CN1392173A - Catalyst for polycondensation process of preparing polyethylene terephthalate - Google Patents
Catalyst for polycondensation process of preparing polyethylene terephthalate Download PDFInfo
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- CN1392173A CN1392173A CN 01113439 CN01113439A CN1392173A CN 1392173 A CN1392173 A CN 1392173A CN 01113439 CN01113439 CN 01113439 CN 01113439 A CN01113439 A CN 01113439A CN 1392173 A CN1392173 A CN 1392173A
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Abstract
The catalyst for the polycondensation process of terephthalic acid and glycol to prepare polyethylene terephthalate is a composition containing glycol antimony, compound A and sodium acetate, where compound a is one or the mixture of manganese acetate, cobalt acetate and zinc acetate. Compared with available technology, the present invention has the advantages of fast polycondensation speed, effective inhibition of side reaction and good colour and luster of the polyethylene terephthalate product.
Description
The invention belongs to a kind of catalyzer that is used for by terephthalic acid and ethylene glycol polyethylene terephthalate polycondensation process, catalyzer contains antimony glycol, sodium-acetate and manganese acetate, Cobaltous diacetate or zinc acetate.
Polyethylene terephthalate (PET) is important synthetic fiber material, can spin polyester filament and polyester staple fiber, civilian or industrial extremely wide purposes arranged all.Simultaneously, PET still is a kind of engineering plastics of excellent property, can make polyester bottles, polyester film etc.PET is civilian or industrial extremely wide purposes is arranged, so the preparation method of PET also is subjected to people's attention all the time very much.
With respect to early stage ester-interchange method, the direct esterification legal system is equipped with PET and has plurality of advantages such as flow process is simple, production cost is low.The direct esterification method claims terephthalic acid (TPA) method again, terephthalic acid and ethylene glycol direct esterification generate intermediate bishydroxyethyl terephthalate (BHET), remove behind the water that produces in the system BHET and carry out polycondensation obtain product P ET in the presence of catalyzer.In esterification process, because the H among the TPA
+Itself has katalysis, so esterification process do not need to add catalyzer in addition, and in polycondensation, and prior art adopts the catalyst system of being made up of antimonous oxide or antimony acetate and acetate then morely.As patent JP80-120, as stablizer, antimonous oxide, sour cobalt and calcium acetate prepare PET as the catalyzer of polycondensation by the TPA method with phosphoric acid salt in 623 introductions, it is said that the PET of preparation has spinning property preferably thus.With respect to simple antimonous oxide or antimony acetate, this compound catalyst system makes the speed of response of polycondensation obviously accelerate, yet its has simultaneously also promoted the carrying out of side reaction, thereby easily causes by product to increase, the PET yellowing of cutting into slices.
The purpose of this invention is to provide a kind of catalyzer that is used for by terephthalic acid and ethylene glycol polyethylene terephthalate reaction polycondensation process, it can not only accelerate the speed of response of polycondensation, the carrying out that can suppress side reaction simultaneously preferably, the PET that obtains section has color and luster preferably.
Catalyzer provided by the invention is the composition that contains antimony glycol, compd A and sodium-acetate, wherein compd A is one or more the mixture in manganese acetate, Cobaltous diacetate or the zinc acetate, the theoretical yield of polyethylene terephthalate came when the amount of each component was applied to above-mentioned reaction in catalyzer, separately based on the theoretical yield of polyethylene terephthalate, wherein antimony glycol is that the amount of antimony ion is 20～800ppm, is preferably 150～650ppm; Compd A is that the total amount of manganese, cobalt or zine ion is 10～200ppm, is preferably 20～150ppm; Sodium-acetate is that the amount of sodium ion is 1～100ppm, is preferably 2～50ppm.
Same as the prior art, can also add an amount of trimethyl phosphite 99 in the reaction as stablizer, this will help to improve the quality of PET product.And catalyzer adds when feeding intake or add before polycondensation and all be fine
Compared with prior art, the invention has the advantages that the speed of response of not only having accelerated polycondensation, and can suppress the carrying out of side reaction effectively, the PET product that obtains has color and luster preferably.
To come below that the invention will be further described by embodiment.
In an embodiment, adopt this catalyzer to carry out the limiting viscosity that polycondensation obtains product P ET section and test with Ubbelohde viscometer, solvent is 25 ℃ phenol and a tetrachloroethane mixture, phenol: tetrachloroethane=1: 1 (weight ratio).The form and aspect of section are by L, a, b value representation, wherein L is the transparency index, a is blue index, b is a yellowness index, according to the GB/T14190-93 standard, adopt automatic color difference meter, light source D65,10 ° of visuals field, automatically measure the numerical value of x, y, z system, and be transformed into L, a, the b system represents chroma data.
Embodiment 1～10:
Preparation process is carried out in having the batch reactor of stirring, and reactor connects a rectifier unit.Reaction raw materials terephthalic acid and ethylene glycol drop into reactor with mol ratio at 1: 1.3, add the catalyst system of aequum, and add the trimethyl phosphite 99 of 40ppm.In reactor, charge into the nitrogen of 0.1～0.2Mpa (gauge pressure) during the reaction beginning.Along with the carrying out of reaction,, keep system pressure about 0.2MPa (gauge pressure) by regulating the outlet valve aperture at rectifier unit top.When temperature of reaction is increased to 220～240 ℃, the water that reaction generates enters rectifier unit with the ethylene glycol steam of carrying secretly to be separated, drainage water and backflow ethylene glycol.The water yield to be discharged during near theoretical value temperature of reaction rise to 250～265 ℃, indicate that esterification finishes substantially this moment.Then system pressure is reduced to negative pressure by normal pressure, and maintain below the 130Pa, temperature of reaction rises to 250 ℃～290 ℃, stops after polycondensation is finished stirring.Product through the Cast Strip, pelletizing, finally obtain product P ET section.
Catalyzer and consumption thereof that polycondensation is used see Table 1, and all based on the theoretical yield of polyethylene terephthalate, the reaction times of polycondensation and the analytical data of product see Table 2 to the amount of each component.Table 1.
Table 2.
| Catalyst system | Catalyst levels (ppm) | |
| Embodiment 1 | Antimony glycol/manganese acetate/sodium-acetate | ???????Sb/Mn/Na＝400/60/20 |
| Embodiment 2 | Antimony glycol/manganese acetate/sodium-acetate | ???????Sb/Mn/Na＝300/50/10 |
| Embodiment 3 | Antimony glycol/Cobaltous diacetate/sodium-acetate | ???????Sb/Co/Na＝400/60/20 |
| Embodiment 4 | Antimony glycol/zinc acetate/sodium-acetate | ???????Sb/Zn/Na＝400/60/10 |
| Embodiment 5 | Antimony glycol/manganese acetate/Cobaltous diacetate/sodium-acetate | ???????Sb/Mn/Co/Na＝350/45/45/20 |
| Embodiment 6 | Antimony glycol/manganese acetate/Cobaltous diacetate/sodium-acetate | ???????Sb/Mn/Co/Na＝267/35/35/10 |
| Embodiment 7 | Antimony glycol/manganese acetate/Cobaltous diacetate/zinc acetate/sodium-acetate | ???????Sb/Mn/Co/Zn/Na＝350/45/45/20/20 |
| Embodiment 8 | Antimony glycol/manganese acetate/Cobaltous diacetate/zinc acetate/sodium-acetate | ???????Sb/Mn/Co/Zn/Na＝267/35/35/10/4.5 |
| Embodiment 9 | Antimony glycol/manganese acetate/Cobaltous diacetate/zinc acetate/sodium-acetate | ???????Sb/Mn/Co/Zn/Na＝267/25/25/10/4.5 |
| Embodiment 10 | Antimony glycol/manganese acetate/Cobaltous diacetate/zinc acetate/sodium-acetate | ???????Sb/Mn/Co/Zn/Na＝267/29/29/10/9 |
| The polycondensation time (min) | Limiting viscosity (dl/g) | ?????L | ?????a | ???b | |
| Embodiment 1 | ????110 | ????0.693 | ????65.1 | ????-1.7 | ???5 |
| Embodiment 2 | ????126 | ????0.685 | ????77.5 | ????-0.2 | ???5 |
| Embodiment 3 | ????115 | ????0.690 | ????80.8 | ????0.7 | ???4 |
| Embodiment 4 | ????122 | ????0.679 | ????79.9 | ????0.6 | ???5 |
| Embodiment 5 | ????110 | ????0.681 | ????79.7 | ????-0.7 | ???2 |
| Embodiment 6 | ????120 | ????0.678 | ????83.7 | ????-0.9 | ???2 |
| Embodiment 7 | ????95 | ????0.678 | ????85.1 | ????-0.4 | ???1 |
| Embodiment 8 | ????102 | ????0.686 | ????77.2 | ????1.5 | ???4 |
| Embodiment 9 | ????125 | ????0.707 | ????78.3 | ????1.1 | ???4 |
| Embodiment 10 | ????110 | ????0.693 | ????84.4 | ????-0.7 | ???2 |
Claims (4)
1, a kind of catalyzer that is used for by terephthalic acid and ethylene glycol polyethylene terephthalate reaction polycondensation process, this catalyzer is for containing antimony glycol, the composition of compd A and sodium-acetate, wherein compd A is a manganese acetate, the mixture of one or more in Cobaltous diacetate or the zinc acetate, the theoretical yield of polyethylene terephthalate came when the amount of each component was applied to above-mentioned reaction in catalyzer, separately based on the theoretical yield of polyethylene terephthalate, wherein antimony glycol is that the amount of antimony ion is 20～800ppm, compd A is a manganese, the total amount of cobalt or zine ion is 10～200ppm, and sodium-acetate is that the amount of sodium ion is 1～100ppm.
2, according to the described catalyzer of claim 1, the amount that it is characterized in that described antimony glycol is that the amount of antimony ion is 150～650ppm.
3, according to the described catalyzer of claim 1, the amount that it is characterized in that described compd A is that the total amount of manganese, cobalt or zine ion is 20～150ppm.
4, according to the described catalyzer of claim 1, the amount that it is characterized in that described sodium-acetate is that the amount of sodium ion is 2～50ppm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01113439 CN1392173A (en) | 2001-06-14 | 2001-06-14 | Catalyst for polycondensation process of preparing polyethylene terephthalate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01113439 CN1392173A (en) | 2001-06-14 | 2001-06-14 | Catalyst for polycondensation process of preparing polyethylene terephthalate |
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| Publication Number | Publication Date |
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| CN1392173A true CN1392173A (en) | 2003-01-22 |
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| CN 01113439 Pending CN1392173A (en) | 2001-06-14 | 2001-06-14 | Catalyst for polycondensation process of preparing polyethylene terephthalate |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1294176C (en) * | 2003-07-09 | 2007-01-10 | 中国石化上海石油化工股份有限公司 | Composite catalyst for preparing modified polyester |
| CN101328261B (en) * | 2008-07-29 | 2011-01-12 | 南京工业大学 | Preparation of high molecular weight poly(butylene succinate) |
| CN101338021B (en) * | 2007-07-03 | 2011-10-05 | 中国石化上海石油化工股份有限公司 | Method for making polyester for manufacturing industrial silk |
| CN104418997A (en) * | 2013-08-21 | 2015-03-18 | 中国科学院大连化学物理研究所 | Synthetic method of polyethylene glycol terephthalate from biomass glycol |
| CN105461906A (en) * | 2015-12-29 | 2016-04-06 | 江苏恒力化纤股份有限公司 | Polyester and preparation method thereof |
| CN108193309A (en) * | 2018-02-10 | 2018-06-22 | 海盐县硕创服装研究所 | Ultra-fine denier polyester filament yarn and preparation method thereof |
-
2001
- 2001-06-14 CN CN 01113439 patent/CN1392173A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1294176C (en) * | 2003-07-09 | 2007-01-10 | 中国石化上海石油化工股份有限公司 | Composite catalyst for preparing modified polyester |
| CN101338021B (en) * | 2007-07-03 | 2011-10-05 | 中国石化上海石油化工股份有限公司 | Method for making polyester for manufacturing industrial silk |
| CN101328261B (en) * | 2008-07-29 | 2011-01-12 | 南京工业大学 | Preparation of high molecular weight poly(butylene succinate) |
| CN104418997A (en) * | 2013-08-21 | 2015-03-18 | 中国科学院大连化学物理研究所 | Synthetic method of polyethylene glycol terephthalate from biomass glycol |
| CN105461906A (en) * | 2015-12-29 | 2016-04-06 | 江苏恒力化纤股份有限公司 | Polyester and preparation method thereof |
| CN105461906B (en) * | 2015-12-29 | 2018-05-18 | 江苏恒力化纤股份有限公司 | A kind of polyester and preparation method thereof |
| CN108193309A (en) * | 2018-02-10 | 2018-06-22 | 海盐县硕创服装研究所 | Ultra-fine denier polyester filament yarn and preparation method thereof |
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