3、PET C4)。 Comparative Examples 3 and 4 are substantially the same as the above examples, except that the catalyst C E powder of the above synthesis example is changed to cerium (III) oxide powder (the amount corresponding to each subsequent 100 g of polyester obtained) The product contained 0.0133 g and 0.0250 g of lanthanum, respectively. Subsequently, the polycondensation reaction was carried out, and the mixture was discharged after 380 min and 305 min, respectively, to obtain a polyester product (polyester PET C3 , PET C4 ).
<比較例<Comparative example 55 、, 66 >聚酯>polyester PET C5 PET C5 、, PET C6 PET C6
比較例5、6分別與上述實施例大致相同,不同之處在於將上述合成例之觸媒C E粉體改變為乙二醇銻(III)粉體(用量相當於致使後續得到的每100 g聚酯產物中分別含有0.0133 g、0.0180 g銻元素)。隨後進行縮聚反應,並分別於反應355 min、245 min後出料,得到聚酯產物(聚酯PET C5、PET C6)。 Comparative Examples 5 and 6 are substantially the same as the above examples, except that the catalyst C E powder of the above synthesis example is changed to ethylene glycol ruthenium (III) powder (the amount equivalent to each subsequent 100 g obtained) The polyester product contained 0.0133 g and 0.0180 g of lanthanum, respectively. Subsequently, the polycondensation reaction was carried out, and the mixture was discharged after 355 min and 245 min, respectively, to obtain a polyester product (polyester PET C5 , PET C6 ).
<色相測量><Hue measurement>
利用日本NIPPON DENSHOKU公司的色差儀(型號為NE4000)分別測量上述實施例及比較例1~6之聚酯PET E及PET C1~PET C6的CIE L*值、a*值及b*值,結果如下表2所示。 The CIE L* value, a* value and b* value of the polyester PET E and PET C1 ~ PET C6 of the above Examples and Comparative Examples 1 to 6 were respectively measured by a color difference meter (model NE4000) of Japan NIPPON DENSHOKU Co., Ltd., and the results were respectively measured. As shown in Table 2 below.
<黏度測量><Viscocity measurement>
分別取上述實施例及比較例1~6之聚酯PET E及PET C1~PET C60.1 g溶於25 mL酚/四氯乙烷(重量比3:2)的混合溶劑中,在30℃下以烏氏黏度計(Ubbelohde viscometer)測量其特性黏度(intrinsic viscosity, IV, [η]),結果所有IV值皆大於0.56 dL/g。 【表2】 <TABLE border="1" borderColor="#000000" width="_0010"><TBODY><tr><td> </td><td> CIE L*值 </td><td> CIE a*值 </td><td> CIE b*值 </td></tr><tr><td> 聚酯PET<sub>E</sub></td><td> 70.8 </td><td> 0.9 </td><td> 1.5 </td></tr><tr><td> 聚酯PET<sub>C1</sub></td><td> 71.0 </td><td> -1.2 </td><td> 5.6 </td></tr><tr><td> 聚酯PET<sub>C2</sub></td><td> 70.4 </td><td> -0.9 </td><td> 6.3 </td></tr><tr><td> 聚酯PET<sub>C3</sub></td><td> 62.9 </td><td> -0.2 </td><td> 14.2 </td></tr><tr><td> 聚酯PET<sub>C4</sub></td><td> 59.6 </td><td> -1.6 </td><td> 2.7 </td></tr><tr><td> 聚酯PET<sub>C5</sub></td><td> 68.8 </td><td> -1.6 </td><td> 5.2 </td></tr><tr><td> 聚酯PET<sub>C6</sub></td><td> 66.6 </td><td> -0.1 </td><td> 3.8 </td></tr></TBODY></TABLE>The PET PET E and the PET C1 ~ PET C6 0.1 g of the above examples and Comparative Examples 1 to 6 were respectively dissolved in a mixed solvent of 25 mL of phenol/tetrachloroethane (3:2 by weight) at 30 ° C. The intrinsic viscosity (IV, [η]) was measured by a Ubbelohde viscometer, and all IV values were greater than 0.56 dL/g. [Table 2] <TABLE border="1"borderColor="#000000"width="_0010"><TBODY><tr><td></td><td> CIE L* value</td><td> CIE a* value</td><td> CIE b* value</td></tr><tr><td> polyester PET<sub>E</sub></td><td> 70.8 </ Td><td> 0.9 </td><td> 1.5 </td></tr><tr><td> polyester PET<sub>C1</sub></td><td> 71.0 </td ><td> -1.2 </td><td> 5.6 </td></tr><tr><td> Polyester PET<sub>C2</sub></td><td> 70.4 </td ><td> -0.9 </td><td> 6.3 </td></tr><tr><td> Polyester PET<sub>C3</sub></td><td> 62.9 </td ><td> -0.2 </td><td> 14.2 </td></tr><tr><td> Polyester PET<sub>C4</sub></td><td> 59.6 </td ><td> -1.6 </td><td> 2.7 </td></tr><tr><td> Polyester PET<sub>C5</sub></td><td> 68.8 </td ><td> -1.6 </td><td> 5.2 </td></tr><tr><td> Polyester PET<sub>C6</sub></td><td> 66.6 </td ><td> -0.1 </td><td> 3.8 </td></tr></TBODY></TABLE>
對於聚酯產品而言,對聚酯產物的色相要求為CIE L*值儘可能大,且CIE b*值儘可能接近0(較佳為不大於2)。由表2可以明顯看出,比較例1~6之聚酯PET C1~PET C6的CIE b*值皆為2.7以上,而實施例之聚酯PET E的CIE L*值足夠大且CIE b*值較接近0,顯示其明度足夠高且較偏白色,故色相較佳。 For polyester products, the hue requirement for the polyester product is such that the CIE L* value is as large as possible and the CIE b* value is as close as possible to zero (preferably no greater than 2). As is apparent from Table 2, the CIE b* values of the polyester PET C1 ~ PET C6 of Comparative Examples 1 to 6 were all 2.7 or more, and the CIE L* value of the polyester PET E of the example was sufficiently large and CIE b* The value is closer to 0, indicating that the brightness is sufficiently high and whiter, so the hue is better.
綜上所述,本發明觸媒的製法及所製得的觸媒,使用於製備聚酯的縮聚反應時可有效改善銻(III)化合物導致聚酯的色相不佳的問題,故確實能達成本發明之目的。In summary, the method for preparing the catalyst of the present invention and the prepared catalyst are used for the polycondensation reaction of preparing a polyester to effectively improve the problem that the ruthenium (III) compound causes a poor hue of the polyester, so that it can be achieved. The object of the invention.
惟以上所述者,僅為本發明之實施例而已,當不能以此限定本發明實施之範圍,凡是依本發明申請專利範圍及專利說明書內容所作之簡單的等效變化與修飾,皆仍屬本發明專利涵蓋之範圍內。However, the above is only the embodiment of the present invention, and the scope of the invention is not limited thereto, and all the equivalent equivalent changes and modifications according to the scope of the patent application and the patent specification of the present invention are still The scope of the invention is covered.
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