CN1200027C - Process for preparing high-molecular aliphatic polyester - Google Patents
Process for preparing high-molecular aliphatic polyester Download PDFInfo
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- CN1200027C CN1200027C CN 03153246 CN03153246A CN1200027C CN 1200027 C CN1200027 C CN 1200027C CN 03153246 CN03153246 CN 03153246 CN 03153246 A CN03153246 A CN 03153246A CN 1200027 C CN1200027 C CN 1200027C
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Abstract
The present invention relates to a method for preparing aliphatic polyester with high molecular weight, which comprises: aliphatic dibasic acid and aliphatic dibasic alcohol react for 1 to 14 hours at 100 to 200 DEG C in decahydronaphthalene solvent, which can obtain aliphatic polyester with high molecular weight, wherein stannous chloride dihydrate, stannous octoate, titanic acid dinbutyl phthalate, isopropyl titanate, etc. are used as catalysts. The present invention has the advantages of simple equipment, low cost, easy control of reactions, high product molecular weight, high yield and high purity of prepared products.
Description
Field of the invention
The invention relates to a preparation method of high molecular weight aliphatic polyester.
Background
The aliphatic polyester can be used as plastic products which are difficult to recycle, such as agricultural mulching films, fishing gears, plastic packaging bags, foamed plastics, disposable tableware, women sanitary products, disposable medical appliances and the like, and plays an important role in solving the increasingly serious white pollution.
The invention of JP2002020474 discloses a preparation method of aliphatic polyester. The method comprises the steps of adding dibasic acid and dihydric alcohol into a decalin solvent, reacting for 1 hour at 150 ℃ by taking divalent organic siloxane as a catalyst, and reacting for 72 hours at 193 ℃ to obtain a product. The number average molecular weight of the product was 73600. The method has the defects of long reaction time, high energy consumption and difficult realization of industrial production.
USP5741882 discloses a preparation method of aliphatic polyester. The method takes dibasic acid dimethyl ester or diethyl ester and dihydric alcohol as raw materials to carry out melt polymerization, and a proton scavenger is added to improve the molecular weight. The disadvantage of this process is the high vacuum required, and therefore the equipment is complex, requiring special expensive equipment; the used raw materials are esters of dibasic acids, so the price is high and the product cost is high.
USP6417266 invention discloses a preparation method of aliphatic polyester. The method comprises the steps of firstly carrying out melt polymerization by taking dibasic acid and dihydric alcohol as raw materials to prepare a prepolymer with the weight-average molecular weight of 10000-100000, and then carrying out solid-phase polymerization by taking organic acid as a raw material, wherein the weight-average molecular weight of the product reaches above 100000 after 100 hours. The method has the disadvantages of overlong reaction time, low production efficiency and difficult industrialization.
JP09077862 discloses a preparation method of aliphatic polyester. The method comprises the steps of adding dibasic acid, dihydric alcohol and a small amount of trifunctional compounds such as glycerol and tartaric acid into o-dichlorobenzene, and reacting for a period of time by using stannous oxide as a catalyst to obtain a product. The method has the defects that the o-dichlorobenzene is high in toxicity, can cause serious environmental pollution and can harm the physical health of operators.
USP5306787 discloses a preparation method of aliphatic polyester. The method is to take dibasic acid and excessive dihydric alcohol as raw materials to carry out melt polymerization to synthesize hydroxyl-terminated polyester prepolymer, and then add diisocyanate as a chain extender to obtain the high molecular weight polyester. The method has the disadvantages that the using amount of the dihydric alcohol is large and needs to be recycled; the reaction temperature is high and is not easy to control; high vacuum pumping is required, and equipment is expensive; and the raw material diisocyanate has high toxicity and is difficult to be used in the fields of medical treatment and food.
USP5428126 invention discloses a preparation method of aliphatic polyester. The method takes dibasic acid and excessive dihydric alcohol as raw materials to carry out melt polymerization, then hydrophilic organic solvent isadded to carry out solution polymerization, and molecular sieve is used as a dehydrating agent, so that the obtained polyester has the weight-average molecular weight of between 15000 and 50000. The method has the disadvantages of complicated procedure; the product has low molecular weight; the molecular sieve can be recycled after high-temperature treatment, is easy to absorb organic small molecular substances, has poor water absorption effect when being repeatedly used, is difficult to obtain high molecular weight, and can influence the product quality because the absorbed organic small molecules deteriorate during high-temperature treatment.
The invention of CP1146466 discloses a preparation method of aliphatic polyester. The method takes lactone (such as caprolactone) and lactide (such as glycolide and lactide) as raw materials to carry out ring-opening polymerization to obtain the high molecular weight polyester. The disadvantages are that the types of monomers are few, the choice is small, and it is difficult to obtain various polyester varieties.
USP5616681 discloses a preparation method of aliphatic polyester. The method takes succinic anhydride and ethylene oxide as raw materials and zirconium octoate as a catalyst to carry out ring-opening polymerization to obtain the polyethylene glycol succinate. The disadvantage is that the ethylene oxide has high toxicity and is not easy to control; the similar monomers have few kinds, and the selection scope is small, so that the diversified polyester varieties are difficult to obtain; easily form polyether chain links and reduce the melting point of the product.
The object of the present invention is to provide a process for producing a high molecular weight aliphatic polyester, which overcomes the above-mentioned disadvantages of the prior art. The method has the advantages of simple equipment, low cost, easy control of reaction, high molecular weight of the product, high yield and high purity of the prepared product.
Disclosure of Invention
The process for producing a high molecular weight aliphatic polyester of the present invention is carried out by:
the aliphatic dibasic acid and aliphatic dihydric alcohol react in a decahydronaphthalene solvent for 1 to 14 hours at a temperature of between 100 and 200 ℃ by taking one or a mixture of stannous chloride, stannous octoate, n-butyl titanate and isopropyl titanate as a catalyst to obtain the high molecular weight aliphatic polyester.
The dibasic acid can be one or more of oxalic acid, 1, 3-malonic acid, 1, 4-succinic acid, 1, 5-glutaric acid, 1, 6-adipic acid, 1, 7-pimelic acid, 1, 8-suberic acid, 1, 9-azelaic acid, 1, 10-sebacic acid, 1, 16-hexadecanedioic acid and 1, 18-octadecanedioic acid.
The dihydric alcohol may be one or more of ethylene glycol, 1, 3-propanediol, 1, 2-butanediol, 1, 3-butanediol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, 1, 7-heptanediol, 1, 8-octanediol, 1, 9-nonanediol, 1, 10-decanediol, 2-methyl-1, 3-propanediol, 1, 20-eicosanediol, and 1, 4-dimethylcyclohexanediol.
The above reaction formula is as follows:
(wherein R is1Is a hydrocarbon group of 1 to 18 carbon atoms, R2Is a hydrocarbon group having 2 to 20 carbon atoms
Compared with the prior art, the invention has the following advantages:
(1) the catalyst used in the invention has simple structure, low price and high catalytic efficiency, and not only can greatly shorten the reaction time, but also can improve the reaction degree and the molecular weight.
(2) The invention replaces melt polymerization with solution polymerization, and has the advantages of simple equipment, no need of vacuum pumping, low reaction temperature, uniform heating and easy control.
(3) The present invention uses decalin as solvent to replace toluene, diphenyl ether, etc. as common solvent in polyester reaction. The decahydronaphthyl is nontoxic, so the environmental pollution is reduced to a great extent. Meanwhile, decahydronaphthalene has high boiling point, so that the decahydronaphthalene can react at higher temperature, and the reaction time is greatly shortened. Decahydronaphthalene is immiscible with water and does not form an azeotropic system, so that the water removal efficiency is high, the reaction is carried out more thoroughly, and higher molecular weight and yield are obtained.
(4) The solvent decalin is easy to recycle, and the dihydric alcohol is not needed to be recycled, so the cost is low.
(5) The invention does not need dehydrating agents such as molecular sieves and the like, can improve the product quality and reduce the cost.
Detailed Description
The invention is further described by the following examples
Example 1
Adding 0.3mol of succinic acid, 0.27-0.33mol of butanediol, 0.005-0.5g of stannous chloride catalyst and 100ml of decalin into a 250ml four-neck flask, installing a mechanical stirrer, a water separator and a thermometer, introducing nitrogen, heating by using a silicon oil bath, reacting for 0.1-12h at 100-180 ℃, and then heating to 150-200 ℃ for reacting for 1-14 h. The total reaction time is 1-14 h. Stopping stirring and heating, cooling the reaction system, pouring out decahydronaphthalene, and dryingin vacuum (0.094Mpa, 120 ℃ for 8h) to obtain the product with the yield of 96.0%. IR: 1717cm-1HNMR: delta 1.69, delta 2.60, delta 4.09, and the area ratio of the trimodal areas is 1: 1, which proves that the obtained product is poly (butylene succinate). The number average molecular weight of the product is 78912 by GPC, and the temperature is 20 ℃ CHCl3The intrinsic viscosity was 1.68 dl/g.
Example 2
The raw materials in example 1 were changed to adipic acid and hexanediol, and the other conditions were the same as in example 1, to obtain a product with a yield of 96.8%. IR: 1727cm-1(ii) a HNMR: delta 1.33, delta 1.62, delta 2.28, delta 4.02, four peaksThe area ratio was 1: 2: 1, confirming that the product was polyhexamethylene adipate. 20 ℃ CHCl3The intrinsic viscosity was 1.65 dl/g.
Example 3
The raw materials in the example 1 are changed into succinic acidAnd hexanediol, the other conditions were the same as in example 1, to give the product in 95.8% yield. IR: 1724cm-1(ii) a HNMR: delta 1.34, delta 1.60, delta 2.58 and delta 4.05, and the area ratio of the four peak areas is 1: 1, thus proving that the obtained product is the poly (hexamethylene succinate). 20 ℃ CHCl3The intrinsic viscosity was 1.51 dl/g.
Example 4
The raw materials in the example 1 are changed into sebacic acid and hexanediol, and the other conditions are the same as the example 1, so that the product is obtained, and the yield is 96.8%. IR: 1729cm-1(ii) a HNMR: delta 1.34, delta 1.59, delta 2.26, delta 4.03, and a peak area ratio of four of 3: 2: 1, the resulting product was confirmed to be polyhexamethylene sebacate. 20 ℃ CHCl3The intrinsic viscosity was 1.69 dl/g.
Example 5
The raw materials in the example 1 are changed into succinic acid and ethylene glycol, and the product is obtained by the same conditions as the example 1, wherein the yield is 94.2%. IR: 1728cm-1(ii) a HNMR: delta 2.64, delta 4.23, the area ratio of the two peaks is 1: 1, and the obtained product is proved to be polyethylene glycol succinate. 20 ℃ CHCl3The intrinsic viscosity was 1.23 dl/g.
Example 6
The catalyst in example 1 was changed to stannous chloride/isopropyl titanate in equimolar ratio and the product was obtained in 95.8% yield under the same conditions as in example 1. IR: 1717cm-1HNMR: delta 1.69, delta 2.60, delta 4.09, and the area ratio of the trimodal areas is 1: 1, which proves that the obtained product is poly (butylene succinate). 20 ℃ CHCl3The intrinsic viscosity was 1.41 dl/g.
Example 7
The catalyst in example 1 was changed to n-butyl titanate, and the product was obtained in the same manner as in example 1 under the other conditions, showing a yield of 95.2%. IR: 1717cm-1HNMR: delta 1.69, delta 2.60, delta 4.09, and the area ratio of the trimodal areas is 1: 1, which proves that the obtained product is poly (butylene succinate). 20 ℃ CHCl3The intrinsic viscosity was 1.13 dl/g.
Example 8
The catalyst in example 1 was changed to stannous octoate, and the product was obtained under the same conditions as in example 1, with a yield of 94.6%. IR: 1717cm-1，HNMR：δ1.69，Delta 2.60, delta 4.0g, the area ratio of the three peaks is 1: 1,the obtained product was proved to be polybutylene succinate. 20 ℃ CHCl3The intrinsic viscosity was 0.78 dl/g. Example 9(67) in a 250ml four-neck flask, 0.27 to 0.33mol of succinic acid, 0.24mol of butanediol, 0.06mol ofethylene glycol, 0.005 to 0.5g of stannous chloride and 100ml of decahydronaphthalene were added, a mechanical stirrer, a water separator and a thermometer were installed, nitrogen was introduced, the mixture was heated in a silicon oil bath, and the mixture was reacted at 100 to 180 ℃ for 0.1 to 12 hours, and then heated to 150 ℃ to 200 ℃ for 1 to 18 hours. The total reaction time is 1-18 h. Stopping stirring and heating, cooling the reaction system, pouring out decahydronaphthalene, and drying in vacuum (0.094Mpa, 120 ℃ for 8h) to obtain the product with the yield of 94.8%. IR: 1720cm-1HNMR: delta 1.66, delta 2.60, delta 4.07, delta 4.25, and the area ratio of the four peak areas is about 1: 4: 5: 4, which proves that the obtained product is poly (butylene succinate) -ethylene succinate. 20 ℃ CHCl3The intrinsic viscosity was 1.23 dl/g.
Example 10
The product was obtained in 95.2% yield under the same conditions as in example 9 except that ethylene glycol in example 9 was changed to hexylene glycol. IR: 1715cm-1HNMR: delta 1.34, delta 1.67, delta 2.59, delta 4.05, and a peak area ratio of four of about 1: 6, which proves that the obtained product is poly (butylene succinate) -hexylene succinate. 20 ℃ CHCl3The intrinsic viscosity was 1.15 dl/g.
Example 11
Adding 0.18mol of succinic acid, 0.12mol of adipic acid, 0.27-0.33mol of butanediol, 0.005-0.5g of stannous chloride and 100ml of decahydronaphthalene into a 250ml four-neck flask, installing a mechanical stirrer, a water separator and a thermometer, introducing nitrogen, heating by using a silicon oil bath, reacting for 0.1-12h at 100-180 ℃, and then heating to 150-200 ℃ for reacting for 1-18 h. The total reaction time is 1-18 h. Stopping stirring and heating, cooling the reaction system, pouring out decahydronaphthalene, and drying in vacuum (0.094Mpa, 120 ℃ for 8h)to obtain the product with the yield of 94.7%. IR: 1720cm-1HNMR: delta 1.65, delta 2.29, delta 2.59 and delta 4.07, the area ratio of four peak areas is 1: 4: 5: 4, and the obtained product is proved to be poly butylene succinate-butylene adipate. 20 ℃ CHCl3The intrinsic viscosity was 1.31 dl/g.
Example 12
The butanediol of example 11 was changed to hexanediol and the product was obtained in 95.6% yield under the same conditions as in example 11. IR: 1725cm-1HNMR: delta 1.32, delta 1.59, delta 2.27, delta 2.57 and delta 4.03, and the area ratio of the five peaks is 1: 1.2: 0.2: 0.8: 1, which proves that the obtained product is poly (butylene succinate) -hexylene succinate. 20 ℃ CHCl3The intrinsic viscosity was 1.33 dl/g.
Example 13
Adding 0.18mol of sebacic acid, 0.12mol of adipic acid, 0.27-0.33mol of hexanediol, 0.005-0.5g of stannous chloride and 100ml of decahydronaphthalene into a 250ml four-neck flask, installing a mechanical stirrer, a water separator and a thermometer, introducing nitrogen, heating by using a silicon oil bath, reacting for 0.1-12h at 100-180 ℃, and then heating to 150-200 ℃ for reacting for 1-18 h. The total reaction time is 1-18 h. Stopping stirring and heating, cooling the reaction system, pouring out decahydronaphthalene, and drying in vacuum (0.094Mpa, 120 ℃ for 8h) to obtain the product with the yield of 94.8%. IR: 1725cm-1HNMR: delta 1.34, delta 1.58, delta 2.26 and delta 4.03, and the area ratio of the four peak areas is 3: 2: 1, thus proving that the obtained product is poly (butylene succinate) -ethylene succinate. 20 ℃ CHCl3The intrinsic viscosity was 1.23 dl/g.
Claims (3)
1. A method for preparing high molecular weight aliphatic polyester is characterized in that: aliphatic dibasic acid and aliphatic dihydric alcohol react in a decalin solvent for 1 to 14 hours at 100 to 200 ℃ by taking any one or more of stannous chloride, stannous octoate, n-butyl titanate and isopropyl titanate as a catalyst to obtain the aliphatic polyester.
2. The process for producing a high molecular weight aliphatic polyester according to claim 1, wherein: the dibasic acid is one or more of oxalic acid, 1, 3-malonic acid, 1, 4-succinic acid, 1, 5-glutaric acid, 1, 6-adipic acid, 1, 7-pimelic acid, 1, 8-suberic acid, 1, 9-azelaic acid, 1, 10-sebacic acid, 1, 16-hexadecanedioic acid and 1, 18-octadecanedioic acid.
3. The process for producing a high molecular weight aliphatic polyester according to claim 1, wherein: the dihydric alcohol is ethylene glycol, 1, 3-propylene glycol, 1, 2-butanediol, 1, 3-butanediol, 1, 4-butanediol, 1, 5-pentanediol, 1; 6-hexanediol, 1, 7-heptanediol, 1, 8-octanediol, 1, 9-nonanediol, 1, 10-decanediol, 2-methyl-1, 3-propanediol, 1, 20-eicosanediol, 1, 4-dimethylcyclohexanediol or a mixture of several kinds thereof.
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| CN 03153246 CN1200027C (en) | 2003-08-11 | 2003-08-11 | Process for preparing high-molecular aliphatic polyester |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100406494C (en) * | 2006-12-06 | 2008-07-30 | 上海振华造漆厂 | Epoxy modified polyester resin for paint of coil back surface and its preparation method |
| CN103724602A (en) * | 2013-12-06 | 2014-04-16 | 江苏盈天化学有限公司 | Method for preparing sebacic acids polyester polyol by using recovered alcohol |
| 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 |
| CN115057998B (en) * | 2022-07-07 | 2023-07-25 | 武汉理工大学 | Method for jointly producing epsilon-caprolactone and polybutylene succinate |
| CN118126504A (en) * | 2024-04-09 | 2024-06-04 | 辽宁石油化工大学 | Preparation method of fully-degradable antibacterial toy material tannin/pentanediol-based polyester |
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