CN1294176C - Composite catalyst for preparing modified polyester - Google Patents
Composite catalyst for preparing modified polyester Download PDFInfo
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- CN1294176C CN1294176C CNB031415091A CN03141509A CN1294176C CN 1294176 C CN1294176 C CN 1294176C CN B031415091 A CNB031415091 A CN B031415091A CN 03141509 A CN03141509 A CN 03141509A CN 1294176 C CN1294176 C CN 1294176C
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- titanium dioxide
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- molybdenum
- dioxide
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Abstract
The present invention relates to a composite catalyst for preparing modified polyester. Terephthalic acid, iso-phthalic acid and ethylene glycol are used as monomers by the modified polyester, the composite catalyst is a composition containing titanium dioxide, silicon dioxide, compounds containing molybdenum, zinc acetate dihydrate and compounds A, wherein the weight ratio of the titanium dioxide to the silicon dioxide is 100 to (6 to 9.5); the weight ratio of the titanium dioxide to the compounds containing molybdenum is 100 to (5 to 40); the weight ratio of the titanium dioxide to the zinc acetate dihydrate is 100 to (5 to 115); the weight ratio of the titanium dioxide to the compounds A is 100 to (5 to 115); the weight ratio of the weight of the titanium dioxide to the total amount of the zinc acetate dihydrate and the compounds A is 100 to (50 to 120). The compounds containing molybdenum are selected from one or the mixture of oxides of the molybdenum or sulfides of the molybdenum, and the compounds A are selected from one or the mixture of manganese triacetate dihydrate or manganese chloride. The catalyst has the advantages of less side reaction of reaction processes and better color of the obtained polyester.
Description
Technical field
The present invention relates to a kind of composite catalyst that is used for making modified poly ester, the compound etc. that composite catalyst contains titanium dioxide, silicon-dioxide and contains molybdenum by terephthalic acid, m-phthalic acid and ethylene glycol.
Background technology
The polyester that is used to make high-shrinkage fiber can adopt chemic modified method to prepare, it is to change the component of reaction diacid in the polyester monocase or the component of reaction glycol, promptly adopt other diacid partly to replace terephthalic acid, or adopt other glycol partly to replace ethylene glycol.Wherein partly replacing terephthalic acid with m-phthalic acid is the method for using always, its advantage is that cost is lower, product performance are better, opens flat 9-78345, spy as Japanese patent laid-open 5-302210, spy and opens flat 9-132832 and specially open flat 9-228154 and introduce.The shortcoming of this method is that the introducing of m-phthalic acid has caused the polycondensation time lengthening, and the polycondensation time increases along with the increase of m-phthalic acid amount.In the manufacturing processed of polyester, esterification does not generally need catalyzer, and polycondensation need be carried out in the presence of catalyzer usually, titaniferous catalyzer commonly used or stibiated catalyzer in the prior art.For this method, as adopt existing titaniferous or stibiated catalyzer, can reduce polycondensation reaction time by increasing catalyst levels, but the result will make side reaction increase, make polyester slice color and luster variation, quality product reduce.
Summary of the invention
The invention provides a kind of composite catalyst that is used for making modified poly ester by terephthalic acid, m-phthalic acid and ethylene glycol, its technical problem to be solved is to reduce the reaction times of polycondensation in the polyester manufacture process behind this composite catalyst of employing, and the adding of catalyzer does not influence the color and luster of polyester slice.
Below be the technical scheme that the present invention solves the problems of the technologies described above:
A kind of composite catalyst that is used to make modified poly ester, modified poly ester is a monomer with terephthalic acid, m-phthalic acid and ethylene glycol, this composite catalyst is the composition that contains titanium dioxide, silicon-dioxide, contains compound, zinc acetate and the compd A of molybdenum.Wherein:
The weight ratio of titanium dioxide and silicon-dioxide is 100: (6～9.5);
Titanium dioxide is 100 with the weight ratio that contains the compound of molybdenum: (5～40);
The weight ratio of titanium dioxide and zinc acetate is 100: (5～115),
The weight ratio of titanium dioxide and compd A is 100: (5～115),
And the weight ratio of titanium dioxide and zinc acetate and compd A total amount is 100: (50～120).
The above-mentioned compound that contains molybdenum is taken from any in the sulfide of the oxide compound of molybdenum or molybdenum or both mixtures; Compd A is taken from any in manganese acetate or the Manganous chloride tetrahydrate or both mixtures.
The weight ratio of titanium dioxide and silicon-dioxide is preferably 100 in the above-mentioned composite catalyst: (7～8.3); Titanium dioxide is preferably 100 with the weight ratio that contains the compound of molybdenum: (8～20); The weight ratio of titanium dioxide and zinc acetate and compd A total amount is preferably 100: (80～100).
Usually zinc acetate, manganese acetate or Manganous chloride tetrahydrate are the hydrated compound that contains crystal water, and this moment, titanium dioxide should be converted into hydrated compound the weight meter of pure compound behind the removal crystal water with their weight ratio.
Make modified poly ester by terephthalic acid, m-phthalic acid and ethylene glycol and should experience esterification, precondensation and polycondensation process, this composite catalyst is mainly used in precondensation and polycondensation process.Catalyzer can add when the feeding intake of esterification simultaneously, catalyst consumption is a benchmark with the total amount of terephthalic acid in the reaction system and m-phthalic acid, total amount in titanium dioxide in the catalyzer and silicon-dioxide is generally 150～300ppm, is preferably 180～250ppm.For whole process of preparation, key of the present invention has provided a kind of catalyst system that is used for precondensation and polycondensation process, other parts and prior art are basic identical in the preparation process of polyester, and conventional additive such as pigment, toning agent, matting agent, lubricant and linking agent etc. can add reaction system.In addition, add stablizer and can further reduce by-products content, thereby obtain higher-quality polyester product, these are all known for those skilled in the art.
Compared with prior art, advantage of the present invention is very tangible, adopts the time that can shorten polycondensation behind this catalyst system, and is basic identical with the polycondensation time that the preparation conventional polyester is required.And side reaction is few in the reaction process, and the polyester slice that obtains has color and luster preferably, can be white or approaching white, and its pairing b* value is between-4 to+4.
Below will the invention will be further described by specific embodiment, because the keying action of manganese acetate or Manganous chloride tetrahydrate is mn ion in the catalyzer, both character are basic identical thus, so only enumerate the embodiment of employing manganese acetate among the embodiment.In like manner, because the oxide compound of molybdenum and the sulfide of molybdenum also have closely similar character, also only enumerate the embodiment of the oxide compound that adopts molybdenum among the embodiment.Those skilled in the art should be able to know the employing of the sulfide of Manganous chloride tetrahydrate and molybdenum by inference according to general general knowledge.
Embodiment
[embodiment 1]
With 2 liters of stainless steel pressure reactor configurations rectifying columns, condenser and pumped vacuum systems.In reactor, drop into 846 gram pure terephthalic acids, 150 gram m-phthalic acids and 484 gram ethylene glycol, and add composite catalyst.
The molar ratio of raw material is:
(terephthalic acid+m-phthalic acid): ethylene glycol=1: 1.3
Terephthalic acid: m-phthalic acid=1: 0.177
The proportioning of composite catalyst is:
Titanium dioxide 0.165 gram
Silicon-dioxide 0.014 gram
Molybdic oxide 0.014 gram
Four hydration manganese acetates, 0.082 gram (amounting to manganese acetate 0.058 gram)
Two hydration zinc acetates, 0.122 gram (amounting to zinc acetate 0.102 gram)
Total amount with terephthalic acid in the reaction system and m-phthalic acid is a benchmark, and in the total amount of titanium dioxide in the catalyzer and silicon-dioxide, the add-on of catalyzer is 180ppm, and other adds toning agent four hydration Cobaltous diacetates 0.230 gram.
Compressive reaction 200 minutes, temperature of reaction are 210～250 ℃, and reaction pressure is 0.05～0.3MPa, and the limit coronite distillates the water of generation, reach esterification yield 96.0% back and finish esterification.Add 0.05 gram stablizer trimethyl phosphite 99 subsequently, enter prepolymerization reaction.Decompression prepolymerization reaction 60 minutes, reaction pressure reduces to absolute pressure 0.1KPa by absolute pressure 101KPa, and temperature of reaction is 250～260 ℃.Then under 270～285 ℃ temperature, keeping reaction pressure is to carry out polycondensation below the absolute pressure 0.1Kpa.
Resulting polymers Cast Strip pelletizing under water.
[embodiment 2]
The proportioning of composite catalyst is:
Titanium dioxide 0.170 gram
Silicon-dioxide 0.012 gram
Molybdic oxide 0.034 gram
Four hydration manganese acetates, 0.082 gram (amounting to manganese acetate 0.058 gram)
Two hydration zinc acetates, 0.122 gram (amounting to zinc acetate 0.102 gram)
All the other are with embodiment 1.
[embodiment 3]
The proportioning of composite catalyst is:
Titanium dioxide 0.206 gram
Silicon-dioxide 0.013 gram
Molybdic oxide 0.021 gram
Four hydration manganese acetates, 0.082 gram (amounting to manganese acetate 0.058 gram)
Two hydration zinc acetates, 0.122 gram (amounting to zinc acetate 0.102 gram)
Total amount with terephthalic acid in the reaction system and m-phthalic acid is a benchmark, counts 220ppm with the total amount of titanium dioxide in the catalyzer and silicon-dioxide.All the other are with embodiment 1.
[embodiment 4]
The proportioning of composite catalyst is:
Titanium dioxide 0.206 gram
Silicon-dioxide 0.013 gram
Molybdic oxide 0.021 gram
Four hydration manganese acetates, 0.120 gram (amounting to manganese acetate 0.085 gram)
Two hydration zinc acetates, 0.120 gram (amounting to zinc acetate 0.100 gram)
Total amount with terephthalic acid in the reaction system and m-phthalic acid is a benchmark, counts 220ppm with the total amount of titanium dioxide in the catalyzer and silicon-dioxide, and all the other are with embodiment 1.
[embodiment 5]
The proportioning of composite catalyst is:
Titanium dioxide 0.206 gram
Silicon-dioxide 0.013 gram
Molybdic oxide 0.021 gram
Four hydration manganese acetates, 0.120 gram (amounting to manganese acetate 0.085 gram)
Two hydration zinc acetates, 0.096 gram (amounting to zinc acetate 0.080 gram)
Total amount with terephthalic acid in the reaction system and m-phthalic acid is a benchmark, counts 220ppm with the total amount of titanium dioxide in the catalyzer and silicon-dioxide, and all the other are with embodiment 1.
[embodiment 6]
The proportioning of composite catalyst is:
Titanium dioxide 0.234 gram
Silicon-dioxide 0.015 gram
Molybdic oxide 0.023 gram
Four hydration manganese acetates, 0.170 gram (amounting to manganese acetate 0.120 gram)
Two hydration zinc acetates, 0.109 gram (amounting to zinc acetate 0.091 gram)
Total amount with terephthalic acid in the reaction system and m-phthalic acid is a benchmark, counts 250ppm with the total amount of titanium dioxide in the catalyzer and silicon-dioxide, and all the other are with embodiment 1.
[embodiment 7]
With 30 liters of stainless steel pressure reactor configurations rectifying columns, condenser and pumped vacuum systems.In reactor, drop into 12.8 kilograms of pure terephthalic acids, 2.3 kilograms of m-phthalic acids, 7.3 kg ethylene glycol and catalyst system.
The proportioning of composite catalyst system is:
Titanium dioxide 3.11 grams
Silicon-dioxide 0.20 gram
Molybdic oxide 0.32 gram
Four hydration manganese acetates, 1.81 grams (amounting to manganese acetate 1.28 grams)
Two hydration zinc acetates, 1.81 grams (amounting to zinc acetate 1.51 grams)
Total amount with terephthalic acid in the reaction system and m-phthalic acid is a benchmark, counts 220ppm with the total amount of titanium dioxide in the catalyzer and silicon-dioxide, and other adds toning agent four hydration Cobaltous diacetates 3.47 grams.
Finish to add 0.8 gram stablizer trimethyl phosphite 99 after the esterification, enter prepolymerization reaction.All the other are with embodiment 1.
[comparative example 1]
Catalyzer is 0.35 gram antimonous oxide, and all the other are with embodiment 1.
[comparative example 2]
Catalyzer is 0.21 gram titanium dioxide, 0.013 gram silicon-dioxide, and all the other are with embodiment 1.
[comparative example 3]
Catalyzer is 5.29 gram antimonous oxides, adds toning agent four hydration Cobaltous diacetates 2.27 grams in addition, and all the other are with embodiment 7.
[comparative example 4]
Catalyzer is 3.17 gram titanium dioxide, 0.20 gram silicon-dioxide, and other adds toning agent four hydration Cobaltous diacetates 3.47 grams, and all the other are with embodiment 7.
The polycondensation reaction time of each embodiment and comparative example, and indexs such as the limiting viscosity that obtains by analysis of polyester slice of preparation, content of carboxyl end group (by-products content in the reflection product), form and aspect are listed in table 1.
Table 1.
| Limiting viscosity (dl/g) | End carboxyl (mol/t) | Form and aspect b* | Polycondensation reaction time (min) | |
| Embodiment 1 | 0.685 | 21 | 2 | 150 |
| Embodiment 2 | 0.688 | 28 | 2 | 150 |
| Embodiment 3 | 0.697 | 26 | 1 | 150 |
| Embodiment 4 | 0.692 | 25 | 2 | 150 |
| Embodiment 5 | 0.693 | 27 | 2 | 150 |
| Embodiment 6 | 0.704 | 28 | 2 | 150 |
| Embodiment 7 | 0.695 | 28 | 2 | 150 |
| Comparative example 1 | 0.626 | 39 | 3 | 155 |
| Comparative example 2 | 0.692 | 36 | 3 | 155 |
| Comparative example 3 | 0.689 | 33 | 5 | 180 |
| Comparative example 4 | 0.696 | 54 | 6 | 180 |
The measuring method of each index is:
Limiting viscosity: with 0.5 gram polyester be dissolved in 100 milliliters of phenol and sym.-tetrachloroethane etc. in the solution of weight mixture, measure its limiting viscosities (I.V.) down in 25 ℃
Content of carboxyl end group: adopt the optics titration measuring.Polyester is dissolved in the mixed solution (weight ratio 70: 30) of neighbour-cresols and chloroform, adds dibromothymolsulfonphthalein and make indicator, the ethanolic soln with the potassium hydroxide of 0.05N carries out titration then.
Form and aspect b*: measure by GB GB/T 14190-1993.
Claims (3)
1, a kind of composite catalyst that is used to make modified poly ester, modified poly ester is a monomer with terephthalic acid, m-phthalic acid and ethylene glycol, this composite catalyst is the composition that contains titanium dioxide, silicon-dioxide, contains compound, zinc acetate and the compd A of molybdenum, wherein:
The weight ratio of titanium dioxide and silicon-dioxide is 100: 6～9.5;
Titanium dioxide is 100: 8～20 with the weight ratio that contains the compound of molybdenum;
The weight ratio of titanium dioxide and zinc acetate is 100: 5～115;
The weight ratio of titanium dioxide and compd A is 100: 5～115;
And the weight ratio of titanium dioxide and zinc acetate and compd A total amount is 100: 50～120;
The above-mentioned compound that contains molybdenum is taken from any in the sulfide of the oxide compound of molybdenum or molybdenum or both mixtures;
Above-claimed cpd A takes from any in manganese acetate or the Manganous chloride tetrahydrate or both mixtures.
2, composite catalyst according to claim 1, the weight ratio that it is characterized in that described titanium dioxide and silicon-dioxide is 100: 7～8.3.
3, composite catalyst according to claim 1, the weight ratio that it is characterized in that described titanium dioxide and zinc acetate and compd A total amount is 100: 80～100.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031415091A CN1294176C (en) | 2003-07-09 | 2003-07-09 | Composite catalyst for preparing modified polyester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031415091A CN1294176C (en) | 2003-07-09 | 2003-07-09 | Composite catalyst for preparing modified polyester |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1566182A CN1566182A (en) | 2005-01-19 |
| CN1294176C true CN1294176C (en) | 2007-01-10 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB031415091A Expired - Lifetime CN1294176C (en) | 2003-07-09 | 2003-07-09 | Composite catalyst for preparing modified polyester |
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5340909A (en) * | 1991-12-18 | 1994-08-23 | Hoechst Celanese Corporation | Poly(1,3-propylene terephthalate) |
| US5561183A (en) * | 1995-08-14 | 1996-10-01 | Sam Yang Co., Ltd. | Preparation method of antibacterial and deodorant polyester for fiber |
| CN1138339A (en) * | 1994-01-07 | 1996-12-18 | 阿克佐诺贝尔公司 | Process for producing polyesters and copolyesters |
| JPH0978345A (en) * | 1995-09-04 | 1997-03-25 | Kuraray Co Ltd | Highly shrinkable fiber and its production |
| JPH09132832A (en) * | 1995-10-30 | 1997-05-20 | Nippon Ester Co Ltd | Polyester heteroshrinkable combined filament yarn |
| CN1368988A (en) * | 1999-04-22 | 2002-09-11 | 齐默尔股份公司 | Process of producing polytrimethylene terephthalate (PTT) |
| CN1392173A (en) * | 2001-06-14 | 2003-01-22 | 中国石化上海石油化工股份有限公司 | Catalyst for polycondensation process of preparing polyethylene terephthalate |
| CN1403193A (en) * | 2002-10-15 | 2003-03-19 | 上海交通大学 | Prepn and application of high-activity titanium catalyst |
| CN1415643A (en) * | 2002-11-12 | 2003-05-07 | 上海华明高技术（集团）有限公司 | Method for preparing polyester and copolyester |
-
2003
- 2003-07-09 CN CNB031415091A patent/CN1294176C/en not_active Expired - Lifetime
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5340909A (en) * | 1991-12-18 | 1994-08-23 | Hoechst Celanese Corporation | Poly(1,3-propylene terephthalate) |
| CN1138339A (en) * | 1994-01-07 | 1996-12-18 | 阿克佐诺贝尔公司 | Process for producing polyesters and copolyesters |
| US5561183A (en) * | 1995-08-14 | 1996-10-01 | Sam Yang Co., Ltd. | Preparation method of antibacterial and deodorant polyester for fiber |
| JPH0978345A (en) * | 1995-09-04 | 1997-03-25 | Kuraray Co Ltd | Highly shrinkable fiber and its production |
| JPH09132832A (en) * | 1995-10-30 | 1997-05-20 | Nippon Ester Co Ltd | Polyester heteroshrinkable combined filament yarn |
| CN1368988A (en) * | 1999-04-22 | 2002-09-11 | 齐默尔股份公司 | Process of producing polytrimethylene terephthalate (PTT) |
| CN1392173A (en) * | 2001-06-14 | 2003-01-22 | 中国石化上海石油化工股份有限公司 | Catalyst for polycondensation process of preparing polyethylene terephthalate |
| CN1403193A (en) * | 2002-10-15 | 2003-03-19 | 上海交通大学 | Prepn and application of high-activity titanium catalyst |
| CN1415643A (en) * | 2002-11-12 | 2003-05-07 | 上海华明高技术（集团）有限公司 | Method for preparing polyester and copolyester |
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| CN1566182A (en) | 2005-01-19 |
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