CN101121778A - Method for preparing titanium series catalyst - Google Patents
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- CN101121778A CN101121778A CNA2006100299786A CN200610029978A CN101121778A CN 101121778 A CN101121778 A CN 101121778A CN A2006100299786 A CNA2006100299786 A CN A2006100299786A CN 200610029978 A CN200610029978 A CN 200610029978A CN 101121778 A CN101121778 A CN 101121778A
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Abstract
The invention relates to a titanium catalyst, mainly aiming to solve the problems of the diol compound of the titanium as a catalyst in the former technology, which has the problems of the low solubility in the ethylene glycol and the poor polyester color difference. The invention uses the technical proposal with the reaction between the titanium compound and diol and the reaction between the product of the precious reaction and the IA metal compound in the periodic table of elements to produce the titanium catalyst to solve the problems well; the invention can be used in the industrial production of the polyester.
Description
Technical field
The present invention relates to a kind of preparation method of Titanium series catalyst.
Background technology
Polyethylene terephthalate is a kind of important industrial raw material, can be widely used in materials such as fiber, sheet, film.
The research autopolyester of polyester catalyst had never stopped since coming out, and industrial production and the more polyester catalyst of research mainly are the catalyzer of antimony, germanium and three series of titanium at present, and wherein using most often, antimony-based catalyst (comprises Sb
2O
3, SbAc
3With antimony glycol etc.), 90% polyester is produced by antimony-based catalyst in the world at present.The shortcoming of antimony-based catalyst is: low activity; Heavy metal catalyst pollutes environment; The polymer belt grey.The germanium series catalysts has satisfactory stability, and the side reaction that causes in reaction process is less, and made PET hue is good, but because resource is few, costs an arm and a leg.Titanium series catalyst has high reactivity, but the polyester that Titanium series catalyst makes exists poor stability and goods yellowing, muddy problem, thereby is never used on a large scale.
More and more pay close attention in the whole world under the background of environment for human survival, the production and selling of green textiles will be the trend of following textiles development, can the developed country that with the European Union is representative reach green textile standards more and more as the condition that comes into the market, development through 10 years, European Union's eco-label (Eco-label) is approved by the human consumer of European Union gradually, the pouplarity of sticking on the Ecolabelling commodity also improves gradually, many downstream manufacturers, especially sportwear manufacturer is very interested in not stibiated polyester, and it is not stibiated that this trend makes that production of polyester producer is devoted to exploitation, eco-friendly catalyzer.
Titanium series catalyst is because it is active high, do not contain heavy metal, thereby be subjected to the favor of numerous polyester producers, Titanium series catalyst also is the research focus of polyester catalyst in recent years, company more than ten American-European and Japan has carried out the development of titanium series polyester catalyst, the domestic research work that also has many companies and research institution to carry out this respect of China.Along with the development of molecular designing and catalyst preparation technology, people expectation is carried out modification on traditional titanate catalyst basis, develop environmental protection, highly active and can overcome the Novel Titanium series catalysts of traditional in the past titanium series polyester catalyst shortcoming.Existing many at present companies announce to have succeeded in developing the Novel Titanium series polyester catalyst of excellent property, and commercially produced product can be provided.This Sustainable development to polyester industrial will bring great promoter action.
CN1328072 and CN1327985 disclose with titanic acid ester and glycol reaction and have generated a kind of diatomic alcohol compounds of granular titanium as polyester catalyst, this pellet type catalyst might bring some application problems in the industrial production of polyester, and reports the form and aspect of the polyester that this catalyzer of employing makes in the patent.
Summary of the invention
Technical problem to be solved by this invention is the bad problem of diatomic alcohol compounds class Titanium series catalyst solvability in ethylene glycol PET hue bad, that make of the titanium that exists in the prior art, and a kind of preparation method of new Titanium series catalyst is provided.The catalyzer that this method makes is the homogeneous phase liquid catalyst, can dissolve each other with ethylene glycol, adopts the polyester of this class Catalyst Production to have the good advantage of form and aspect.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of preparation method of Titanium series catalyst may further comprise the steps:
A) titanium compound and dibasic alcohol were reacted 0.01～48 hour under-20～300 ℃ of temperature condition, wherein titanium compound is Ti (OR)
4, R is the alkyl that is selected from 1～10 carbon atom; Diatomic alcohol compounds is to be selected from the dibasic alcohol with 2～10 carbon atoms;
B) reaction product of above-mentioned a) step was reacted 0.01～48 hour under 0～200 ℃ of temperature condition with the metallic compound that is selected among the periodic table of elements IA, got the homogeneous phase liquid condition titanium series catalyst; Wherein the mol ratio of dibasic alcohol and titanium compound is 0.5～100: 1, and the mol ratio of metallic compound and titanium compound is 0.01～10: 1.
In the technique scheme a) in the step temperature of reaction preferable range of titanium compound and dibasic alcohol be 0～200 ℃, the reaction times preferable range is 0.1～20 hour; B) the temperature of reaction preferable range of step is 0～180 ℃, and the reaction times preferable range is 0.05～24 hour.
In the technique scheme, the preferred version of titanium compound is selected from least a in metatitanic acid tetramethyl ester, tetraethyl titanate, metatitanic acid orthocarbonate, titanium isopropylate or the tetrabutyl titanate.The dibasic alcohol preferred version is selected from ethylene glycol, 1,2-propylene glycol, 1,3 propylene glycol, 1,4-butyleneglycol or 1, at least a in the 6-hexylene glycol.The metallic compound preferred version is selected from the periodic table of elements at least a in the lithium among the IA, sodium or the potassium compound.
The mol ratio preferable range of dibasic alcohol and titanium compound is 1～8: 1 in the technique scheme, when the mol ratio of pure and mild titanium compound less than 1 the time, the catalyst tolerates water-based that makes is bad.The mol ratio preferable range of metallic compound and titanium compound is 0.1～5: 1.
In the technique scheme, b) preferred version of raw material is also to comprise phosphorus compound in the raw material in the step reaction.The phosphorus compound preferred version is selected from trimethyl phosphite 99, triethyl phosphate, tricresyl phosphate propyl ester, tricresyl phosphate isopropyl ester, tributyl phosphate or the triphenylphosphate at least a.The mol ratio preferable range of phosphorus compound and titanium compound is＞0～10: 1, and more preferably scope is 0.1～6: 1.The catalyzer preferred version is the homogeneous phase liquid catalyst, can dissolve each other with ethylene glycol.
The preparation method of Titanium series catalyst is as follows among the present invention:
With general formula is Ti (OR)
4Titanium compound and diol reaction, the product that obtains and at least a metallic compound that is selected from IA in the periodic table of elements with or the phosphorus compound reaction obtain the homogeneous phase liquid condition titanium series catalyst.
The preparation method of polyester is as follows:
In the preparation process of polyester of the present invention, raw material uses di-carboxylic acid or its to become ester derivative and dibasic alcohol, and preferred version uses aromatic dicarboxylate or its to become ester derivative and aliphatic dihydroxy alcohol.
Be used for di-carboxylic acid of the present invention and comprise the aromatic dicarboxylate, as terephthalic acid, phthalic acid, m-phthalic acid, naphthalic acid, biphenyl dicarboxylic acid, and alicyclic carboxylic acid such as cyclohexane dicarboxylic acid etc., preferred version is a terephthalic acid.
The example of dibasic alcohol comprises aliphatic dihydroxy alcohol such as ethylene glycol, 1, ammediol, propylene glycol, 1, and 4-butyleneglycol etc., preferred version is an ethylene glycol.
Preparation process of polyester of the present invention, can adopt known preparation process of polyester, the first step is carried out esterification by terephthalic acid or dimethyl terephthalate (DMT) and ethylene glycol, obtains prepolymer, esterification is carried out at 230～270 ℃, and pressure is 0.2～0.3MPa.Second step was carried out polycondensation under high vacuum, 280～310 ℃ of temperature of reaction, and pressure is lower than 130Pa.The adding of catalyzer can join in the reaction system simultaneously with phthalic acid or dimethyl terephthalate (DMT) and ethylene glycol, also can join in the reaction system after phthalic acid or dimethyl terephthalate (DMT) and glycol reaction generate prepolymer.
In the present invention, the limiting viscosity of polyester and form and aspect etc. are tested by the following method:
1) limiting viscosity: the mixed liquid of phenol-tetrachloroethane is made solvent, uses determination of ubbelohde viscometer under 25 ℃ the temperature.
2) form and aspect: the pellet sample is measured with the Gardner automatic colour difference meter after 1 hour 135 ℃ of processing.
The present invention is by adopting earlier by titanium compound and diol reaction, the reaction after product again with the periodic table of elements in IA's or the reaction of reacted product and phosphorus compound after again with the periodic table of elements in the reaction product of metallic compound of IA as the catalyzer of production polyester, the inventor is surprised to find, the polyester that the liquid catalyst that adopts the inventive method to make is used to prepare has good form and aspect, has obtained better technical effect.
The present invention is further elaborated below by embodiment.
Embodiment
[embodiment 1]
The preparation of catalyst A
In the reactor that agitator, condenser and thermometer are housed, add ethylene glycol 12.4 grams (0.2 mole), in reactor, slowly splash into titanium isopropylate 28.4 grams (0.1 mole), separate out white depositions, reacted 2 hours down at 70 ℃, with the product centrifugation, and with distilled water wash residue 3 times, with product 70 ℃ of following vacuum-dryings.Obtain the white powder material.
Dried white powder material is placed the reactor that has agitator, condenser and thermometer, add Lithium Acetate 13.2 grams (0.2 mole), trimethyl phosphite 99 28 grams (0.2 mole) and ethylene glycol 200 grams, reaction 3 hours becomes homogeneous liquid to system under 150 ℃ of temperature of reaction, obtains catalyst A.
The preparation of polyester
Restrain terephthalic acids and 316 gram ethylene glycol and catalyst A (based on the amount of the polyester that generates with 500, the weight of titanium atom is 10ppm), the mixed slurry that is made into, join in the polymeric kettle, carry out esterification, esterification temperature is 230～255 ℃, and pressure is 0.25MPa, discharges the water that reaction generates by rectifier unit.Reduce to normal pressure after esterification finishes, vacuumize and be decompressed to system pressure and be lower than 130Pa, temperature of reaction rises to 280 ℃ gradually simultaneously, when system reaction stopped reaction after reach required viscosity, afterwards reaction product is extruded with bar shaped continuously from the polymeric kettle bottom, cooling, pelletizing are for performance test.
Test result sees Table 1.
[embodiment 2]
In the reactor that agitator, condenser and thermometer are housed, add ethylene glycol 24.8 grams (0.4 mole), in reactor, slowly splash into tetraethyl titanate 22.8 grams (0.1 mole), separate out white depositions, reacted 2 hours down at 70 ℃, with the product centrifugation, and with distilled water wash residue 3 times, with product 70 ℃ of following vacuum-dryings.Obtain the white powder material.
Dried white powder material is placed the reactor that has agitator, condenser and thermometer, add yellow soda ash 2.1 grams (0.02 mole), trimethyl phosphite 99 28 grams (0.2 mole) and ethylene glycol 200 grams, reaction 3 hours becomes homogeneous liquid to system under 150 ℃ of temperature of reaction, obtains catalyst B.
The preparation of polyester
Prepare polyester by similarly to Example 1 method, adopt catalyst B as catalyzer (based on the amount of the polyester that generates, the weight of titanium atom is 10ppm).
Test result sees Table 1.
[embodiment 3]
In the reactor that agitator, condenser and thermometer are housed, add ethylene glycol 36.9 grams (0.6 mole), in reactor, slowly splash into titanium isopropylate 28.4 grams (0.1 mole), separate out white depositions, reacted 2 hours down at 70 ℃, with the product centrifugation, and with distilled water wash residue 3 times, with product 70 ℃ of following vacuum-dryings.Obtain the white powder material.
Dried white powder material is placed the reactor that has agitator, condenser and thermometer, add sodium-acetate 1.64 grams (0.02 mole), trimethyl phosphite 99 14 grams (0.1 mole) and ethylene glycol 200 grams, reaction 3 hours becomes homogeneous liquid to system under 150 ℃ of temperature of reaction, obtains catalyzer C.
The preparation of polyester
Prepare polyester by similarly to Example 1 method, adopt catalyzer C as catalyzer (based on the amount of the polyester that generates, the weight of titanium atom is 10ppm).
Test result sees Table 1.
[embodiment 4]
In the reactor that agitator, condenser and thermometer are housed, add 1,2-propylene glycol 15.2 grams (0.2 mole), in reactor, slowly splash into titanium isopropylate 28.4 grams (0.1 mole), separate out white depositions, reacted 2 hours down at 70 ℃, with the product centrifugation, and with distilled water wash residue 3 times, with product 70 ℃ of following vacuum-dryings.Obtain the white powder material.
Dried white powder material is placed the reactor that has agitator, condenser and thermometer, add Potassium ethanoate 19.6 grams (0.2 mole), triethyl phosphate 72.8 grams (0.4 mole) and ethylene glycol 200 grams, reaction 3 hours becomes homogeneous liquid to system under 150 ℃ of temperature of reaction, obtains catalyzer D.
The preparation of polyester
Prepare polyester by similarly to Example 1 method, adopt catalyzer D as catalyzer (based on the amount of the polyester that generates, the weight of titanium atom is 10ppm).
Test result sees Table 1.
[embodiment 5]
In the reactor that agitator, condenser and thermometer are housed, add ethylene glycol 12.4 grams (0.2 mole), in reactor, slowly splash into tetrabutyl titanate 34 grams (0.1 mole), separate out white depositions, reacted 2 hours down at 70 ℃, with the product centrifugation, and with distilled water wash residue 3 times, with product 70 ℃ of following vacuum-dryings.Obtain the white powder material.
Dried white powder material is placed the reactor that has agitator, condenser and thermometer, add Potassium ethanoate 39.2 grams (0.4 mole), triethyl phosphate 18.2 grams (0.1 mole) and ethylene glycol 200 grams, reaction 3 hours becomes homogeneous liquid to system under 150 ℃ of temperature of reaction, obtains catalyzer E.
The preparation of polyester
Prepare polyester by similarly to Example 1 method, adopt catalyzer E as catalyzer (based on the amount of the polyester that generates, the weight of titanium atom is 10ppm).
Test result sees Table 1.
[embodiment 6]
The preparation of catalyzer F
In the reactor that agitator, condenser and thermometer are housed, add butyleneglycol 18 grams (0.2 mole), in reactor, slowly splash into titanium isopropylate 28.4 grams (0.1 mole), separate out white depositions, reacted 2 hours down at 70 ℃, with the product centrifugation, and with distilled water wash residue 3 times, with product 70 ℃ of following vacuum-dryings.Obtain the white powder material.
Dried white powder material is placed the reactor that has agitator, condenser and thermometer, add Lithium Acetate 13.2 grams (0.2 mole), ethylene glycol 200 grams, reaction 3 hours becomes homogeneous liquid to system under 150 ℃ of temperature of reaction, obtains catalyzer F.
The preparation of polyester
Prepare polyester by similarly to Example 1 method, adopt catalyzer F as catalyzer (based on the amount of the polyester that generates, the weight of titanium atom is 10ppm).
Test result sees Table 1.
[embodiment 7]
The preparation of catalyzer G
In the reactor that agitator, condenser and thermometer are housed, add ethylene glycol 12.4 grams (0.2 mole), in reactor, slowly splash into tetrabutyl titanate 34 grams (0.1 mole), separate out white depositions, reacted 0.3 hour down at 130 ℃, with the product centrifugation, and with distilled water wash residue 3 times, with product 70 ℃ of following vacuum-dryings.Obtain the white powder material.
Dried white powder material is placed the reactor that has agitator, condenser and thermometer, add potassium oxalate 37.2 grams (0.2 mole), trimethyl phosphite 99 28 grams (0.2 mole) and ethylene glycol 200 grams, reaction 0.5 hour becomes homogeneous liquid to system under 180 ℃ of temperature of reaction, obtains catalyzer G.
The preparation of polyester
Prepare polyester by similarly to Example 1 method, adopt catalyzer G as catalyzer (based on the amount of the polyester that generates, the weight of titanium atom is 10ppm).
Test result sees Table 1.
[embodiment 8]
The preparation of catalyzer H
In the reactor that agitator, condenser and thermometer are housed, add ethylene glycol 12.4 grams (0.2 mole), in reactor, slowly splash into tetrabutyl titanate 34 grams (0.1 mole), separate out white depositions, reacted 20 hours down at 20 ℃, with the product centrifugation, and with distilled water wash residue 3 times, with product 70 ℃ of following vacuum-dryings.Obtain the white powder material.
Dried white powder material is placed the reactor that has agitator, condenser and thermometer, add Lithium Acetate 13.2 grams (0.2 mole), tributyl phosphate 53.2 grams (0.2 mole) and ethylene glycol 200 grams, reaction 24 hours becomes homogeneous liquid to system under 25 ℃ of temperature of reaction, obtains catalyzer H.
The preparation of polyester
Prepare polyester by similarly to Example 1 method, adopt catalyzer H as catalyzer (based on the amount of the polyester that generates, the weight of titanium atom is 10ppm).
Test result sees Table 1.
[embodiment 9]
The preparation of catalyst I
In the reactor that agitator, condenser and thermometer are housed, add ethylene glycol 12.4 grams (0.2 mole), in reactor, slowly splash into tetrabutyl titanate 34 grams (0.1 mole), separate out white depositions, reacted 2 hours down at 70 ℃, with the product centrifugation, and with distilled water wash residue 3 times, with product 70 ℃ of following vacuum-dryings.Obtain the white powder material.
Dried white powder material is placed the reactor that has agitator, condenser and thermometer, add Lithium Acetate 13.2 grams (0.2 mole), trimethyl phosphite 99 56 grams (0.4 mole) and ethylene glycol 200 grams, reaction 3 hours becomes homogeneous liquid to system under 150 ℃ of temperature of reaction, obtains catalyst I.
The preparation of polyester
Prepare polyester by similarly to Example 1 method, adopt catalyst I as catalyzer (based on the amount of the polyester that generates, the weight of titanium atom is 10ppm).
Test result sees Table 1.
[embodiment 10]
In the reactor that agitator, condenser and thermometer are housed, add ethylene glycol 24.8 grams (0.4 mole), in reactor, slowly splash into tetraethyl titanate 22.8 grams (0.1 mole), separate out white depositions, reacted 6 hours down at 150 ℃, with the product centrifugation, and with distilled water wash residue 3 times, with product 70 ℃ of following vacuum-dryings.Obtain the white powder material.
Dried white powder material is placed the reactor that has agitator, condenser and thermometer, add yellow soda ash 2.1 grams (0.02 mole), trimethyl phosphite 99 28 grams (0.2 mole) and ethylene glycol 200 grams, reaction 10 hours becomes homogeneous liquid to system under 100 ℃ of temperature of reaction, obtains catalyzer J.
The preparation of polyester
Prepare polyester by similarly to Example 1 method, adopt catalyzer J as catalyzer (based on the amount of the polyester that generates, the weight of titanium atom is 10ppm).
Test result sees Table 1.
[comparative example 1]
Prepare polyester by similarly to Example 1 method, adopt antimony acetate as catalyzer (based on the amount of the polyester that generates, the weight of antimony atoms is 150ppm).
Table 1
| Catalyzer | Catalyst levels (ppm metal) | Esterification time (min) | Polymerization time (min) | Limiting viscosity (dL/g) | L | a | b | |
| Embodiment 1 | Catalyst A | 10 | 90 | 80 | 0.660 | 88.6 | -1.20 | 3.30 |
| Embodiment 2 | Catalyst B | 10 | 90 | 80 | 0.658 | 88.9 | -1.25 | 3.17 |
| Embodiment 3 | Catalyzer C | 10 | 90 | 80 | 0.663 | 89.0 | -1.28 | 3.40 |
| Embodiment 4 | Catalyzer D | 10 | 90 | 80 | 0.655 | 89.3 | -1.26 | 3.08 |
| Embodiment 5 | Catalyzer E | 10 | 90 | 80 | 0.655 | 88.0 | -1.02 | 3.40 |
| Embodiment 6 | Catalyzer F | 10 | 90 | 80 | 0.672 | 88.7 | -1.34 | 4.20 |
| Embodiment 7 | Catalyzer G | 10 | 90 | 80 | 0.662 | 88.2 | -1.23 | 3.31 |
| Embodiment 8 | Catalyzer H | 10 | 90 | 80 | 0.665 | 88.4 | -1.30 | 3.26 |
| Embodiment 9 | Catalyst I | 10 | 90 | 80 | 0.659 | 88.3 | -1.21 | 3.05 |
| Embodiment 10 | Catalyzer J | 10 | 90 | 80 | 0.660 | 89.0 | -1.22 | 3.21 |
| Comparative example 1 | SbAc3 | 150 | 90 | 80 | 0.662 | 87.8 | -1.30 | 3.27 |
Claims (10)
1. the preparation method of a Titanium series catalyst may further comprise the steps:
A) titanium compound and dibasic alcohol were reacted 0.01～48 hour under-20～300 ℃ of temperature condition, wherein titanium compound is Ti (OR)
4, R is the alkyl that is selected from 1～10 carbon atom; Diatomic alcohol compounds is to be selected from the dibasic alcohol with 2～10 carbon atoms;
B) reaction product of above-mentioned a) step was reacted 0.01～48 hour under 0～200 ℃ of temperature condition with the metallic compound that is selected among the periodic table of elements IA, got the homogeneous phase liquid condition titanium series catalyst;
Wherein the mol ratio of dibasic alcohol and titanium compound is 0.5～100: 1, and the mol ratio of metallic compound and titanium compound is 0.01～10: 1.
2. the preparation method of Titanium series catalyst according to claim 1 is characterized in that titanium compound is selected from least a in metatitanic acid tetramethyl ester, tetraethyl titanate, metatitanic acid orthocarbonate, titanium isopropylate or the tetrabutyl titanate.
3. the preparation method of Titanium series catalyst according to claim 1 is characterized in that dibasic alcohol is selected from ethylene glycol, 1,2-propylene glycol, 1,3 propylene glycol, 1,4-butyleneglycol or 1, at least a in the 6-hexylene glycol; The mol ratio of dibasic alcohol and titanium compound is 1～8: 1.
4. the preparation method of Titanium series catalyst according to claim 1, the temperature of reaction that it is characterized in that titanium compound and dibasic alcohol is 0～200 ℃, the reaction times is 0.1～20 hour.
5. the preparation method of Titanium series catalyst according to claim 1 is characterized in that metallic compound is selected from least a in lithium, sodium or the potassium compound among the periodic table of elements IA.
6. the preparation method of Titanium series catalyst according to claim 1 is characterized in that b) temperature of reaction in the step is 0 ℃～180 ℃; Reaction times is 0.05～24 hour.
7. the preparation method of Titanium series catalyst according to claim 1 is characterized in that b) reaction raw materials in the step also comprises phosphorus compound, the mol ratio of phosphorus compound and titanium compound is＞0～10: 1.
8. the preparation method of Titanium series catalyst according to claim 7, the mol ratio that it is characterized in that phosphorus compound and titanium compound is 0.1～6: 1.
9. the preparation method of Titanium series catalyst according to claim 7 is characterized in that phosphorus compound is selected from least a in trimethyl phosphite 99, triethyl phosphate, tricresyl phosphate propyl ester, tricresyl phosphate isopropyl ester, tributyl phosphate or the triphenylphosphate.
10. the preparation method of Titanium series catalyst according to claim 1 is characterized in that catalyzer is the homogeneous phase liquid catalyst, can dissolve each other with ethylene glycol.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102477151A (en) * | 2010-11-25 | 2012-05-30 | 东丽纤维研究所（中国）有限公司 | Catalyst for preparation of polyester, its preparation method, and production method of polyester |
| CN103131000A (en) * | 2011-11-29 | 2013-06-05 | 东丽纤维研究所（中国）有限公司 | Polyester catalyst and preparation method thereof |
| CN103172846A (en) * | 2011-12-23 | 2013-06-26 | 东丽纤维研究所（中国）有限公司 | Process for preparing polyester |
| CN105273176A (en) * | 2014-07-03 | 2016-01-27 | 中国石油化工股份有限公司 | Catalyst used for preparation of polyester, preparation method and application thereof |
| CN106589331A (en) * | 2015-10-19 | 2017-04-26 | 中国石油化工股份有限公司 | Polyester film preparation method |
| CN106589341A (en) * | 2015-10-19 | 2017-04-26 | 中国石油化工股份有限公司 | Preparation method for polytrimethylene terephthalate |
| CN107513154A (en) * | 2017-09-14 | 2017-12-26 | 江苏景宏新材料科技有限公司 | A kind of titanium series polyester catalyst and its method for producing copolyesters |
| CN114479038A (en) * | 2020-10-23 | 2022-05-13 | 中国石油化工股份有限公司 | Titanium catalyst and preparation method and application thereof |
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- 2006-08-11 CN CNA2006100299786A patent/CN101121778A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102477151A (en) * | 2010-11-25 | 2012-05-30 | 东丽纤维研究所（中国）有限公司 | Catalyst for preparation of polyester, its preparation method, and production method of polyester |
| CN102477151B (en) * | 2010-11-25 | 2015-08-19 | 东丽纤维研究所（中国）有限公司 | The method of polyester preparing catalyst and preparation method thereof and production polyester |
| CN103131000A (en) * | 2011-11-29 | 2013-06-05 | 东丽纤维研究所（中国）有限公司 | Polyester catalyst and preparation method thereof |
| CN103172846A (en) * | 2011-12-23 | 2013-06-26 | 东丽纤维研究所（中国）有限公司 | Process for preparing polyester |
| CN105273176A (en) * | 2014-07-03 | 2016-01-27 | 中国石油化工股份有限公司 | Catalyst used for preparation of polyester, preparation method and application thereof |
| CN106589331A (en) * | 2015-10-19 | 2017-04-26 | 中国石油化工股份有限公司 | Polyester film preparation method |
| CN106589341A (en) * | 2015-10-19 | 2017-04-26 | 中国石油化工股份有限公司 | Preparation method for polytrimethylene terephthalate |
| CN106589331B (en) * | 2015-10-19 | 2019-09-06 | 中国石油化工股份有限公司 | The preparation method of polyester film |
| CN107513154A (en) * | 2017-09-14 | 2017-12-26 | 江苏景宏新材料科技有限公司 | A kind of titanium series polyester catalyst and its method for producing copolyesters |
| CN107513154B (en) * | 2017-09-14 | 2020-08-21 | 江苏景宏新材料科技有限公司 | Titanium polyester catalyst and method for producing copolyester by using same |
| CN114479038A (en) * | 2020-10-23 | 2022-05-13 | 中国石油化工股份有限公司 | Titanium catalyst and preparation method and application thereof |
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