CN101935391B - Preparation method of high-molecular-weight aliphatic polyester - Google Patents
Preparation method of high-molecular-weight aliphatic polyester Download PDFInfo
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Abstract
The invention discloses a preparation method of high-molecular-weight aliphatic polyester, comprising the following steps of: using monomer aliphatic diacid diester and aliphatic diol as reaction materials; reacting the reaction materials and a catalyst in a nitrogen atmosphere for 1-5 hours under the condition of normal pressure and temperature of 160-200 DEG C; and reacting for 1-6 hours under the conditions of absolute pressure of 30-300Pa and temperature of 190-240 DEG C to obtain the high-molecular-weight aliphatic polyester as an objective product of the invention. The obtained high-molecular-weight aliphatic polyester has weight average molecular weight Mw value of 50-250k and a molecular weight distribution Mw/Mn value of 1.9-2.2. Compared with the prior art, the invention has the advantages of few by-products, high product yield, mild operation condition, low device cost and stable product quality and is suitable for industrial production.
Description
Technical field
The present invention relates to the preparation method of aliphatic polyester, be specifically related to a kind of method for preparing high-molecular aliphatic polyester with aliphatic diacid and aliphatic diol by transesterification reaction.
Background technology
Aliphatic polyester is a kind of important macromolecular material, especially as Biodegradable material, easily by the decomposition of the enzyme in natural multiple-microorganism or the animal and plant body, metabolism, has simultaneously excellent mechanical performances, can fundamentally solve one of effective way of white pollution problems, in the fields such as packing, tableware, medical treatment product, agricultural film, slow-release material and bio-medical material, have very widely and use.
In the prior art, US Patent No. 5310782A discloses a kind of with aliphatic diacid and aliphatic diol polycondensation, prepare the method for aliphatic polyester, but the aliphatic polyester molecular weight that makes only is about 30000.US Patent No. 6120895A discloses and has a kind ofly carried out chain extension and prepare the high molecular method of high-molecular-weight aliphatic by adding isocyanic ester, but because the method needs to add the larger isocyanic ester of toxicity as chainextender in preparation process, thereby make the use range of its product be subject to larger restriction.
The Chinese patent CN1861660A of Tsing-Hua University's application discloses a kind of synthetic method for preparing aliphatic polyester with diprotic acid and dibasic alcohol, adopts precondensation and vacuum polycondensation two-step approach, adds the aliphatic polyester that the 3rd monomer diprotic acid obtains high molecular.The shortcoming such as but there is product in the method small molecule by-product is more, product yield is low.The Chinese patent CN1424339A of Chinese Academy of Sciences's physics and chemistry application discloses a kind of method with Succinic Acid and butyleneglycol single stage method synthetic macromolecule amount poly butylene succinate (PBS), because it is harsh that the method requires processing condition, thereby industrialization promotion has larger difficulty.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of preparation method of high-molecular aliphatic polyester, and lower to overcome in the existing method yield, the aliphatic polyester molecular weight product is little, and processing condition are harsh, are difficult to the shortcomings such as industrialization promotion.
Technical conceive of the present invention is such: take polymerization single polymerization monomer aliphatic diacid diester and aliphatic diol as reaction raw materials, in nitrogen atmosphere, carry out the normal pressure transesterification reaction under the catalyst action, then under reduced pressure, carry out the vacuum transesterification reaction, namely obtain target product high-molecular aliphatic polyester of the present invention.
Technical scheme of the present invention is specific as follows:
With polymerization single polymerization monomer aliphatic diacid diester, aliphatic diol, with catalyzer in nitrogen atmosphere, normal pressure, reaction is 1-5 hour under 160-200 ℃ the condition, at 30-300Pa, reaction is 1-6 hour under 190-240 ℃ the condition, namely obtains target product high-molecular aliphatic polyester of the present invention.
Described polymerization single polymerization monomer is aliphatic diacid diester and aliphatic diol.
Described aliphatic diacid diester is selected from: ethylene dimethyl, diethyl oxalate, dimethyl malonate, diethyl malonate, dimethyl succinate, diethyl succinate, dimethyl adipate, diethylene adipate, suberic acid dimethyl ester, suberic acid diethyl ester.
Described aliphatic diol is selected from: ethylene glycol, propylene glycol, butyleneglycol, pentanediol, hexylene glycol, ethohexadiol.
Described catalyzer is selected from: one or more arbitrary combination in tosic acid, titanic acid ester, germanic acid ester, antimonous oxide, zinc acetate, manganese acetate, the cadmium acetate.
According to technical scheme of the present invention, the mol ratio of described aliphatic diacid diester and aliphatic diol is 1: 1-1.4, preferred 1: 1～1.2; The mass ratio 100 of described aliphatic diacid diester and catalyzer: 0.05-0.5.
The high-molecular aliphatic polyester by product that obtains with preparation method of the present invention is few, and its weight-average molecular weight Mw value is 50k-250k, and its molecular weight distribution mw/mn value is 1.9-2.2.
Compared with prior art, the present invention removes continuously methyl alcohol or ethanol in reaction process, can obtain the aliphatic polyester of high molecular, and the methyl alcohol of removing and ethanol can also reclaim by condensation and reuse, and lowers to pollute to be beneficial to environmental protection.The inventive method by product is few, and product yield is high, and in full-bodied polymerization system, it is easier that removal methyl alcohol or ethanol are removed water compared to existing technology, the process conditions milder, and equipment cost is lower.
The high-temperature stability of polymerizable raw material monomer aliphatic diacid diester of the present invention is much better than the aliphatic diacid that prior art adopts, and reaction process is not used any toxic substance, the constant product quality that makes substantially.
Embodiment
Below in conjunction with specific embodiment technical scheme of the present invention is described in further detail, but it does not limit technical scheme of the present invention.
Embodiment 1
In with the reaction unit of heating, stirring, temperature regulator, add respectively dimethyl succinate 73.0 grams (0.5mol), ethylene glycol 34.1 grams (0.55mol), wherein the mol ratio of dimethyl succinate and ethylene glycol is 1: 1.1, tosic acid 0.02 gram, zinc acetate 0.02 gram, under nitrogen atmosphere, stir and heat up, the control temperature of reaction is 170 ℃ under the normal pressure, reacted 5 hours, then heat up control vacuum 300Pa, 210 ℃ of temperature of reaction, proceed to react 6 hours, obtain polyethylene glycol succinate 81.8 grams.After testing, product weight-average molecular weight Mw value is 53.5k, and the molecular weight distribution mw/mn value is 2.2.
Embodiment 2
In with the reaction unit of heating, stirring, temperature regulator, add respectively diethylene adipate 50.5 grams (0.25mol), butyleneglycol 27.0 grams (0.3mol), wherein the mol ratio of diethylene adipate and butyleneglycol is 1: 1.2, tosic acid 0.05 gram, titanic acid ester 0.1 gram, antimonous oxide 0.05 gram, under nitrogen atmosphere, stir and heat up, the control temperature of reaction is 180 ℃ under the normal pressure, reacts 3 hours, then heats up, control vacuum 30Pa, 240 ℃ of temperature of reaction proceed to react 6 hours, obtain poly adipate succinic acid ester 59.6 grams.After testing, product weight-average molecular weight Mw value is 216.2k, and the molecular weight distribution mw/mn value is 1.9.
Embodiment 3
In with the reaction unit of heating, stirring, temperature regulator, add respectively dimethyl succinate 73.0 grams (0.5mol), butyleneglycol 40.9 grams (0.5mol), wherein the mol ratio of dimethyl succinate and butyleneglycol is 1: 1, tosic acid 0.1 gram, germanic acid ester 0.1 gram, under nitrogen atmosphere, stir and heat up, the control temperature of reaction is 180 ℃ under the normal pressure, reacted 3 hours, then heat up control vacuum 30Pa, 230 ℃ of temperature of reaction, proceed to react 4 hours, obtain poly butylene succinate 87.7 grams.After testing, product weight-average molecular weight Mw value is 197.0k, and the molecular weight distribution mw/mn value is 2.0.
Embodiment 4
In with the reaction unit of heating, stirring, temperature regulator, add respectively diethyl malonate 80.0 grams (0.5mol), hexylene glycol 82.6 grams (0.7mol), wherein the mol ratio of diethyl malonate and hexylene glycol is 1: 1.4, tosic acid 0.2 gram, manganese acetate 0.2 gram, under nitrogen atmosphere, stir and heat up, the control temperature of reaction is 180 ℃ under the normal pressure, reacted 3 hours, then heat up control vacuum 30Pa, 230 ℃ of temperature of reaction, proceed to react 3 hours, obtain poly adipate succinic acid ester 112.3 grams.After testing, product weight-average molecular weight Mw value is 154.2k, and the molecular weight distribution mw/mn value is 1.9.
Embodiment 5
In with the reaction unit of heating, stirring, temperature regulator, add respectively ethylene dimethyl 59.0 grams (0.5mol), butyleneglycol 49.5 grams (0.55mol), wherein the mol ratio of diethyl malonate and hexylene glycol is 1: 1.1, tosic acid 0.05 gram, germanic acid ester 0.05 gram, under nitrogen atmosphere, stir and heat up, the control temperature of reaction is 180 ℃ under the normal pressure, reacted 1 hour, then heat up control vacuum 100Pa, 200 ℃ of temperature of reaction, proceed to react 2 hours, obtain poly-oxalic acid butanediol ester 80.5 grams.After testing, product weight-average molecular weight Mw value is 76.1k, and the molecular weight distribution mw/mn value is 1.9.
Should be noted that at last, above embodiment is only unrestricted in order to technical scheme of the present invention to be described, although with reference to preferred embodiment the present invention is had been described in detail, those of ordinary skill in the art is to be understood that, can make amendment or be equal to replacement the technical scheme of invention, and not breaking away from the spirit and scope of technical solution of the present invention, it all should be encompassed in the claim scope of the present invention.
Claims (5)
1. the preparation method of a high-molecular aliphatic polyester, it is characterized in that, comprise the steps: with heating, stir, add respectively dimethyl succinate 73.0 grams in the reaction unit of temperature regulator, ethylene glycol 34.1 grams, wherein the mol ratio of dimethyl succinate and ethylene glycol is 1:1.1, tosic acid 0.02 gram, zinc acetate 0.02 gram, stir under nitrogen atmosphere and heat up, the control temperature of reaction is 170 ℃ under the normal pressure, reacts 5 hours, then heat up, control vacuum 300Pa, 210 ℃ of temperature of reaction proceed to react 6 hours, obtain polyethylene glycol succinate 81.8 grams, after testing, product weight-average molecular weight Mw value is 53.5k, and the molecular weight distribution mw/mn value is 2.2.
2. the preparation method of a high-molecular aliphatic polyester, it is characterized in that, comprise the steps: with heating, stir, add respectively diethylene adipate 50.5 grams in the reaction unit of temperature regulator, butyleneglycol 27.0 grams, wherein the mol ratio of diethylene adipate and butyleneglycol is 1:1.2, tosic acid 0.05 gram, titanic acid ester 0.1 gram, antimonous oxide 0.05 gram stirs under nitrogen atmosphere and heats up, the control temperature of reaction is 180 ℃ under the normal pressure, reacted 3 hours, and then heated up, control vacuum 30Pa, 240 ℃ of temperature of reaction, proceed to react 6 hours, obtain poly adipate succinic acid ester 59.6 grams, after testing, product weight-average molecular weight Mw value is 216.2k, and the molecular weight distribution mw/mn value is 1.9.
3. the preparation method of a high-molecular aliphatic polyester, it is characterized in that, comprise the steps: with heating, stir, add respectively dimethyl succinate 73.0 grams in the reaction unit of temperature regulator, butyleneglycol 40.9 grams, wherein the mol ratio of dimethyl succinate and butyleneglycol is 1:1, tosic acid 0.1 gram, germanic acid ester 0.1 gram, stir under nitrogen atmosphere and heat up, the control temperature of reaction is 180 ℃ under the normal pressure, reacts 3 hours, then heat up, control vacuum 30Pa, 230 ℃ of temperature of reaction proceed to react 4 hours, obtain poly butylene succinate 87.7 grams, after testing, product weight-average molecular weight Mw value is 197.0k, and the molecular weight distribution mw/mn value is 2.0.
4. the preparation method of a high-molecular aliphatic polyester, it is characterized in that, comprise the steps: with heating, stir, add respectively diethyl malonate 80.0 grams in the reaction unit of temperature regulator, hexylene glycol 82.6 grams, wherein the mol ratio of diethyl malonate and hexylene glycol is 1:1.4, tosic acid 0.2 gram, manganese acetate 0.2 gram, stir under nitrogen atmosphere and heat up, the control temperature of reaction is 180 ℃ under the normal pressure, reacts 3 hours, then heat up, control vacuum 30Pa, 230 ℃ of temperature of reaction proceed to react 3 hours, obtain poly adipate succinic acid ester 112.3 grams, after testing, product weight-average molecular weight Mw value is 154.2k, and the molecular weight distribution mw/mn value is 1.9.
5. the preparation method of a high-molecular aliphatic polyester, it is characterized in that, comprise the steps: with heating, stir, add respectively ethylene dimethyl 59.0 grams in the reaction unit of temperature regulator, butyleneglycol 49.5 grams, wherein the mol ratio of diethyl malonate and hexylene glycol is 1:1.1, tosic acid 0.05 gram, germanic acid ester 0.05 gram, stir under nitrogen atmosphere and heat up, the control temperature of reaction is 180 ℃ under the normal pressure, reacts 1 hour, then heat up, control vacuum 100Pa, 200 ℃ of temperature of reaction proceed to react 2 hours, obtain poly-oxalic acid butanediol ester 80.5 grams, after testing, product weight-average molecular weight Mw value is 76.1k, and the molecular weight distribution mw/mn value is 1.9.
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Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102219891B (en) * | 2011-05-13 | 2012-07-25 | 北京理工大学 | Method for preparing poly-oxalate-1,4-butylene |
| CN102304220B (en) * | 2011-07-20 | 2012-09-26 | 上海焦化有限公司 | Preparation method of aliphatic polydiacid diol ester |
| CN102718948B (en) * | 2012-07-03 | 2014-03-12 | 常州大学 | Method for preparing aliphatic polyoxalate |
| CN102746493B (en) * | 2012-07-09 | 2014-04-23 | 旭阳化学技术研究院有限公司 | Preparation method of all-biological-base poly butylenes succinate (PBS) |
| KR20140031011A (en) | 2012-09-04 | 2014-03-12 | 삼성정밀화학 주식회사 | Method for continuous production of biodegradable aliphatic polyester |
| JP6519484B2 (en) * | 2013-12-24 | 2019-05-29 | 東洋製罐グループホールディングス株式会社 | Polyoxalate |
| CN106750202B (en) * | 2016-12-18 | 2018-10-09 | 浙江交通科技股份有限公司 | A kind of method of ester-interchange method poly butylene succinate |
| CN110205344A (en) * | 2019-06-04 | 2019-09-06 | 电子科技大学 | A kind of dendritic polyhydroxy narrow ditribution polyester and preparation method thereof |
| CN115490838B (en) * | 2021-10-19 | 2023-09-19 | 源创核新(北京)新材料科技有限公司 | High molecular weight aliphatic polyoxalate and preparation method thereof |
| CN114605622B (en) * | 2022-03-31 | 2024-04-02 | 苏州瀚海新材料有限公司 | Aliphatic polyester with malonic acid structure, and preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1088945A (en) * | 1992-12-24 | 1994-07-06 | 株式会社鲜京工业 | Thermoplasticity Biodegradable resin and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1088945A (en) * | 1992-12-24 | 1994-07-06 | 株式会社鲜京工业 | Thermoplasticity Biodegradable resin and preparation method thereof |
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