CN1544506A - Method for preparing composite polyether polycondensation catalyst and using method thereof - Google Patents
Method for preparing composite polyether polycondensation catalyst and using method thereof Download PDFInfo
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- CN1544506A CN1544506A CNA2003101087748A CN200310108774A CN1544506A CN 1544506 A CN1544506 A CN 1544506A CN A2003101087748 A CNA2003101087748 A CN A2003101087748A CN 200310108774 A CN200310108774 A CN 200310108774A CN 1544506 A CN1544506 A CN 1544506A
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Abstract
The invention relates to a process for preparing polyethylene polycondensation composite catalyst and method of use, subjecting aluminum compounds, ethylene glycol and benzene to inverse flow reaction, filtering and drying to obtain aluminium ethylene glycol, mixing aluminium ethylene glycol, sulfonic acid compound and ethylene glycol, thus the polyester polycondensated composite catalyst can be obtained, which can be used for preparing thermoplastic polyester and copolyester with relative molecular weight greater than 10 thousand.
Description
Technical field
The present invention relates to a kind of Preparation of catalysts method and application thereof, be meant especially to be used for polyester polycondensation reaction, the preparation method and the application thereof of the composite catalyst of forming by aluminum compound and sulfoacid compound.
Background technology
Polyester is widely used as raw materials such as fabric, packing, industry silk and engineering plastics at present, and since appearance and industrialization, the chemist never stopped the research of various catalyzer, and had formed many patents, now was summarized as follows:
One, relate to adopt the antimony based compound be polyester polycondensation catalyst patents such as CN1299839, CN1319620 are arranged.Because its catalytic activity of antimony based compound is lower, makes the polyester product whiteness poor easily; Because the toxicity of itself easily causes environmental pollution in spinning process, total cost of production is increased again.
Two, relate to that to adopt the germanium based compound be that the Foshan heavenly steed polyester slice factory etc. of having of polyester polycondensation catalyst is representative.Germanium based compound catalyzer has good strainability, and spinning process is polluted low; Its product whiteness is good; But its price is very expensive, has influenced the popularity of using.
Three, relate to adopt titanium sub-group compound be polyester polycondensation catalyst patents such as CN1403193, CN00816585, CN1244546A, CN1393482, US60/092032, US09895990, US3056817 are arranged.Titanium series catalyst has comprised inorganic salt (oxalic acid lithia titanium, titanium dioxide) or organosilane ester (tetrabutyl titanate, tetrabutyl titanate).Titanium sub-group compound is that polyester polycondensation catalyst exists poor stability and polyester product yellowing, muddy shortcoming.And a large amount of side reaction in the polycondensation process, make its product end carboxyl raise, glycol ether content rises, and fusing point descends.Though above patent improves to some extent to the problems referred to above, can not effectively suppress the thermal destruction of polyester all the time.
Four, relate to employing do not contain antimony, germanium, titanium system polyester catalyst patents such as JP7187097, JP14678197, CN1220677 are arranged is representative, they are all to contain the solution of aluminum compound and basic cpd, because the catalytic activity of aluminum compound is little, these patents fail to solve activity problems.JP0005728, CN1373780 patent also provide a kind of new polyester catalyzer that contains aluminum compound and phosphorus compound in addition, because the adding of phosphorus compound, solved the active insufficient problem of aluminum compound, but phosphorus compound related in this patent has suitable toxicity mostly, and some still is huge poison, and this has all brought bigger problem and inconvenience for production, transportation, storage, polyester.
Summary of the invention
The problem to be solved in the present invention provides a kind of nontoxic, polycondensation of polyester composite catalyst that cost is low is made up of aluminum compound and sulfoacid compound.
For addressing this problem, take following technical scheme:
(1) be 1: 3～5: 0.1～0.2 to mix by weight with chemical pure aluminum compound (in the weight of aluminium), ethylene glycol and benzene; Place glassware to carry out back flow reaction in this mixture, temperature is controlled at 120～170 ℃, refluxes 2～4 hours, progressively removes and anhydrates and benzene, after filtration, obtains the mixture of ethylene glycol and ethylene glycol aluminium; Is 150～200 ℃ of following vacuum dryings with the mixture of ethylene glycol and ethylene glycol aluminium in temperature, and vacuum tightness is less than 20～100Pa, and the time is to dry under the condition in 2～5 hours, obtains a kind of ethylene glycol aluminium of white crystal.
With above-mentioned ethylene glycol aluminium and chemical pure sulfoacid compound (in the weight of Phenylsulfonic acid), ethylene glycol be by weight 1: 1～2: 50～100 fully mix after, make the composite catalyst of polycondensation of polyester of the form of suspension of ethylene glycol.
(2) in the contained composition of described composite catalyst, wherein aluminum compound is to be selected from a kind of in the following compound, and they are aluminum oxide, aluminium hydroxide.
(3) in the contained composition of described composite catalyst, wherein sulfoacid compound is to be selected from a kind of in the following compound, and they are Phenylsulfonic acid, toluene sulfonic acide, to benzene disulfonic acid, terephthalic acid sulfonic acid.
(4) make composite catalyst and comprise aluminum compound and sulfoacid compound, the consumption of its aluminum compound in the use (in the weight of aluminium) is 0.002～0.2% with the weight percent of terephthalic acid; The consumption of its sulfoacid compound (in the weight of Phenylsulfonic acid) is 0.01～0.5% with the weight percent of terephthalic acid.
(5) composite catalyst is to add after the esterification of polyreaction, before the polycondensation.
(6) composite catalyst of the present invention preparation can be used for preparing relative molecular weight greater than 10000 thermoplastic polyester and copolyesters.
Advantage of the present invention has provided a kind of composite catalyst that contains aluminum compound and sulfoacid compound, and it is different from the composite catalyst of aluminum compound and phosphorus compound, and it had both solved the active insufficient problem of aluminum compound, had solved the toxic problem of phosphorus compound again; This composite catalyst makes waste treatment simple because of not containing heavy metals such as antimony, helps environmental protection; Characteristics such as its synthetic polyester has that form and aspect are good, side reaction and thermal degradation reaction are few; Its raw material is easy to get low price simultaneously.
Embodiment
Embodiment 1
10 gram chemical pure aluminium sesquioxides, 1 gram benzene and 50 gram ethylene glycol are mixed; Place glassware to carry out back flow reaction in this mixture, temperature is controlled at 140 ℃, refluxes 3 hours, progressively removes and anhydrates and benzene, after filtration, obtains the mixture of ethylene glycol and ethylene glycol aluminium; At 180 ℃ of following vacuum dryings, vacuum tightness is at 60 ± 10Pa with the mixture of ethylene glycol and ethylene glycol aluminium, and the time is 5 hours, obtains a kind of ethylene glycol aluminium 22.3 grams of white crystal form.
Get ethylene glycol aluminium 0.15 gram, chemical pure Phenylsulfonic acid 0.30 gram and ethylene glycol 5 grams and stir, as the composite catalyst of polycondensation of polyester.
392 gram terephthalic acids, 248 gram ethylene glycol are added in 2.5 liters the polymeric kettle and carry out esterification, temperature is controlled at 230 ± 10 ℃, reaction times is 3 hours, after esterification finishes, add above-mentioned composite catalyst, carry out polycondensation, in 1 hour temperature is risen to 285 ℃, vacuum tightness is 70Pa, and polycondensation is 2 hours with this understanding.The limiting viscosity that obtains polyester is 0.657, form and aspect L value 78.9, form and aspect b value 2.13.
Embodiment 2
Digesting pure cerium hydroxide aluminium, 1 gram benzene and 50 gram ethylene glycol with 7.8 mixes; Place glassware to carry out back flow reaction in this mixture, temperature is controlled at 150 ℃, refluxes 4 hours, progressively removes and anhydrates and benzene, after filtration, obtains the mixture of ethylene glycol and ethylene glycol aluminium; At 180 ℃ of following vacuum dryings, vacuum tightness is less than 50 ± 10Pa with the mixture of ethylene glycol and ethylene glycol aluminium, and the time is 4.5 hours, obtains a kind of ethylene glycol aluminium 23.2 grams of white crystal form.
Get ethylene glycol aluminium 0.20 gram, chemical pure toluene sulfonic acide 0.49 gram and ethylene glycol 8 grams and stir, as the composite catalyst of polycondensation of polyester.
490 gram terephthalic acids, 310 gram ethylene glycol are added in 2.5 liters the polymeric kettle and carry out esterification, temperature is controlled at 240 ± 10 ℃, reaction times is 3 hours, after esterification finishes, add above-mentioned composite catalyst, carry out polycondensation, in 1 hour temperature is risen to 285 ℃, vacuum tightness is 70Pa, and polycondensation is 2 hours with this understanding.The limiting viscosity that obtains polyester is 0.627, form and aspect L value 79.1, form and aspect b value 2.23.
Embodiment 3
10 gram chemical pure aluminium sesquioxides, 1 gram benzene and 50 gram ethylene glycol are mixed; Place glassware to carry out back flow reaction in this mixture, temperature is controlled at 140 ℃, refluxes 3 hours, progressively removes and anhydrates and benzene, after filtration, obtains the mixture of ethylene glycol and ethylene glycol aluminium; At 180 ℃ of following vacuum dryings, vacuum tightness is at 60 ± 10Pa with the mixture of ethylene glycol and ethylene glycol aluminium, and the time is 5 hours, obtains a kind of ethylene glycol aluminium 22.3 grams of white crystal form.
Get ethylene glycol aluminium 0.15 gram, chemical pure stirs benzene disulfonic acid 0.22 gram and ethylene glycol 5 grams, as the composite catalyst of polycondensation of polyester.
392 gram terephthalic acids, 248 gram ethylene glycol are added in 2.5 liters the polymeric kettle and carry out esterification, temperature is controlled at 230 ± 10 ℃, reaction times is 3 hours, after esterification finishes, add above-mentioned composite catalyst, carry out polycondensation, in 1 hour temperature is risen to 285 ℃, vacuum tightness is 70Pa, and polycondensation is 2 hours with this understanding.The limiting viscosity that obtains polyester is 0.601, form and aspect L value 80.2, form and aspect b value 2.21.
Embodiment 4
Digesting pure cerium hydroxide aluminium, 1 gram benzene and 50 gram ethylene glycol with 7.8 mixes; Place glassware to carry out back flow reaction in this mixture, temperature is controlled at 150 ℃, refluxes 4 hours, progressively removes and anhydrates and benzene, after filtration, obtains the mixture of ethylene glycol and ethylene glycol aluminium; At 180 ℃ of following vacuum dryings, vacuum tightness is less than 50 ± 10Pa with the mixture of ethylene glycol and ethylene glycol aluminium, and the time is 4.5 hours, obtains a kind of ethylene glycol aluminium 23.2 grams of white crystal form.
Get ethylene glycol aluminium 0.20 gram, chemical pure terephthalic acid sulfonic acid 0.63 gram and ethylene glycol 8 grams and stir, as the composite catalyst of polycondensation of polyester.
490 gram terephthalic acids, 310 gram ethylene glycol are added in 2.5 liters the polymeric kettle and carry out esterification, temperature is controlled at 240 ± 10 ℃, reaction times is 3 hours, after esterification finishes, add above-mentioned composite catalyst, carry out polycondensation, in 1 hour temperature is risen to 285 ℃, vacuum tightness is 70Pa, and polycondensation is 2 hours with this understanding.The limiting viscosity that obtains polyester is 0.586, form and aspect L value 81.3, form and aspect b value 2.42.
Claims (3)
1. the preparation method of a polycondensation of polyester composite catalyst is characterized in that:
A. be 1: 3～5: 0.1～0.2 to mix by weight with aluminum compound, ethylene glycol and benzene, described aluminum compound is aluminum oxide or aluminium hydroxide; This mixture is placed glassware, is 120～170 ℃ in temperature, and back flow reaction is 2～4 hours, progressively removes and anhydrates and benzene, obtains the mixture of ethylene glycol and ethylene glycol aluminium after filtration;
B. the mixture with ethylene glycol and ethylene glycol aluminium is 150～200 ℃ in temperature, and vacuum tightness is less than being 20～100Pa, and the time is to dry under 2～5 hours the condition, obtains a kind of ethylene glycol aluminium of white crystal;
C. with above-mentioned ethylene glycol aluminium and sulfoacid compound (in the weight of Phenylsulfonic acid), ethylene glycol be by weight 1: 1～2: 50～100 fully mix after, make the composite catalyst of the polycondensation of polyester of glycolic suspension form, described sulfoacid compound is Phenylsulfonic acid, toluene sulfonic acide, to benzene disulfonic acid or terephthalic acid sulfonic acid.
2. the using method of polycondensation of polyester composite catalyst is characterized in that the consumption (in the weight of aluminium) of aluminum compound in the composite catalyst ingredient and the weight percent of terephthalic acid are 0.002～0.2%; The consumption of sulfoacid compound (in the weight of Phenylsulfonic acid) is 0.01～0.5% with the weight percent of terephthalic acid.
3. the using method of polycondensation of polyester composite catalyst as claimed in claim 2 is characterized in that composite catalyst adds after the esterification of polyreaction, before the polycondensation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200310108774 CN1223623C (en) | 2003-11-21 | 2003-11-21 | Method for preparing composite polyether polycondensation catalyst and using method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN 200310108774 CN1223623C (en) | 2003-11-21 | 2003-11-21 | Method for preparing composite polyether polycondensation catalyst and using method thereof |
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| CN1544506A true CN1544506A (en) | 2004-11-10 |
| CN1223623C CN1223623C (en) | 2005-10-19 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102234370A (en) * | 2010-04-23 | 2011-11-09 | 常州化学研究所 | Aluminum catalyst for polyester synthesis, preparation method thereof and usage method thereof |
| CN107868238A (en) * | 2017-11-29 | 2018-04-03 | 中国石油化工股份有限公司 | A kind of preparation method and application of heavy metal free polyester polycondensation catalyst |
| CN109467749A (en) * | 2018-10-22 | 2019-03-15 | 杭州如墨科技有限公司 | A kind of production technology of the polynary aluminium alcoholates of nanoscale |
-
2003
- 2003-11-21 CN CN 200310108774 patent/CN1223623C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102234370A (en) * | 2010-04-23 | 2011-11-09 | 常州化学研究所 | Aluminum catalyst for polyester synthesis, preparation method thereof and usage method thereof |
| CN102234370B (en) * | 2010-04-23 | 2012-08-08 | 常州化学研究所 | Aluminum catalyst for polyester synthesis, preparation method thereof and usage method thereof |
| CN107868238A (en) * | 2017-11-29 | 2018-04-03 | 中国石油化工股份有限公司 | A kind of preparation method and application of heavy metal free polyester polycondensation catalyst |
| CN107868238B (en) * | 2017-11-29 | 2019-12-17 | 中国石油化工股份有限公司 | Preparation method and application of heavy metal-free polyester polycondensation catalyst |
| CN109467749A (en) * | 2018-10-22 | 2019-03-15 | 杭州如墨科技有限公司 | A kind of production technology of the polynary aluminium alcoholates of nanoscale |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1223623C (en) | 2005-10-19 |
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