CN111892703B - Biodegradable thermoplastic polyester elastic material and preparation method thereof - Google Patents
Biodegradable thermoplastic polyester elastic material and preparation method thereof Download PDFInfo
- Publication number
- CN111892703B CN111892703B CN202010596361.2A CN202010596361A CN111892703B CN 111892703 B CN111892703 B CN 111892703B CN 202010596361 A CN202010596361 A CN 202010596361A CN 111892703 B CN111892703 B CN 111892703B
- Authority
- CN
- China
- Prior art keywords
- reaction
- polyethylene glycol
- elastic material
- sebacic acid
- polyester elastic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/672—Dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/88—Post-polymerisation treatment
- C08G63/90—Purification; Drying
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2230/00—Compositions for preparing biodegradable polymers
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention relates to a biodegradable thermoplastic polyester elastic material and a preparation method thereof. The method comprises the following steps: mixing sebacic acid and polyethylene glycol, stirring, carrying out esterification reaction under a vacuum condition, adding a catalyst, carrying out pre-condensation reaction under the vacuum condition, continuously reacting the obtained prepolymer, and purifying. The reaction monomer adopted by the method is simple, non-toxic and non-irritant, has good biological safety, is widely applied in biomedicine, and the obtained material has good biocompatibility and biodegradability.
Description
Technical Field
The invention belongs to the field of biodegradable high polymer materials and preparation thereof, and particularly relates to a biodegradable thermoplastic polyester elastic material and a preparation method thereof.
Background
The biodegradable high molecular material has important significance in biomedicine and has wide application in the fields of tissue engineering, drug release, biosensing and the like. Biodegradable polyesters are the most common class of biodegradable polymeric materials, and include both thermoplastic and thermoset types. Thermoplastic biodegradable polyesters such as polylactic acid, polyglycolic acid, polycaprolactone and copolymers thereof, have good processability and higher mechanical strength, have been successfully applied in the fields of surgical sutures, internal fixation of fractures, tissue engineering, drug sustained release and the like, but are not suitable for soft tissue engineering because of high crystallinity, high modulus, poor elasticity and slow degradation. Poly-sebacic acid glycerol ester, poly-citric acid polyethylene glycol ester and derivative polymers thereof are a plurality of thermosetting biodegradable polyester materials which are researched more, have good elasticity and degradability, are more suitable for being applied to soft tissue engineering such as cardiac muscle, blood vessel, nerve conduit and the like, but have harsh preparation conditions, need to be solidified, are not dissolved in any solvent after being crosslinked, can not be subjected to secondary melting processing, and are greatly limited in practical application. Thermoplastic elastomers are a more specific class of polymeric materials and are characterized by combining the processability of thermoplastic materials with the high elasticity of thermoset materials, making them both plastic and highly elastic. At present, the reports on thermoplastic elastomers in biodegradable high molecular materials are less, and the development of biodegradable thermoplastic elastomer materials is of great significance for promoting the solution of many problems in the biomedical field.
Sebacic acid and polyethylene glycol are two common reaction monomers used for preparing biodegradable high polymer materials, and various biodegradable materials prepared by directly taking sebacic acid and polyethylene glycol as raw materials are reported. For example, polyethylene glycol is dicarboxylated and then reacts with sebacic acid to obtain poly (sebacic acid-polyethylene glycol) anhydride (chemical reagent, 2007,29(3): 161-163); polysebacic anhydride reacts with polyethylene glycol to obtain polysebacic anhydride-polyethylene glycol block copolymer (ion exchange and adsorption, 2008,24(3): 246-253); or the PEG-SA polyester (Polymer,2006,47:3760-3766) is obtained by the solution polymerization of sebacoyl chloride and polyethylene glycol. The materials mainly utilize the high hydrophilicity of polyethylene glycol to improve the hydrophilicity of polyanhydride materials, or form a hydrophilic-hydrophobic block copolymer to form hydrogel with certain water absorption and retention functions, and the adopted polyethylene glycol has higher molecular weight (Mn is more than or equal to 400). The material is mainly used as a functional material for constructing a drug controlled release carrier or hydrogel, cannot be used as a structural material, and does not have the performance of a thermoplastic elastomer.
Disclosure of Invention
The invention aims to solve the technical problem of providing a biodegradable thermoplastic polyester elastic material and a preparation method thereof so as to fill the blank in the prior art.
The invention provides a biodegradable thermoplastic polyester elastic material, which is prepared by carrying out melt polycondensation on sebacic acid and polyethylene glycol under a catalyst, reacting hydroxyl and carboxyl among molecules, dehydrating, condensing, polymerizing and purifying.
The polyester elastic material is high molecular weight linear poly (sebacic acid-polyethylene glycol) ester, and the structural formula of the poly (sebacic acid-polyethylene glycol) ester is as follows:
The number average molecular weight (Mn) of the polyester elastic material can reach 13 multiplied by 104g·mol-1Above, the polydispersity index (Mw/Mn) is between 1.2 and 4.
The molecular weight of the polyethylene glycol is 100-400g & mol-1。
The catalyst is one of stannous octoate, stannous chloride, stannous octoate/p-toluenesulfonic acid and stannous chloride/p-toluenesulfonic acid.
The polymerization reaction temperature is 120-280 ℃, the pressure is lower than 3325Pa, and the reaction time is 4-50 hours.
The invention also provides a preparation method of the biodegradable thermoplastic polyester elastic material, which comprises the following steps:
mixing sebacic acid and polyethylene glycol in a molar ratio of 0.99:1-1.10:1, stirring, carrying out esterification reaction under a vacuum condition, adding a catalyst, carrying out pre-condensation reaction under the vacuum condition, continuously reacting the obtained prepolymer, and purifying to obtain the biodegradable thermoplastic polyester elastic material.
The stirring is as follows: stirring the mixture at the temperature of 160 ℃ under the protection of nitrogen until the sebacic acid is completely dissolved.
The technological parameters of the esterification reaction are as follows: the reaction temperature is 120 ℃ and 180 ℃, the pressure is 0.1-4000Pa, and the reaction time is 0.5-8 hours.
The catalyst is any one or more of catalysts capable of catalyzing polyester polymerization; preferably a tin-based catalyst; more preferably, the molar amount of the p-toluenesulfonic acid is equal to that of the stannous octoate or the stannous chloride, and the molar amount of the stannous octoate or the stannous chloride is 0.0005 to 0.02 times (preferably 0.001 to 0.02 times) that of the hydroxyl group or the carboxyl group in the reaction system.
The technological parameters of the pre-condensation reaction are as follows: the reaction temperature is 120-180 ℃, the pressure is 0.1-3000Pa, and the reaction time is 2-20 hours.
The technological parameters of the continuous reaction are as follows: the reaction temperature is 180 ℃ and 280 ℃, the pressure is lower than 3000Pa, and the reaction time is 1-20 hours.
The purification method comprises the following steps: dissolving a polyester primary product in a good solvent, stirring to dissolve the polyester to obtain a polymer solution, and then dropping the polymer solution into a poor solvent to generate a precipitate, namely a purified product; this purification step may be performed multiple times; the good solvent and the poor solvent may be arbitrarily combined.
The good solvent is any one of tetrahydrofuran, acetone, trichloromethane, dichloromethane, N-dimethylformamide, dimethyl sulfoxide, 1, 4-dioxane and hexafluoroisopropanol.
The poor solvent is any one of water, methanol, ethanol, ether and petroleum ether.
The mass volume ratio of the polyester primary product to the good solvent is 5-30%, and the volume ratio of the good solvent to the poor solvent is 1:2-1: 10.
The purification times are 1-5 times.
The invention also provides application of the biodegradable thermoplastic polyester elastic material.
The polymerization reaction of the invention is direct melt polycondensation of sebacic acid and polyethylene glycol, and the reaction system contains no other components except monomers and catalysts. The product obtained after the synthesis reaction is an initial product, the molecular weight distribution of the product is wide, and the product with higher relative molecular weight can be obtained through a certain purification step.
The molecular chain of the biodegradable thermoplastic polyester elastic material is linear, and the material can be dissolved in various organic solvents, such as tetrahydrofuran, acetone, trichloromethane, dichloromethane, dimethyl sulfoxide, N-dimethylformamide, 1, 4-dioxane, hexafluoroisopropanol and the like, and is insoluble in water, methanol, ethanol, diethyl ether and the like. The material is in a semi-crystalline solid state at normal temperature, the glass transition temperature of the material is lower than 0 ℃, the material is in a high-elastic state at normal temperature, the elastic modulus is 0.01-2MPa, and the elongation at break is more than 1700%. The polyester material has good solubility, processability, mechanical strength, high elasticity, biocompatibility, biodegradability and thermoplasticity.
Advantageous effects
(1) The reaction monomer adopted by the invention is simple, non-toxic and non-irritant, has good biological safety, can be widely applied in biomedicine, and the obtained material has good biocompatibility and biodegradability.
(2) The thermoplastic polyester elastic material has good solubility, processability and high elasticity, and the elastic modulus of the thermoplastic polyester elastic material is matched with human soft tissues, so that the thermoplastic polyester elastic material can meet the requirements of various biomedical applications.
Drawings
FIG. 1 is a graph of the infrared spectrum of the material obtained in example 1;
FIG. 2 shows the NMR spectrum of the material obtained in example 1 (1H-NMR) chart;
FIG. 3 is a uniaxial tensile stress-strain plot of the material obtained in example 1;
FIG. 4 is a graph of cyclic tensile stress-strain for the material obtained in example 1;
FIG. 5 is a graph of uniaxial tensile stress-strain curves for the material obtained in example 1 and the material obtained in comparative example 1.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Example 1
(1) Adding 0.05mol of sebacic acid (Chinese medicine, AR) and 0.05mol of polyethylene glycol-200 (Vocko) into a 250ml two-neck flask, stirring for 0.5h at the temperature of 140 ℃ under the protection of nitrogen, and forming a clear and transparent liquid after the sebacic acid is completely dissolved;
(2) reducing the pressure of the reaction system to 3000Pa at 140 ℃, and stirring for reaction for 6 hours;
(3) adding 0.0001mol of stannous octoate and 0.0001mol of p-toluenesulfonic acid into a reaction system together, and reacting at 160 ℃ and 3000Pa for 6 h;
(4) slowly raising the temperature to 260 ℃ within 4h, then reducing the pressure to 100Pa, and continuously reacting for 8h to obtain a high-molecular-weight polyester elastic material primary product;
(5) dissolving the obtained polyester primary product in tetrahydrofuran to obtain 10% (w/v) polymer solution, dropwise adding the solution into methanol, wherein the volume ratio of the tetrahydrofuran to the methanol is 1:4, and generating precipitate; and repeating the purification for 3 times, and drying the precipitate obtained in the last time in vacuum for 2 days to obtain the purified polyester elastic material.
FIG. 1 shows that: the infrared spectrum of the material obtained in example 1, at 1730cm-1The strong stretching vibration peak of ester bond C ═ O shows that the dehydration condensation reaction of hydroxyl and carboxyl occurs between sebacic acid and polyethylene glycol-200 to generate ester bond, and the length of the ester bond is 3400cm-1The broad absorption peak for the hydroxyl group was very weak, indicating that the hydroxyl group in polyethylene glycol-200 was almost completely consumed.
FIG. 2 shows that: the hydrogen spectrogram of the material obtained in example 1 has characteristic peaks of sebacic acid and polyethylene glycol, wherein three peaks of delta 1.30, 1.61 and 2.35ppm are attributed to sebacic acid molecules, three peaks of delta 3.67, 3.70 and 4.23ppm are attributed to polyethylene glycol-200, and the molar ratio of the polyethylene glycol to the sebacic acid is calculated to be 1:1.02, which is consistent with the theoretical charging ratio.
FIG. 3 shows: the material obtained in example 1 has good mechanical properties, the elastic modulus is about 0.2MPa and is close to that of many natural soft tissues, and the elongation at break of the obtained material exceeds 1700%, which shows that the material has good elasticity and toughness and is not easy to be broken, and the elongation at break of the natural artery and vein is far exceeded (< 500%). (test temperature is room temperature, tensile rate is 10mm/min)
FIG. 4 shows that: the material obtained in example 1 has good elasticity and recovery capability, when the material is pulled to the strain of 100%, the material can be quickly recovered to be close to the original shape after the external force is removed, and the shape of the obtained material can still be quickly recovered after 10 times of uninterrupted stretching with 100% strain, which indicates that the obtained material is a good elastic material. (test temperature is room temperature, stretching speed is 10mm/min, strain range is 20-100%, cycle time is 10 times, residence time is 0s)
Example 2
(1) Adding 0.05mol of sebacic acid (Chinese medicine, AR) and 0.05mol of polyethylene glycol-200 (Vocko) into a 250ml two-neck flask, stirring for 0.5h at the temperature of 140 ℃ under the protection of nitrogen, and forming a clear and transparent liquid after the sebacic acid is completely dissolved;
(2) reducing the pressure of the reaction system to 3325Pa at 140 ℃, and stirring for reaction for 6 hours;
(3) adding 0.00025mol of stannous octoate and 0.00025mol of p-toluenesulfonic acid into a reaction system together, and reacting at 180 ℃ and 3000Pa for 4 hours;
(4) slowly raising the temperature to 260 ℃ within 4h, then reducing the pressure to 100Pa, and continuously reacting for 4h to obtain a high-molecular-weight polyester elastic material primary product;
(5) dissolving the obtained polyester primary product in tetrahydrofuran to obtain 10% (w/v) polymer solution, dropwise adding the solution into methanol, wherein the volume ratio of the tetrahydrofuran to the methanol is 1:4, and generating precipitate; and repeating the purification for 3 times, and drying the precipitate obtained in the last time in vacuum for 2 days to obtain the purified polyester elastic material.
Example 3
(1) Adding 0.05mol of sebacic acid (Chinese medicine, AR) and 0.05mol of polyethylene glycol-200 (Vocko) into a 250ml two-neck flask, stirring for 0.5h at the temperature of 140 ℃ under the protection of nitrogen, and forming a clear and transparent liquid after the sebacic acid is completely dissolved;
(2) reducing the pressure of the reaction system to 3000Pa at 140 ℃, and stirring for reaction for 6 hours;
(3) adding 0.001mol of stannous octoate and 0.001mol of p-toluenesulfonic acid into a reaction system, slowly increasing the temperature from 140 ℃ to 260 ℃ within 6h under 3000Pa, then reducing the pressure to 100Pa, and continuing to react for 1h to obtain a high-molecular-weight polyester elastic material primary product;
(4) dissolving the obtained polyester primary product in tetrahydrofuran to obtain 10% (w/v) polymer solution, dropwise adding the solution into methanol, wherein the volume ratio of the tetrahydrofuran to the methanol is 1:4, and generating precipitate; and repeating the purification for 3 times, and drying the precipitate obtained in the last time in vacuum for 2 days to obtain the purified polyester elastic material.
Comparative example 1
(1) Adding 0.05mol of sebacic acid (national drug, AR) and 0.05mol of glycerol (national drug, AR) into a 250ml single-neck flask, stirring for 0.5h at the temperature of 140 ℃ under the protection of nitrogen, and forming a clear and transparent liquid after the sebacic acid is completely dissolved;
(2) stirring and reacting for 24 hours at the temperature of 120 ℃ under the protection of nitrogen;
(3) reducing the pressure to 3000Pa at 120 ℃, and stirring for reacting for 48 hours to obtain a prepolymer of polypropylene sebacate and glycerol sebacate;
(4) and (4) curing the polypropylene sebacate prepolymer obtained in the step (3) at the temperature of 120 ℃ and under the pressure of 100Pa for 48 hours to obtain a cured polypropylene sebacate elastomer.
FIG. 5 shows that: the material obtained in example 1, as a thermoplastic material, has an elastic modulus close to that of the thermoset material obtained in comparative example 1, but the elongation at break of the material obtained in example 1 is much greater than that of the material in comparative example 1.
Claims (9)
1. A biodegradable thermoplastic polyester elastic material is prepared by melt polycondensation of sebacic acid and polyethylene glycol under a catalyst, reaction of hydroxyl and carboxyl between molecules, dehydration condensation polymerization and purification;
the polyester elastic material is high molecular weight linear poly (sebacic acid-polyethylene glycol) ester, and the structural formula of the poly (sebacic acid-polyethylene glycol) ester is as follows:
the molecular weight of the polyethylene glycol is 100-400 g.mol-1。
2. The material of claim 1, wherein the catalyst is one of stannous octoate, stannous chloride, stannous octoate/p-toluene sulfonic acid, and stannous chloride/p-toluene sulfonic acid.
3. A method for preparing a biodegradable thermoplastic polyester elastic material comprises the following steps:
sebacic acid and polyethylene glycol are mixed by molMixing the raw materials in a ratio of 0.99:1-1.10:1, stirring, carrying out esterification reaction under a vacuum condition, adding a catalyst, carrying out pre-condensation reaction under the vacuum condition, continuously reacting the obtained prepolymer, and purifying to obtain the biodegradable thermoplastic polyester elastic material; wherein the molecular weight of the polyethylene glycol is 100-400 g.mol-1。
4. The method of claim 3, wherein the agitating is: stirring the mixture at the temperature of 160 ℃ under the protection of nitrogen until the sebacic acid is completely dissolved.
5. The method according to claim 3, wherein the esterification reaction has the following process parameters: the reaction temperature is 120 ℃ and 180 ℃, the pressure is 0.1-4000Pa, and the reaction time is 0.5-8 hours.
6. The method as claimed in claim 3, wherein the catalyst is one of stannous octoate, stannous chloride, stannous octoate/p-toluenesulfonic acid and stannous chloride/p-toluenesulfonic acid, the molar amount of the p-toluenesulfonic acid is equal to that of the stannous octoate or stannous chloride, and the molar amount of the stannous octoate or stannous chloride is 0.0005-0.02 times of that of hydroxyl or carboxyl in the reaction system.
7. The method according to claim 3, wherein the process parameters of the precondensation reaction are: the reaction temperature is 120-180 ℃, the pressure is 0.1-3000Pa, and the reaction time is 2-20 hours.
8. The method of claim 3, wherein the process parameters of the continuous reaction are: the reaction temperature is 180 ℃ and 280 ℃, the pressure is lower than 3000Pa, and the reaction time is 1-20 hours.
9. Use of the polyester elastomer material according to claim 1 in biomedicine.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010596361.2A CN111892703B (en) | 2020-06-28 | 2020-06-28 | Biodegradable thermoplastic polyester elastic material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010596361.2A CN111892703B (en) | 2020-06-28 | 2020-06-28 | Biodegradable thermoplastic polyester elastic material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111892703A CN111892703A (en) | 2020-11-06 |
| CN111892703B true CN111892703B (en) | 2021-07-20 |
Family
ID=73207240
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010596361.2A Active CN111892703B (en) | 2020-06-28 | 2020-06-28 | Biodegradable thermoplastic polyester elastic material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111892703B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112807491A (en) * | 2020-12-31 | 2021-05-18 | 东华大学 | Elastic tissue engineering scaffold with communicated macroporous structure and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104629026A (en) * | 2015-02-15 | 2015-05-20 | 东华大学 | Biomedical polybasic copolymerized crosslinked polyester elastomer material and preparation method thereof |
| CN110078880A (en) * | 2018-01-26 | 2019-08-02 | 华东理工大学 | Isocyanate-crosslinked polyethylene glycol decanedioic acid glyceride bioelastomer and its preparation method and application |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4815164B2 (en) * | 2005-08-11 | 2011-11-16 | 日本精化株式会社 | Moisturizer and cosmetic and skin external preparations containing the same |
-
2020
- 2020-06-28 CN CN202010596361.2A patent/CN111892703B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104629026A (en) * | 2015-02-15 | 2015-05-20 | 东华大学 | Biomedical polybasic copolymerized crosslinked polyester elastomer material and preparation method thereof |
| CN110078880A (en) * | 2018-01-26 | 2019-08-02 | 华东理工大学 | Isocyanate-crosslinked polyethylene glycol decanedioic acid glyceride bioelastomer and its preparation method and application |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111892703A (en) | 2020-11-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR100453130B1 (en) | Sequentially Ordered Biodegradable Lactide(Glycolide or Lactide/Glycolide)/ε-Caprolactone Multi-Block Copolymer and Process for the Preparation Thereof | |
| JP2986509B2 (en) | Modified polyester resin composition, method for producing the same, and use thereof | |
| US8309137B2 (en) | DL-lactide-ε-caprolactone copolymers | |
| EP0580386A1 (en) | Aromatic polyanhydrides | |
| CN100558787C (en) | A kind of preparation method of full biodegradation polyester copolymer | |
| JP3554282B2 (en) | Medical biodegradable ternary block copolymer and method for producing the same | |
| CN113024783B (en) | Method for synthesizing degradable block copolymer hydrogel | |
| CN111892703B (en) | Biodegradable thermoplastic polyester elastic material and preparation method thereof | |
| Lee et al. | Synthesis and Properties of ABA Block Copoly (ester-ethers) Comprising Poly (L-lactide)(A) and Poly (oxypropylene-co-oxyethylene)(B) with Different Molecular Weights. | |
| Zhao et al. | Preparation of degradable polymenthide and its elastomers from biobased menthide via organocatalyzed ring-opening polymerization and UV curing | |
| CN101519494B (en) | Preparation method of high molecular weight poly-morpholine-2,5-dione derivative and preparation method of the copolymer thereof | |
| JPH01108226A (en) | Block, copolymer, its production, copolymer film and copolymer fiber | |
| CN109320699B (en) | Thermoplastic aliphatic-aromatic copolyester elastomer and preparation method thereof | |
| CN114369232A (en) | Renewable degradable thermoplastic elastomer and preparation method thereof | |
| Li et al. | Microwave-assisted ring-opening polymerization of poly (glycolic acid-co-lactic acid) copolymers | |
| CN102898636B (en) | Novel polyester material containing controlled side chain carboxyl number, and preparation method thereof | |
| CN113881021B (en) | Terpolymer, suture and preparation method and application thereof | |
| Lu et al. | Microwave-assisted ring-opening copolymerization of ɛ-caprolactone and 2-Phenyl-5, 5-bis (oxymethyl) trimethylene carbonate | |
| CN113004499B (en) | Biodegradable polyester elastomer and preparation method and application thereof | |
| CN114106299B (en) | Preparation method of lactone and lactide block copolymer | |
| CN118240185A (en) | Method for synthesizing high molecular weight medical aliphatic polyester material | |
| CN114479037B (en) | Biodegradable polyester elastomer material and preparation method thereof | |
| Liu et al. | Regulation of ester contents enabled tunable thermal and mechanical properties of poly (ester amide) | |
| CN117069923A (en) | Block copolymer based on polylactic acid and preparation method thereof | |
| CN116262814A (en) | Degradable copolyester synthesized by one-pot method and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |