CN102344561B - Environment friendly polyester polycondensation catalyst and method for preparing polyester by using the same - Google Patents
Environment friendly polyester polycondensation catalyst and method for preparing polyester by using the same Download PDFInfo
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- CN102344561B CN102344561B CN201010244269.6A CN201010244269A CN102344561B CN 102344561 B CN102344561 B CN 102344561B CN 201010244269 A CN201010244269 A CN 201010244269A CN 102344561 B CN102344561 B CN 102344561B
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Abstract
The invention discloses an environment friendly polyester polycondensation catalyst and a method for preparing polyester by using the catalyst. The catalyst has a following structure, wherein, M represents doped metal ions, and X represents anions. The catalyst is prepared by the following steps: dissolving aluminium compound in glycol, adding an aqueous solution doped with metal salt at the temperature of 80-95 DEG C, stirring for 0.5-2 h at the temperature of 80-95 DEG C, then heating to 95-120 DEG C and stirring for 0.5-1 h, and finally adding stabilizing agent, phosphorous compound, and mixing uniformly. The stabilizing agent, phosphorous compound, and the aluminium compound can be separately added in the reaction system. The activity of the liquid aluminium catalyst is equal to that of the antimony catalyst, and the polyester hue of the liquid aluminium catalyst is equal to that of the antimony catalyst.
Description
Technical field
The invention belongs to polyester art, be specifically related to a kind of environmental friendliness polyester polycondensation catalyst and its preparation method and application.
Background technology
Polyester (polyethylene terephthalate, be called for short PET), having excellent chemical property and mechanical property, is one of most important synthon, and also to have with fields such as, film and engineering plastics at bottle and apply more widely.
Since polyester comes out, the research of polyester catalyst never stopped.Current industrial production and the more catalyzer of research mainly contain Sb, Ge and Ti tri-series, and because Sb series catalysts is at polymerization velocity, well balance between polymer performance and polyester Cephalosporins, the polyester of more than 90% adopts Sb series catalysts.But because Sb is heavy metal, in catalyst production process, the allotment of catalyzer and process, and polyester production process and polyester processing use procedure in, unavoidably detrimentally affect is caused to people and environment.Along with the reinforcement of environmental consciousness, to the use growing interest of Sb, Sb content requirement in the packing material of many restricted conditions, particularly contact food is proposed stricter.
Ge is precious metal, expensive, and more rare, limits widely using of Ge series catalysts, is generally used for the preparation of particular polyesters.Ti series catalysts is studied comparatively early, early application inorganic titanium (titanium potassium oxalate(T.P.O.), potassium fluotitanate) and organic titanium (tetrabutyl titanate and isopropyl titanate), along with going deep into of research, in recent years develop again multiple Titanium series catalyst, as the C94 of Acordis company, the titanium catalyst of the trade mark EcocatB and EcocatT of Zimmer company, the AC400 of ICI Synetix company, AC300, AC240 etc., but the shortcoming of all failing to solve the more yellow and poor heat stability of titanium catalyst polyester form and aspect.
Existing polycondensation of polyester Al catalysts document (as CN00812597, JP2005054010) just describes and is jointly used as polyester catalyst with certain aluminum compound or with aluminum compound and other metallic compound, there is no concrete Al catalysts preparation method report, also do not relate to the catalyzer of various different structure, catalytic activity and Catalysis Rate are still undesirable.
Summary of the invention
The object of this invention is to provide a kind of not containing the polyester polycondensation catalyst of heavy metal antimony, not germanic and titanium compound in this catalyzer.The present invention's aluminum compound is as polyester polycondensation catalyst, and its catalytic activity is suitable with antimony-based catalyst, overcomes the shortcoming that titanium catalyst polyester form and aspect are more yellow, cheap, and owing to being liquid state, easy to use.
Another object of the present invention is to provide a kind of preparation method of above-mentioned catalyzer.
A further object of the invention is to provide a kind of application of above-mentioned catalyzer.
Object of the present invention can be reached by following measures:
A kind of environmental friendliness polyester polycondensation catalyst, is characterized in that the liquid aluminium catalyzer of the hydrolysis-type of this metal ion mixing mainly has following structure:
Wherein M is doped metal ion, is preferably zinc, calcium, copper, magnesium, cobalt, sodium, lithium, caesium or strontium, most preferably is zinc, calcium, cobalt, sodium or lithium.X is negatively charged ion, is preferably selected from Cl
-, CH
3cOO
-, HOCH
2cH
2o
-, NO
3 -or SO
4 2-in one or more.
This catalyzer is prepared by following methods: be first dissolved in ethylene glycol by aluminum compound, the aqueous solution of doped metal salt is added at 80 ~ 95 DEG C, stirring is continued 0.5 ~ 2 hour at 80 ~ 95 DEG C, be warming up to 95 ~ 120 DEG C again and continue stirring 0.5 ~ 1 hour, add stablizer phosphorus compound after cooling (to room temperature) and mix.Stablizer phosphorus compound also can separate with aluminum compound and joins in reaction system.
Aluminum compound be selected from aluminum chloride, aluminum isopropylate, ethylene glycol aluminium, Burow Solution (as aluminium monoacetate, aluminium hydroxyacetate, aluminium acetate), aluminium hydroxide, aluminium chlorohydroxide, al formate, aluminum ethylate, aluminium diethyl monochloride, aluminum alkyls, aluminum alkyls partial hydrolystate, Aluctyl, trimethyl carbinol aluminium, aluminum nitrate, Tai-Ace S 150 or aluminum benzoate one or more; Be preferably aluminum chloride, Burow Solution or ethylene glycol aluminium.
The consumption of doped metal salt is 10 ~ 40% of aluminum compound quality, doped metal salt is selected from one or more in soluble zinc salt, calcium salt, mantoquita, magnesium salts, cobalt salt, sodium salt, lithium salts, cesium salt or strontium salt, is preferably zinc salt, calcium salt, cobalt salt, sodium salt or lithium salts.
The consumption of phosphorus compound is 10 ~ 40% of aluminum compound quality, phosphorus compound is selected from phosphoric acid, phosphorous acid, Hypophosporous Acid, 50, mixture of n-butyl, p isopropylbenzoic acid ester, triphenylphosphate, polyphosphoric acid, methyl acid phosphate, ethyl phosphonic acid, trimethyl phosphite 99, phosphenylic acid, tolyl phosphoric acid, 4-carboxyl phenyl phosphonic acids, 2, 3-dicarboxyphenyi phosphonic acids, phenyl Hypophosporous Acid, 50, phenylbenzene Hypophosporous Acid, 50, 2-hydroxy ethyl methyl phospho acid, 2-hydroxyphenylmethyl phospho acid, 2-hydroxyethyl phenyl phosphinic acid, hydroxymethyl phenyl Hypophosporous Acid, 50, 9, 10-dihydro-10 oxa--2, 3-carboxylic propyl group-10 phospho hetero phenanthrene-10 oxide compound, one or more in oxidation inhibitor 1222 or its hydrolyzate or antioxidant 1010, most preferably be phosphoric acid, trimethyl phosphite 99 or phosphenylic acid.
A kind of environmental friendliness polyester polycondensation catalyst prepares the method for polyester, by reaction system terephthalic acid and ethylene glycol 200 ~ 270 DEG C, first carry out esterification under pressure 0.1 ~ 0.3MPa, after esterification, reaction system reduces pressure intensification gradually, then carries out polyreaction at 275 ~ 285 DEG C; Environmental friendliness polyester polycondensation catalyst according to claim 1 adds reaction system before esterification or between esterification and polyreaction; The consumption of catalyzer counts 10 ~ 100ppm of polyester with the quality of aluminium element.One more specifically method is: in 2L reactor, add terephthalic acid, ethylene glycol, and Al catalysts prepared by aforesaid method, 200 ~ 270 DEG C, esterification under pressure 0.1 ~ 0.3MPa (gauge pressure), after water outlet to be esterified terminates substantially, reaction system reduces pressure intensification gradually, in 45 minutes, vacuum is less than 100Pa, temperature of reaction system 275 ~ 285 DEG C, and when reaching rated characteristic viscosity, polyreaction terminates, through water-cooled, pelletizing can obtain Al catalysts polyester.Here Al catalysts both can add before esterification, also can add after esterification, can add titanium dioxide, silicon-dioxide, the powders such as barium sulfate in reaction system, or various toning agent, as cobalt salt, and cyanometer, purple degree meter, erythrometer etc.
In polyester, aluminium content is at 10 ~ 100ppm, the metal ion 1 ~ 40ppm of doping, phosphorus content 1 ~ 50ppm.The polyester polycondensation catalyst of the special construction prepared by present method, there is excellent catalytic activity and Catalysis Rate, add in reaction system compared to aluminum compound and doped metal salt simply being mixed, the catalyst activity prepared in the process of the present invention is high, and catalyzed polycondensation speed is faster.Liquid aluminium series polyester catalyst of the present invention is liquid, easy to use.Owing to not containing antimony, this catalyzer is a kind of environment-friendly catalyst.This catalyzer can add before esterification, also can add in reaction system after esterification.Do not occur with the polyester of this catalyst preparing the shortcoming that Titanium series catalyst PET hue is more yellow, catalytic activity is suitable with antimony-based catalyst.
Embodiment
Embodiment 1:
10 grams of aluminum chlorides are dissolved in 90 grams of ethylene glycol, solution is heated to 90 DEG C, continue stirring adds 10 gram of 15% concentration zinc acetate aqueous solution after 10 minutes at this temperature, stir at 90 DEG C after 30 minutes, be warmed up to 110 DEG C, continuation stirring cool to room temperature after 50 minutes, adds 1.6 grams of phosphoric acid and stirs, obtained environmental friendliness polyester polycondensation catalyst, for subsequent use; Its skeleton symbol is as follows:
wherein X is Cl
-, M is Zn.
350 grams of terephthalic acids are added in 2L reactor, 220 grams of ethylene glycol, and liquid aluminium catalyzer 1 gram prepared by aforesaid method, 200 ~ 250 DEG C, esterification under pressure 0.25MPa (gauge pressure), water outlet to be esterified terminates esterification when reaching theoretical water outlet 95%, reactor pressure is let out to normal pressure, to reduce pressure gradually intensification, after 45 minutes, reactor vacuum is less than 100Pa, temperature of reaction system 275 ~ 285 DEG C, after 85 minutes, reach rated characteristic viscosity polyreaction again terminate, through water-cooled, pelletizing can obtain Al catalysts polyester.Limiting viscosity 0.67, end carboxyl 20mol/ ton, glycol ether 1.6%, form and aspect L 85, a-1.6, b1.4.
Embodiment 2
10 grams of Burow Solutions (in aluminium monoacetate, aluminium hydroxyacetate, aluminium acetate one or more) are dissolved in 90 grams of ethylene glycol, solution is heated to 90 DEG C, continue stirring adds 5 gram of 15% concentration zinc acetate aqueous solution after 10 minutes at this temperature, 3 grams of sodium-acetate 15% solution, 1 gram of Lithium Acetate 15% aqueous solution, stir at 90 DEG C after 35 minutes, be warmed up to 110 DEG C, continuation stirring cool to room temperature after 30 minutes, add 2 grams of trimethyl phosphite 99s to stir, obtained environmental friendliness polyester polycondensation catalyst, for subsequent use; Its skeleton symbol is as follows:
Wherein X is CH
3cOO
-, M is Zn, Na, Li.
350 grams of terephthalic acids are added in 2L reactor, 220 grams of ethylene glycol, and liquid aluminium catalyzer 1 gram prepared by aforesaid method, 205 ~ 250 DEG C, esterification under pressure 0.25MPa (gauge pressure), water outlet to be esterified terminates esterification when reaching theoretical water outlet 95%, reactor pressure is let out to normal pressure, to reduce pressure gradually intensification, after 45 minutes, reactor vacuum is less than 100Pa, temperature of reaction system 276 ~ 286 DEG C, after 90 minutes, reach rated characteristic viscosity polyreaction again terminate, through water-cooled, pelletizing can obtain Al catalysts polyester.Limiting viscosity 0.66, end carboxyl 21.5mol/ ton, glycol ether 1.5%, form and aspect L 86, a-1.4, b1.9.
Embodiment 3
10 grams of ethylene glycol al dissolutions are in 90 grams of ethylene glycol, solution adds the calcium acetate aqueous solution of 5 gram of 15% concentration after being heated to 90 DEG C, 5 grams of Cobaltous diacetate 15% solution, stir at 90 DEG C after 30 minutes, be warmed up to 100 DEG C, continue stirring after 30 minutes, cool to room temperature adds 2.2 grams of phosphenylic acids, obtained environmental friendliness polyester polycondensation catalyst, for subsequent use; Its skeleton symbol is as follows:
Wherein X is HOCH
2cH
2o
-, M is Ca or Co.
350 grams of terephthalic acids are added in 2L reactor, 220 grams of ethylene glycol, and liquid aluminium catalyzer 1 gram prepared by aforesaid method, 203 ~ 255 DEG C, esterification under pressure 0.25MPa (gauge pressure), water outlet to be esterified terminates esterification when reaching theoretical water outlet 95%, reactor pressure is let out to normal pressure, to reduce pressure gradually intensification, after 45 minutes, reactor vacuum is less than 100Pa, temperature of reaction system 272 ~ 286 DEG C, after 93 minutes, reach rated characteristic viscosity polyreaction again terminate, through water-cooled, pelletizing can obtain Al catalysts polyester.Limiting viscosity 0.68, end carboxyl 21.0mol/ ton, glycol ether 1.8%, form and aspect L 86, a-1.8, b1.2.
Comparative example 1
350 grams of terephthalic acids are added in 2L reactor, 220 grams of ethylene glycol, and 0.0892 gram of ethylene glycol aluminium, the calcium acetate of 0.0446 gram of 15% concentration, the Cobaltous diacetate of 0.0446 gram of 15% concentration, 0.0196 gram of phosphenylic acid, at 200 ~ 255 DEG C, esterification under pressure 0.25MPa (gauge pressure), water outlet to be esterified terminates esterification when reaching theoretical water outlet 95%, reactor pressure is let out to normal pressure, to reduce pressure gradually intensification, after 45 minutes, reactor vacuum is less than 100Pa, temperature of reaction system 273 ~ 285 DEG C, after 125 minutes, reach rated characteristic viscosity polyreaction again terminate, through water-cooled, pelletizing can obtain Al catalysts polyester.Limiting viscosity 0.67, end carboxyl 23.0mol/ ton, glycol ether 1.7%, form and aspect L 85, a-1.6, b3.0.
Comparative example 2
350 grams of terephthalic acids are added in 2L reactor, 220 grams of ethylene glycol, 0.16 gram of Antimony Triacetate, 200 ~ 250 DEG C, esterification under pressure 0.25MPa (gauge pressure), water outlet to be esterified terminates esterification when reaching theoretical water outlet 95%, let out to normal pressure by reactor pressure, intensification of reducing pressure gradually, in 45 minutes, reactor vacuum is less than 100Pa, temperature of reaction system 275 ~ 285 DEG C, when about needing within 95 minutes, to reach rated characteristic viscosity, polyreaction terminates, and through water-cooled, pelletizing can obtain antimony catalyst polyester.Limiting viscosity 0.68, end carboxyl 22.2mol/ ton, glycol ether 1.8%, form and aspect L 85.8, a-1.9, b 2.4.
Claims (4)
1. the preparation method of an environmental friendliness polyester polycondensation catalyst, it is characterized in that first aluminum compound being dissolved in ethylene glycol, the aqueous solution of soluble zinc salt is added at 80 ~ 95 DEG C, stirring is continued 0.5 ~ 2 hour at 80 ~ 95 DEG C, be warming up to 95 ~ 120 DEG C again and continue stirring 0.5 ~ 1 hour, add stablizer phosphorus compound after cooling and mix; Described aluminum compound is aluminum chloride, Burow Solution or ethylene glycol aluminium; The consumption of soluble zinc salt is 10 ~ 40% of aluminum compound quality.
2. environmental friendliness polyester polycondensation catalyst according to claim 1, it is characterized in that the consumption of phosphorus compound is 10 ~ 40% of aluminum compound quality, described phosphorus compound is selected from phosphoric acid, phosphorous acid, Hypophosporous Acid, 50, p isopropylbenzoic acid ester, triphenylphosphate, polyphosphoric acid, methyl acid phosphate, ethyl phosphonic acid, trimethyl phosphite 99, phosphenylic acid, tolyl phosphoric acid, 4-carboxyl phenyl phosphonic acids, 2, 3-dicarboxyphenyi phosphonic acids, phenyl Hypophosporous Acid, 50, phenylbenzene Hypophosporous Acid, 50, 2-hydroxy ethyl methyl phospho acid, 2-hydroxyphenylmethyl phospho acid, 2-hydroxyethyl phenyl phosphinic acid, hydroxymethyl phenyl Hypophosporous Acid, 50, 9, 10-dihydro-10 oxa--2, one or more in 3-carboxylic propyl group-10 phospho hetero phenanthrene-10 oxide compound or oxidation inhibitor 1222 or its hydrolyzate.
3. environmental friendliness polyester polycondensation catalyst according to claim 2, is characterized in that described phosphorus compound is phosphoric acid, trimethyl phosphite 99 or phosphenylic acid.
4. prepare the method for polyester with environmental friendliness polyester polycondensation catalyst for one kind, it is characterized in that by reaction system terephthalic acid and ethylene glycol 200 ~ 270 DEG C, first carry out esterification under pressure 0.1 ~ 0.3MPa, after esterification, reaction system reduces pressure intensification gradually, then carries out polyreaction at 275 ~ 285 DEG C; Environmental friendliness polyester polycondensation catalyst according to claim 1 adds reaction system before esterification or between esterification and polyreaction; The consumption of catalyzer counts 10 ~ 100ppm of polyester with the quality of aluminium element.
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| CN103012766A (en) * | 2011-09-26 | 2013-04-03 | 常州化学研究所 | Preparation method for synthesizing aluminum series catalyst by utilizing polyester and application thereof |
| CN106608967B (en) * | 2016-11-07 | 2018-10-16 | 北京服装学院 | A kind of composite catalyst for synthesizing polyethylene terephthalate |
| 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 |
| EP3925758A4 (en) * | 2019-02-14 | 2022-08-24 | Toyobo Co., Ltd. | Biaxially stretched polyester film |
| CN113583220B (en) * | 2020-04-30 | 2023-05-02 | 中国石油化工股份有限公司 | Environment-friendly polyester polycondensation catalyst and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1192758A (en) * | 1995-06-08 | 1998-09-09 | 纳幕尔杜邦公司 | Catalyst, processes and polymer products therefrom |
| WO2001014448A1 (en) * | 1999-08-24 | 2001-03-01 | Toyo Boseki Kabushiki Kaisha | Polymerization catalysts for polyesters, polyesters produced with the same and process for production of polyesters |
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| KR100872634B1 (en) * | 2001-01-18 | 2008-12-09 | 토요 보세키 가부시기가이샤 | Polymerization catalyst for polyester, polyester, and process for producing the same |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1192758A (en) * | 1995-06-08 | 1998-09-09 | 纳幕尔杜邦公司 | Catalyst, processes and polymer products therefrom |
| WO2001014448A1 (en) * | 1999-08-24 | 2001-03-01 | Toyo Boseki Kabushiki Kaisha | Polymerization catalysts for polyesters, polyesters produced with the same and process for production of polyesters |
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