CN101628972A - Method for preparing poly (ethylene succinate) - Google Patents
Method for preparing poly (ethylene succinate) Download PDFInfo
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Abstract
The invention discloses a method for preparing poly (ethylene succinate), which comprises the following steps: putting succinic acid, glycol and a catalyst into a reaction device, wherein the molar ratio of the succinic acid to the glycol is 1-3:1 and the molar ratio of the catalyst to the succinic acid is 1:1-1,000; adding high boiling solvent into the system for reaction at a temperature of between 100 and 180 DEG C for 1 to 5 hours, and then performing reaction at a temperature of between 180 and 240 DEG C for 8 to 24 hours; and finally, removing the solvent, taking diisocyanate, diacyl chloride or binary anhydride as a chain extender, and performing reaction at a temperature of between 50 and 200 DEG C for 0.5 to 5 hours. The polyester prepared by the method has number-average molecular weight more than 200,000, is thermoplastic, and has good mechanical performance.
Description
Technical field
The invention belongs to aliphatic polyester and preparation method thereof technical field, be specifically related to a kind of high molecular polyethylene glycol succinate preparation method.
Background technology
The conventional plastic industrial expansion is satisfying social needs, and enriches people's life and the time also is accompanied by expending of Nonrenewable resources such as the generation of a large amount of non-degradable rubbish and oil, pollutes and the shortage of resources problem thereby caused serious environmental.Petroleum hydrocarbon raw material is Nonrenewable resources, because the gradually exhausted and price of oil soars, the mankind concentrate on attention on the reproducible Biological resources once more, thereby with the wide carbohydrate raw material (glucose in source, starch, the grain potato, vegetable fibre etc.), replacing petroleum to produce synthesis of chemicals, degradation material, bioenergy etc. is the effective way that addresses this problem.Wherein, aliphatic polyester is under the effect of extensive microorganism that exists of nature or animal and plant body endoenzyme, can finally be decomposed into carbonic acid gas and water and back to nature, be the biodegradable plastic of tool development prospect, has been subjected to the extensive concern of countries in the world governments, scientific research institution and industrial community.
Aliphatic polyester is as biodegradable plastic, and development in recent years is rapid, has realized industrialization in states such as the U.S., Japan and Europe, enters the practical stage.At present, commercial aliphatic polyester mainly contains poly(lactic acid) (PLA), polycaprolactone (PCL), PHA (PHAs) and poly butylene succinate (PBS) and polyethylene glycol succinate (PES).Wherein, the PBS kind polyester is the good aliphatic polyester of a class over-all properties of twentieth century exploitation at the beginning of the nineties, the processing characteristics of PBS kind polyester and the use properties all polyolefine material with general are close, owing to having the extensive attention that biological degradability and good and economic are subjected to various countries concurrently, Japan is developed it as the general-purpose plastics with biological degradability.PES is to be main raw material with aliphatic dibasic acid, dibasic alcohol, related raw material both can satisfy the demands by petroleum product, Succinic Acid, the ethylene glycol that can produce by the biological fermentation approach by natural products such as cellobiose, milk industry by product whey, glucose, fructose, lactose, maltose, mannitol, seminose, sucrose, wood sugars also, realization also is expected to further reduce significantly raw materials cost from the green cyclic production of nature, back to nature.Bibliographical information, the pyrolysis peak temperature of PES is about 340 ℃, shows that it not only has good thermostability, can carry out safe processing and production, and have the good mechanical performance, its ultimate tensile strength is greater than 30MPa, tension set reaches 380%, can replace general-purpose plastics.As seen, compare with PBS, not only raw material sources are abundant, raw materials cost is lower but also its elongation at break will be higher than PBS (300%) for PES, and shock strength is 6 times of PBS, and degradation speed is faster.Although domestic research to PES just begins, there is not commercially produced product to release as yet, from raw material sources, still be that PES all is environment friendly polyester that a class has potentiality from performance and the cost angle of PES no matter.
Summary of the invention
The purpose of this invention is to provide a kind of method for preparing poly (ethylene succinate).Its polyester number-average molecular weight of polyethylene glycol succinate of the present invention preparation can reach 200,000, has actual application value and with low cost and degradation speed is faster.
For achieving the above object, method for preparing poly (ethylene succinate) provided by the invention utilizes Succinic Acid and ethylene glycol to carry out solution polycondensation, and the preparation estrodur performed polymer passes through vulcabond, binary acyl chlorides and dibasic acid anhydride chain extension more earlier; Its step is as follows:
Succinic Acid and ethylene glycol, catalyzer and solvent are joined in the reaction unit, under nitrogen protection, be warming up to 100-180 ℃ of reaction 1-5 hour; Then be warming up to 180-240 ℃ of reaction 8-24 hour, steam solvent, obtain the hydroxyl telechelic polyester performed polymer;
Calculate with 100 parts of hydroxyl telechelic polyester performed polymers of above-mentioned parts by weight, add vulcabond, diacid chloride or the dibasic acid anhydride of 1-15 weight part therein, at 50-200 ℃, 10-1000Pa reacted 0.5-5 hour down, got target product;
The mol ratio of Succinic Acid and ethylene glycol is 1-3: 1;
Catalyzer is the catalyzer that esterification is used, and its consumption is the 0.1-100% of Succinic Acid mole number;
Solvent is dimethyl sulfoxide (DMSO), N, at least a in dinethylformamide, N-Methyl pyrrolidone, perhydronaphthalene, dodecane and the tetramethylene sulfone;
Chainextender is 2,4-tolylene diisocyanate, 4,4 '-diphenylmethanediisocyanate, hexamethylene diisocyanate, 3,3 '-dimethyl diphenyl base-4, at least a in 4 '-vulcabond, oxalyl chloride, hexanedioyl chlorine, terephthalyl chloride, malonic anhydride, Succinic anhydried and the Tetra hydro Phthalic anhydride.
Described preparation method, wherein, the mol ratio of Succinic Acid and ethylene glycol is 1-1.5: 1.
Described preparation method, wherein, catalyzer is at least a in tin protochloride, tetrabutyl titanate, isopropyl titanate, iron trichloride, antimonous oxide, the tosic acid.
The present invention has the following advantages:
1) the present invention adopts the prepared polyester of solution method, the molecular weight height, and narrow molecular weight distribution has good heat-resistant and impact property, and cost is low, can be used as plastics and uses.
2) technology of the present invention is simple, is easy to grasp and control.
Embodiment
The present invention utilizes Succinic Acid and ethylene glycol to carry out solution polycondensation, earlier the preparation estrodur performed polymer; By vulcabond, binary acyl chlorides and dibasic acid anhydride chain extension, prepare weight-average molecular weight at 105000-178000, the aliphatic polyester of number-average molecular weight between 55000-81000 again.Molecular weight is measured with the gel infiltration method, and with N, dinethylformamide is a moving phase, and polystyrene is a standard specimen, 25 ± 0.5 ℃ of mensuration.
The mol ratio of Succinic Acid and ethylene glycol is generally 1-3 in the polycondensation process: 1, and more excellent ratio is 1.-1.5: 1.
Heat up in two stages in the solution polycondensation process, the temperature of reaction of fs is 100-180 ℃; The subordinate phase temperature of reaction is 180-240 ℃.
The high boiling solvent that solution polymerization is adopted comprises: dimethyl sulfoxide (DMSO), N, dinethylformamide, N-Methyl pyrrolidone, perhydronaphthalene, dodecane and tetramethylene sulfone etc.
The process that polycondensation prepares hydroxyl telechelic polyester is divided into two stages, and the fs is a solution polycondensation under normal pressure, and subordinate phase is a melt polymerization under reduced pressure.At first be Succinic Acid and excessive butyleneglycol solution polycondensation under the effect of catalyzer, collect and generate 80% of the water yield that steam solvent then, melt polymerization is reduced to below 3 until acid number.Used vacuum tightness is at 10-1000Pa.
Used catalyzer is the custom catalysts of esterification in the polymerization process, as: a kind of in tosic acid, tin protochloride, tetrabutyl titanate, isopropyl titanate, iron trichloride, the antimonous oxide or their mixture.
Chainextender of the present invention is 2,4-tolylene diisocyanate, 4,4 '-diphenylmethanediisocyanate, hexamethylene diisocyanate, 3,3 '-dimethyl diphenyl base-4,4 '-vulcabond, oxalyl chloride, hexanedioyl chlorine, terephthalyl chloride, malonic anhydride, Succinic anhydried and Tetra hydro Phthalic anhydride.
Estrodur performed polymer with 100 parts of weight calculates, and the consumption of chainextender is the 1-15 weight part.Chain extending reaction carried out under 50-200 ℃ 0.5-5 hour.
According to above-mentioned true mode, the present invention all can realize, enumerate part embodiment, but the present invention is not limited only to these.
Embodiment 1
In reaction unit, add 18.60g ethylene glycol, 23.60g Succinic Acid and 0.0567g tin protochloride; the dimethyl sulfoxide (DMSO) of 150mL; under nitrogen protection; slowly system is warming up to 120 ℃; and reaction 5 hours under this temperature, then slowly be warming up to 170 ℃ and under this temperature, continue to react 10 hours, steam solvent; at 230 ℃, melt polymerization is 1 hour under the 500Pa.After the cooling, in reaction unit, add the 2,4 toluene diisocyanate of 2.5g, and reaction 2 hours under 150 ℃, 100Pa, product.The weight-average molecular weight of products therefrom is 133000, and molecular weight distribution is 1.67.Tensile strength with the film of this product preparation is 27.8MPa.Elongation at break is 335%.
Embodiment 2
In reaction unit, add 13.64g ethylene glycol, 23.60g Succinic Acid and 0.149g antimonous oxide; the N-Methyl pyrrolidone of 150mL; under nitrogen protection; slowly system is warming up to 160 ℃; and reaction 3 hours under this temperature, then slowly be warming up to 195 ℃ and under this temperature, continue to react 12 hours, steam solvent; at 240 ℃, melt polymerization is 2 hours under the 1000Pa.After the cooling, in reaction unit, add the 2,4 toluene diisocyanate of 2.20g, and reaction 1.5 hours under 170 ℃, 1000Pa, product.The weight-average molecular weight of products therefrom is 152000, and molecular weight distribution is 1.85.Tensile strength with the film of this product preparation is 32.5MPa, and elongation at break is 375%.
Embodiment 3
In reaction unit, add 16.12g ethylene glycol, 23.60g Succinic Acid and 0.0567g tin protochloride; the N of 150mL; dinethylformamide; under nitrogen protection, slowly system is warming up to 100 ℃, and under this temperature, reacted 5 hours; then slowly be warming up to 160 ℃ and under this temperature, continue reaction 18 hours; steam solvent, at 210 ℃, melt polymerization is 1 hour under the 1000Pa.After the cooling, in reaction unit, add 4 of 3.80g, 4 '-diphenylmethanediisocyanate, and reaction 1 hour under 200 ℃, 1000Pa, product.The weight-average molecular weight of products therefrom is 161000, and molecular weight distribution is 1.76.Tensile strength with the film of this product preparation is 39.8MPa, and elongation at break is 325%.
Embodiment 4
In reaction unit, add 14.88g ethylene glycol, 23.60g Succinic Acid and 0.283g tetrabutyl titanate.And then in reaction unit, add the tetramethylene sulfone of 120mL; under nitrogen protection; slowly system is warming up to 120 ℃; and under this temperature, reacted 3 hours; then slowly be warming up to 200 ℃ and under this temperature, continue reaction 12 hours; steam solvent then, at 230 ℃, melt polymerization is 2 hours under the 500Pa.After the cooling, in reaction unit, add the oxalyl chloride of 2.60g, and 50 ℃, 1000Pa reaction 1 hour, product.The weight-average molecular weight of products therefrom is 176200, and molecular weight distribution is 1.75.Tensile strength with the film of this product preparation is 39.2MPa, and elongation at break is 370%.
Embodiment 5
In reaction unit, add 14.88g ethylene glycol, 23.60g Succinic Acid and 0.034g tetrabutyl titanate.And then in reaction unit, add the tetramethylene sulfone of 120mL; under nitrogen protection; slowly system is warming up to 120 ℃; and under this temperature, reacted 3 hours; then slowly be warming up to 210 ℃ and under this temperature, continue reaction 8 hours; steam solvent then, at 210 ℃, melt polymerization is 1 hour under the 100Pa.After the cooling, in reaction unit, add the terephthalyl chloride of 3.20g, and reaction 0.5 hour under 150 ℃, 1000Pa, product.The weight-average molecular weight of products therefrom is 145700, and molecular weight distribution is 1.85, is 31.2MPa with the tensile strength of the film of this product preparation, and elongation at break is 325%.
Embodiment 6
In reaction unit, add 16.12g ethylene glycol, 23.60g Succinic Acid and 0.170g tosic acid.And then in reaction unit, add the tetramethylene sulfone of 150mL; under nitrogen protection; slowly system is warming up to 120 ℃; and under this temperature, reacted 3 hours; then slowly be warming up to 210 ℃ and under this temperature, continue reaction 8 hours; steam solvent, at 240 ℃, melt polymerization is 1 hour under the 300Pa.After the cooling, in reaction unit, add the Succinic anhydried of 2.20g, and reaction 5 hours under 190 ℃, 100Pa, product.The weight-average molecular weight of products therefrom is 164500, and molecular weight distribution is 1.68.Tensile strength with the film of this product preparation is 33.4Mpa, and elongation at break is 325%.
Embodiment 7
In reaction unit, add 16.12g ethylene glycol, 23.60g Succinic Acid and 0.162g iron trichloride.And then in reaction unit, add the perhydronaphthalene of 120mL; under nitrogen protection; slowly system is warming up to 120 ℃, and reaction 3 hours under this temperature, then slowly is warming up to 170 ℃ and under this temperature, continue to react 20 hours; steam solvent; at 210 ℃, melt polymerization is 1 hour under the 500Pa, adds the Tetra hydro Phthalic anhydride of 3.80g then in reaction unit; and reaction 5 hours under 170 ℃, 500Pa, product.The weight-average molecular weight of products therefrom is 155600, and molecular weight distribution is 1.78.Tensile strength with the film of this product preparation is 32.8MPa, and elongation at break is 338%.
Embodiment 8
In reaction unit, add 17.36g ethylene glycol, 23.60g Succinic Acid and 0.162g tin protochloride.And then in reaction unit, add the perhydronaphthalene of 120mL; under nitrogen protection; slowly system is warming up to 120 ℃; and under this temperature, reacted 3 hours; then slowly be warming up to 170 ℃ and under this temperature, continue reaction 10 hours; steam solvent, at 230 ℃, melt polymerization is 1 hour under the 1000Pa.After the cooling, add the hexamethylene diisocyanate of 3.80g in reaction unit, reaction is 2 hours under 180 ℃, 500Pa, product.The weight-average molecular weight of products therefrom is 192800, and molecular weight distribution is 1.98.Tensile strength with the film of this product preparation is 39.7MPa, and elongation at break is 390%.
Embodiment 9
In reaction unit, add 16.12g ethylene glycol, 23.60g Succinic Acid and 0.162g iron trichloride.And then in reaction unit, add the dodecane of 150mL; under nitrogen protection; slowly system is warming up to 120 ℃; and under this temperature, reacted 3 hours; then slowly be warming up to 170 ℃ and under this temperature, continue reaction 10 hours; steam solvent, at 240 ℃, melt polymerization is 2 hours under the 100Pa.After the cooling, in reaction unit, add 3 of 3.50g, 3 '-dimethyl diphenyl base-4,4 '-vulcabond, and reaction 3 hours under 180 ℃, 500Pa, product.The weight-average molecular weight of products therefrom is 207800, and molecular weight distribution is 1.88, is 39.5MPa with the tensile strength of the film of this product preparation, and elongation at break is 394%.
Embodiment 10
In reaction unit, add 15.50g ethylene glycol, 23.60g Succinic Acid and 0.228g isopropyl titanate.And then in reaction unit, add the dodecane of 150mL; under nitrogen protection; slowly system is warming up to 140 ℃; and under this temperature, reacted 3 hours; then slowly be warming up to 170 ℃ and under this temperature, continue reaction 15 hours; steam solvent, at 220 ℃, melt polymerization is 1 hour under the 100Pa.After the cooling, in reaction unit, add the malonyl chloride of 2.80g.And reaction 2 hours under 60 ℃, 1000Pa, product.The weight-average molecular weight of products therefrom is 198000, and molecular weight distribution is 1.85.Tensile strength with the film of this product preparation is 39.2MPa, and elongation at break is 375%.
Embodiment 11
In reaction unit, add 14.88g ethylene glycol, 23.60g Succinic Acid and 0.291g antimonous oxide; the dodecane of 150mL; under nitrogen protection; slowly system is warming up to 140 ℃; and reaction 3 hours under this temperature, then slowly be warming up to 240 ℃ and under this temperature, continue to react 12 hours, steam solvent; at 220 ℃, melt polymerization is 1 hour under the 100Pa.After the cooling, in reaction unit, add the hexanedioyl chlorine of 3.20g.And reaction 2 hours under 100 ℃, 1000Pa, product.The weight-average molecular weight of products therefrom is 210800, and molecular weight distribution is 1.77.Tensile strength with the film of this product preparation is 40.8MPa, and elongation at break is 402%.
Claims (3)
1, a kind of method for preparing poly (ethylene succinate) utilizes Succinic Acid and ethylene glycol to carry out solution polycondensation, and the preparation estrodur performed polymer passes through vulcabond, binary acyl chlorides and dibasic acid anhydride chain extension more earlier; Its step is as follows:
A) Succinic Acid and ethylene glycol, catalyzer and solvent are joined in the reaction unit, under nitrogen protection, be warming up to 100-180 ℃ of reaction 1-5 hour; Then be warming up to 180-240 ℃ of reaction 8-24 hour, steam solvent, obtain the hydroxyl telechelic polyester performed polymer;
B) calculate with 100 parts of hydroxyl telechelic polyester performed polymers of above-mentioned parts by weight, add vulcabond, diacid chloride or the dibasic acid anhydride of 1-15 weight part therein,, under the 10-1000Pa, reacted 0.5-5 hour, get target product at 50-200 ℃;
The mol ratio of Succinic Acid and ethylene glycol is 1-3: 1;
Catalyzer is the catalyzer that esterification is used, and its consumption is the 0.1-100% of Succinic Acid mole number;
Solvent is dimethyl sulfoxide (DMSO), N, at least a in dinethylformamide, N-Methyl pyrrolidone, perhydronaphthalene, dodecane and the tetramethylene sulfone;
Chainextender is 2,4-tolylene diisocyanate, 4,4 '-diphenylmethanediisocyanate, hexamethylene diisocyanate, 3,3 '-dimethyl diphenyl base-4, at least a in 4 '-vulcabond, oxalyl chloride, hexanedioyl chlorine, terephthalyl chloride, malonic anhydride, Succinic anhydried and the Tetra hydro Phthalic anhydride.
2, preparation method as claimed in claim 1, wherein, the mol ratio of Succinic Acid and ethylene glycol is 1-1.5: 1.
3, preparation method as claimed in claim 1, wherein, catalyzer is at least a in tin protochloride, tetrabutyl titanate, isopropyl titanate, iron trichloride, antimonous oxide, the tosic acid.
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| CN102604051A (en) * | 2012-01-17 | 2012-07-25 | 陕西科技大学 | Poly(butylene succinate) and preparation method thereof |
| CN103215749A (en) * | 2013-04-24 | 2013-07-24 | 浙江理工大学 | Preparation method of aliphatic series copolyester melt-blow non-woven fabrics capable of being completely biologically degraded |
| CN103788379A (en) * | 2012-10-29 | 2014-05-14 | 中国石油化工股份有限公司 | Modified polyethylene glycol succinate and preparation methods thereof |
| CN103842403A (en) * | 2011-09-02 | 2014-06-04 | 三星精密化学株式会社 | Production method for a biodegradable polyester copolymer resin |
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| DE4337432A1 (en) * | 1993-11-03 | 1995-05-04 | Bayer Ag | Use of polyester polyols as binder component in two-component polyurethane coatings |
| CN1300213C (en) * | 2004-10-26 | 2007-02-14 | 四川大学 | Ternary copoly ester capable of biological degradation and its preparation method |
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| CN103842403B (en) * | 2011-09-02 | 2016-03-23 | 三星精密化学株式会社 | The preparation method of biodegradable polyethylene terephthalate copolymer resin |
| CN102604051A (en) * | 2012-01-17 | 2012-07-25 | 陕西科技大学 | Poly(butylene succinate) and preparation method thereof |
| CN102604051B (en) * | 2012-01-17 | 2014-06-04 | 陕西科技大学 | Poly(butylene succinate) and preparation method thereof |
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| CN104861093A (en) * | 2014-02-26 | 2015-08-26 | 中国石油化工股份有限公司 | Method for reducing polymer polymericular weight |
| CN104861095A (en) * | 2014-02-26 | 2015-08-26 | 中国石油化工股份有限公司 | Method for reducing polymer molecular weight |
| CN104861093B (en) * | 2014-02-26 | 2017-08-25 | 中国石油化工股份有限公司 | A kind of method for reducing polymer molecular weight |
| CN104861095B (en) * | 2014-02-26 | 2017-09-26 | 中国石油化工股份有限公司 | A kind of method for reducing polymer molecular weight |
| CN115821594A (en) * | 2022-12-05 | 2023-03-21 | 清远市齐力合成革有限公司 | Bass for permeable synthetic leather and preparation method thereof |
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