CN1392174A - Process for preparing polyethylene terephthalate - Google Patents
Process for preparing polyethylene terephthalate Download PDFInfo
- Publication number
- CN1392174A CN1392174A CN 01113440 CN01113440A CN1392174A CN 1392174 A CN1392174 A CN 1392174A CN 01113440 CN01113440 CN 01113440 CN 01113440 A CN01113440 A CN 01113440A CN 1392174 A CN1392174 A CN 1392174A
- Authority
- CN
- China
- Prior art keywords
- polyethylene terephthalate
- consumption
- acetate
- reaction
- catalyst system
- 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.)
- Granted
Links
Abstract
The production process of polyethylene terephthalate with terephthalic acid and glycol includes the esterification of terephthalic acid and glycol at 220-263 deg.c and the polycondensation at temperature of 250-290 deg.c and pressure below 130 Pa in the presence of catalyst system. The catalyst system contains glycol antimony, compound A and sodium acetate, where compound A is one or the mixture of manganese acetate, cobalt acetate and zinc acetate. 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 method by terephthalic acid and ethylene glycol polyethylene terephthalate, the used catalyst system of polycondensation contains one or more the mixture in antimony glycol, sodium-acetate and manganese acetate, Cobaltous diacetate or the 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 method by terephthalic acid and ethylene glycol polyethylene terephthalate, it has adopted a kind of compound catalyst system in polycondensation process, 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.
Method by terephthalic acid and ethylene glycol polyethylene terephthalate provided by the invention comprises following process:
1) terephthalic acid and ethylene glycol carry out esterification under 220 ℃～263 ℃, generate the intermediate bishydroxyethyl terephthalate;
2) from reaction system, remove the water of generation;
3) the intermediate bishydroxyethyl terephthalate carries out polycondensation and obtains polyethylene terephthalate in the presence of catalyst system, the polycondensation temperature is 250 ℃～290 ℃, reaction pressure is less than 130Pa, this catalyst system contains antimony glycol, compd A and sodium-acetate, and compd A is one or more the mixture in manganese acetate, Cobaltous diacetate or the zinc acetate.
The consumption of catalyst system obtains the theoretical yield of polyethylene terephthalate based on this reaction, and wherein the consumption of antimony glycol is that the amount of antimony ion is 20～800ppm, preferably 150～650ppm; The consumption of compd A is that the total amount of manganese, cobalt or zine ion is 10～200ppm, preferably 20～150ppm; The consumption of sodium-acetate is that the amount of sodium ion is 1～100ppm, preferably 2～50ppm.
The raw material molar ratio of reaction is generally terephthalic acid/ethylene glycol=1: (1.1～1.5).Same as the prior art, add an amount of trimethyl phosphite 99 will help to improve the PET product as stablizer quality in the reaction.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, the limiting viscosity of product P ET section is tested with Ubbelohde viscometer, and 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.Raw material 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.
Catalyst system 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) | Property 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 (6)
1, a kind of method by terephthalic acid and ethylene glycol polyethylene terephthalate comprises following process:
1) terephthalic acid and ethylene glycol carry out esterification under 220 ℃～263 ℃, generate the intermediate bishydroxyethyl terephthalate;
2) from reaction system, remove the water of generation;
3) the intermediate bishydroxyethyl terephthalate carries out polycondensation and obtains polyethylene terephthalate in the presence of catalyst system, the polycondensation temperature is 250 ℃～290 ℃, reaction pressure is less than 130Pa, this catalyst system contains antimony glycol, compd A and sodium-acetate, and compd A is one or more the mixture in manganese acetate, Cobaltous diacetate or the zinc acetate.
2, according to the described method for preparing polyethylene terephthalate of claim 1, it is characterized in that the consumption of described catalyst system obtains the theoretical yield of polyethylene terephthalate based on this reaction, wherein the consumption of antimony glycol is that the amount of antimony ion is 20～800ppm, the consumption of compd A is that the total amount of manganese, cobalt or zine ion is 10～200ppm, and the consumption of sodium-acetate is that the amount of sodium ion is 1～100ppm.
3, according to the described method for preparing polyethylene terephthalate of claim 2, the consumption that it is characterized in that described catalyst system obtains the theoretical yield of polyethylene terephthalate based on this reaction, and wherein the consumption of antimony glycol is that the amount of antimony ion is 150～650ppm.
4, according to the described method for preparing polyethylene terephthalate of claim 2, the consumption that it is characterized in that described catalyst system is for obtaining the theoretical yield of polyethylene terephthalate based on this reaction, wherein the consumption of compd A is that the total amount of manganese, cobalt or zine ion is 20～150ppm.
5, according to the described method for preparing polyethylene terephthalate of claim 2, the consumption that it is characterized in that described catalyst system obtains the theoretical yield of polyethylene terephthalate based on this reaction, and wherein the consumption of sodium-acetate is that the amount of sodium ion is 2～50ppm.
6,, it is characterized in that described reaction raw materials molar ratio is terephthalic acid/ethylene glycol=1: (1.1～1.5) according to claim 1,2,3, the 4 or 5 described methods that prepare polyethylene terephthalate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011134402A CN1156511C (en) | 2001-06-14 | 2001-06-14 | Process for preparing polyethylene terephthalate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011134402A CN1156511C (en) | 2001-06-14 | 2001-06-14 | Process for preparing polyethylene terephthalate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1392174A true CN1392174A (en) | 2003-01-22 |
| CN1156511C CN1156511C (en) | 2004-07-07 |
Family
ID=4660166
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB011134402A Expired - Lifetime CN1156511C (en) | 2001-06-14 | 2001-06-14 | Process for preparing polyethylene terephthalate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1156511C (en) |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100509911C (en) * | 2004-05-05 | 2009-07-08 | 沙特基础工业公司 | Process for the production of polyethylene terephthalate copolyester, copolyester obtained thereby and use and catalyst useful in the process |
| US7655746B2 (en) | 2005-09-16 | 2010-02-02 | Eastman Chemical Company | Phosphorus containing compounds for reducing acetaldehyde in polyesters polymers |
| US7709593B2 (en) | 2006-07-28 | 2010-05-04 | Eastman Chemical Company | Multiple feeds of catalyst metals to a polyester production process |
| US7709595B2 (en) | 2006-07-28 | 2010-05-04 | Eastman Chemical Company | Non-precipitating alkali/alkaline earth metal and aluminum solutions made with polyhydroxyl ether solvents |
| US7745368B2 (en) | 2006-07-28 | 2010-06-29 | Eastman Chemical Company | Non-precipitating alkali/alkaline earth metal and aluminum compositions made with organic hydroxyacids |
| US7838596B2 (en) | 2005-09-16 | 2010-11-23 | Eastman Chemical Company | Late addition to effect compositional modifications in condensation polymers |
| US7932345B2 (en) | 2005-09-16 | 2011-04-26 | Grupo Petrotemex, S.A. De C.V. | Aluminum containing polyester polymers having low acetaldehyde generation rates |
| US8431202B2 (en) | 2005-09-16 | 2013-04-30 | Grupo Petrotemex, S.A. De C.V. | Aluminum/alkaline or alkali/titanium containing polyesters having improved reheat, color and clarity |
| US8557950B2 (en) | 2005-06-16 | 2013-10-15 | Grupo Petrotemex, S.A. De C.V. | High intrinsic viscosity melt phase polyester polymers with acceptable acetaldehyde generation rates |
| US8563677B2 (en) | 2006-12-08 | 2013-10-22 | Grupo Petrotemex, S.A. De C.V. | Non-precipitating alkali/alkaline earth metal and aluminum solutions made with diols having at least two primary hydroxyl groups |
| US9267007B2 (en) | 2005-09-16 | 2016-02-23 | Grupo Petrotemex, S.A. De C.V. | Method for addition of additives into a polymer melt |
| CN108059833A (en) * | 2017-12-07 | 2018-05-22 | 常州市沃兰特电子有限公司 | A kind of preparation method of high tear type cable sheath insulation material |
-
2001
- 2001-06-14 CN CNB011134402A patent/CN1156511C/en not_active Expired - Lifetime
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100509911C (en) * | 2004-05-05 | 2009-07-08 | 沙特基础工业公司 | Process for the production of polyethylene terephthalate copolyester, copolyester obtained thereby and use and catalyst useful in the process |
| US8987408B2 (en) | 2005-06-16 | 2015-03-24 | Grupo Petrotemex, S.A. De C.V. | High intrinsic viscosity melt phase polyester polymers with acceptable acetaldehyde generation rates |
| US8557950B2 (en) | 2005-06-16 | 2013-10-15 | Grupo Petrotemex, S.A. De C.V. | High intrinsic viscosity melt phase polyester polymers with acceptable acetaldehyde generation rates |
| US7838596B2 (en) | 2005-09-16 | 2010-11-23 | Eastman Chemical Company | Late addition to effect compositional modifications in condensation polymers |
| US7799891B2 (en) | 2005-09-16 | 2010-09-21 | Eastman Chemical Company | Phosphorus containing compounds for reducing acetaldehyde in polyesters polymers |
| US7932345B2 (en) | 2005-09-16 | 2011-04-26 | Grupo Petrotemex, S.A. De C.V. | Aluminum containing polyester polymers having low acetaldehyde generation rates |
| US8431202B2 (en) | 2005-09-16 | 2013-04-30 | Grupo Petrotemex, S.A. De C.V. | Aluminum/alkaline or alkali/titanium containing polyesters having improved reheat, color and clarity |
| US8791187B2 (en) | 2005-09-16 | 2014-07-29 | Grupo Petrotemex, S.A. De C.V. | Aluminum/alkyline or alkali/titanium containing polyesters having improved reheat, color and clarity |
| US7655746B2 (en) | 2005-09-16 | 2010-02-02 | Eastman Chemical Company | Phosphorus containing compounds for reducing acetaldehyde in polyesters polymers |
| US9267007B2 (en) | 2005-09-16 | 2016-02-23 | Grupo Petrotemex, S.A. De C.V. | Method for addition of additives into a polymer melt |
| US7745368B2 (en) | 2006-07-28 | 2010-06-29 | Eastman Chemical Company | Non-precipitating alkali/alkaline earth metal and aluminum compositions made with organic hydroxyacids |
| US7709595B2 (en) | 2006-07-28 | 2010-05-04 | Eastman Chemical Company | Non-precipitating alkali/alkaline earth metal and aluminum solutions made with polyhydroxyl ether solvents |
| US7709593B2 (en) | 2006-07-28 | 2010-05-04 | Eastman Chemical Company | Multiple feeds of catalyst metals to a polyester production process |
| US8563677B2 (en) | 2006-12-08 | 2013-10-22 | Grupo Petrotemex, S.A. De C.V. | Non-precipitating alkali/alkaline earth metal and aluminum solutions made with diols having at least two primary hydroxyl groups |
| CN108059833A (en) * | 2017-12-07 | 2018-05-22 | 常州市沃兰特电子有限公司 | A kind of preparation method of high tear type cable sheath insulation material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1156511C (en) | 2004-07-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP1325055B1 (en) | Process for producing poly(1,4-cyclohexylenedimethylene 1,4-cyclohexanedicarboxylate) and the reactor grade polyester therefrom | |
| CN1156511C (en) | Process for preparing polyethylene terephthalate | |
| JP3748819B2 (en) | Catalyst for producing polyester and method for producing polyester using the same | |
| US8901271B2 (en) | Process for making polyethylene terephthalate | |
| EP0091180A2 (en) | Catalyst system for polycondensation of ethylene terephthalate prepolymer | |
| CN100572447C (en) | Polyester resin composition, manufacture method and moulding product | |
| US3528946A (en) | Acetylacetonates as polycondensation catalysts in transesterification method of preparing polyesters | |
| CN1392173A (en) | Catalyst for polycondensation process of preparing polyethylene terephthalate | |
| CN100386361C (en) | Method of synthesizing non fiber use modified copolyester using ethylene glycol titanium catalysis | |
| JP3998942B2 (en) | Catalyst for producing polyester and method for producing polyester using the same | |
| TWI473832B (en) | Process for making polyethylene terephthalate | |
| US3734891A (en) | Transesterification catalysts for production of poly (c4 to c12 alkyleneterephthalate | |
| JP4591187B2 (en) | Method for producing polybutylene terephthalate | |
| US2956985A (en) | Metal salts of dithiocarbamic acids as catalysts in the production of polyesters | |
| CN1272359C (en) | Process for preparing modified polyester for the preparation of polyester fibre with high elasticity | |
| US3459711A (en) | Manufacture of linear fiber-forming polyesters | |
| JP2009024088A (en) | Polyester resin for rubber reinforcing fiber, and method for producing the same | |
| JP2000191764A (en) | Polyester-polymerization catalyst, polyester produced by using the same and production of polyester | |
| JP2002241482A (en) | Polyethylene naphthalate and production method of polyethylene naphthalate | |
| JP4930665B2 (en) | Polyester polymerization catalyst and polyester production method (orthoester) | |
| JP4582393B2 (en) | Polyester production method | |
| JP2002227037A (en) | Spun-dyed polyester yarn | |
| CN1266190C (en) | Prepolycondensation and polycondensation catalyst for preparing modified polyester | |
| JPS58117216A (en) | Production of polyester | |
| US3427288A (en) | Salts of ethylene diamine tetraacetic acid as polycondensation catalysts |
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 | ||
| CX01 | Expiry of patent term |
Granted publication date: 20040707 |
|
| CX01 | Expiry of patent term |