CN1272359C - Process for preparing modified polyester for the preparation of polyester fibre with high elasticity - Google Patents
Process for preparing modified polyester for the preparation of polyester fibre with high elasticity Download PDFInfo
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- CN1272359C CN1272359C CN 03141506 CN03141506A CN1272359C CN 1272359 C CN1272359 C CN 1272359C CN 03141506 CN03141506 CN 03141506 CN 03141506 A CN03141506 A CN 03141506A CN 1272359 C CN1272359 C CN 1272359C
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Abstract
The present invention relates to a method for preparing modified polyester used for high-shrinkage polyester fibers. Terephthalic acid, iso-phthalic acid and ethylene glycol are used as monomers, and the process of the method orderly comprises an esterification reaction, a pre-polycondensation reaction and a polycondensation reaction. The pre-polycondensation reaction and the polycondensation reaction are carried out under the condition of a composite catalyst, the catalyst is a composition containing titanium dioxide, silicon dioxide, compounds containing molybdenum 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 compounds A is 100 to (30 to 100). The compounds A are selected from one or the mixture of manganese triacetate dihydrate or manganese chloride, the total amount of the terephthalic acid and the iso-phthalic acid is taken as a reference for the dosage of the catalyst, and the total amount of the titanium dioxide and the silicon dioxide in the catalyst is from 150 to 300 ppm. The present invention has the advantages of less side reaction in reaction processes and better color of obtained polyester.
Description
Technical field
The present invention relates to a kind of preparation method who is used to make the modified poly ester of high-shrinkage fiber, the monomer of polyester is 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 preparation method who makes high-shrinkage fiber with modified poly ester, the monomer of polyester is terephthalic acid, m-phthalic acid and ethylene glycol.This method has adopted a kind of new polycondensation catalyst system, and technical problem to be solved is to reduce the reaction times of polycondensation in the polyester manufacture process, 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 preparation method who makes high-shrinkage fiber with modified poly ester, the monomer of polyester is terephthalic acid, m-phthalic acid and ethylene glycol, this method comprises following process successively:
1) terephthalic acid, m-phthalic acid and ethylene glycol carry out esterification, the molar ratio of raw material is a terephthalic acid: m-phthalic acid=1.0: 0.03～1.0, (terephthalic acid+m-phthalic acid): ethylene glycol=1.0: 1.1～1.5, temperature of reaction is 210～250 ℃, reaction pressure is 0.05～0.3MPa, distillate the water of generation in the reaction process, esterification yield reaches 95.0% at least and finishes esterification;
2) esterification reaction product carries out precondensation and polycondensation successively in the presence of a kind of composite catalyst, and the prepolymerization reaction temperature is 250～270 ℃, progressively reduce pressure during the reaction beginning, and be absolute pressure 0.3～1KPa until pressure, the reaction times is 30～90 minutes; The polycondensation temperature is 270～290 ℃, and reaction pressure is absolute pressure 0.01～0.5KPa, and the reaction times is 120～180 minutes, the Cast Strip pelletizing of polycondensation resulting polymers.
Above-mentioned composite catalyst is to contain titanium dioxide, silicon-dioxide, contain the compound of molybdenum and the composition of compd A, 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 compd A is 100: (30～100).
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.
Catalyst consumption is a benchmark with the total amount of terephthalic acid in the reaction system and m-phthalic acid, counts 150～300ppm with the total amount of titanium dioxide in the catalyzer and silicon-dioxide.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 compd A is preferably 100: (50～80).
Catalyst consumption is a benchmark with the total amount of terephthalic acid in the reaction system and m-phthalic acid, is preferably 180～250ppm in the total amount of titanium dioxide in the catalyzer and silicon-dioxide.
Usually 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.
Key of the present invention is to have adopted a kind of new catalyst system in 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 essence of the present invention is polycondensation and has adopted a kind of new composite catalyst, other parts and prior art in all reactions steps are basic identical, so embodiment and comparative example will be paid attention to the description of catalyzer.In addition, the keying action of manganese acetate or Manganous chloride tetrahydrate is mn ion in the catalyzer, and both character are basic identical thus, so only enumerate the embodiment that adopts 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, 0.118 gram (amounting to manganese acetate 0.083 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, 0.118 gram (amounting to manganese acetate 0.083 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, 0.118 gram (amounting to manganese acetate 0.083 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, 0.176 gram (amounting to manganese acetate 0.124 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, 0.234 gram (amounting to manganese acetate 0.165 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, 0.331 gram (amounting to manganese acetate 0.234 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, 2.66 grams (amounting to manganese acetate 1.87 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 | 0.683 | 21 | 2 | 150 |
| Embodiment 2 | 0.689 | 27 | 2 | 150 |
| Embodiment 3 | 0.696 | 25 | 1 | 150 |
| Embodiment 4 | 0.693 | 24 | 1 | 150 |
| Embodiment 5 | 0.693 | 27 | 2 | 150 |
| Embodiment 6 | 0.700 | 28 | 2 | 150 |
| Embodiment 7 | 0.697 | 27 | 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 (5)
1, a kind of preparation method who makes high-shrinkage fiber with modified poly ester, the monomer of polyester is terephthalic acid, m-phthalic acid and ethylene glycol, this method comprises following process successively:
1) terephthalic acid, m-phthalic acid and ethylene glycol carry out esterification, the molar ratio of raw material is a terephthalic acid: m-phthalic acid=1.0: 0.03～1.0, (terephthalic acid+m-phthalic acid): ethylene glycol=1.0: 1.1～1.5, temperature of reaction is 210～250 ℃, reaction pressure is 0.05～0.3MPa, distillate the water of generation in the reaction process, esterification yield reaches 95.0% at least and finishes esterification;
2) esterification reaction product carries out precondensation and polycondensation successively in the presence of a kind of composite catalyst, and the prepolymerization reaction temperature is 250～270 ℃, progressively reduce pressure during the reaction beginning, and be absolute pressure 0.3～1KPa until pressure, the reaction times is 30～90 minutes; The polycondensation temperature is 270～290 ℃, and reaction pressure is absolute pressure 0.01～0.5KPa, and the reaction times is 120～180 minutes, the Cast Strip pelletizing of polycondensation resulting polymers,
It is characterized in that above-mentioned composite catalyst is to contain titanium dioxide, silicon-dioxide, contain the compound of molybdenum and the composition of compd A, wherein:
The weight ratio of titanium dioxide and silicon-dioxide is 100: 6～9.5;
Titanium dioxide is 100: 5～40 with the weight ratio that contains the compound of molybdenum;
The weight ratio of titanium dioxide and compd A is 100: 30～100;
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,
Catalyst consumption is a benchmark with the total amount of terephthalic acid in the reaction system and m-phthalic acid, counts 150～300ppm with the total amount of titanium dioxide in the catalyzer and silicon-dioxide.
2, the preparation method of modified poly ester according to claim 1 is characterized in that the weight ratio of titanium dioxide and silicon-dioxide is 100: 7～8.3 in the described composite catalyst.
3, the preparation method of modified poly ester according to claim 1 is characterized in that titanium dioxide is 100: 8～20 with the weight ratio that contains the compound of molybdenum in the described composite catalyst.
4, the preparation method of modified poly ester according to claim 1 is characterized in that the weight ratio of titanium dioxide and compd A is 100: 50～80 in the described composite catalyst.
5, according to the preparation method of claim 1,2,3 or 4 described modified poly esters, it is characterized in that described catalyst consumption is a benchmark with the total amount of terephthalic acid in the reaction system and m-phthalic acid, counts 180～250ppm with the total amount of titanium dioxide in the catalyzer and silicon-dioxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03141506 CN1272359C (en) | 2003-07-09 | 2003-07-09 | Process for preparing modified polyester for the preparation of polyester fibre with high elasticity |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03141506 CN1272359C (en) | 2003-07-09 | 2003-07-09 | Process for preparing modified polyester for the preparation of polyester fibre with high elasticity |
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| CN1566176A CN1566176A (en) | 2005-01-19 |
| CN1272359C true CN1272359C (en) | 2006-08-30 |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100396829C (en) * | 2005-07-11 | 2008-06-25 | 中国石化仪征化纤股份有限公司 | Preparation of multi-stage shrinkage polyester fibre by one-step method |
| CN101787583A (en) * | 2010-03-13 | 2010-07-28 | 浙江理工大学 | Method for preparing continuous polymerization directly-spun high-shrinkage polyester filaments |
| CN101787584A (en) * | 2010-03-13 | 2010-07-28 | 浙江东华纤维制造有限公司 | Method for preparing continuous polymerization directly-spun high-shrinkage polyester staple fibers |
| CN101781811B (en) * | 2010-03-13 | 2011-12-07 | 浙江东华纤维制造有限公司 | Method for preparing continuous polymerization directly-spun cation-dyeable high-shrinkage polyester staple fibers |
| CN103572400B (en) * | 2012-08-06 | 2016-01-06 | 中国石油化工股份有限公司 | A kind of processing method of vortex spinning special polyester staple fiber |
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