CN102234370A - Aluminum catalyst for polyester synthesis, preparation method thereof and usage method thereof - Google Patents
Aluminum catalyst for polyester synthesis, preparation method thereof and usage method thereof Download PDFInfo
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- CN102234370A CN102234370A CN 201010154081 CN201010154081A CN102234370A CN 102234370 A CN102234370 A CN 102234370A CN 201010154081 CN201010154081 CN 201010154081 CN 201010154081 A CN201010154081 A CN 201010154081A CN 102234370 A CN102234370 A CN 102234370A
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Abstract
The invention discloses an aluminum catalyst for polyester synthesis, a preparation method thereof and a usage method thereof. The catalyst which is aluminum glycol and is special for a polycondensation reaction in a polyester synthesis process of terephthalic acid and glycol is prepared through reacting aluminum/aluminum alcoholates/lithium aluminum hydride with glycol. The catalyst, which has less toxicity, allows the molecular weight of PET catalyzed by the catalyst to achieve more than 30,000, can coexist with polycondensation products, has no influence on the quality of the PET, allows requirements of environmental protection to be satisfied and requirements of activity to be guaranteed, has a high activity on the PET synthesizing reaction, and has low cost, is a novel catalyst for the condensation polymerization of PET synthesis.
Description
Technical field
The invention belongs to catalysis technical field, relating in particular to a kind of is synthetic PET polycondensation aluminum-based catalyst, its preparation method and using method of raw material with ethylene glycol and terephthalic acid.
Background technology
Polyester be by polyvalent alcohol and polyprotonic acid polycondensation and the polymkeric substance general name.Mainly refer to polyethylene terephthalate (PET), also comprise line style thermoplastic resins such as polybutylene terephthalate (PBT) and polyarylester traditionally.Be a class excellent performance, broad-spectrum engineering plastics.
On the PET manufacture, can adopt terephthalic acid or dimethyl terephthalate (DMT) and ethylene glycol to carry out esterification or transesterify production terephthalic acid two (2-hydroxyethyl) ester, then it is carried out polycondensation and obtain PET with catalyzer high temperature under vacuum.The fiber level PET mainly adopts terephthalic acid and the production of ethylene glycol direct esterification-polycondensation process both at home and abroad at present.Polycondensation catalyst plays crucial effects in the production process of polyester, activity of such catalysts often can characterize with the viscosity of product, and viscosity is big more, and activity is high more.
The PET synthetic catalyst is as the essential and of paramount importance component of the synthetic institute of PET, and its research and development are more more leading than PET study on the synthesis, also wide many of the related scope of people's research contents.For example, from the strong acid class catalyzer of knowing such as sulfuric acid, to solid acid, metal oxide, the carboxylate salt of metal, alkoxide, hydrocarbonylation thing, nitrogenous or sulfur organic catalyzer and compound and/or load class catalyzer or the like, the chemical element that relates to comprises tens of kinds of elements in basic metal, alkaline-earth metal, carbon family, nitrogen family, chalcogen and the transition metal (comprising rare earth metal).People are by a large amount of discovering, the compound of above-mentioned many elements can be used as PET synthetic catalyzer.But the uncertainty that influenced by reaction conditions to exist owing to catalytic activity, stability maybe can not satisfy the PET quality requirements, in fact, has only metallic antimony, germanium, titanium, tin to be suitable as the synthetic of industrialization PET or produces.Now metal catalyst that exploitation in the PET PET industry is used (antimony system, titanium system, germanium system, tin system and aluminum-based catalyst etc.) and enzyme catalyst are briefly introduced:
Antimony-based catalyst: in antimony-based catalyst, antimonous oxide, antimony acetate and in recent years the antimony glycol of preliminary commercial application be most important representative.Do not obtain as yet at other catalyzer under the condition of important breakthrough, people are by the improvement to antimony-based catalyst, or the antimony catalyst system improves catalytic activity or improvement product P ET quality is still considerable research direction and theme to develop new containing.Contain aspect the antimony catalyst system research foundation novel, mostly people are to improve catalytic performance by research antimony composite catalyst system, for example use antimony compounds, Cobaltous diacetate, manganese acetate, zinc and magnesium, calcium cpd, rare earth compound etc. to form composite catalyzing antimony system.Because the antimony compounds is poisonous, therefore in use be restricted.
Titanium series catalyst: Titanium series catalyst is because have higher activity in recent years, compare more environmental protection, more economical and enjoy people to pay close attention to antimony-based catalyst, Titanium series catalyst has following several at present: titanium dioxide, titanium isopropylate, tetra-n-butyl titanate, titanium ethylene glycolate, metatitanic acid four phenyl esters, titanium acetylacetone.The advantage of Titanium series catalyst is active higher, low price obtains easily, shortcoming is that these catalyzer are because not anti-hydrolysis or activity can not get effective control in whole catalyzed reaction, therefore in reaction, often show as degradation under poor catalyst stability, catalyze side reactions aggravation, synthetic PET muddiness, yellowing, the PET performance index, need suppress yellowing with toner.
Germanium series catalysts: the organometallic complex that germanium dioxide and germanium are arranged commonly used.The germanium dioxide powder of the Britain Moldform company development nineties, with its catalysis synthesizing polyester, germanium dioxide stability is better, the reaction conditions gentleness, in the reaction process side reaction less, the stablizer phosphoric acid of adding is not had an effect with catalyzer, the gained polyester slice is a pure white, and transparency is higher.But because the germanium resource scarcity costs an arm and a leg, and volatilizees from reaction system easily, so this type of catalyzer is suitable for the polyester product high-grade with preparation.
The tin series catalysts: commonly used having is following several: stannous oxalate, Dibutyltin oxide, stannous octoate, methyl ethyl diketone tin, the tin series catalysts also has tin protochloride, glass putty, stannic oxide and tin acetate etc. in addition.With this type of catalyst synthesizing polyester, better catalytic activity, but the gained PET hue is not so good as antimony-based catalyst, and tin is poisonous, so this type of catalyzer is not applied to industrial production.
Make catalyzer with enzyme, have the following advantages: 1) enzymic catalytic reaction has selectivity; 2) use enzymic catalytic reaction, conditions such as temperature, pressure and pH value are gentle; 3) enzyme can be reused, and is nontoxic, compliance with environmental protection requirements; 4) enzyme catalysis belongs to homogeneous catalysis, in the synthesizing polyester process, does not require and must dewater and reduce pressure.The enzyme of catalysis polycondensation commonly used has first silk yeast fermentoid, pig pancreas enzyme, false unicellular enzyme etc.
The characteristics that aluminum-based catalyst has is cheap, toxicity is low, the application of aluminum current series catalysts has begun to present good prospect, substitutes antimony fully, Titanium series catalyst also is an inevitable trend.There is the aluminum compound catalyzer of catalytic activity that aluminum phosphate, Tai-Ace S 150, aluminum nitrate, aluminum chloride, aluminium sesquioxide, aluminium hydroxide are arranged to polycondensation, aluminium powder, clay (kaolin, mica, polynite, mother-in-law's thread soil, sepiolite etc.), the 4A-molecular sieve, the 5A-molecular sieve, aluminium phosphate molecular sieve, aluminum alkyls (trimethyl aluminium, triethyl aluminum, tri-propyl aluminum etc.) etc.Nontoxic or the low toxicity of aluminum-based catalyst, there is not problem of environmental pollution, the catalytic activity height, can shortens the reaction times, improve the unit production capacity.The metal remained amount only is tens of/one of antimony in PET, more helps spinning; The PET transparency increases, gray scale disappears, as adopt the L value that light PET is arranged of aluminum-based catalyst production to improve 10% than the L value of the PET that adopts antimony-based catalyst to produce at least, do not contain heavy metal and objectionable impurities, can be used for producing high-grade film and packing bottle, help HUMAN HEALTH and environmental protection more; Aspect partially modified PET production, can eliminate the disadvantageous effect that antimony-based catalyst and associated additives effect bring fully.Aspect the related industries influence, the appearance of aluminum-based catalyst and the unique property that it had have also proposed new demand for PET properties-correcting agent or additive etc.
Summary of the invention
It is little that the object of the invention is to introduce a kind of toxicity, to synthetic pet reaction active high novel aluminum series catalysts and this Preparation of catalysts method and using method.
For achieving the above object, the present invention proposes that a kind of polyester is synthetic uses aluminum-based catalyst, is used for the polycondensation of synthesis step, and this catalyzer is an ethylene glycol aluminium, is exclusively used in the polycondensation in terephthalic acid and the glycol reaction synthesizing polyester process.
Above-mentioned ethylene glycol aluminium makes with glycol reaction by pure aluminum, aluminium alcoholates, lithium aluminum hydride are one of any.
Above-mentioned aluminium alcoholates can be selected from one or more in aluminum methylate, aluminum ethylate, Tripropoxyaluminum, aluminum isopropylate, Tributyl aluminate, aluminium secondary butylate, the trimethyl carbinol aluminium.
Preparation method's step of above-mentioned ethylene glycol aluminium is:
1) ethylene glycol is inserted in the reaction flask heat temperature raising to 150 ℃;
2) slowly add lithium aluminum hydride, pure aluminium powder, aluminium flake or aluminium alcoholates, after adding temperature is risen to 180 ℃, to the reaction end;
3) reaction solution was refluxed 50～70 minutes;
4) will reflux back solution decompression distillation, filtration, vacuum-drying promptly get ethylene glycol aluminium.
Above-mentioned steps 2) when selecting pure aluminum for use, needs with subchloride of mercury or catalysis of iodine reaction.
Above-mentioned steps 2) when selecting aluminium alcoholates for use, needing in step 2) reaction is initial feeds nitrogen in step 3) refluxes the process that finishes.
Above-mentioned polyester is synthetic with aluminum-based catalyst in use, in the polycondensation molar ratio range of raw material be ethylene glycol than terephthalic acid between 1.2～1.5.
Above-mentioned polyester is synthetic with aluminum-based catalyst in use, and the release time of catalyzer is after esterification, when polycondensation is initial.
The present invention has following characteristics:
(1) this proposition of the present invention is the synthetic PET aluminum-based catalyst of raw material with ethylene glycol and terephthalic acid, toxicity is little, can coexist with polycondensation product, the quality of PET is not had influence, can satisfy environmental protection requirement, can guarantee active requirement again, to synthetic PET reactive behavior height, gained PET viscosity is all more than 0.75dl/g, and other aluminum-based catalysts that use at present, the product viscosity is all below 0.6dl/g, so the present invention is the catalyzer of new and effective synthetic PET polycondensation.
(2) use the synthetic PET of ethylene glycol aluminium provided by the invention catalysis, the molecular weight of gained PET can reach more than 30,000, significantly promotes the PET quality.
(2) catalyzer of the present invention's proposition easily makes, and is with low cost.Preparation ethylene glycol Al catalysts is that the ethylene glycol that generates etc. is non-also can be by recycling, compliance with environmental protection requirements, and save energy, thus cost is declined to a great extent.
(4) the present invention adopts solution synthetic, utilizes ethylene glycol aluminium catalysis synthetic PET color and luster white, avoids using toning agent.
Embodiment
Embodiment 1
The preparation of ethylene glycol aluminium: use lithium aluminum hydride, aluminium alcoholates, aluminium flake, aluminium powder to do the aluminium source, with glycol reaction, all can obtain ethylene glycol aluminium, ethylene glycol is excessive in each raw material, and ethylene glycol and aluminium source mol ratio can reach 4: 1～6: 1.
The ethylene glycol aluminum is equipped with step:
1) ethylene glycol is dropped in the reaction flask heat temperature raising to 150 ℃;
2) slowly add lithium aluminum hydride, pure aluminium powder, aluminium flake or aluminium alcoholates, after adding temperature is risen to 180 ℃,,, need and feed nitrogen in the reflux course afterwards in reaction process if use aluminium alcoholates to be raw material to the reaction end; If use aluminium simple substance to be raw material, need before reaction, in ethylene glycol, to add the subchloride of mercury of aluminium simple substance weight 0.5%～1% or iodine as catalyzer;
3) refluxed again 50～70 minutes;
4) will reflux back solution decompression distillation, filtration, vacuum-drying promptly get ethylene glycol aluminium.
The using method of ethylene glycol aluminium in terephthalic acid and ethylene glycol polycondensation synthesizing polyester process:
Reaction with 9g aluminium flake and 200ml ethylene glycol, 0.07g subchloride of mercury is a catalyzer, the mixture to product after reaction finishes filters earlier, carries out underpressure distillation then, get product ethylene glycol aluminium at last, calculating the aluminium flake transformation efficiency by mass ratio before and after the reaction is 60%.Terephthalic acid 180g and ethylene glycol 84.1g are added in the reactor, after stirring, carry out esterification, 240 ℃～260 ℃ reactions down of temperature of reaction, aquifer yield reaches the back stopped reaction more than 95% of theoretical amount, 0.1g ethylene glycol al dissolution is added reactor as catalyzer in ethylene glycol, the polycondensation temperature is about 280 ℃, carries out prepolymerization reaction earlier, carries out polycondensation then, pressure carried out below the 50Pa about half an hour, and the time can suitably be adjusted according to the condensation temperature difference.With products obtained therefrom under certain pressure fast cooling take out and draw wire.
Embodiment 2
The standby trimethyl carbinol aluminium of ethylene glycol aluminum is the aluminium source, feeds intake than 1: 40 with trimethyl carbinol aluminium and quality of glycol, and reaction beginning finishes logical nitrogen to refluxing, and makes ethylene glycol aluminium by the method for embodiment 1.Calculating trimethyl carbinol aluminium transformation efficiency by detection gas phase distillate is 80%.
The using method of the ethylene glycol aluminium that makes in terephthalic acid and ethylene glycol polycondensation synthesizing polyester process is with embodiment 1.
Embodiment 3
The standby Tributyl aluminate of ethylene glycol aluminum is the aluminium source, feeds intake than 1: 40 with Tributyl aluminate and quality of glycol, and reaction beginning finishes logical nitrogen to refluxing, and makes ethylene glycol aluminium by the method for embodiment 1.Calculating the Tributyl aluminate transformation efficiency by detection gas phase distillate is 80%.
The using method of the ethylene glycol aluminium that makes in terephthalic acid and ethylene glycol polycondensation synthesizing polyester process is with embodiment 1.
Embodiment 4
The standby lithium aluminum hydride of ethylene glycol aluminum is the aluminium source, feeds intake than 1: 10 with lithium aluminum hydride and quality of glycol, makes ethylene glycol aluminium by the method for embodiment 1.Calculating the lithium aluminum hydride transformation efficiency by the ultimate analysis product is 90%.
The using method of the ethylene glycol aluminium that makes in terephthalic acid and ethylene glycol polycondensation synthesizing polyester process is with embodiment 1.
Embodiment 5
The standby aluminum ethylate of ethylene glycol aluminum, aluminum isopropylate are the aluminium source, feed intake than 1: 1: 80 with quality of glycol with aluminum ethylate, aluminum isopropylate, and reaction beginning finishes logical nitrogen to refluxing, and make ethylene glycol aluminium by the method for embodiment 1.Calculate aluminum ethylate and the aluminum isopropylate transformation efficiency is 80% by the ultimate analysis product.
The using method of the ethylene glycol aluminium that makes in terephthalic acid and ethylene glycol polycondensation synthesizing polyester process is with embodiment 1.
Viscosity such as following table that catalyzer that embodiment 1～5 all polycondensations are used and reacted PET product are measured with black formula viscosmeter:
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | |
| The aluminium source of preparation dealing with alcohol aluminium | Aluminium flake | Trimethyl carbinol aluminium | Tributyl aluminate | Lithium aluminum hydride | Aluminum ethylate and aluminum isopropylate |
| Synthetic PET limiting viscosity (dl/g) | 0.83 | 0.82 | 0.83 | 0.85 | 0.81 |
Claims (8)
1. a polyester is synthetic uses aluminum-based catalyst, is used for the polycondensation of synthesis step, and it is characterized in that: this catalyzer is an ethylene glycol aluminium, is exclusively used in the polycondensation in terephthalic acid and the glycol reaction synthesizing polyester process.
2. the synthetic preparation method with aluminum-based catalyst of a polyester as claimed in claim 1 is characterized in that: described ethylene glycol aluminium makes with glycol reaction by pure aluminum, aluminium alcoholates, lithium aluminum hydride are one of any.
3. the synthetic preparation method with aluminum-based catalyst of polyester as claimed in claim 2, it is characterized in that: described aluminium alcoholates can be selected from one or more in aluminum methylate, aluminum ethylate, Tripropoxyaluminum, aluminum isopropylate, Tributyl aluminate, aluminium secondary butylate, the trimethyl carbinol aluminium.
4. the synthetic preparation method of polyester as claimed in claim 3 with aluminum-based catalyst, it is characterized in that: this preparation method's step is:
1) ethylene glycol is inserted in the reaction flask heat temperature raising to 150 ℃;
2) slowly add lithium aluminum hydride, pure aluminium powder, aluminium flake or aluminium alcoholates, after adding temperature is risen to 180 ℃, to the reaction end;
3) reaction solution was refluxed 50～70 minutes;
4) will reflux back solution decompression distillation, filtration, vacuum-drying promptly get ethylene glycol aluminium.
5. the synthetic preparation method with aluminum-based catalyst of polyester as claimed in claim 4 is characterized in that: described step 2) when selecting pure aluminum for use, need with subchloride of mercury or catalysis of iodine reaction.
6. the synthetic preparation method with aluminum-based catalyst of polyester as claimed in claim 4 is characterized in that: described step 2) when selecting aluminium alcoholates for use, need in step 2) reaction is initial feeds nitrogen in step 3) refluxes the process that finishes.
7. the synthetic using method with aluminum-based catalyst of a polyester as claimed in claim 1 is characterized in that: in the polycondensation molar ratio range of raw material be ethylene glycol than terephthalic acid between 1.2～1.5.
8. the synthetic using method with aluminum-based catalyst of polyester as claimed in claim 7, it is characterized in that: the release time of catalyzer is after esterification, when polycondensation is initial.
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| CN2010101540812A CN102234370B (en) | 2010-04-23 | 2010-04-23 | Aluminum catalyst for polyester synthesis, preparation method thereof and usage method thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102627759A (en) * | 2012-03-21 | 2012-08-08 | 东华大学 | Polyester catalyst with attapulgite as carrier, preparation thereof and application thereof |
| CN103275306A (en) * | 2013-05-31 | 2013-09-04 | 南京工业大学 | Method for preparing grease-based polyol through direct esterification interesterification of illegal cooking oil |
| CN112480379A (en) * | 2020-12-14 | 2021-03-12 | 新凤鸣集团股份有限公司 | Production method for reducing consumption of polyester catalyst |
| CN112759751A (en) * | 2021-01-19 | 2021-05-07 | 中国纺织科学研究院有限公司 | Catalyst for polyester synthesis and preparation method and application thereof |
| CN115894877A (en) * | 2021-08-06 | 2023-04-04 | 中国科学院成都有机化学有限公司 | Catalyst and method for synthesizing polyethylene terephthalate |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1544506A (en) * | 2003-11-21 | 2004-11-10 | 上海丝绸集团股份有限公司 | Method for preparing composite polyether polycondensation catalyst and using method thereof |
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- 2010-04-23 CN CN2010101540812A patent/CN102234370B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1544506A (en) * | 2003-11-21 | 2004-11-10 | 上海丝绸集团股份有限公司 | Method for preparing composite polyether polycondensation catalyst and using method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 《Inorg.Chem.》 19951231 Graeme J.Gainsford,et al. Ethylene glycolate derivatives of aluminum:tetra-,penta-,and hexacoordination 5244-5251 1-8 第34卷, 第21期 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102627759A (en) * | 2012-03-21 | 2012-08-08 | 东华大学 | Polyester catalyst with attapulgite as carrier, preparation thereof and application thereof |
| CN102627759B (en) * | 2012-03-21 | 2014-01-29 | 东华大学 | Polyester catalyst with attapulgite as carrier, preparation thereof and application thereof |
| CN103275306A (en) * | 2013-05-31 | 2013-09-04 | 南京工业大学 | Method for preparing grease-based polyol through direct esterification interesterification of illegal cooking oil |
| CN112480379A (en) * | 2020-12-14 | 2021-03-12 | 新凤鸣集团股份有限公司 | Production method for reducing consumption of polyester catalyst |
| CN112759751A (en) * | 2021-01-19 | 2021-05-07 | 中国纺织科学研究院有限公司 | Catalyst for polyester synthesis and preparation method and application thereof |
| CN115894877A (en) * | 2021-08-06 | 2023-04-04 | 中国科学院成都有机化学有限公司 | Catalyst and method for synthesizing polyethylene terephthalate |
| CN115894877B (en) * | 2021-08-06 | 2024-02-13 | 中国科学院成都有机化学有限公司 | Catalyst and method for synthesizing polyethylene glycol terephthalate |
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Effective date of registration: 20190912 Address after: 213164. Five floor, building 2, Changzhou science and Education City, No. 801 middle Wu Road, Jiangsu, Changzhou Co-patentee after: Chengdu Organic Chemicals Co., Ltd., Chinese Academy of Sciences Patentee after: Changzhou Institute of Chemistry Address before: 213164. Five floor, building 2, Changzhou science and Education City, No. 801 middle Wu Road, Jiangsu, Changzhou Patentee before: Changzhou Institute of Chemistry |
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