CN103819662A - Method for synthesizing aliphatic-aromatic copolyester - Google Patents
Method for synthesizing aliphatic-aromatic copolyester Download PDFInfo
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- CN103819662A CN103819662A CN201410042660.6A CN201410042660A CN103819662A CN 103819662 A CN103819662 A CN 103819662A CN 201410042660 A CN201410042660 A CN 201410042660A CN 103819662 A CN103819662 A CN 103819662A
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Abstract
The invention discloses a method for synthesizing aliphatic-aromatic copolyester. The method comprises the following steps: (1) performing an esterification reaction, that is, firstly adding dihydric alcohol, an aromatic monomer and tetra-n-butyl titanate as a catalyst into a reaction system for esterification reaction, and then adding an aliphatic monomer and stannous octoate catalyst to continue esterification reaction; (2) under the vacuum condition that the vacuum degree is smaller than 200 Pa, adding the tetra-n-butyl titanate into the reaction system in the step (1) for polycondensation to obtain the product, namely aliphatic aromatic copolyester. The method has the advantages of small consumption of catalysts, short reaction time, increase polymerization speed, good color of the product and high molecular weight.
Description
Technical field
The present invention relates to a kind of method of synthetic fat family-aromatic copolyester, especially relate to a kind of method that uses composite catalyst synthesising biological degradable aliphatic-aromatic copolyester, belong to Biodegradable polymer material technical field.
Background technology
In more than the 80 year short time, macromolecular material has been penetrated into the every field of national economy and all respects of people's life, and still with strong momentum development.Wherein, the feature such as plastics, light weight durable with it, good processability is subject to people's favor.But, after most of plastics use and abandon, can not biological degradation, bring " white pollution ", packed many environmental pollutions and the safety problems such as poisoning.And, most plastics are all from petroleum-based polyolefine (polyethylene, polypropylene, polystyrene, polyvinyl chloride etc.), cannot recycle, day by day exhausted along with petroleum resources, make limited petroleum resources and the demand that increases rapidly between contradiction further outstanding.Therefore, development Biodegradable polymer material becomes the demand of development sustainable society, environmental protection and recycling economy.Biodegradable polymer material can be decomposed into low molecular compound or water and carbonic acid gas by the microorganism in environment, selects Biodegradable material part substituted for plastic can reduce environmental pollution and shortage of resources problem.
Aliphatic polyester is member important in biodegradable polymer.There are many Biodegradable materials all to realize and having commercially produced.For example: Japan is clear has produced synthetics poly butylene succinate (PBS) and the copolyesters (PBSA) take Bionolle as trade(brand)name with company, Cargill company of the U.S. has produced the bio-based Wholly-degradable material poly(lactic acid) (PLA) take NatureWorks as trade(brand)name, biodegradable polymer 3-hydroxybutyrate ester (PHB) and its copolyesters take Biopol as trade(brand)name that Britain's Imperial Chemical Industries (ICI) company produces.Although aliphatic polyester uses on market, its cost is high, poor being widely used of limiting aliphatic polyester of thermal characteristics.The thermal characteristics and the mechanical property that improve in recent years biodegradable aliphatic polyester have become hot issue.
Because aromatic polyester has good thermal characteristics and mechanical property, people consider phenyl ring unit to be incorporated in aliphatic polyester main chain, carry out the synthetic aliphatic-aromatic copolyester that has good physicals and still have biodegradability.Be in the news about synthetic, the performance of aliphatic-aromatic copolyester and the research of biological degradation behavior.The Eastar Bio of the Ecoflex of BASF as far as our knowledge goes and Eastman Chemical Company is take BDO, hexanodioic acid and terephthalic acid as raw material.In addition, the Biomax that also has E.I.Du Pont Company to produce, it is the copolyesters of polyethylene terephthalate (PET) and other aliphatic monomers.
In copolyesters synthetic reaction process, not only transesterification reaction, esterification and polycondensation are subject to the impact of catalyzer, and the use of catalyzer has impact more significantly to thermostability and the color and luster etc. of side reaction, product.So the use of catalyzer is one of topmost factor in whole synthetic reaction process.Since began one's study synthesizing of polyester from Carothers in 1931, improved the aspects such as product yield and relative molecular mass, raising product mechanics and thermal characteristics, organo-metallic catalyst is being played the part of important role always.Mainly contain at present germanium (Ge) series catalysts, titanium (Ti) series catalysts and antimony (Sb) series catalysts.Wherein, have the advantages such as whiteness is high, the transparency is good by the polyester slice of germanium series catalysts (as germanium dioxide) catalysis synthesized, but germanium series catalysts activity is poor, in synthetic product, ether link content is higher, and germanium series catalysts price is more expensive, is difficult to widespread use; Titanium series catalyst has higher catalytic activity, and not containing heavy metal, safety and environmental protection, but Titanium series catalyst easily promotes the carrying out of side reaction, so the thermostability of product and color and luster are poor; Antimony-based catalyst (as antimony acetate) is the most frequently used catalyzer in present synthesizing polyester reaction, and antimony-based catalyst catalytic activity is high, and low price, little to side reaction promoter action, but antimony-based catalyst has certain toxicity, the jaundice of synthetic product.
Summary of the invention
For solving the deficiencies in the prior art, the object of the present invention is to provide the method for synthetic fat family-aromatic copolyester that a kind of catalyst levels is few, the reaction times is short, polymerization rate is fast, product color and luster is good, molecular weight is high.
For achieving the above object, the present invention is achieved by the following technical solutions:
A method for synthetic fat family-aromatic copolyester, is characterized in that, comprises the following steps:
(1) esterification: first by dibasic alcohol, aromatic monomer, the positive butyl ester of catalyzer metatitanic acid four adds in reaction system, under the protection atmosphere of nitrogen, carry out esterification, temperature of reaction is 160 ℃, reaction times is 2h, and then add the sub-tin of aliphatic monomer and octoate catalyst, under the protection atmosphere of nitrogen, heat up temperature to 180 ℃, proceed esterification, reaction times is 2h, the mol ratio of described aromatic monomer and the add-on of aliphatic monomer is (1-4): 1, and the mol ratio of described aromatic monomer and aliphatic monomer sum and dibasic alcohol is 1:(1.0 ~ 1.5), and the quality that adds of described catalyzer metatitanic acid four positive butyl esters is dibasic alcohol, aliphatic monomer and aromatic monomer add 0.4 of total mass ~ 0.5 ‰, the quality that adds of the described sub-tin of octoate catalyst is dibasic alcohol, aliphatic monomer and aromatic monomer add 0.2 of total mass ~ 0.3 ‰,
(2) polycondensation: be less than in vacuum tightness under the vacuum condition of 200 Pa; in reaction system step (1) Suo Shu, add the positive butyl ester of catalyzer metatitanic acid four; under the protection atmosphere of stirring and nitrogen; be warming up to 260 ℃; carry out polycondensation; react 65 min, obtain product aliphatic-aromatic copolyester
In step (2), the add-on of catalyzer metatitanic acid four positive butyl esters is identical with the add-on of catalyzer metatitanic acid four positive butyl esters in step (1).
Further, described dibasic alcohol is BDO.Described aromatic monomer is dimethyl terephthalate (DMT).Described aromatic monomer is hexanodioic acid.
Further, the mol ratio of described aromatic monomer and aliphatic monomer sum and dibasic alcohol is 1:(1.1 ~ 1.5).
More preferably, the mol ratio of described aromatic monomer and aliphatic monomer sum and dibasic alcohol is 1:1.3.
The invention has the beneficial effects as follows: what the present invention adopted is direct melt polycondensation reaction, simplify synthesis technique, reduce side reaction, make the color and luster of product fine, and the present invention is in reaction process, adopt two kinds of catalyzer, it is composite catalyst, form efficient, nontoxic catalyst system, compared with single catalyzer, having polymerization rate obviously improves, the polycondensation time can shorten to 60 ~ 70 min from 10h, and the molecular weight of product is higher, simultaneous reactions process is steady, in addition, the present invention still obtains the product of higher molecular weight in the situation that not adding any chainextender, make the copolyesters product that finally obtains pure, there is no chainextender, stablizer, the additives such as oxidation inhibitor.
Embodiment
Below in conjunction with specific embodiment, the present invention is carried out to concrete introduction.
embodiment 1
By 58.5 g1; 4-butyleneglycol and 48.5 g dimethyl terephthalate (DMT) add respectively in the four-hole boiling flask of 250 ml; and add positive butyl ester 0.07 g of catalyzer metatitanic acid four; mechanical stirring; under nitrogen protection; be heated to 160 ℃, isothermal reaction to the by-product carbinol producing approaches theoretical amount, approximately reacts 2 h.Then toward the hexanodioic acid that adds 36.5 g in reaction system, and sub-tin 0.04 g of octoate catalyst, to stir, still nitrogen protection, is warming up to 180 ℃, and isothermal reaction to the amount of the small molecular by product water producing approaches theoretical value, and approximately the reaction times is 2 h.Finally in reaction system, add positive butyl ester 0.07 g of catalyzer metatitanic acid four; under the condition of stirring and nitrogen protection; slowly be warming up to 260 ℃; in this process, slowly provide vacuum final vacuum to reach < 200 Pa; isothermal reaction 65 min; under nitrogen protection, take out product, product is poly-(mutual-phenenyl two acid bromide two alcohol ester/tetramethylene adipate) copolyesters.
Through above-mentioned product is tested, its result is as follows:
Product is thermal characteristics: 136 ℃ of melt temperatures, temperature when thermal weight loss 5% is 341 ℃.
Mechanical property: tensile strength 13.4 MPa, elongation at break 876 %.
embodiment 2
By 58.5 g1; 4-butyleneglycol and 58.3 g dimethyl terephthalate (DMT) add respectively in the four-hole boiling flask of 250 ml; and add positive butyl ester 0.07 g of catalyzer metatitanic acid four; mechanical stirring; under nitrogen protection; be heated to 160 ℃, isothermal reaction to the by-product carbinol producing approaches theoretical amount, approximately reacts 2 h.Then toward the hexanodioic acid that adds 29.2 g in reaction system, and sub-tin 0.04 g of octoate catalyst, to stir, still nitrogen protection, is warming up to 180 ℃, and isothermal reaction to the amount of the small molecular by product water producing approaches theoretical value, and approximately the reaction times is 2 h.Finally in reaction system, add positive butyl ester 0.07 g of catalyzer metatitanic acid four; under the condition of stirring and nitrogen protection; slowly be warming up to 260 ℃; in this process, slowly provide vacuum final vacuum to reach < 200 Pa; isothermal reaction 65 min; under nitrogen protection, take out product, product is poly-(mutual-phenenyl two acid bromide two alcohol ester/tetramethylene adipate) copolyesters.
Through above-mentioned product is tested, its result is as follows:
Thermal characteristics: 156 ℃ of melt temperatures, temperature when thermal weight loss 5% is 347 ℃.
Mechanical property: tensile strength 17.4 MPa, elongation at break 608 %.
embodiment 3
By 58.5 g1; 4-butyleneglycol and 68 g dimethyl terephthalate (DMT) add respectively in the four-hole boiling flask of 250 ml; and add positive butyl ester 0.07 g of catalyzer metatitanic acid four; mechanical stirring; under nitrogen protection; be heated to 160 ℃, isothermal reaction to the by-product carbinol producing approaches theoretical amount, approximately reacts 2 h.Then toward the hexanodioic acid that adds 21.9 g in reaction system, and sub-tin 0.04 g of octoate catalyst, to stir, still nitrogen protection, is warming up to 180 ℃, and isothermal reaction to the amount of the small molecular by product water producing approaches theoretical value, and approximately the reaction times is 2 h.Finally in reaction system, add positive butyl ester 0.07 g of catalyzer metatitanic acid four; under the condition of stirring and nitrogen protection; slowly be warming up to 260 ℃; in this process, slowly provide vacuum final vacuum to reach < 200 Pa; isothermal reaction 65 min; under nitrogen protection, take out product, product is poly-(mutual-phenenyl two acid bromide two alcohol ester/tetramethylene adipate) copolyesters.
Through above-mentioned product is tested, its result is as follows:
Thermal characteristics: 178 ℃ of melt temperatures, temperature when thermal weight loss 5% is 364 ℃.
Mechanical property: tensile strength 21.5 MPa, elongation at break 337 %.
embodiment 4
By 58.5 g1; 4-butyleneglycol and 77.7 g dimethyl terephthalate (DMT) add respectively in the four-hole boiling flask of 250 ml; and add positive butyl ester 0.075 g of catalyzer metatitanic acid four; mechanical stirring; under nitrogen protection; be heated to 160 ℃, isothermal reaction to the by-product carbinol producing approaches theoretical amount, approximately reacts 2 h.Then toward the hexanodioic acid that adds 14.6 g in reaction system, and sub-tin 0.045 g of octoate catalyst, to stir, still nitrogen protection, is warming up to 180 ℃, and isothermal reaction to the amount of the small molecular by product water producing approaches theoretical value, and approximately the reaction times is 2 h.Finally in reaction system, add positive butyl ester 0.075 g of catalyzer metatitanic acid four; under the condition of stirring and nitrogen protection; slowly be warming up to 260 ℃; in this process, slowly provide vacuum final vacuum to reach < 200 Pa; isothermal reaction 65 min; under nitrogen protection, take out product, product is poly-(mutual-phenenyl two acid bromide two alcohol ester/tetramethylene adipate) copolyesters.
Through above-mentioned product is tested, its result is as follows:
Thermal characteristics: 196 ℃ of melt temperatures, temperature when thermal weight loss 5% is 366 ℃.
Mechanical property: tensile strength 32.4 MPa, elongation at break 133 %.
Known by embodiment 1-4: what the present invention adopted is direct melt polycondensation reaction, simplify synthesis technique, reduce side reaction, make the color and luster of product fine, and the present invention is in reaction process, adopt two kinds of catalyzer, it is composite catalyst, form efficient, nontoxic catalyst system, compared with single catalyzer, having polymerization rate obviously improves, the polycondensation time can shorten to 60 ~ 70 min from 10h, and the molecular weight of product is higher, simultaneous reactions process is steady, in addition, the present invention still obtains the product of higher molecular weight in the situation that not adding any chainextender, make the copolyesters product that finally obtains pure, there is no chainextender, stablizer, the additives such as oxidation inhibitor.
The present invention is illustrated according to above-described embodiment, should be appreciated that above-described embodiment does not limit the present invention in any form, and all employings are equal to replaces or the technical scheme that obtains of equivalent transformation mode, within all dropping on protection scope of the present invention.
Claims (6)
1. a method for synthetic fat family-aromatic copolyester, is characterized in that, comprises the following steps:
(1) esterification: first by dibasic alcohol, aromatic monomer, the positive butyl ester of catalyzer metatitanic acid four adds in reaction system, under the protection atmosphere of nitrogen, carry out esterification, temperature of reaction is 160 ℃, reaction times is 2h, and then add the sub-tin of aliphatic monomer and octoate catalyst, under the protection atmosphere of nitrogen, heat up temperature to 180 ℃, proceed esterification, reaction times is 2h, the mol ratio of described aromatic monomer and the add-on of aliphatic monomer is (1-4): 1, and the mol ratio of described aromatic monomer and aliphatic monomer sum and dibasic alcohol is 1:(1.0 ~ 1.5), and the quality that adds of described catalyzer metatitanic acid four positive butyl esters is dibasic alcohol, aliphatic monomer and aromatic monomer add 0.4 of total mass ~ 0.5 ‰, the quality that adds of the described sub-tin of octoate catalyst is dibasic alcohol, aliphatic monomer and aromatic monomer add 0.2 of total mass ~ 0.3 ‰,
(2) polycondensation: be less than in vacuum tightness under the vacuum condition of 200 Pa; in reaction system step (1) Suo Shu, add the positive butyl ester of catalyzer metatitanic acid four; under the protection atmosphere of stirring and nitrogen; be warming up to 260 ℃; carry out polycondensation; react 65 min, obtain product aliphatic-aromatic copolyester
In step (2), the add-on of catalyzer metatitanic acid four positive butyl esters is identical with the add-on of catalyzer metatitanic acid four positive butyl esters in step (1).
2. the method for a kind of synthetic fat family-aromatic copolyester according to claim 1, is characterized in that, described dibasic alcohol is BDO.
3. the method for a kind of synthetic fat family-aromatic copolyester according to claim 1, is characterized in that, described aromatic monomer is dimethyl terephthalate (DMT).
4. the method for a kind of synthetic fat family-aromatic copolyester according to claim 1, is characterized in that, described aromatic monomer is hexanodioic acid.
5. the method for a kind of synthetic fat family-aromatic copolyester according to claim 1, is characterized in that, the mol ratio of described aromatic monomer and aliphatic monomer sum and dibasic alcohol is 1:(1.1 ~ 1.5).
6. the method for a kind of synthetic fat family-aromatic copolyester according to claim 5, is characterized in that, the mol ratio of described aromatic monomer and aliphatic monomer sum and dibasic alcohol is 1:1.3.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018045930A1 (en) * | 2016-09-09 | 2018-03-15 | 珠海万通化工有限公司 | Polyester resin and preparation method therefor |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1807485A (en) * | 2004-12-30 | 2006-07-26 | 中国石油化工股份有限公司 | Biodegradable linear random copolyester and its preparation method and uses |
| CN101864068A (en) * | 2009-04-15 | 2010-10-20 | 中国石油天然气股份有限公司 | Preparation method of polybutylene terephthalate/adipate butanediol copolyester |
| CN102443149A (en) * | 2011-10-28 | 2012-05-09 | 金发科技股份有限公司 | Continuous production method for biodegradable aliphatic-aromatic copolyester |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1807485A (en) * | 2004-12-30 | 2006-07-26 | 中国石油化工股份有限公司 | Biodegradable linear random copolyester and its preparation method and uses |
| CN101864068A (en) * | 2009-04-15 | 2010-10-20 | 中国石油天然气股份有限公司 | Preparation method of polybutylene terephthalate/adipate butanediol copolyester |
| CN102443149A (en) * | 2011-10-28 | 2012-05-09 | 金发科技股份有限公司 | Continuous production method for biodegradable aliphatic-aromatic copolyester |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018045930A1 (en) * | 2016-09-09 | 2018-03-15 | 珠海万通化工有限公司 | Polyester resin and preparation method therefor |
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Application publication date: 20140528 |