CN102875786A - Synthetic method and application for polydentate ligand chelating titanium catalyst used for polyester preparation - Google Patents
Synthetic method and application for polydentate ligand chelating titanium catalyst used for polyester preparation Download PDFInfo
- Publication number
- CN102875786A CN102875786A CN2011101943004A CN201110194300A CN102875786A CN 102875786 A CN102875786 A CN 102875786A CN 2011101943004 A CN2011101943004 A CN 2011101943004A CN 201110194300 A CN201110194300 A CN 201110194300A CN 102875786 A CN102875786 A CN 102875786A
- Authority
- CN
- China
- Prior art keywords
- titanium
- polydentate ligand
- methyne
- add
- series catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention relates to a synthetic method and an application for a polydentate ligand chelating titanium catalyst used for polyester preparation. The polydentate ligand chelating titanium catalyst is obtained by reacting a polydentate ligand and equimolar titanium halide or titanium alkoxide in a tetrahydrofuran solution under the protection of nitrogen. The catalyst is added into to-be-polycondensated dihydric acid, dihydric alcohol or oligoester in a body manner for catalyzing polycondensation reaction to obtain high molecular weight polyester or copolyester. The catalyst has the advantages of convenient preparation, high catalytic activity, good heat stability, etc.
Description
Technical field
The present invention relates to a kind of polydentate ligand chelating Titanium series catalyst, particularly synthetic method and the application of a kind of polyester polydentate ligand chelating for subsequent use Titanium series catalyst.
Background technology
Polyethylene terephthalate (be called for short PET) was invented in nineteen forty-four, took the lead in realizing suitability for industrialized production in Britain in 1949, because it has good taking and the performance such as high strength, became the kind of output maximum in the man-made fiber.
China mainly comes from the synthon part to the demand of polyester product, and these synthon are most of to be used in the middle of the textile production.China is maximum in the world synthon producing country and country of consumption, and the output of synthon and consumption account for respectively 1/4th and 1/3rd of global total amount.Along with the development of new technology of preparing and the exploitation of functional polyester, the purposes of PET no longer mainly is confined to fiber, the fields such as all kinds of containers, wrapping material, film, film, engineering plastics have been extended to, at present, PET is replacing aluminium, glass, pottery, paper, timber, iron and steel and other synthetic materialss more and more, and the family of polyester is also continuing expansion.
Antimony-based catalyst is the catalyzer that polyester industrial generally adopts, and antimony-based catalyst can promote polycondensation greatly, and less to the promotion degree of thermal degradation reaction, the antimony glycol that principal item has antimonous oxide, antimony acetate and is subject in recent years extensive concern.Sb
2O
3And Sb (Ac)
3Active moderate, side reaction is few, to the thermal destruction efficiency ratio Ge of PET
4+, Ti
4+And Sn
4+All low.Sb
2O
3Main polycondensation catalyst as poly terephthalic acid dimethyl ester (DMT) route and early stage PTA route, general and stablizer H
3PO
4Or its ester share.Sb (Ac)
3As the single polycondensation catalyst of PTA route, at room temperature can with EG with its wiring solution-forming, then be directly used in the preparation of PTA slurry.Antimony glycol also begins to obtain the concern of production of polyester enterprise as the upgraded product of traditional antimony-based catalyst.Separate out owing to have metallic antimony in the polycondensation process, therefore have the polyester product blackout or the problem such as foreign matter is arranged, and antimony is harmful to HUMAN HEALTH, exists the problem of contaminate environment, has been subject in the use certain restriction.For example, Japan has forbidden that antimony containing compounds is used for producing with the PET of Food Contact, and Korea S limits then that the antimony massfraction should be below 0.02% among the PET, and European Union stipulates that then the antimony content in the environmental protection utmost point PET fiber must not be greater than 260ppm.
Titanium series catalyst is compared with antimony system, and nontoxic, addition is less, and polycondensation reaction time is short.Titanium series catalyst commonly used is inorganic salt (such as potassium fluotitanate, titanium potassium oxalate(T.P.O.) etc.) and the organic titanate (such as tetrabutyl titanate, isopropyl titanate etc.) of titanium.When tetrabutyl titanate used at the DMT route, catalyst levels was few, and speed of reaction is fast, can Reaction time shorten.But when it is used for the PTA route, because the side reaction that exists in hydrolytic action and the polycondensation process worsens the polyester quality, show the form and aspect yellowing, end carboxyl and glycol ether content increase, melting point depression.In order to improve titanium catalyst to the impact of polyester kind, regulate the structure of catalyzer, the side reaction that control condensation polymerization process exists is crucial.Start with from the structure of design catalyzer, improve the stability of titanium catalyst by introducing polydentate ligand, and obtain high catalytic activity.
Summary of the invention
The objective of the invention is to solve above-mentioned deficiency, the synthetic of a kind of polyester polydentate ligand chelating for subsequent use Titanium series catalyst is provided and used.
Realize that technical scheme of the present invention is: a kind of polyester polydentate ligand chelating for subsequent use Titanium series catalyst, its structural formula is as follows:
In the formula, R is a kind of in chlorine, bromine, methoxyl group, oxyethyl group, isopropoxy, n-butoxy or the phenoxy group; X is a kind of in methylene radical, ethylidene, methyl methyne or the phenyl methyne; Y is a kind of in methylene radical, ethylidene, methyl methyne or the phenyl methyne; Z is a kind of in methylene radical, ethylidene, methyl methyne or the phenyl methyne.
Above-mentioned polydentate ligand chelating Titanium series catalyst, when R is chlorine in the described structural formula, X, Y, Z are identical group, for a kind of in methylene radical, ethylidene, methyl methyne or the phenyl methyne.
Above-mentioned polydentate ligand chelating Titanium series catalyst, when R is n-butoxy in the described structural formula, X, Y, Z are identical group, for a kind of in methylene radical, ethylidene, methyl methyne or the phenyl methyne.
Above-mentioned polydentate ligand chelating Titanium series catalyst, when R is isopropoxy in the described structural formula, X, Y, Z are identical group, for a kind of in methylene radical, ethylidene, methyl methyne or the phenyl methyne.
The synthetic method of a kind of polyester polydentate ligand chelating for subsequent use Titanium series catalyst may further comprise the steps:
(1) under nitrogen environment, add polydentate ligand and anhydrous tetrahydro furan in the reactor of drying, stirring at room 10min is uniformly dispersed part, wherein, the ratio of polydentate ligand mole number and anhydrous tetrahydro furan volume number is 4: (10-20), obtain polydentate ligand solution;
(2) at another dry container, add respectively anhydrous tetrahydro furan, titanium halide or alkyl titanium oxide with the mole number such as polydentate ligand in the step (1), wherein titanium halide or alkyl titanium oxide mole number and the anhydrous tetrahydro furan volume ratio of counting are 2: (5-20), stirring makes dissolution of solid, leave standstill 25-30min, obtain compound titanium solution;
(3) the polydentate ligand solution that step (1) is obtained slowly adds in the compound titanium solution of step (2), stirring reaction 3-12h, and solvent removed in vacuo obtains white solid;
(4) in the white solid of step (3), add anhydrous tetrahydro furan dissolving and stirring 10-30min, after the vacuum filtration, filtrate is concentrated, add hexanaphthene, wherein the volume ratio of anhydrous tetrahydro furan and hexanaphthene is (5-20): (10-40), separate out white powder, obtain the Titanium series catalyst of polydentate ligand chelating.
Above-mentioned polydentate ligand is the polyhydroxy amine compounds.
Above-mentioned titanium halide is titanium tetrachloride, and alkyl titanium oxide is tetraisopropoxy titanium or four titanium n-butoxide.
The application of a kind of polyester polydentate ligand chelating for subsequent use Titanium series catalyst, polyester polydentate ligand chelating for subsequent use Titanium series catalyst joins its condensation polymerization reaction acquisition polyester or copolyesters of catalysis in diprotic acid, dibasic alcohol or the oligomer ester for the treatment of polycondensation in the mode of body.
The application of above-mentioned polydentate ligand chelating Titanium series catalyst, polyester polydentate ligand chelating for subsequent use Titanium series catalyst add total amount and count 10-200ppm with the diprotic acid for the treatment of polycondensation, more preferably 30-120ppm.
The application of above-mentioned polydentate ligand chelating Titanium series catalyst, polyester polydentate ligand chelating for subsequent use Titanium series catalyst can cooperate a kind of use in phosphoric acid, phosphorous acid, phosphoric acid ester and the phosphorous acid ester, phosphorus compound can add before esterification or after the esterification, namely add in oligomer ester, wherein the content of phosphorus compound is counted 1-150ppm with diprotic acid.
The present invention has positive effect: (1) preparation method is simple, convenient; (2) catalyst is active high; (3) catalyzer Heat stability is good.
Embodiment
(embodiment 1)
Under nitrogen atmosphere, in the reactor of drying, add the trolamine of 1.49g and the anhydrous tetrahydro furan of 40ml, stirring at room 10min is uniformly dispersed part, in another dry flask, add 1.89g titanium tetrachloride and 20ml anhydrous tetrahydro furan, stirring makes and is uniformly dispersed, then in 30min, slowly add triethanolamine solution obtained above in the compound titanium solution, stirring reaction 5h, solvent removed in vacuo, get white solid and add the dissolving of 20ml anhydrous tetrahydro furan and stir 10min, after the vacuum filtration, that filtrate is concentrated, add the 40ml hexanaphthene, separate out white powder and be designated as titanium catalyst A.
(embodiment 2)
Under nitrogen atmosphere, in the reactor of drying, add the trolamine of 1.49g and the anhydrous tetrahydro furan of 40ml, stirring at room 10min is uniformly dispersed part, in another dry flask, add 3.40g tetra-n-butyl titanate and 20ml anhydrous tetrahydro furan, stirring makes and is uniformly dispersed, then in 30min, slowly add triethanolamine solution obtained above in the compound titanium solution, stirring reaction 4h, solvent removed in vacuo gets white solid and adds the dissolving of 30ml anhydrous tetrahydro furan and stir 20min, after the vacuum filtration, filtrate is concentrated, add the 40ml hexanaphthene, separate out white powder, be designated as titanium catalyst B.
(embodiment 3)
Under nitrogen atmosphere, in the reactor of drying, add the trolamine of 1.49g and the anhydrous tetrahydro furan of 40ml, stirring at room 10min is uniformly dispersed part, in another dry flask, add 2.84g titanium isopropylate and 30ml anhydrous tetrahydro furan, stirring makes and is uniformly dispersed, then in 25min, slowly add triethanolamine solution obtained above in the compound titanium solution, stirring reaction 10h, solvent removed in vacuo gets white solid and adds the dissolving of 40ml anhydrous tetrahydro furan and stir 20min, after the vacuum filtration, filtrate is concentrated, add the 20ml hexanaphthene, separate out white powder, be designated as titanium catalyst C.
(embodiment 4)
Under nitrogen atmosphere, in the reactor of drying, add the tri-isopropanolamine of 1.91g and the anhydrous tetrahydro furan of 20ml, stirring at room 10min is uniformly dispersed part, in another dry flask, add 3.40g tetra-n-butyl titanate and 20ml anhydrous tetrahydro furan, stirring makes and is uniformly dispersed, then in 30min, slowly add tri-isopropanolamine solution obtained above in the compound titanium solution, stirring reaction 12h, solvent removed in vacuo gets white solid and adds the dissolving of 20ml anhydrous tetrahydro furan and stir 20min, after the vacuum filtration, filtrate is concentrated, add the 30ml hexanaphthene, separate out white powder, be designated as titanium catalyst D.
(embodiment 5)
Under nitrogen atmosphere, in the reactor of drying, add the tri-isopropanolamine of 1.91g and the anhydrous tetrahydro furan of 30ml, stirring at room 10min is uniformly dispersed part, in another dry flask, add 2.84g titanium isopropylate and 20ml anhydrous tetrahydro furan, stirring makes and is uniformly dispersed, then in 30min, slowly add tri-isopropanolamine solution obtained above in the compound titanium solution, stirring reaction 8h, solvent removed in vacuo gets white solid and adds the dissolving of 10ml anhydrous tetrahydro furan and stir 20min, after the vacuum filtration, filtrate is concentrated, add the 20ml hexanaphthene, separate out white powder, be designated as titanium catalyst E.
(embodiment 6)
Under the nitrogen protection respectively with the 16.6g terephthalic acid; 9.3g ethylene glycol; 10.5mg titanium catalyst A; 2.5mg phosphoric acid adds reactor; carry out esterification at 180-240 ℃; weigh the degree of esterification according to the amount of fractionation water outlet; when the amount that distillates water be theoretical amount more than 95% after; add an amount of stablizer; vacuumize decompression behind the rising system temperature to 275 ℃, keep carrying out condensation polymerization 1h, discharging under the high vacuum condition; the water-cooled pelletizing gets the PET section, and the limiting viscosity of product is 0.62dl/g.
(embodiment 7)
Under the nitrogen protection respectively with the 16.6g terephthalic acid; 9.3g ethylene glycol; 15.5mg titanium catalyst B; 2.5mg phosphoric acid adds reactor; carry out esterification at 180-240 ℃; weigh the degree of esterification according to the amount of fractionation water outlet; when the amount that distillates water be theoretical amount more than 95% after; add an amount of stablizer; vacuumize decompression behind the rising system temperature to 275 ℃, keep carrying out condensation polymerization 1h, discharging under the high vacuum condition; the water-cooled pelletizing gets the PET section, and the limiting viscosity of product is 0.60dl/g.
(embodiment 8)
Under the nitrogen protection respectively with the 16.6g terephthalic acid; 9.3g ethylene glycol; 12.5mg titanium catalyst C; 2.5mg phosphoric acid adds reactor; carry out esterification at 180-240 ℃; weigh the degree of esterification according to the amount of fractionation water outlet; when the amount that distillates water be theoretical amount more than 95% after; add an amount of stablizer; vacuumize decompression behind the rising system temperature to 275 ℃, keep carrying out condensation polymerization 1h, discharging under the high vacuum condition; the water-cooled pelletizing gets the PET section, and the limiting viscosity of product is 0.63dl/g.
(embodiment 9)
Under the nitrogen protection respectively with the 16.6g terephthalic acid; 9.3g ethylene glycol, 11.2mg titanium catalyst D, 2.5mg phosphoric acid adds reactor; carry out esterification at 180-240 ℃; weigh the degree of esterification according to the amount of fractionation water outlet, when the amount that distillates water be theoretical amount more than 95% after, vacuumize decompression behind the rising system temperature to 275 ℃; keep carrying out condensation polymerization 1h under the high vacuum condition; discharging, water-cooled pelletizing get the PET section, and the limiting viscosity of product is 0.61dl/g.
(embodiment 10)
Under the nitrogen protection respectively with the 16.6g terephthalic acid, 9.3g ethylene glycol, 14.1mg titanium catalyst E; add reactor; carry out esterification at 180-240 ℃, weigh the degree of esterification according to the amount of fractionation water outlet, when the amount that distillates water be theoretical amount more than 95% after; add the 2.0mg triphenyl phosphite; vacuumize decompression behind the rising system temperature to 275 ℃, keep carrying out condensation polymerization 1h, discharging under the high vacuum condition; the water-cooled pelletizing gets the PET section, and the limiting viscosity of product is 0.65dl/g.
(embodiment 11)
Under the nitrogen protection respectively with the 16.6g terephthalic acid; 6.6g dodecanedioic acid; 12.0g ethylene glycol; 32.8mg titanium catalyst E; add reactor; carry out esterification at 180-240 ℃; weigh the degree of esterification according to the amount of fractionation water outlet; when the amount that distillates water be theoretical amount more than 95% after, add 0.19mg phosphorous acid, vacuumize decompression behind the rising system temperature to 275 ℃; keep carrying out condensation polymerization 2h under the high vacuum condition; discharging, the water-cooled pelletizing gets copolyester section, and the limiting viscosity of product is 0.60dl/g.
(embodiment 12)
Under the nitrogen protection respectively with the 16.6g terephthalic acid; 9.3g ethylene glycol, the 30mg antimonous oxide, 2.5mg phosphoric acid adds reactor; carry out esterification at 180-240 ℃; weigh the degree of esterification according to the amount of fractionation water outlet, when the amount that distillates water be theoretical amount more than 95% after, vacuumize decompression behind the rising system temperature to 275 ℃; keep carrying out condensation polymerization 1h under the high vacuum condition; discharging, water-cooled pelletizing get the PET section, and the limiting viscosity of product is 0.59dl/g.
Above-described specific embodiment; purpose of the present invention, technical scheme and beneficial effect are further described; institute is understood that; the above only is specific embodiments of the invention; be not limited to the present invention; within the spirit and principles in the present invention all, any modification of making, be equal to replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. polyester polydentate ligand chelating for subsequent use Titanium series catalyst, it is characterized in that: its structural formula is as follows:
In the formula, R is a kind of in chlorine, bromine, methoxyl group, oxyethyl group, isopropoxy, n-butoxy or the phenoxy group; X is a kind of in methylene radical, ethylidene, methyl methyne or the phenyl methyne; Y is a kind of in methylene radical, ethylidene, methyl methyne or the phenyl methyne; Z is a kind of in methylene radical, ethylidene, methyl methyne or the phenyl methyne.
2. polydentate ligand chelating Titanium series catalyst according to claim 1 is characterized in that: when R is chlorine in the structural formula, and X, Y, Z are identical group, for a kind of in methylene radical, ethylidene, methyl methyne or the phenyl methyne.
3. polydentate ligand chelating Titanium series catalyst according to claim 1 is characterized in that: when R is n-butoxy in the structural formula, and X, Y, Z are identical group, for a kind of in methylene radical, ethylidene, methyl methyne or the phenyl methyne.
4. polydentate ligand chelating Titanium series catalyst according to claim 1 is characterized in that: when R is isopropoxy in the structural formula, and X, Y, Z are identical group, for a kind of in methylene radical, ethylidene, methyl methyne or the phenyl methyne.
5. the synthetic method of a polyester polydentate ligand chelating for subsequent use Titanium series catalyst may further comprise the steps:
(1) under nitrogen environment, add polydentate ligand and anhydrous tetrahydro furan in the reactor of drying, stirring at room 10min is uniformly dispersed part, wherein, the ratio of polydentate ligand mole number and anhydrous tetrahydro furan volume number is 4: (10-20), obtain polydentate ligand solution;
(2) at another dry container, add respectively anhydrous tetrahydro furan, titanium halide or alkyl titanium oxide with the mole number such as polydentate ligand in the step (1), wherein titanium halide or alkyl titanium oxide mole number and the anhydrous tetrahydro furan volume ratio of counting are 2: (5-20), stirring makes dissolution of solid, leave standstill 25-30min, obtain compound titanium solution;
(3) the polydentate ligand solution that step (1) is obtained slowly adds in the compound titanium solution of step (2), stirring reaction 3-12h, and solvent removed in vacuo obtains white solid;
(4) in the white solid of step (3), add anhydrous tetrahydro furan dissolving and stirring 10-30min, after the vacuum filtration, filtrate is concentrated, add hexanaphthene, wherein the volume ratio of anhydrous tetrahydro furan and hexanaphthene is (5-20): (10-40), separate out white powder, obtain the Titanium series catalyst of polydentate ligand chelating.
6. polydentate ligand according to claim 5 is the polyhydroxy amine compounds.
7. titanium halide according to claim 5 is titanium tetrachloride, and alkyl titanium oxide is tetraisopropoxy titanium or four titanium n-butoxide.
8. the application of a polyester polydentate ligand chelating for subsequent use Titanium series catalyst is characterized in that: the mode with body joins its condensation polymerization reaction acquisition polyester or copolyesters of catalysis in diprotic acid, dibasic alcohol or the oligomer ester for the treatment of polycondensation.
9. the application of polydentate ligand chelating Titanium series catalyst according to claim 8 is characterized in that: add total amount and count 10-200ppm with the diprotic acid for the treatment of polycondensation, more preferably 30-120ppm.
10. the application of polydentate ligand chelating Titanium series catalyst according to claim 8, it is characterized in that: can cooperate a kind of use in phosphoric acid, phosphorous acid, phosphoric acid ester and the phosphorous acid ester, phosphorus compound can add before esterification or after the esterification, namely add in oligomer ester, wherein the content of phosphorus compound is counted 1-150ppm with diprotic acid.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN2011101943004A CN102875786A (en) | 2011-07-12 | 2011-07-12 | Synthetic method and application for polydentate ligand chelating titanium catalyst used for polyester preparation |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN2011101943004A CN102875786A (en) | 2011-07-12 | 2011-07-12 | Synthetic method and application for polydentate ligand chelating titanium catalyst used for polyester preparation |
Publications (1)
Publication Number | Publication Date |
---|---|
CN102875786A true CN102875786A (en) | 2013-01-16 |
Family
ID=47477327
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN2011101943004A Pending CN102875786A (en) | 2011-07-12 | 2011-07-12 | Synthetic method and application for polydentate ligand chelating titanium catalyst used for polyester preparation |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN102875786A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108641069A (en) * | 2018-04-09 | 2018-10-12 | 福建锦兴环保科技有限公司 | A kind of polyester Titanium series catalyst and its preparation process |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1402653A (en) * | 1999-12-02 | 2003-03-12 | 纳幕尔杜邦公司 | Esterification catalyst compositions and use thereof |
CN1703440A (en) * | 2002-10-03 | 2005-11-30 | 东丽株式会社 | Polyester resin compositions, catalyst for polyester production, polyester film, and magnetic recording medium |
CN101981083A (en) * | 2008-03-28 | 2011-02-23 | 伊科聚合物股份有限公司 | A new titanium-based catalyst showing excellent activity and selectivity in polycondensation reactions |
-
2011
- 2011-07-12 CN CN2011101943004A patent/CN102875786A/en active Pending
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1402653A (en) * | 1999-12-02 | 2003-03-12 | 纳幕尔杜邦公司 | Esterification catalyst compositions and use thereof |
CN1703440A (en) * | 2002-10-03 | 2005-11-30 | 东丽株式会社 | Polyester resin compositions, catalyst for polyester production, polyester film, and magnetic recording medium |
CN101981083A (en) * | 2008-03-28 | 2011-02-23 | 伊科聚合物股份有限公司 | A new titanium-based catalyst showing excellent activity and selectivity in polycondensation reactions |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108641069A (en) * | 2018-04-09 | 2018-10-12 | 福建锦兴环保科技有限公司 | A kind of polyester Titanium series catalyst and its preparation process |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US6316584B1 (en) | Method for producing polyesters and copolyesters | |
CN106800643B (en) | A kind of preparation method of high-fire resistance isobide type atactic polyester | |
CN110054765B (en) | Preparation method and application of silicon-titanium composite homogeneous catalyst for polyester synthesis | |
CN109180916B (en) | Continuous preparation method of PTT polyester | |
CZ288250B6 (en) | Process for preparing polyesters and copolyesters | |
CN1720216A (en) | Catalyst and process | |
CN1074429C (en) | Thermoplastic polyester continuous production process | |
CN103709383A (en) | Titanium-based polyester catalyst as well as preparation method and application thereof | |
CN104558574A (en) | Titanium polyester catalyst | |
CN106243331A (en) | A kind of preparation method of poly-furandicarboxylic acid glycol ester | |
CN102617842A (en) | Antimony/ titanium composite catalyst and application thereof in method for preparing polyethylene glycol terephthalate (PET) copolyesters | |
CN113388100A (en) | Catalyst system for synthesis of aliphatic-aromatic copolyester and application thereof | |
CN109400856B (en) | Method for catalytically synthesizing polytrimethylene terephthalate with high intrinsic viscosity and good hue by adopting metal composite catalyst | |
JP4134710B2 (en) | Titanium catalyst solution for producing polyester and method for producing polyester using the same | |
KR101386223B1 (en) | Catalyst composition for preparing polyesters, and method for preparing polyesters using the same | |
JP5455570B2 (en) | Titanium-containing mixture and its application to polyesterification reaction | |
CN102875786A (en) | Synthetic method and application for polydentate ligand chelating titanium catalyst used for polyester preparation | |
KR101385721B1 (en) | Complex metal oxide, and method for preparing polyesters using the same | |
CN109666131B (en) | Preparation method of polybutylene terephthalate resin | |
CN114075330B (en) | Aluminum polyester catalyst and preparation method and application thereof | |
CN1210326C (en) | Prepn of copolyester containing glycol naphthalendicarboxylate | |
KR101721770B1 (en) | Eco-friendly thermoplastic polyester resin composition having good color and reheating rroperty | |
CN104558554A (en) | Preparation method of polyester resin | |
US3758535A (en) | Process of reacting a silicon compound with a titanium compound | |
KR20110077820A (en) | Catalyst compound for moulded container by using titanium catalyst compound and thermoplastic homopolyester and copolyester resin by using the same |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20130116 |