CN101148500A - Method for preparing titanium series polyester catalyst - Google Patents
Method for preparing titanium series polyester catalyst Download PDFInfo
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- CN101148500A CN101148500A CNA2006101162386A CN200610116238A CN101148500A CN 101148500 A CN101148500 A CN 101148500A CN A2006101162386 A CNA2006101162386 A CN A2006101162386A CN 200610116238 A CN200610116238 A CN 200610116238A CN 101148500 A CN101148500 A CN 101148500A
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Abstract
The present invention is the technological scheme of one polyester preparing titanium catalyst, which is reaction resultant obtained through the first reaction of titanium compound and water and the subsequent reaction with IA metal compound. The titanium catalyst of the present invention is superior to available similar catalyst prepared through the reaction between titanate and water and with low dissolubility in ethylene glycol and poor hue of the prepared polyester. The titanium catalyst is applied in industrial production of polyester.
Description
Technical field
The present invention relates to a kind of preparation method of titanium series polyester 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 polyester catalyst has high reactivity, but the polyester that titanium series polyester 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 polyester catalyst is because it is active high, do not contain heavy metal, thereby be subjected to the favor of numerous polyester producers, titanium series polyester 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 polyester catalyst 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.
CN1138339 discloses the titanium series polyester catalyst that adopts titanic acid ester and silicon ester cohydrolysis to make, and this class catalyzer has higher activity, but the PET hue that makes is bad, and hue value is compared still higher with adopting antimony-based catalyst.
CN1259969 discloses the titanium series polyester catalyst that the co-precipitation of titanic acid ester metallizing thing makes, and the PET hue that this class catalyzer makes is still bad, does not solve the problem of the polyester jaundice that titanium series polyester catalyst makes.
The catalyzer of above-mentioned patent disclosure all is a solid catalyst, and the solubleness in ethylene glycol is lower.
Summary of the invention
Technical problem to be solved by this invention is that the titanium series polyester catalyst solubleness in ethylene glycol that is made by the reaction of titanic acid ester and water that exists in the prior art is low, the problem of the PET hue difference that makes, and a kind of preparation method of new titanium series polyester 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 polyester catalyst may further comprise the steps:
A) titanium compound and water were reacted 0.1～48 hour under 0～100 ℃ of temperature condition, wherein titanium compound is Ti (OR)
4, R is the alkyl that is selected from 1～10 carbon atom;
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 homogeneous phase liquid titanium polyester catalyzer;
Wherein the mol ratio of water 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 water be 10 ℃～70 ℃, the reaction times preferable range is 0.1～20 hour.B) the temperature of reaction preferable range in the 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 mol ratio preferable range of water and titanium compound is 1～50: 1, more preferably scope is 4～20: 1, when the mol ratio of water and titanium compound less than 4 the time, the catalyst tolerates water-based that makes is bad, when the mol ratio of water and titanium compound greater than 20 the time, the solvability of prepared catalyzer in ethylene glycol is bad.The metallic compound preferred version is selected from least a in lithium, sodium or the potassium compound among the periodic table of elements IA.The mol ratio preferable range of metallic compound and titanium compound is 0.1～5: 1.
In the technique scheme, b) the reaction raw materials preferred version in the step is that to comprise also in the raw material that phosphorus compound, phosphorus compound preferred version are 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.
Catalyzer preferred version of the present invention is the homogeneous phase liquid catalyst, more preferably the homogeneous phase liquid catalyst of scheme for dissolving each other with ethylene glycol.
The preparation method of titanium series polyester catalyst of the present invention is as follows:
With general formula is Ti (OR)
4Titanium compound and water reaction product that obtains and at least a metallic compound reaction that is selected from IA in the periodic table of elements, obtain homogeneous phase liquid titanium polyester catalyzer.
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 water reaction, reacted 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 producing polyester, the inventor is surprised to find, the polyester that the liquid catalyst that adopts the inventive method to make prepares 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 titanium isopropylate 28.4 grams (0.1 mole) and dehydrated alcohol 30 grams, mix.In reactor, slowly splash into the mixing solutions that distilled water 9 restrains (0.5 mole) and dehydrated alcohol 30 grams.Separate out white depositions, drip to finish post-heating to 70 ℃ reaction 1 hour, with the product centrifugation, and with distilled water wash residue 3 times, drying.
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 tetraethyl titanate 22.8 grams (0.1 mole), tetraethyl orthosilicate 4.16 grams (0.2 mole) and dehydrated alcohol 30 grams, mix.In reactor, slowly splash into the mixing solutions that distilled water 14.4 restrains (0.8 mole) and dehydrated alcohol 30 grams.Separate out white depositions, drip to finish post-heating to 70 ℃ reaction 1 hour, with the product centrifugation, and with distilled water wash residue 3 times, drying.
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 titanium isopropylate 28.4 grams (0.1 mole), tetraethyl orthosilicate 4.16 grams (0.2 mole) and dehydrated alcohol 30 grams, mix.In reactor, slowly splash into the mixing solutions that distilled water 14.4 restrains (0.8 mole) and dehydrated alcohol 30 grams.Separate out white depositions, drip to finish post-heating to 70 ℃ reaction 1 hour, with the product centrifugation, and with distilled water wash residue 3 times, drying.
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 titanium isopropylate 28.4 grams (0.1 mole), tetraethyl orthosilicate 4.16 grams (0.2 mole) and dehydrated alcohol 30 grams, mix.In reactor, slowly splash into the mixing solutions that distilled water 14.4 restrains (0.8 mole) and dehydrated alcohol 30 grams.Separate out white depositions, drip to finish post-heating to 70 ℃ reaction 1 hour, with the product centrifugation, and with distilled water wash residue 3 times, drying.
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 tetrabutyl titanate 34 grams (0.1 mole), tetraethyl orthosilicate 4.16 grams (0.2 mole) and dehydrated alcohol 30 grams, mix.In reactor, slowly splash into the mixing solutions that distilled water 14.4 restrains (0.8 mole) and dehydrated alcohol 30 grams.Separate out white depositions, drip to finish post-heating to 70 ℃ reaction 1 hour, with the product centrifugation, and with distilled water wash residue 3 times, drying.
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 catalyst A
In the reactor that agitator, condenser and thermometer are housed, add titanium isopropylate 28.4 grams (0.1 mole) and dehydrated alcohol 30 grams, mix.In reactor, slowly splash into the mixing solutions that distilled water 14.4 restrains (0.8 mole) and dehydrated alcohol 30 grams.Separate out white depositions, drip to finish post-heating to 70 ℃ reaction 1 hour, with the product centrifugation, and with distilled water wash residue 3 times, drying.
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
Restrain terephthalic acids and 316 gram ethylene glycol and catalyzer F (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 7]
The preparation of catalyzer G
In the reactor that agitator, condenser and thermometer are housed, add titanium isopropylate 28.4 grams (0.1 mole) and dehydrated alcohol 30 grams, mix.In reactor, slowly splash into the mixing solutions that distilled water 28.8 restrains (1.6 moles) and dehydrated alcohol 30 grams.Separate out white depositions, drip to finish post-heating to 70 ℃ reaction 1 hour, with the product centrifugation, and with distilled water wash residue 3 times, drying.
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 to 3 hours systems become homogeneous liquid under 150 ℃ of temperature of reaction, obtain catalyzer G.
The preparation of polyester
Restrain terephthalic acids and 316 gram ethylene glycol and catalyzer G (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 8]
The preparation of catalyzer H
In the reactor that agitator, condenser and thermometer are housed, add titanium isopropylate 28.4 grams (0.1 mole) and dehydrated alcohol 30 grams, mix.In reactor, slowly splash into the mixing solutions that distilled water 28.8 restrains (1.6 moles) and dehydrated alcohol 30 grams.Separate out white depositions, drip to finish post-heating to 80 ℃ reaction 0.2 hour, with the product centrifugation, and with distilled water wash residue 3 times, drying.
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 0.3 hour becomes homogeneous liquid to system under 180 ℃ of temperature of reaction, obtains catalyzer H.
The preparation of polyester
Restrain terephthalic acids and 316 gram ethylene glycol and catalyzer H (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 9]
The preparation of catalyst I
In the reactor that agitator, condenser and thermometer are housed, add titanium isopropylate 28.4 grams (0.1 mole) and dehydrated alcohol 30 grams, mix.In reactor, slowly splash into the mixing solutions that distilled water 28.8 restrains (1.6 moles) and dehydrated alcohol 30 grams.Separate out white depositions, drip to finish post-heating and reacted 20 hours to I0 ℃, with the product centrifugation, and with distilled water wash residue 3 times, drying.
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 12 hours becomes homogeneous liquid to system under 100 ℃ of temperature of reaction, obtains catalyst I.
The preparation of polyester
Restrain terephthalic acids and 316 gram ethylene glycol and catalyst I (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 10]
In the reactor that agitator, condenser and thermometer are housed, add titanium isopropylate 28.4 grams (0.1 mole), tetraethyl orthosilicate 4.16 grams (0.2 mole) and dehydrated alcohol 30 grams, mix.In reactor, slowly splash into the mixing solutions that distilled water 14.4 restrains (0.8 mole) and dehydrated alcohol 30 grams.Separate out white depositions, drip to finish post-heating to 50 ℃ reaction 6 hours, with the product centrifugation, and with distilled water wash residue 3 times, drying.
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 20 hours becomes homogeneous liquid to system under 30 ℃ 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 polyester catalyst may further comprise the steps:
A) titanium compound and water were reacted 0.1～48 hour under 0～100 ℃ of temperature condition, wherein titanium compound is Ti (OR)
4, R is the alkyl that is selected from 1～10 carbon atom;
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, and getting titanium is liquid catalyst;
Wherein the mol ratio of water and titanium compound is 0.5～100: 1, and the mol ratio of metallic compound and titanium compound is 0.01～10: 1.
2. according to the preparation method of the described titanium series polyester catalyst of claim 1, it 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; The mol ratio of water and titanium compound is 4～20: 1.
3. according to the preparation method of the described titanium series polyester catalyst of claim 1, the temperature of reaction that it is characterized in that titanium compound and water is 10～70 ℃, and the reaction times is 0.1～20 hour.
4. according to the preparation method of the described titanium series polyester catalyst of claim 1, it is characterized in that metallic compound is selected from the periodic table of elements at least a in the lithium among the IA, sodium or the potassium compound.
5. according to the preparation method of the described titanium series polyester catalyst of claim 1, the mol ratio that it is characterized in that metallic compound and titanium compound is 0.1～5: 1.
6. according to the preparation method of the described titanium series polyester catalyst of claim 1, it is characterized in that b) temperature of reaction in the step is 0 ℃～180 ℃; Reaction times is 0.05～24 hour.
7. according to the preparation method of the described titanium series polyester catalyst of claim 1, it 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. according to the preparation method of the described titanium series polyester catalyst of claim 7, it 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.
9. according to the preparation method of the described titanium series polyester catalyst of claim 7, the mol ratio that it is characterized in that phosphorus compound and titanium compound is 0.1～6: 1.
10. according to the preparation method of the described titanium series polyester catalyst of claim 1, it is characterized in that catalyzer is the homogeneous phase liquid catalyst, can dissolve each other with ethylene glycol.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103665362A (en) * | 2012-08-31 | 2014-03-26 | 中国石油化工股份有限公司 | Method for preparing polyester |
| CN114479040A (en) * | 2020-10-26 | 2022-05-13 | 中国石油化工股份有限公司 | Polyester catalyst, and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| GB9725419D0 (en) * | 1997-12-02 | 1998-01-28 | Tioxide Specialties Ltd | Esterification catalysts |
| TW548291B (en) * | 1999-06-24 | 2003-08-21 | Teijin Ltd | Catalyst for producing a polyester and process for producing the polyester by using same |
| JP4393004B2 (en) * | 2001-02-06 | 2010-01-06 | 三菱化学株式会社 | Polyester resin |
| CN1164641C (en) * | 2001-07-05 | 2004-09-01 | 济南齐鲁化纤集团有限责任公司 | High-activity catalyst and its application in synthesizing polyester |
| CN1250608C (en) * | 2003-06-04 | 2006-04-12 | 中国石化集团天津石油化工公司 | Titanium composite catalyst for polyester and copolyester synthesis |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103665362A (en) * | 2012-08-31 | 2014-03-26 | 中国石油化工股份有限公司 | Method for preparing polyester |
| CN103665362B (en) * | 2012-08-31 | 2016-06-01 | 中国石化仪征化纤有限责任公司 | The preparation method of polyester |
| CN114479040A (en) * | 2020-10-26 | 2022-05-13 | 中国石油化工股份有限公司 | Polyester catalyst, and preparation method and application thereof |
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