CN116041679A - Polycarbonate biodegradable elastomer and preparation method thereof - Google Patents
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Abstract
A polycarbonate biodegradable elastomer and a preparation method thereof belong to the technical field of carbon dioxide-based copolymers. The method is characterized in that: the copolymer is a copolymer with a ternary block structure of phthalic anhydride, alkylene oxide and carbon dioxide, wherein phthalic anhydride and alkylene oxide are polymerized into a molecule chain segment of the poly-phthalate, and a polycarbonate molecule chain segment obtained by polymerizing alkylene oxide and carbon dioxide is segmented between the molecule chain segments of the poly-phthalate at two ends. The preparation method comprises the steps of preheating mixed liquor of alkylene oxide and phthalic anhydride, and adding the preheated mixed liquor into a reaction kettle; filling carbon dioxide under pressure to carry out ring-opening copolymerization; then adding mixed solution of alkylene oxide and phthalic anhydride under pressure to continue the reaction. The copolymer forms a hard-soft-hard block structure, so that the copolymer has good elasticity and can be used as an elastomer.
Description
Technical Field
The invention belongs to the technical field of carbon dioxide-based copolymers, and particularly relates to a polycarbonate biodegradable elastomer.
Background
The traditional plastic materials such as polyethylene, polypropylene and the like are difficult to degrade and enter the environment after being abandoned to cause serious white pollution, so that the development of biodegradable plastic materials and the development of good thermal property and mechanical property are very necessary. The excessive emission of carbon dioxide has caused obvious global warming, and the recovery and utilization of carbon dioxide are of great significance in reducing carbon emission and further improving climate conditions.
Alkylene oxideThe polymethyl ethylene carbonate (PPC) generated by carbon dioxide copolymerization is transparent and completely degradable environment-friendly plastic, the tensile strain at break is 600% -1200%, but the vitrification temperature is lower (T) g =30-40 ℃). Chinese patent CN111378101a discloses a terpolymer of alkylene oxide, phthalic anhydride, carbon dioxide (PPCP) which can raise the glass transition temperature to (tg=40 ℃ to 50 ℃) on the basis of PPC, but because its molecular structure arrangement cannot form an elastomer structure, its tensile strain at break is greatly reduced compared with PPC. At present, a polycarbonate elastomer is still lacking, and the polycarbonate biodegradable elastomer fills the domestic blank.
Disclosure of Invention
The invention aims to solve the technical problems that: overcomes the defects of the prior art and provides a polycarbonate biodegradable elastomer with good heat resistance and a preparation method thereof.
The technical scheme adopted for solving the technical problems is as follows: the polycarbonate biodegradable elastomer is characterized in that: is a copolymer with a ternary block structure of phthalic anhydride, alkylene oxide and carbon dioxide, wherein polycarbonate molecule chain segments are segmented between two ends of the molecule chain segments of the polyphthalate ester.
In the polycarbonate biodegradable elastomer, the physical properties of the molecular chain segments of the polyphthalate have higher hardness, namely high compressive strength, small elastic modulus and difficult deformation; the polycarbonate molecular chain segment has softer physical properties, namely small compressive strength and easy deformation under pressure. The copolymer takes a polyphthalate molecular chain segment with high hardness as the first and the last segments of a molecular chain, and takes a softer polycarbonate molecular chain segment as the middle connecting segment to form a hard-soft-hard block structure, so that the copolymer has good elasticity and can be used as an elastomer. Meanwhile, the structural form can also improve the temperature resistance of the copolymer because the two ends of the molecular weight are benzene ring structures.
Preferably, the above polycarbonate biodegradable elastomer has the structural formula:
Wherein a is more than or equal to 1 and less than or equal to 5000, b is more than or equal to 1 and less than or equal to 10000, c is more than or equal to 1 and less than or equal to 5000,0, d is more than or equal to 280, and R is one or more of-H or alkyl with carbon number less than 6; a. b, c and d are integers.
In the structural formula, the larger the ratio of the sum of a and c to b is, the larger the proportion of the molecular chain segments of the polyphthalate is, and the larger the compressive strength and the impact strength of the corresponding elastomer are; conversely, the larger the elongation at break, the better the elasticity. However, when the content of the molecular segment of the polyphthalate in the copolymer exceeds 50% by weight, the present copolymer will suffer from a problem of difficulty in degradation.
Preferably, in the polycarbonate biodegradable elastomer, the content of the molecular chain segment of the polyphthalate in the copolymer with the block structure is 10-60 wt%, and the content of the molecular chain segment of the polycarbonate is 40-90 wt%. Under the preferable chain segment proportion, the product of the invention has better performances, and has higher physical strength and better elongation at break as a degradable elastomer, and meanwhile, the temperature resistance is also obviously improved.
Preferably, the Tg of the polycarbonate biodegradable elastomer is 51.8-54.2 ℃, the tensile strain at break is 276-314%, and the compression set is 40-48%.
The preparation method of the polycarbonate biodegradable elastomer comprises the following steps:
1) Preheating mixed solution of alkylene oxide and phthalic anhydride to 30-100 ℃, and adding the mixed solution into a reaction kettle;
2) A catalyst is added at the reaction temperature of 30-100 ℃, and third monomer carbon dioxide is filled to the reaction pressure of 0.1-4 MPa for ring-opening copolymerization;
3) Adding the mixed solution of alkylene oxide and phthalic anhydride preheated to 30-100 ℃ under pressure for continuous reaction, and sequentially performing devolatilization, drying and granulation after the reaction is finished.
According to the invention, alkylene oxide and phthalic anhydride are premixed into a mixed solution, and then the mixed solution is directly added into a reaction kettle to realize liquid-phase high-pressure feeding, so that segmented feeding and segmented polymerization are realized, and a hard-soft-hard block structure with a poly phthalate molecular chain segment at two ends and a polycarbonate molecular chain segment in the middle part is formed. Compared with PPC, the glass transition temperature of the material is improved, an elastomer material is formed, and the tensile strain at break is high; the invention also provides a preparation method of the composite. The content of the components conforming to the hard-soft-hard block structure in the copolymer obtained by polymerization in a sectional feeding and sectional polymerization mode can reach more than 75%, and the whole copolymer has good elasticity.
The catalysis of the copolymerization reaction can use a traditional metal catalyst or a nonmetal catalyst, and the nonmetal catalyst is a catalyst compounded by Lewis acid/alkali in order to avoid the introduction of metal components.
Preferably, in the preparation method of the polycarbonate biodegradable elastomer, the catalyst in the step 2) is tetra-n-butyl ammonium bromide or a composite catalyst of tetra-n-propyl ammonium bromide and triethylboron according to a molar ratio of 1:1-10. The preferable catalyst has more stable reaction and better selectivity, and can preferentially extend and copolymerize from one side of the alkylene oxide of the molecular chain segment of the polyphthalate after being filled with carbon dioxide, so that the free molecular chain of the polycarbonate is reduced; and after the phthalic anhydride and the alkylene oxide are supplemented, the copolymer is preferentially copolymerized with polycarbonate molecular chains to form end parts, and the content of components conforming to a hard-soft-hard block structure in the obtained copolymer is obviously improved. More preferably, the catalyst is a composite catalyst of tetra-n-butyl ammonium bromide or tetra-n-propyl ammonium bromide and triethylboron according to a molar ratio of 1:7.3-10.
The amount of catalyst used is one of the key factors affecting the reaction rate and the degree of polymerization. Preferably, in the preparation method of the polycarbonate biodegradable elastomer, the molar ratio of the catalyst in the step 2) to the phthalic anhydride input in the step 1) is 1:40-3000. The catalyst with the dosage can meet basic production requirements, and the content of the components in the obtained copolymer conforming to the structure can meet the basic requirement of using the copolymer as an elastomer. More preferred catalysts have a molar ratio of phthalic anhydride of 1:1400 to 2800. More preferably, the amount of the catalyst used can give an elastomer copolymer having a higher degree of polymerization, and the content of the component conforming to the above elastomer structure is also higher, and may be 89% by weight or more in accordance with other preferable process conditions.
Preferably, in the preparation method of the polycarbonate biodegradable elastomer, the molar ratio of the alkylene oxide to the phthalic anhydride in the mixed solution of the alkylene oxide and the phthalic anhydride in the step 1) is 2-50:1. The ratio of alkylene oxide to phthalic anhydride affects mainly the length of each segment of the molecule in the present block copolymer, and at this ratio, a copolymer elastomer conforming to the above structure can be obtained. More preferably, the molar ratio of the alkylene oxide to the phthalic anhydride in the step 1) is 22-40:1. Under the preferable proportion, the length of the end part of the molecular chain segment of the polyphthalate can be better controlled, so that the physical strength of the copolymer product can be ensured, and the elasticity can be kept relatively high.
Preferably, in the preparation method of the polycarbonate biodegradable elastomer, the mass ratio of the mixed solution of the alkylene oxide and the phthalic anhydride added in the step 1) to the mixed solution of the alkylene oxide and the phthalic anhydride added in the step 3) is 1:0.1-10. The length of the molecular chain segments of the polyphthalate at the two ends of the copolymer is not required to be identical, and the physical strength and elasticity of the product can be ensured by the block copolymer formed under the proportion.
Preferably, in the preparation method of the polycarbonate biodegradable elastomer, the reaction temperature in the step 2) is 40-80 ℃, and the reaction pressure is 0.5-2 MPa. Under the preferable process conditions, the molecular weight of the obtained block copolymer is larger, the content of the components conforming to the structure of the elastomer is also higher, and the total reaction time is preferably controlled to be 5-12 hours.
Compared with the prior art, the polycarbonate biodegradable elastomer and the preparation method thereof have the following beneficial effects: according to the invention, the alkylene oxide and the phthalic anhydride are mixed in advance and then added into the reaction kettle, so that liquid-phase high-pressure feeding can be realized, and thus segmented feeding and segmented polymerization are realized, a hard-soft-hard block structure is generated, compared with PPC, the glass transition temperature of the material is improved, an elastomer material is formed, and the breaking tensile strain is high. According to the invention, the alkylene oxide and the phthalic anhydride are fully mixed in advance at the reaction temperature, and the temperature of the alkylene oxide and the phthalic anhydride can not be influenced when the alkylene oxide and the phthalic anhydride are added into the reactor in a segmented manner, so that the continuous stability of the reaction is ensured.
Detailed Description
The present invention will be specifically described below by way of examples. All materials are commercially available, unless otherwise indicated.
Example 1
1) Preparing a mixed solution of propylene oxide and phthalic anhydride according to a molar ratio of 30:1, preheating to 70 ℃, and adding the mixed solution into a reaction kettle in an anhydrous and anaerobic environment;
2) Adding a catalyst at the reaction temperature of 70 ℃, wherein the molar ratio of the catalyst to phthalic anhydride added in the step 1) is 1:2000, and the catalyst is a composite catalyst of tetra-n-butyl ammonium bromide and triethylboron according to the molar ratio of 1:8.7; and third monomer carbon dioxide is filled to the reaction pressure of 1.5MPa, and ternary ring-opening copolymerization reaction is carried out for 6h;
3) Adding the mixed solution of the epoxypropane and the phthalic anhydride preheated to 70 ℃ under pressure for continuous reaction for 2 hours, wherein the mass ratio of the mixed solution of the epoxypropane and the phthalic anhydride added in the step 1) is 1:1, cooling, decompressing and stopping the reaction after the reaction is finished, dissolving the generated glue solution by using chloroform, precipitating and separating by using ethanol, devolatilizing, granulating and drying to obtain the pure material.
The prepared polycarbonate biodegradable elastomer is subjected to thermal performance and mechanical property analysis,the test results are: tg=54.0 ℃, tensile strain at break=311%, compression set=42%, and impact strength of the unnotched simply supported beam 36kJ/m 2 The content of the components conforming to the above structural formula in the pure material obtained in this example was detected to be 91% by weight, the content of the polytrimethylene phthalate molecular chain segments in the molecular chain of the obtained elastomer structure was found to be 24% by weight on average, the content of the polytrimethylene carbonate molecular chain segments was found to be 72% by weight on average, and the balance was propylene oxide self-polymerization segments.
Example 2
1) Preparing mixed solution of ethylene oxide and phthalic anhydride according to the molar ratio of 40:1, preheating to 80 ℃, and adding the mixed solution into a reaction kettle in an anhydrous and anaerobic environment;
2) Adding a catalyst at the reaction temperature of 80 ℃ in a molar ratio of 1:2800 to phthalic anhydride added in the step 1), wherein the catalyst is a composite catalyst of tetra-n-propyl ammonium bromide and triethylboron according to a molar ratio of 1:7.3; and third monomer carbon dioxide is filled to the reaction pressure of 0.5MPa, and ternary ring-opening copolymerization reaction is carried out for 5h;
3) Adding the mixed solution of the ethylene oxide and the phthalic anhydride preheated to 80 ℃ under pressure for continuous reaction for 2 hours, wherein the mass ratio of the mixed solution of the ethylene oxide and the phthalic anhydride added in the step 1) is 1:0.5, cooling, decompressing and stopping the reaction after the reaction is finished, dissolving the generated glue solution by using chloroform, precipitating and separating out by using ethanol, devolatilizing, granulating and drying to obtain the pure material.
The prepared polycarbonate biodegradable elastomer is subjected to thermal performance and mechanical property analysis, and the test result is as follows: tg=53.1 ℃, tensile strain at break=312%, compression set=41%, and impact strength of the unnotched simple beam 33kJ/m 2 The content of the component conforming to the above structural formula in the copolymer obtained in this example was detected to be 82% by weight. The content of the polyethylene phthalate molecular chain segments in the molecular chain of the obtained elastomer structure is 19 weight percent on average, the content of the polyethylene carbonate molecular chain segments is 77 weight percent on average, and the balance is the ethylene oxide self-polymerization segment.
Example 3
1) The method comprises the steps of (1) preparing mixed solution of epoxy cyclohexane and phthalic anhydride according to a molar ratio of 22:1, preheating to 40 ℃, and adding the mixed solution into a reaction kettle in an anhydrous and anaerobic environment;
2) Adding a catalyst at the reaction temperature of 40 ℃, wherein the molar ratio of the catalyst to phthalic anhydride added in the step 1) is 1:1400, and the catalyst is a composite catalyst of tetra-n-propyl ammonium bromide and triethylboron according to the molar ratio of 1:10; and filling third monomer carbon dioxide to the reaction pressure of 2MPa, and performing ternary ring-opening copolymerization reaction for 7h;
3) Adding the mixed solution of the epoxy cyclohexane and the phthalic anhydride preheated to 40 ℃ under pressure for continuous reaction for 3 hours, wherein the mass ratio of the mixed solution of the epoxy cyclohexane and the phthalic anhydride added in the step 1) is 1:2, cooling, decompressing and stopping the reaction after the reaction is finished, dissolving the generated glue solution by using chloroform, precipitating and separating out by using ethanol, devolatilizing, granulating and drying to obtain the pure material.
The prepared polycarbonate biodegradable elastomer is subjected to thermal performance and mechanical property analysis, and the test result is as follows: tg=54.1 ℃, tensile strain at break=308%, compression set=45%, and impact strength of a non-notched simply supported beam 37kJ/m 2 The content of the component conforming to the above structural formula in the copolymer obtained in this example was found to be 88% by weight. The content of the polycyclohexyl phthalate molecular chain segment in the molecular chain of the obtained elastomer structure is 31wt% on average, the content of the polycyclohexyl carbonate molecular chain segment is 65wt% on average, and the balance is the alkylene oxide self-polymerization section.
Example 4
1) 1, 2-epoxybutane and phthalic anhydride are prepared into mixed solution according to a molar ratio of 50:1, preheated to 30 ℃, and added into a reaction kettle in an anhydrous and anaerobic environment;
2) Adding a catalyst at the reaction temperature of 30 ℃, wherein the molar ratio of the catalyst to phthalic anhydride added in the step 1) is 1:40, and the catalyst is a composite catalyst of tetra-n-butyl ammonium bromide and triethylboron according to the molar ratio of 1:1; and filling third monomer carbon dioxide to the reaction pressure of 4MPa, and performing ternary ring-opening copolymerization reaction for 9h;
3) Adding the mixed solution of the 1, 2-epoxybutane and the phthalic anhydride preheated to 30 ℃ under pressure for continuous reaction for 3 hours, wherein the mass ratio of the mixed solution of the 1, 2-epoxybutane and the phthalic anhydride added in the step 1) is 1:10, cooling, decompressing and stopping the reaction after the reaction is finished, dissolving the generated glue solution by using chloroform, precipitating and separating out by using ethanol, devolatilizing, granulating and drying to obtain the pure material.
The prepared polycarbonate biodegradable elastomer is subjected to thermal performance and mechanical property analysis, and the test result is as follows: tg=51.8deg.C, tensile strain at break=314%, compression set=40%, and impact strength of the unnotched simply supported beam 28kJ/m 2 The content of the component conforming to the above structural formula in the copolymer obtained in this example was examined to be 84% by weight. The content of the molecular chain of the obtained elastomer structure is 10.1 weight percent on average, the content of the molecular chain of the polybutyl phthalate is 85.3 weight percent on average, and the balance is the epoxybutane self-polymerization section.
Example 5
1) Preparing a mixed solution of cyclopentane epoxide and phthalic anhydride according to a molar ratio of 2:1, preheating to 100 ℃, and adding the mixed solution into a reaction kettle in an anhydrous and anaerobic environment;
2) Adding a catalyst at the reaction temperature of 100 ℃, wherein the molar ratio of the catalyst to phthalic anhydride added in the step 1) is 1:3000, and the catalyst is a composite catalyst of tetra-n-butyl ammonium bromide and triethylboron according to the molar ratio of 1:10; and filling third monomer carbon dioxide to the reaction pressure of 0.1MPa, and carrying out ternary ring-opening copolymerization reaction for 4h;
3) Adding the mixed solution of the cyclopentane epoxide and the phthalic anhydride preheated to 100 ℃ under pressure for continuous reaction for 1h, wherein the mass ratio of the mixed solution of the cyclopentane epoxide and the phthalic anhydride added in the step 1) is 1:0.1, cooling, pressure release and termination of the reaction are carried out after the reaction is finished, the generated glue solution is dissolved by chloroform, ethanol is used for precipitation, and the pure material is obtained through devolatilization, granulation and drying.
The prepared polycarbonate biodegradable elastomer is subjected to thermal performance and mechanical property analysis, and the test result is as follows: tg=54.2 ℃, tensile strain at break=276%, compression set=48%, and impact strength of the unnotched simple beam 34kJ/m 2 The content of the component conforming to the above structural formula in the copolymer obtained in this example was found to be 78% by weight. In the molecular chain of the obtained elastomer structure, polyphthaleneThe content of the molecule chain segment of the carbonic acid cyclopentene ester is 68wt% on average, the content of the molecule chain segment of the carbonic acid cyclopentene ester is 26wt% on average, and the balance is the alkylene oxide self-polymerization section. The elastomer of this example has not been biodegradable.
Comparative example 1
The material ratios and process conditions were the same as in example 1, except that the materials were added to the autoclave at once. Tg=48.9 ℃, elongation at break=15%, compression set=100%.
Compared with the random structure of the terpolymer of alkylene oxide-phthalic anhydride-carbon dioxide, the polycarbonate biodegradable elastomer prepared by the invention has the advantages that the glass transition temperature of the material is increased and the elastomer material is formed compared with PPC. The invention can be applied to the modification of PPC materials and can lead the application of the PPC materials to be wider.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the invention in any way, and any person skilled in the art may make modifications or alterations to the disclosed technical content to the equivalent embodiments. However, any simple modification, equivalent variation and variation of the above embodiments according to the technical substance of the present invention still fall within the protection scope of the technical solution of the present invention.
Claims (10)
1. A biodegradable polycarbonate elastomer characterized by: the copolymer is a copolymer with a ternary block structure of phthalic anhydride, alkylene oxide and carbon dioxide, wherein phthalic anhydride and alkylene oxide are polymerized into a molecule chain segment of the poly-phthalate, and a polycarbonate molecule chain segment obtained by polymerizing alkylene oxide and carbon dioxide is segmented between the molecule chain segments of the poly-phthalate at two ends.
2. The biodegradable polycarbonate elastomer according to claim 1, characterized in that it has the structural formula:
Wherein a is more than or equal to 1 and less than or equal to 5000, b is more than or equal to 1 and less than or equal to 10000, c is more than or equal to 1 and less than or equal to 5000,0, d is more than or equal to 280, and R is one or more of-H or alkyl with carbon number less than 6; a. b, c and d are integers.
3. The biodegradable polycarbonate elastomer according to claim 1, characterized in that: in the block structure copolymer, the content of the molecular chain segments of the polyphthalate is 10-60 wt%, and the content of the molecular chain segments of the polycarbonate is 40-90 wt%.
4. The biodegradable polycarbonate elastomer according to claim 1, characterized in that: the Tg of the elastomer is 51.8-54.2 ℃, the tensile strain at break is 276-314%, and the compression set is 40-48%.
5. A method for preparing the polycarbonate-based biodegradable elastomer according to any one of claims 1 to 4, comprising the steps of:
1) Preheating mixed solution of alkylene oxide and phthalic anhydride to 30-100 ℃, and adding the mixed solution into a reaction kettle;
2) A catalyst is added at the reaction temperature of 30-100 ℃, and third monomer carbon dioxide is filled to the reaction pressure of 0.1-4 MPa for ring-opening copolymerization;
3) Adding the mixed solution of alkylene oxide and phthalic anhydride preheated to 30-100 ℃ under pressure for continuous reaction, and sequentially performing devolatilization, drying and granulation after the reaction is finished.
6. The method for producing a polycarbonate-based biodegradable elastomer according to claim 5, characterized in that: the catalyst in the step 2) is tetra-n-butyl ammonium bromide or a composite catalyst of tetra-n-propyl ammonium bromide and triethylboron according to a molar ratio of 1:1-10.
7. The method for producing a polycarbonate-based biodegradable elastomer according to claim 6, characterized in that: the molar ratio of the catalyst in the step 2) to the phthalic anhydride input in the step 1) is 1:40-3000.
8. The method for producing a polycarbonate-based biodegradable elastomer according to claim 5, characterized in that: the molar ratio of the alkylene oxide to the phthalic anhydride in the mixed solution of the alkylene oxide and the phthalic anhydride in the step 1) is 2-50:1.
9. The method for producing a polycarbonate-based biodegradable elastomer according to claim 5, characterized in that: the mass ratio of the mixed solution of the alkylene oxide and the phthalic anhydride added in the step 1) to the mixed solution of the alkylene oxide and the phthalic anhydride added in the step 3) is 1:0.1-10.
10. The method for producing a polycarbonate-based biodegradable elastomer according to claim 5, characterized in that: the reaction temperature in the step 2) is 40-80 ℃ and the reaction pressure is 0.5-2 MPa.
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| CN116333279A (en) * | 2023-05-29 | 2023-06-27 | 山东联欣环保科技有限公司 | Polycarbonate toughening resin |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111378101A (en) * | 2020-04-26 | 2020-07-07 | 中山大学 | Preparation method of biodegradable carbon dioxide-based polyester-polycarbonate terpolymer |
| CN114524930A (en) * | 2021-09-24 | 2022-05-24 | 山东联欣环保科技有限公司 | Quaternary copolymer containing phthalic anhydride and ethylene oxide |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111378101A (en) * | 2020-04-26 | 2020-07-07 | 中山大学 | Preparation method of biodegradable carbon dioxide-based polyester-polycarbonate terpolymer |
| CN114524930A (en) * | 2021-09-24 | 2022-05-24 | 山东联欣环保科技有限公司 | Quaternary copolymer containing phthalic anhydride and ethylene oxide |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116333279A (en) * | 2023-05-29 | 2023-06-27 | 山东联欣环保科技有限公司 | Polycarbonate toughening resin |
| CN116333279B (en) * | 2023-05-29 | 2024-04-12 | 山东联欣环保科技有限公司 | Polycarbonate toughening resin |
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