CN1250608C - Titanium composite catalyst for polyester and copolyester synthesis - Google Patents
Titanium composite catalyst for polyester and copolyester synthesis Download PDFInfo
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- CN1250608C CN1250608C CN 03129983 CN03129983A CN1250608C CN 1250608 C CN1250608 C CN 1250608C CN 03129983 CN03129983 CN 03129983 CN 03129983 A CN03129983 A CN 03129983A CN 1250608 C CN1250608 C CN 1250608C
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Abstract
The present invention relates to a titanium series composite catalyst for the synthesis of polyester and copolyester, particularly to a titanium series composite catalyst which can be used as a polycondensation reaction catalyst in the synthesis process of polyester and copolyester. The catalyst is prepared by the simultaneous alkaline hydrolysis and precipitation of a titanium compound, the compound of one kind of element selected from the IVA family, and the compound of one to three kinds of elements selected from the families of IA, IIA, IIIA, IIIB, VIIB and VIII, wherein the titanium compound is isopropyl titanate, tetrabutyl titanate, etc. The composite catalyst has very high activity. The preferable use amount of a raw material of ester or low polyester of the catalyst on the basis of polycondensation reaction is from 15 to 40 ppm, and the b value of a made polyester slice is from 2 to 4. The polycondensation catalyst is used for synthesizing polyester, copolyester, polyurethane and polyether ester. The synthetic polyester can be used for producing fiber, a thin film, a polyester bottle, a plate material, a profiled material, and particularly the fiber and the thin film.
Description
Technical field
The present invention relates to a kind of preparation method who can be used in polyester and the copolyesters building-up process as the titanium series composite catalyst of polycondensation catalyst.
Background technology
Polyester is polyethylene terephthalate (PET) particularly, and owing to there being multiple premium properties to be widely used, especially trevira is the maximum kind of synthon, is dominating man-made fiber market always.Several years ago because in great demand, each macrocyclic polyester factory enhances production capacities one after another, causes whole world PET production capacity surplus, and product price drops, Market competition.In order to improve the market competitiveness, polyester company removes and constantly adjusts the product mix, and develops outside the non-polyester, seeks to reduce the effective way of polyester cost one after another.At present, the effective ways that can effectively reduce the production of polyester cost have two: the one, by improving PET single line throughput, continue to expand the scale of production; The 2nd, by optimizing technology, methods such as development effective catalyst improve quality and output that original device is produced PET.The simple single line throughput that improves can be brought certain negative impact, and therefore, each major company all lays stress on by the development raw catalyst improves the product production of original device and qualitatively.
Behind nineteen forty-seven Britain ICI company invention polyester, it is catalyzer (Sb that production of polyester mainly adopts antimony compounds
2O
3Or Sb (OAc)
3), antimony-based catalyst is compared with other catalyzer, has active higherly, and price is low, to advantages such as the promoter action of side reaction are less, therefore is used widely.The polyester device in the whole world 90% all adopts antimony-based catalyst at present, but antimony-based catalyst has faced new challenge in recent years, and the first, in order to adapt to the keen competition of polyester market, must seek active higher catalyzer; The second, antimony-based catalyst has infringement to human body, simultaneously contaminate environment when the polyster fibre post-treatment.Polyester enterprise in various countries' is all at the non-antimony-based catalyst of active development for this reason.
Acordis company report in 1999, developing trade names is the non-toxic efficient catalyzer of C-94, is a kind of TiO
2/ SiO
2Catalyzer is fit to produce PET, polybutylene terephthalate (PBT) and Poly(Trimethylene Terephthalate) (PTT), and its patent is published in nineteen ninety-five.After this, various countries have delivered a large amount of patents.2000, Toray company delivered patent, has invented ZrO
2/ SiO
2Catalyzer, product form and aspect and spinning property are better; TiO has invented in Toyobo company
2Nanocatalyst, the energy rapid polymerization; Mitsui chemical company adopts titanium chloride to be hydrolyzed to Primary Catalysts, and magnesium compound is a promotor, and the polyester quality that makes is better.Dupont company develops the Tyzor TPT catalyzer of reactions such as titanic acid ester and toxilic acid, and this catalyzer is a liquid, and it is better to make the PET quality; Calendar year 2001 Teijin company adopts titanic acid ester and trimellitic acid anhydride reactant to make catalyzer, with this Catalyst Production PET, and good spinnability, the spinning jet deposition is less; Calendar year 2001 Atofina company delivers patent, with Li
2TiO (C
2O
4) and Li
2(C
2O
4)
2Be catalyzer, polymerization velocity is fast.
Holland Akzo Novel N.V. Corp delivered patent (CN 1124257A) in 1996, had invented TiO
2/ SiO
2Or TiO
2/ ZrO
2Catalyzer, polycondensation reaction time is than Sb
2O
3Shorten, but polycondensation product b value higher (6.5-10.4) was delivered patent (CN 1259969A) again, and had been invented titanium compound and IA in 2000, IIA, VIIA, IB, IIB, IIIB, there is polycondensation product b value also higher (6.95-20.58) equally in the two-component catalyst of the compound of the metallic element of IVB family hydrolysis simultaneously preparation, the problem that color is yellow partially.
The Titanium series catalyst of above-mentioned company exploitation has been kept very high catalytic activity, but the product poor heat stability, the color jaundice shows that the b value is higher, therefore, keeps the highly active while of catalyzer, improves the difficult point of form and aspect for the development Titanium series catalyst.
Summary of the invention
A kind of polyester and copolyesters synthetic titanium series composite catalyst of being used for, it is characterized in that: catalyzer is a multicomponent catalyst, by the compound of titanium compound and a kind of IVA family element and a kind of, two kinds, even three kinds be selected from IA, IIA, IIIA, IB, IIIB, VIIB, the compound of the metallic element of VIII family, under alkaline condition by co-precipitation, or fractional precipitation, or three to five component catalysts that are prepared from of first co-precipitation fractional precipitation method again hydrolysis, wherein titanium compound is a butyl (tetra) titanate, isopropyl titanate, the 3rd, the 4th, the compound of the 5th component metals element is acetate or nitrate; IVA family element is Si, Ge, Sn; Three, the metallic element of the 4th, the 5th component is Li, Na, K, Mg, Ca, Al, La, Ce, Zn, Mn, Co; The mol ratio of titanium Ti and IVA family atoms metal is 20: 1-1: 1; The mol ratio of Ti and other atoms metal is 25: 1-2: 1.
The mol ratio of titanium Ti and IVA family atoms metal is preferably 19: 1-12: 1; The mol ratio of Ti and other atoms metal is for being preferably 25: 1-20: 1.
The compound of elements corresponding is hydrolyzed under alkaline condition, and its scope is hydrolyzed solution pH value 7-12, is best with pH7-9.
The alkali of regulator solution pH value is ammoniacal liquor, NaOH or KOH.
A kind of using method that is used for polyester and copolyesters synthetic titanium series composite catalyst is: multicomponent catalyst adds with body form or ethylene glycol solution form and is used for synthetic the treat ester of polycondensation or the raw material of oligomer ester, or treats in the ester or oligomer ester of polycondensation with body form or the adding of ethylene glycol solution form.
A kind of using method that is used for polyester and copolyesters synthetic titanium series composite catalyst is: based on the synthetic ester of polycondensation or the raw material dimethyl terephthalate (DMT) DMT or the terephthalic acid PTA meter of oligomer ester treated, the total add-on of catalyzer is 10-60ppm, with 15-40ppm the best.
A kind of using method that is used for polyester and copolyesters synthetic titanium series composite catalyst is: in reaction system, add phosphorus compound as thermo-stabilizer, consumption is that phosphorus content is 5-100ppm in the stablizer, in raw material DMT or PTA.
A kind of using method that is used for polyester and copolyesters synthetic titanium series composite catalyst is: the phosphorus compound as thermo-stabilizer is trimethyl phosphite 99 TMP, triethyl phosphate TEP, triphenylphosphate TPP, tributyl phosphate TBP, phosphoric acid or phosphorous acid.
The objective of the invention is with on the basis of titanium as the main body catalyzer, introduce silicon and one to three kind of atoms metal as cocatalyst, make the titanium series composite catalyst, on the basis that does not change existing polyester production process condition, kept the high reactivity of catalyzer to polyester polycondensation reaction, suppress side reaction simultaneously, synthetic PET product form and aspect improve, the b value that shows product reduces, and the L value improves, and the thermostability of product is also fine.At the same time, catalyst levels has also reduced significantly, treats that in production the ester of polycondensation or the raw material dimethyl terephthalate (DMT) (DMT) or the PTA of oligomer ester are 10-60ppm only, is preferably 15-40ppm.
Specific embodiment
Among the present invention one uses the method introducing of hydrolysis under alkaline condition with the form of acetate or nitrate to three kinds of atoms metals.Catalyzer can have multiple preparation method.Method one: coprecipitation method.The alcoholic solution that at first prepares the ethanol of the acetate of metal or nitrate, titanium compound and silicon compound or ethylene glycol etc. by proportioning, next dropping pH value in above-mentioned solution is that the alcohol solution of 7-10 is hydrolyzed, precipitation appears in dropping time 15-60min, continues to stir 0.5-1hr again; Method two: step-by-step precipitation method.The first step: the alcoholic solution that at first prepares the ethanol of the acetate of metal or nitrate or ethylene glycol etc. by proportioning, next dropping pH value in above-mentioned solution is that the alcohol solution of 7-10 is hydrolyzed, precipitation appears in dropping time 15-60min, continues to stir 0.5-1hr again.Second step: in the mixed solution that the first step makes, drip the alcoholic solution of titanium compound and silicon compound, drip time 15-60min, continue to stir 0.5-1hr afterwards again; Method three: first part co-precipitation, step-by-step precipitation method again.The alcoholic solution that at first prepares the ethanol of the acetate of metal or nitrate and part titanium compound, silicon compound or ethylene glycol etc., the alcohol solution that drips pH value and be 7-10 in above-mentioned solution is hydrolyzed, and the pH of alcohol solution is with NaOH or KOH or NH
3H
2O regulates, and drips time 15-60min, makes precipitation, after continuing to stir 0.5-1hr, inwardly drips the alcoholic solution of remaining titanium compound and silicon compound again, drips time 15-60min, continues to stir 0.5-1hr afterwards again.
By above-mentioned three kinds of products that method makes,, obtain polycondensation catalyst through separation, vacuum-drying, pulverizing.
The catalyzer that makes joins in the raw material of producing the ester for the treatment of polycondensation or oligomer ester in the mode of body or ethylene glycol solution, also can join in the ester or oligomer ester for the treatment of polycondensation.The catalyzer total amount that adds treats that with production the ester of polycondensation or the raw material DMT or the PTA of oligomer ester count 10-60ppm, and optimum amount is 15-40ppm.
The catalyzer that makes can use separately.In the phosphorus compounds such as adding TMP, TEP, TPP, TBP, phosphoric acid and phosphorous acid any can further improve the thermostability and the form and aspect of product as stablizer.Stablizer can join in the raw material of producing the ester treat polycondensation or oligomer ester, also can add in the ester or oligomer ester for the treatment of polycondensation, and wherein phosphorus content is 5-100ppm in the stablizer, in raw material DMT or PTA.
The catalyzer that makes can be used for producing polyester, copolyesters, urethane, polyether ester, and the polyester that makes can be used for producd fibers, film, polyester bottles, sheet material, section bar.In particular for the production polyester bottles, the transparency is high, does not have " misty grey ".
Among the embodiment capability and performance of PET product is analyzed, analytical procedure adopts GB/T14190-93.
Limiting viscosity: with the automatic viscosity determinator test of the Nanjing NCY-2 of Ai Dier Science and Technology Ltd.
Fusing point test: French SETARAM DSC141 differential scanning instrument test
End carboxyl test: test with chemical titration
Colourity test: with the full-automatic colour examining colour-difference-metre test of the TC-PIIG of Beijing Optical Instrument Factory
Glycol ether test: test with Tianjin, island GC-TAG hydrogen flame gas-chromatography
Molecular weight distribution: test with the U.S.'s 150C of Waters company gel chromatography
Embodiment 1
Coprecipitation method prepares catalyzer Ti/Si//Mg/Mn/Co
The four water acetic acid magnesium of 0.30g (1.5mmol), the four water acetic acid manganese of 0.37g (1.5mmol), the cobalt nitrate hexahydrate of 1.3g (4.47mmol), the isopropyl titanate of 11.37g (40mmol), the tetraethoxy of 0.52g (2.5mmol) are dissolved in the 200ml ethanol, make solution A; 0.66gNaOH is dissolved in the 18g water, adds 50ml ethanol and make solution B.Under laboratory temperature, solution B is added drop-wise in the solution A, drips time 40min, make precipitation, continue to stir 1hr afterwards.With precipitate and separate, washing vacuum-drying 20 hours, pulverizing, obtain the pulverulent polycondensation catalyzer.
Embodiment 2
Step-by-step precipitation method prepares catalyzer Ti/Si//Mg/Mn/Co
The first step: the four water acetic acid magnesium of 0.30g (1.5mol), the four water acetic acid manganese of 0.37g (1.5mmol), the cobalt nitrate hexahydrate of 1.3g (4.47mmol) are dissolved in the 150ml ethanol, make solution A, 0.66gNaOH is dissolved in the 18g water, adds 50ml ethanol and make solution B.Under laboratory temperature, solution B is added drop-wise in the solution A, drips time 30min, make precipitation, continue to stir 15min.Second step: the isopropyl titanate of 11.37g (40mmol), the tetraethoxy of 0.52g (2.5mmol) are dissolved in the 50ml ethanol, make solution C, under laboratory temperature, solution C is added drop-wise in the mixture that the first step makes, drips time 30min, continue to stir 1hr afterwards again.With precipitate and separate, drying, pulverizing, obtain the pulverulent polycondensation catalyzer.
Embodiment 3
Elder generation's part co-precipitation, step-by-step precipitation method prepares catalyzer Ti/Si//Mg/Mn/Co again
The first step: the four water acetic acid magnesium of 0.30g (1.5mmol), the four water acetic acid manganese of 0.37g (1.5mmol), the cobalt nitrate hexahydrate of 1.3g (4.47mmol) are dissolved in the 150ml ethanol, the isopropyl titanate, the 0.26g 1.25mmol that add 5.69g (20mmol) again) tetraethoxy, make solution A; 0.66gNaOH is dissolved in the 18g water, adds 50ml ethanol and make solution B.Under laboratory temperature solution B is added drop-wise in the solution A, the dropping time is 20min, makes precipitation, continues to stir 0.5hr afterwards again.Second step: the isopropyl titanate of remaining 5.69g (20mmol), the tetraethoxy of 0.26g (1.25mmol) are dissolved in the 50ml ethanol, make solution C, under laboratory temperature, solution C is added drop-wise in the mixture that the first step makes, the dropping time is 25min, continues to stir 1hr afterwards again.With precipitate and separate, washing, drying, pulverizing, obtain the pulverulent polycondensation catalyzer.
Embodiment 4-9 has provided the preparation method of different components catalyst activity component, and 1-3 compares with implementation column, just forms variation has taken place, and the preparation method is basic identical.Employed titanium compound is an isopropyl titanate, silicon compound is a tetraethoxy, and the compound of the active atoms metal of adjusting catalyst of the composition of catalyst activity component, introducing, used alkali, the Preparation of catalysts method of adjusting hydrolysising condition are all listed in table 1.
Table 1
| Embodiment | Active ingredient is formed and proportioning | Alkali | The preparation method | |
| Form | Proportioning (mol ratio) | |||
| Embodiment 1 | Ti/Si//Mg/Mn/Co | 80/5/3/3/9 | NaOH | Method 1 |
| Embodiment 2 | Ti/Si//Mg/Mn/Co | 80/5/3/3/9 | NaOH | Method 2 |
| Embodiment 3 | Ti/Si//Mg/Mn/Co | 80/5/3/3/9 | NaOH | Method 3 |
| Embodiment 4 | Ti/Si//Mg/Mn/Co | 85/5/1.25/1.25/9 | NaOH | Method 1 |
| Embodiment 5 | Ti/Si//Mg/Mn/Co | 85/5/1.25/1.25/9 | NaOH | Method 2 |
| Embodiment 6 | Ti/Si//Mg/Mn/Co | 85/5/1.25/1.25/9 | NaOH | Method 3 |
| Embodiment 7 | Ti/Si/Zn/Sn | 95/5/20/5 | NaOH | Method 1 |
| Embodiment 8 | Ti/Si//La/Zn/Sn | 50/10/20/10/10 | NaOH | Method 1 |
| Embodiment 9 | Ti/Si/La/Ce | 60/10/15/15 | NaOH | Method 1 |
Embodiment 10-18 has provided the result that the part catalyzer that makes among the embodiment 1-9 is applied to the DMT route, and comparative example 1 has provided Sb
2O
3The result who obtains.
In embodiment 10-21, DMT and the 405g ethylene glycol of 600g are added reactor, add transesterification catalyst magnesium acetate 0.18g, manganese acetate 0.12g, under 175～215 ℃, carry out transesterification reaction, weigh the degree that transesterification reaction is carried out according to the amount that distillates methyl alcohol, when the amount that distillates methyl alcohol be theoretical amount more than 95% after, add polycondensation catalyst, and add an amount of reaction promoter, (add the amount of catalyzer, auxiliary agent) all in DMT.Go out ethylene glycol at 215～245 ℃, decompression is found time then, carries out polycondensation under high vacuum condition under 275 ℃, treats that the limiting viscosity of polycondensation product reaches about 0.64, gets final product discharging, and feed liquid gets the PET section through water-cooled, pelletizing.Catalyzer and auxiliary agent also can directly join in the starting raw material of reaction.Experimental result is listed in the table 2.
Table 2
| Embodiment | The polycondensation catalyst add-on | TMP/ ppm | Polycondensation time/min | The PET quality | |||||
| Catalyzer | /ppm | η | The B value | The L value | - COOH | Tm.p/℃ | |||
| Embodiment 10 | Embodiment 1 | 20 | 360 | 109 | 0.645 | 2.30 | 60.73 | 7.76 | 254.1 |
| Embodiment 11 | Embodiment 2 | 20 | 360 | 106 | 0.654 | 3.28 | 62.54 | 8.62 | 257.2 |
| Embodiment 12 | Embodiment 3 | 20 | 360 | 103 | 0.660 | 1.55 | 63.23 | 6.98 | 256.3 |
| Embodiment 13 | Embodiment 1 | 30 | 360 | 97 | 0.638 | 2.05 | 64.20 | 8.25 | 255.6 |
| Embodiment 14 | Embodiment 2 | 30 | 360 | 93 | 0.652 | 3.18 | 61.52 | 7.69 | 254.7 |
| Embodiment 15 | Embodiment 3 | 30 | 360 | 92 | 0.658 | 2.97 | 61.28 | 7.92 | 255.9 |
| Embodiment 16 | Embodiment 4 | 20 | 360 | 100 | 0.637 | 3.04 | 61.14 | 8.16 | 252.5 |
| Embodiment 17 | Embodiment 5 | 20 | 360 | 95 | 0.641 | 1.89 | 62.16 | 6.89 | 254.3 |
| Embodiment 18 | Embodiment 6 | 20 | 360 | 88 | 0.644 | 3.24 | 60.50 | 7.24 | 259.2 |
| Embodiment 19 | Embodiment 7 | 30 | 360 | 105 | 0.635 | 3.47 | 61.34 | 7.58 | 258.2 |
| Embodiment 20 | Embodiment 8 | 40 | 360 | 110 | 0.648 | 2.98 | 61.1 | 8.03 | 257.8 |
| Embodiment 21 | Embodiment 9 | 30 | 360 | 106 | 0.657 | 3.45 | 60.8 | 7.32 | 254.6 |
| The comparative example 1 | Sb 2O 3 | 300 | 360 | 113 | 0.649 | 2.86 | 55.8 | 25.09 | 251.7 |
Embodiment 22-27 has provided the situation that the part catalyzer that makes among the embodiment 1-9 is applied to the PTA route.Comparative example 2 has provided Sb
2O
3The result who obtains.
In embodiment 22-27,500gPTA and 2458 ethylene glycol are added reactor, under 230-235 ℃, 0.15-0.25Mpa, carry out esterification, weigh the degree that esterification is carried out according to the amount that distillates water, after esterification finished, reaction system pressure was reduced to normal pressure automatically.Add polycondensation catalyst then, and adopt suitable form to add an amount of reaction promoter (TMP, TiO
2Deng), the add-on of catalyst adjuvant is all in PTA, and decompression is found time then, carries out polycondensation under high vacuum condition under 275 ℃, treats that the limiting viscosity of polycondensation product reaches about 0.64, gets final product discharging, and feed liquid gets the PET section through water-cooled, pelletizing.Catalyzer and auxiliary agent also can directly join in the starting raw material of reaction.Experimental result is listed in the table 3.
Table 3
| Embodiment | Polycondensation catalyst | TM P/pp m | Polycondensation time/min | The PET quality | ||||||
| Catalyzer | Consumption/ppm | Joining day | η | The B value | -COOH | The L value | Tm.p/ ℃ | |||
| Embodiment 22 | Embodiment 1 | 20 | 1 | 36 | 123 | 0.642 | 20 | 60.54 | 8.30 | 254.2 |
| Embodiment 23 | Embodiment 2 | 20 | 1 | 36 | 125 | 0.605 | 25 | 61.14 | 6.62 | 258.3 |
| Embodiment 24 | Embodiment 3 | 20 | 1 | 36 | 109 | 0.636 | 3.55 | 60.23 | 7.98 | 255.7 |
| Embodiment 25 | Embodiment 4 | 20 | 2 | 36 | 118 | 0.643 | 2.45 | 62.04 | 7.96 | 256.8 |
| Embodiment 26 | Embodiment 5 | 20 | 2 | 36 | 114 | 0.642 | 2.18 | 61.75 | 7.29 | 254.7 |
| Embodiment 27 | Embodiment 6 | 20 | 2 | 36 | 109 | 0.638 | 2.67 | 60.28 | 8.15 | 255.6 |
| The comparative example 2 | Embodiment 4 | 300 | 1 | 90 | 116 | 0.647 | 3.04 | 55.81 | 15.6 | 253.8 |
Annotate: the joining day 1: before transesterification reaction, add polycondensation catalyst; Joining day 2: in the ester for the treatment of polycondensation or oligomer ester, add polycondensation catalyst
Claims (10)
1. one kind is used for polyester and copolyesters synthetic titanium series composite catalyst, it is characterized in that: catalyzer is a multicomponent catalyst, by the compound of titanium compound and a kind of IVA family element and a kind of, two kinds, even three kinds be selected from IA, IIA, IIIA, IB, IIIB, VIIB, the compound of the metallic element of VIII family, under alkaline condition by co-precipitation, or fractional precipitation, or three to five component catalysts that are prepared from of first co-precipitation fractional precipitation method again hydrolysis, wherein titanium compound is a butyl (tetra) titanate, isopropyl titanate, the 3rd, the 4th, the compound of the 5th component metals element is acetate or nitrate; IVA family element is Si, Ge, Sn; Three, the metallic element of the 4th, the 5th component is Li, Na, K, Mg, Ca, Al, La, Ce, Zn, Mn, Co; The mol ratio of titanium Ti and IVA family atoms metal is 20: 1-1: 1; The mol ratio of Ti and other atoms metal is 25: 1-2: 1.
2. a kind of polyester and copolyesters synthetic titanium series composite catalyst of being used for according to claim 1, it is characterized in that: the mol ratio of titanium Ti and IVA family atoms metal is 19: 1-12: 1; The mol ratio of Ti and other atoms metal is 25: 1-20: 1.
3. a kind of polyester and copolyesters synthetic titanium series composite catalyst of being used for according to claim 2, it is characterized in that: the compound of elements corresponding is hydrolyzed under alkaline condition, and its scope is hydrolyzed solution pH value 7-12.
4. a kind of polyester and copolyesters synthetic titanium series composite catalyst of being used for according to claim 3, it is characterized in that: the compound of elements corresponding is hydrolyzed under alkaline condition, and its scope is hydrolyzed solution pH value 7-9.
5. according to claim 3 or 4 described a kind of polyester and copolyesters synthetic titanium series composite catalysts of being used for, it is characterized in that: the alkali of regulator solution pH value is ammoniacal liquor, NaOH or KOH.
6. using method that is used for polyester and copolyesters synthetic titanium series composite catalyst, it is characterized in that: multicomponent catalyst adds with body form or ethylene glycol solution form and is used for synthetic the treat ester of polycondensation or the raw material of oligomer ester, or treats in the ester or oligomer ester of polycondensation with body form or the adding of ethylene glycol solution form.
7. a kind of using method that is used for polyester and copolyesters synthetic titanium series composite catalyst according to claim 6, it is characterized in that: based on the synthetic ester of polycondensation or the raw material dimethyl terephthalate (DMT) DMT or the terephthalic acid PTA meter of oligomer ester treated, the total add-on of catalyzer is 10-60ppm.
8. a kind of using method that is used for polyester and copolyesters synthetic titanium series composite catalyst according to claim 7, it is characterized in that: based on the synthetic ester of polycondensation or the raw material dimethyl terephthalate (DMT) DMT or the terephthalic acid PTA meter of oligomer ester treated, the total add-on of catalyzer is 15-40ppm.
9. a kind of using method that is used for polyester and copolyesters synthetic titanium series composite catalyst according to claim 8,, it is characterized in that: in reaction system, add phosphorus compound as thermo-stabilizer, consumption is that phosphorus content is 5-100ppm in the stablizer, in raw material DMT or PTA.
10. a kind of using method that is used for polyester and copolyesters synthetic titanium series composite catalyst according to claim 9 is characterized in that: the phosphorus compound as thermo-stabilizer is trimethyl phosphite 99 TMP, triethyl phosphate TEP, triphenylphosphate TPP, tributyl phosphate TBP, phosphoric acid or phosphorous acid.
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| CN101148500B (en) * | 2006-09-20 | 2010-12-22 | 中国石油化工股份有限公司 | Method for preparing titanium series polyester catalyst |
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| CN1320026C (en) * | 2004-12-29 | 2007-06-06 | 中国石化集团天津石油化工公司 | Preparation of liquid titanium polyester polycondensation catalyst |
| CN100453577C (en) * | 2006-03-23 | 2009-01-21 | 华东理工大学华昌聚合物有限公司 | Process for producing terephthalic unsaturated polyester resin by using terephthalic acid rinsing residue |
| KR100970685B1 (en) * | 2006-06-28 | 2010-07-15 | 사까이가가꾸고오교가부시끼가이샤 | Polycondensation catalyst for producing polyester and method for producing polyester using the same |
| CN101250258B (en) * | 2008-04-03 | 2010-12-08 | 马世金 | Method for producing bio-degradable copolyester by employing composite catalyst |
| CN102702497B (en) * | 2012-06-07 | 2014-03-05 | 昆山天洋热熔胶有限公司 | Preparation method of polyester catalyst |
| CN103467713B (en) * | 2013-09-04 | 2017-01-25 | 新疆蓝山屯河化工股份有限公司 | Low-carboxylated biodegradable polyester and production method thereof |
| CN105694009A (en) * | 2014-11-25 | 2016-06-22 | 上海凯众材料科技股份有限公司 | Zirconium/cerium-montmorillonite composite catalyst, and preparation method for polyester glycol |
| TWI738470B (en) * | 2019-10-30 | 2021-09-01 | 柏瑞克股份有限公司 | Catalyst for use in esterification reaction and synthesis method thereof |
| CN111286805B (en) * | 2019-12-31 | 2022-07-05 | 浙江东太新材料有限公司 | Method for preparing titanium-based delustering polyester fiber by melt direct spinning and product |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101148500B (en) * | 2006-09-20 | 2010-12-22 | 中国石油化工股份有限公司 | Method for preparing titanium series polyester catalyst |
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