CN116003749A - Synthesis method of bio-based high molecular weight poly (butylene succinate) - Google Patents
Synthesis method of bio-based high molecular weight poly (butylene succinate) Download PDFInfo
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Abstract
The invention belongs to the technical field of organic synthesis, and particularly relates to a synthesis method of bio-based high-molecular-weight polybutylene succinate. According to the invention, the proportion of monomers used for producing the poly (butylene succinate) is adjusted, succinic acid and 1, 4-butanediol are utilized for esterification and pre-polycondensation to obtain a product with higher molecular weight, and then the product is further subjected to transesterification with the bio-based succinic acid dialkanol ester, so that the production of the bio-based high molecular weight poly (butylene succinate) is realized in a two-step polycondensation mode. The synthesis method of the invention not only can obtain higher molecular weight, but also can avoid the harsh conditions of high temperature and high vacuum. According to the invention, the bio-based succinic acid dialkanol ester is added in the later reaction period, so that the original water generated in polycondensation is changed into the dialkanol generated, the esterification difficulty is reduced, the molecular weight of an intermediate product is increased, and meanwhile, the reaction temperature is reduced, thereby achieving the purposes of reducing energy consumption, saving time and improving the product quality.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to a synthesis method of bio-based high-molecular-weight butylene succinate.
Background
The bio-based polybutylene succinate is also called PBS, and has the chemical structure:
because of a large number of ester bonds in the molecular chain, the material is easy to be metabolized and decomposed by various microorganisms in nature or enzymes in animals and plants after being used, and finally converted into water and carbon dioxide, thus being a green material capable of realizing complete ecological cycle production from nature.
At present, three synthesis methods of polybutylene succinate (PBS) are mainly adopted, namely a direct esterification method, an ester exchange method and a chain extension method. The main process routes of the three methods are compared as follows:
1. direct esterification: the preparation method comprises the steps of firstly carrying out esterification reaction on succinic acid and excessive butanediol at a low temperature under nitrogen, carrying out intermolecular dehydration to generate hydroxyl-terminated oligomers, and then removing dihydric alcohol from the oligomers under the conditions of high temperature and high vacuum degree by the action of a catalyst to obtain the PBS with high molecular weight. In addition, the direct esterification method can be classified into three methods, i.e., solution polycondensation, melt polycondensation, and solution melting, depending on whether a solution is used or not. The direct esterification method has the disadvantage of a large number of byproducts, and requires high temperature and high vacuum.
2. Transesterification process: under the action of a catalyst, the equimolar amount of dimethyl diacid and 1, 4-butanediol are subjected to transesterification reaction, the dialkanol is removed to obtain PBS prepolymer, and the PBS with high content is obtained under the conditions of high vacuum and high temperature. The disadvantage of this process is the relatively low relative molecular weight of the final product.
3. Chain extension method: the active group of the chain extender is utilized to react with the hydroxyl end or carboxyl end of the PBS prepolymer, so as to achieve the effect of chain extension and improve the relative molecular weight of the product. The disadvantage of this method is that the chain extender has a certain toxicity, remains in the product, and affects the range of use of the product.
The water produced in the latter stage of the direct esterification process is difficult to remove from the reaction system, and in order to achieve a higher molecular weight, the temperature and vacuum must be increased, and the reaction time must be increased. Therefore, the method aims at the technical problems in the prior art, improves the direct esterification method by utilizing the bio-based raw material, and adjusts the reaction sequence and the process parameters, thereby avoiding high temperature in the reaction process and shortening the reaction time.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a synthesis method of bio-based high molecular weight poly (butylene succinate) (PBS), which combines a transesterification method and a direct esterification method, so that the high molecular weight can be obtained, the harsh conditions of high temperature and high vacuum are avoided, the synthesis period is finally reduced, and the energy consumption is reduced, so that a high-quality bio-based PBS product is obtained.
Based on the above purpose, the invention adopts the following technical scheme:
a synthesis method of bio-based high molecular weight polybutylene succinate (PBS), the process route of the method is as follows:
(one)
(II)
The synthesis method of the bio-based high molecular weight polybutylene succinate (PBS) comprises the following steps:
(1) And (3) normal pressure reaction: mixing bio-based succinic acid and 1, 4-Butanediol (BDO) and placing the mixture into a reaction container (four-necked flask), then adding a catalyst under the condition of forming inert atmosphere in the reaction container, heating to 130-160 ℃ while stirring to perform pre-polycondensation reaction, wherein the reaction time is 1-4 h to obtain a reactant, water is continuously generated in the reaction process, and an oil-water separator is used for removing water during the reaction until the water quantity separated in the oil-water separator is not obviously increased;
(2) Negative pressure reaction I: pumping the reaction container to a negative pressure state by a vacuum pump, wherein the negative pressure is 50-1000 Pa, then heating to 160-230 ℃ under the negative pressure condition for reaction, wherein the reaction time is 1-4 h, and the molecular weight of the pre-polycondensation reactant in the step (1) is further increased;
(3) Negative pressure reaction II: adding bio-based succinic acid dialkanol ester into the product obtained in the step (2) by using a constant pressure titration funnel to carry out transesterification reaction, wherein the reaction temperature is 160-230 ℃, the reaction time is 1-2 h, the molecular weight of reactants is further improved in the reaction process, and simultaneously the bio-based succinic acid dialkanol ester is further reacted with hydroxyl in the material to remove dialkanol; and after the reaction is finished, carrying out post-treatment on the materials to obtain a final product.
Further, in the step (1), a precondensation reaction is carried out by adopting a bio-based monomer (bio-based succinic acid) and a 1, 4-butanediol monomer, wherein the molar ratio of the bio-based succinic acid to the 1, 4-butanediol is (35-55): 75-45, preferably (38-47): 62-53, more preferably (42-47): 58-53).
In the step (1), an inert atmosphere is formed by introducing nitrogen into the reaction vessel to remove air.
Further, in the step (1), the addition amount of the catalyst is 0.1 to 0.2 percent, preferably 0.1 percent, of the total mass of the bio-based succinic acid, the 1, 4-butanediol and the catalyst; the catalyst is a nontoxic metal catalyst and/or a nonmetallic catalyst, preferably tetrabutyl titanate.
Further, in the step (1), the total amount of materials added during the reaction is 1/3 to 1/2 of the volume of the reaction vessel.
Further, in the step (1), the reaction temperature is preferably 150 to 160 ℃; the reaction time is preferably 1 to 2.5 hours, more preferably 1.5 to 2.5 hours.
Further, in the step (2), the negative pressure of the reaction system is preferably 50 to 500Pa, more preferably 50 to 300a.
Further, in the step (2), the reaction temperature is preferably 190 to 230 ℃, more preferably 200 to 220 ℃.
Further, in the step (2), the reaction time is preferably 1 to 3 hours, more preferably 1.5 to 2.5 hours.
Further, in step (3), the bio-based dialkanol succinate includes, but is not limited to, dimethyl succinate, diethyl succinate, dibutyl succinate, and the like.
Further, in the step (3), the amount of the dialkyl biobased succinate added is 1 to 10%, preferably 4 to 9%, more preferably 5 to 9% of the total mass of the bio-based succinic acid and the 1, 4-butanediol.
Further, in the step (3), the reaction time is preferably 1.5 to 2 hours.
Further, in the step (3), the post-treatment of the reaction-finished material is as follows: and (3) placing the materials after the reaction in organic alcohol, separating out precipitate under the normal temperature condition, filtering, centrifuging and drying to obtain the product.
Further preferably, in the step (3), the post-treatment operation of the material after the reaction is finished is specifically as follows:
placing the materials after the reaction in organic alcohol, stirring at normal temperature, filtering, separating out polymer (sediment) with the size of 20-100 meshes, centrifuging for 50-10 min under the pressure of 1.80-2.0 MPa, and drying at 40-50 ℃ for 1-2 hours after centrifuging to obtain the product; the organic alcohol is methanol, ethanol, etc.
According to the invention, the proportion of monomers (succinic acid and 1, 4-butanediol) used for producing the poly (butylene succinate) is adjusted, succinic acid and 1, 4-butanediol are utilized for esterification and pre-polycondensation to obtain a product with higher molecular weight, and then the product is further subjected to transesterification reaction with bio-based succinic acid dialkanol ester, so that the molecular weight is further improved, and the production of the bio-based high molecular weight poly (butylene succinate) is realized in a two-step polycondensation mode.
Compared with the prior art, the synthesis process for preparing the bio-based poly (dialkanol succinate) by using the succinic acid and the 1, 4-butanediol by adopting a mode of adding the bio-based poly (dialkanol succinate) has the following advantages:
1. based on the existing bio-based high molecular weight butylene succinate (PBS) synthesis process, the esterification reaction is easier to carry out by combining the transesterification method with the direct esterification method, adding the bio-based succinic acid dialkanol ester in the reaction process and using the bio-based succinic acid dialkanol ester to replace part of bio-based succinic acid.
2. The invention improves the molecular weight to ensure that the obtained product has high intrinsic viscosity, thereby improving the quality of the product; according to the synthesis process, a new catalyst is not needed in the reaction process, so that the entering of intermediate oxygen is avoided, and the yellowing of the product color is avoided.
3. Compared with the direct polymerization method in the prior art, the prepared PBS has lower acidity, can improve the compatibility with other assistants and the dispersibility of the assistants when in use, and improves the yield of finished products.
4. According to the invention, the bio-based succinic acid dialkanol ester is added in the later reaction period, so that the original water generated in polycondensation is changed into the dialkanol generated, the esterification difficulty is reduced, the molecular weight of an intermediate product is increased, and meanwhile, the reaction temperature is reduced, thereby achieving the purposes of reducing energy consumption, saving time and improving the product quality.
5. The synthesis process disclosed by the invention can solve the problems of overhigh reaction temperature and longer reaction time in the existing bio-based poly (dialkanol succinate) synthesis process.
6. In the process of producing bio-based poly (succinic acid) dialkanol ester, the bio-based succinic acid and the bio-based 1, 4-butanediol are pre-polycondensed to reach a certain molecular weight, and then a certain amount of bio-based succinic acid dialkanol ester is added, so that the esterification reaction is easier to carry out, and the molecular weight is easier to double.
7. The by-product dialkanol (mainly methanol and the like) obtained in the reaction process is easier to remove from the reaction system, the reaction activation energy is reduced, the reaction time is shortened, conditions favorable for the reaction to be performed in a super forward direction are created, the product quality and the molecular weight of the product are further improved, the energy consumption is reduced, the reverse period is shortened, and the purpose of improving the productivity is realized.
Drawings
FIG. 1 is a process flow diagram of the present invention.
Detailed Description
In order to make the technical objects, technical solutions and advantageous effects of the present invention more apparent, the technical solutions of the present invention will be further described with reference to specific examples, which are intended to illustrate the present invention but are not to be construed as limiting the present invention, and specific techniques or conditions are not specified in the examples, and are performed according to techniques or conditions described in the literature in the art or according to the product specifications.
In the following examples, the instruments used in the reaction process include four-necked flasks, mechanical agitators, oil-water separators, spherical condensing tubes, oil baths, vacuum pumps, nitrogen cylinders, constant pressure titration funnels, etc., which are all common devices in the prior art, and the specific methods of use employ conventional methods in the prior art.
Example 1
A method for synthesizing bio-based high molecular weight polybutylene succinate (PBS) comprises the following specific steps:
(1) And (3) normal pressure reaction: mixing bio-based succinic acid and 1, 4-Butanediol (BDO) according to the molar ratio of 45:55, placing the mixture into a reaction container (four-neck flask), repeatedly introducing nitrogen into the reaction container for three times to replace air, adding a catalyst (tetrabutyl titanate), stirring and heating to 148 ℃ to perform reaction, and realizing the pre-condensation of the bio-based succinic acid and the 1, 4-butanediol, wherein the reaction time is 1.8h, the reactants are obtained, the total amount of the added materials is 1/2 of the volume of the reaction container during the reaction, water is continuously generated during the reaction, and an oil-water separator is used for removing water until the water amount separated in the oil-water separator is not obviously increased any more during the reaction; the addition amount of the catalyst is 0.1 percent of the total mass of the bio-based succinic acid, the 1, 4-butanediol and the catalyst;
(2) Negative pressure reaction I: pumping the reaction container to a negative pressure state by using a vacuum pump, wherein the negative pressure (absolute pressure) is 300Pa, then slowly heating to 210 ℃ under the negative pressure condition for reaction, and the reaction time is 2 hours, wherein the molecular weight of the pre-polycondensation reactant in the step (1) is further increased;
(3) Negative pressure reaction II: adding dimethyl succinate (DMS) into the reactant obtained in the step (2) by using a constant pressure titration funnel to carry out transesterification reaction, wherein the reaction temperature is 210 ℃, the reaction time is 1.5h, the molecular weight of the reactant is further improved in the reaction process, and simultaneously dimethyl succinate and hydroxyl in the material are further reacted to remove dialkanol (mainly methanol and the like); the amount of the dimethyl succinate added is 9% of the total mass of the bio-based succinic acid and the 1, 4-butanediol;
and (3) placing the materials after the reaction in methanol, stirring at normal temperature, filtering, separating out a polymer (sediment) with the size of 20-100 meshes, centrifuging for 10min under the pressure of 1.8MPa, and drying at 50 ℃ for 1.5 hours after centrifuging to obtain the product with the intrinsic viscosity of 1.79dL/g.
Example 2
Example 2 differs from example 1 in that only the molar ratio of bio-based succinic acid to 1,4 butanediol in step (1) was changed to 42:58.
Example 3
Example 3 differs from example 1 in that the amount of dimethyl succinate in step (3) is reduced to 7% of the total mass of bio-based succinic acid and 1,4 butanediol.
Example 4
Example 4 differs from example 1 in that only the reaction temperature of step (3) was changed to 220 ℃.
Example 5
Example 5 differs from example 1 in that only the reaction time of step (3) was changed to 2h.
Example 6
Example 6 differs from example 1 in that only the reaction time of step (1) was changed to 2h.
Example 7
Example 6 differs from example 1 in that only the reaction temperature of step (2) was changed to 200 ℃.
The reaction conditions of examples 1 to 7 and the properties of the resulting products are shown in Table 1 (the test was carried out according to national standard GB/T30294-2013).
Table 1 product index under different conditions and resulting product Performance comparison
As can be seen from Table 1, when the reaction temperature is controlled at 148 ℃ and the reaction time is 2 hours, the negative pressure (absolute pressure) is 300Pa, and at the same time, the reaction temperature is controlled at about 200-220 ℃ during the negative pressure reaction, the reaction time is 2 hours, and the DMS addition amount is 7-9%, the intrinsic viscosity of the obtained product can be more than 1.75dL/g, and the indexes such as color value and the like also meet the I-type product requirements in national standard GB/T30294-2013. The intrinsic viscosity of the existing commercial products is mostly smaller than 1.75dL/g, the color values are also mostly unbalanced, and compared with the common commercial products, the product prepared by the invention has the advantages of high intrinsic viscosity and good chromaticity. In addition, the synthetic method of the invention also has higher yield (quality yield).
It should be noted that the above-described embodiments are only for explaining the present invention and do not limit the present invention in any way. The invention has been described with reference to exemplary embodiments, but it is understood that the words which have been used are words of description and illustration, rather than words of limitation. Modifications may be made to the invention as defined in the appended claims, and the invention may be modified without departing from the scope and spirit of the invention. Although the invention is described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, as the invention extends to all other means and applications which perform the same function.
Claims (10)
1. The synthesis method of the bio-based high molecular weight polybutylene succinate is characterized by comprising the following steps of:
(1) And (3) normal pressure reaction: mixing bio-based succinic acid and 1, 4-butanediol, placing the mixture in a reaction container, adding a catalyst under the condition of forming inert atmosphere in the reaction container, heating to 130-160 ℃ while stirring, and performing pre-polycondensation reaction for 1-4 hours to obtain a reactant;
(2) Negative pressure reaction I: pumping the reaction container to a negative pressure state, wherein the negative pressure is 50-1000 Pa, and then heating to 160-230 ℃ under the negative pressure condition to react for 1-4 hours;
(3) Negative pressure reaction II: adding bio-succinic acid dialkanol ester into the product obtained in the step (2) to carry out transesterification reaction, wherein the reaction temperature is 160-230 ℃ and the reaction time is 1-2 hours; and after the reaction is finished, carrying out post-treatment on the materials to obtain a final product.
2. The synthesis method according to claim 1, wherein in the step (1), the molar ratio of bio-based succinic acid to 1, 4-butanediol is (35-55): 75-45.
3. The synthesis method according to claim 1, wherein in the step (1), the catalyst is added in an amount of 0.1 to 0.2% based on the total mass of the bio-based succinic acid, the 1, 4-butanediol and the catalyst.
4. The synthesis method according to claim 1, wherein in the step (1), the reaction temperature is 150-160 ℃; the reaction time is 1-2.5 h.
5. The synthesis method according to claim 1, wherein in the step (2), the negative pressure is 50 to 500pa; the reaction temperature is 190-230 ℃; the reaction time is preferably 1 to 3 hours.
6. The synthetic method of claim 1 wherein in step (3) the bio-based dialkanol succinate comprises, but is not limited to, dimethyl succinate, diethyl succinate, dibutyl succinate.
7. The synthesis method according to claim 1, wherein in the step (3), the amount of the bio-based succinic acid dialkanol ester is added to be 1-10% of the total mass of bio-based succinic acid and 1,4 butanediol.
8. The synthesis method according to claim 1, wherein in the step (3), the reaction time is 1.5 to 2 hours.
9. The method according to claim 1, wherein in the step (3), the post-treatment of the reaction-terminated material is: and (3) placing the materials after the reaction in organic alcohol, separating out precipitate under the normal temperature condition, filtering, centrifuging and drying to obtain the product.
10. The method according to claim 9, wherein in the step (3), the post-treatment operation of the material after the completion of the reaction is specifically:
and (3) placing the materials after the reaction in organic alcohol, stirring at normal temperature, filtering, separating out precipitates with the size of 20-100 meshes, centrifuging for 50-10 min under the pressure of 1.80-2.0 MPa, and drying at the temperature of 40-50 ℃ for 1-2 hours after centrifuging to obtain the product.
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