CN101148499B - Titanium series catalyst - Google Patents
Titanium series catalyst Download PDFInfo
- Publication number
- CN101148499B CN101148499B CN2006101162371A CN200610116237A CN101148499B CN 101148499 B CN101148499 B CN 101148499B CN 2006101162371 A CN2006101162371 A CN 2006101162371A CN 200610116237 A CN200610116237 A CN 200610116237A CN 101148499 B CN101148499 B CN 101148499B
- Authority
- CN
- China
- Prior art keywords
- titanium
- compound
- series catalyst
- polyester
- catalyzer
- 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.)
- Active
Links
Landscapes
- Polyesters Or Polycarbonates (AREA)
Abstract
The present invention is one technological scheme of titanium catalyst of the reaction resultant of titanium compound, diol and metal compound. The titanium catalyst of the present invention is superior to available similar catalyst, which has poor 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 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.
The present invention adopts reaction product by titanium compound, dibasic alcohol, phosphorus compound and metallic compound as the catalyzer of producing polyester, this catalyzer is the homogeneous phase liquid catalyst, can dissolve each other with ethylene glycol, the polyester that adopts this catalyzer to make has good form and aspect.
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 that has titanium in the prior art, and a kind of new Titanium series catalyst is provided.This catalyzer 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 Titanium series catalyst comprises the reaction product of following raw material:
(A) have the titanium compound of following general formula:
Ti(OR)
4
R is the alkyl that is selected from 1～10 carbon atom;
(B) be selected from dibasic alcohol with 2～10 carbon atoms;
(C) be selected from least a alkali metal compound in lithium, sodium or the potassium among the periodic table of elements IA;
Also comprise (D) component phosphorus compound in the raw material, (D) the component phosphorus compound is selected from least a phosphate compounds in trimethyl phosphite 99, triethyl phosphate, tricresyl phosphate propyl ester, tricresyl phosphate isopropyl ester, tributyl phosphate or the triphenylphosphate;
The preparation method of Titanium series catalyst is as follows: 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; Wherein the mol ratio of dibasic alcohol and titanium compound is 0.5～100: 1, and the mol ratio of alkali metal compound and titanium compound is 0.01～10: 1.
In the technique scheme, the preferred version of titanium compound is to be 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 for being 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 preferable range of alkali metal compound and titanium compound is 0.1～5: 1; 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 mol ratio preferable range of dibasic alcohol and titanium compound is 1～8: 1, 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 catalyzer preferred version 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 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, 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 its HunterL value (brightness), a value (form and aspect of Huang-indigo plant) and b value (red-green form and aspect) with the color-view automatic colour difference meter of BYKGardner company 135 ℃ of processing after 1 hour.Wherein, the L value is high more, and brightness is big more; B value height then polyester slice is yellow partially.For the present invention, wish to pursue high L value, low b value.
The present invention is by adopting reaction product by titanium compound, dibasic alcohol, phosphorus compound and metallic compound as the catalyzer of producing polyester, the inventor is surprised to find, the polyester of the Preparation of Catalyst that employing makes 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 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 oxalate 37.2 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 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 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), tributyl phosphate 53.2 grams (0.2 mole) and ethylene glycol 200 grams, reaction 3 hours becomes homogeneous liquid to system under 150 ℃ 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.
[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 |
| Comparative example 1 | SbAc3 | 150 | 90 | 80 | 0.662 | 87.8 | -1.30 | 3.27 |
Claims (9)
1. Titanium series catalyst comprises the reaction product of following raw material:
(A) have the titanium compound of following general formula:
Ti(OR)
4
R is the alkyl that is selected from 1～10 carbon atom;
(B) be selected from dibasic alcohol with 2～10 carbon atoms;
(C) be selected from least a alkali metal compound in lithium, sodium or the potassium among the periodic table of elements IA;
Also comprise (D) component phosphorus compound in the raw material, (D) the component phosphorus compound is selected from least a phosphate compounds in trimethyl phosphite 99, triethyl phosphate, tricresyl phosphate propyl ester, tricresyl phosphate isopropyl ester, tributyl phosphate or the triphenylphosphate;
The preparation method of Titanium series catalyst is as follows: 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; Wherein the mol ratio of dibasic alcohol and titanium compound is 0.5～100: 1, and the mol ratio of alkali metal compound and titanium compound is 0.01～10: 1.
2. 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. 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.
4. Titanium series catalyst according to claim 1, the mol ratio that it is characterized in that dibasic alcohol and titanium compound is 1～8: 1.
5. Titanium series catalyst according to claim 1, the mol ratio that it is characterized in that phosphorus compound and titanium compound is＞0～10: 1.
6. Titanium series catalyst according to claim 6, the mol ratio that it is characterized in that phosphorus compound and titanium compound is 0.1～6: 1;
7. titanium series polyester catalyst according to claim 1, the mol ratio that it is characterized in that alkali metal compound and titanium compound is 0.1～5: 1.
8. Titanium series catalyst according to claim 1 is characterized in that catalyzer is the homogeneous phase liquid catalyst.
9. Titanium series catalyst according to claim 9 is characterized in that catalyzer is the homogeneous phase liquid catalyst, can dissolve each other with ethylene glycol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2006101162371A CN101148499B (en) | 2006-09-20 | 2006-09-20 | Titanium series catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2006101162371A CN101148499B (en) | 2006-09-20 | 2006-09-20 | Titanium series catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101148499A CN101148499A (en) | 2008-03-26 |
| CN101148499B true CN101148499B (en) | 2010-08-11 |
Family
ID=39249210
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2006101162371A Active CN101148499B (en) | 2006-09-20 | 2006-09-20 | Titanium series catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101148499B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101942078B (en) * | 2009-07-06 | 2012-06-27 | 中国石油化工股份有限公司 | Titanium polyester catalyst for preparing polyester |
| CN102219890B (en) * | 2010-04-15 | 2013-03-06 | 中国石油化工股份有限公司 | Method for producing titanium polyester |
| CN104558574B (en) * | 2013-10-28 | 2017-03-15 | 中国石油化工股份有限公司 | Titanium series polyester catalyst |
| 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 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1035916B1 (en) * | 1997-12-02 | 2001-09-05 | ACMA Limited | Esterification catalysts |
| CN1327879A (en) * | 2001-07-05 | 2001-12-26 | 济南齐鲁化纤集团有限责任公司 | Ti-series compound and/or carried catalyst and its preparing process |
| CN1644601A (en) * | 2004-12-29 | 2005-07-27 | 中国石化集团天津石油化工公司 | Preparation of liquid titanium polyester polycondensation catalyst |
-
2006
- 2006-09-20 CN CN2006101162371A patent/CN101148499B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1035916B1 (en) * | 1997-12-02 | 2001-09-05 | ACMA Limited | Esterification catalysts |
| CN1327879A (en) * | 2001-07-05 | 2001-12-26 | 济南齐鲁化纤集团有限责任公司 | Ti-series compound and/or carried catalyst and its preparing process |
| CN1644601A (en) * | 2004-12-29 | 2005-07-27 | 中国石化集团天津石油化工公司 | Preparation of liquid titanium polyester polycondensation catalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101148499A (en) | 2008-03-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101121777B (en) | Titanium series polyester catalyst | |
| CN101323661B (en) | Process for producing polyester | |
| CN101942078B (en) | Titanium polyester catalyst for preparing polyester | |
| CN101942076B (en) | Preparation method of polyester | |
| CN101121778A (en) | Method for preparing titanium series catalyst | |
| CN102382287B (en) | Liquid titanium catalyst for polyester and copolyester and preparation method thereof | |
| CN105273176B (en) | Catalyst of polyester preparation and its preparation method and application | |
| CN102219894A (en) | Method for producing semi-dulling titanium series polyester | |
| CN102219890B (en) | Method for producing titanium polyester | |
| CN103772684B (en) | The production method of the polyester of titanium catalysis | |
| CN1962720B (en) | Preparation method of catalyst for producing polyester | |
| CN101148499B (en) | Titanium series catalyst | |
| CN103539928B (en) | Titanium series polyester catalyst and the method for producing semi-dull polyester | |
| CN1962715B (en) | Method for making polyester | |
| CN103772685B (en) | The production method of high-end carboxyl titanium polyester | |
| CN1962723A (en) | Preparation method of titanium series catalyst for polyester | |
| CN103539926B (en) | The production method of titanium polyester | |
| CN101173038B (en) | Method for producing polyester | |
| CN100567364C (en) | Be used to produce the catalyzer of polyester | |
| CN101148500B (en) | Method for preparing titanium series polyester catalyst | |
| CN100554307C (en) | Produce the method for polyester | |
| CN103772672B (en) | The production method of full-dull titanium polyester | |
| CN109575262B (en) | Production method of semi-dull titanium polyester | |
| CN103739834B (en) | The production method of solid phase titanium polyester | |
| CN104558554A (en) | Preparation method of polyester resin |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |