CN107057045B - Glucose derivative lactone-cyclic lactone polymer and preparation method thereof - Google Patents
Glucose derivative lactone-cyclic lactone polymer and preparation method thereof Download PDFInfo
- Publication number
- CN107057045B CN107057045B CN201710039639.4A CN201710039639A CN107057045B CN 107057045 B CN107057045 B CN 107057045B CN 201710039639 A CN201710039639 A CN 201710039639A CN 107057045 B CN107057045 B CN 107057045B
- Authority
- CN
- China
- Prior art keywords
- lactone
- glucose derivative
- caprolactone
- cyclic lactone
- cyclic
- 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
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
- C08G63/08—Lactones or lactides
-
- 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
- C08G63/78—Preparation processes
Abstract
The invention discloses a glucose derivative lactone-cyclic lactone copolymer which is formed by polymerizing glucose derivative lactone and cyclic lactone, wherein the molar ratio of the glucose derivative lactone to the cyclic lactone is 0: 100-100: 0, and the dosage of the cyclic lactone is not 0. The invention also discloses a preparation method of the glucose derivative lactone-cyclic lactone copolymer. The copolymer of the glucose derivative and the cyclic lactone has excellent nontoxicity, no irritation, good biocompatibility and degradation performance, can be thoroughly decomposed into gluconic acid and 6-hydroxycaproic acid by pancreatic lipase, can be thoroughly decomposed into water and carbon dioxide by cells, and has potential prospects in biological materials and environmental materials.
Description
Technical Field
The invention relates to a glucose derivative lactone-cyclic lactone polymer and a preparation method thereof.
Background
Saccharides are not only used as one of basic substances of life, but also participate in a plurality of activities in vivo, wherein some bioactive saccharides have wide pharmacological activity, and besides physiological activities such as anticoagulation, anti-inflammation, antivirus, blood fat reduction, blood sugar reduction and the like, many saccharides also have biological functions of resisting tumors. In addition, glucose and glucose derivatives contain a plurality of hydroxyl groups, and the branched chain can also be selected from polar groups such as alcoholic hydroxyl groups, carboxyl groups, aldehyde groups and the like. If the copolymers are made from glucose derivatives, these groups can exert different functions, giving the copolymers particular properties. For example, hydroxyl and amino can improve the hydrophilic property of the material to improve the hydrophilicity and accelerate the degradation of the polymer, and meanwhile, provide anchor points for the adhesion of cells, are beneficial to the adhesion growth of the cells and accelerate the healing of tissues; for example, hydroxyl and other polar functional groups can form hydrogen bonds or ester bonds with the drug, and the compound is a natural drug carrier, so that the compound has a good prospect in the aspect of future implantation targeted drug delivery treatment. In addition, the copolymer prepared by using the glucose derivative as the raw material can be thoroughly decomposed into water and carbon dioxide, and can be used as an environment-friendly material. Meanwhile, glucose derivatives such as gluconolactone, glucurolactone, and the like are very inexpensive, and the cost for industrial application is very low.
However, the reports of using glucose derivatives to prepare copolymers are very few, mainly because the presence of hydroxyl groups in glucose derivatives can cause too many reactions in the synthesis process, and finally cause oxidative crosslinking to cause polymerization failure, and the use of measures such as hydroxyl protection to synthesize copolymers can involve multiple steps such as hydroxyl protection and deprotection, which is tedious in process and unfavorable for industrial production.
Disclosure of Invention
In view of the above situation, the present invention provides a novel method for preparing a copolymer from a glucose derivative, and also provides a copolymer prepared by the method.
The glucose derivative lactone-cyclic lactone copolymer is formed by polymerizing glucose derivative lactone and cyclic lactone, wherein the molar ratio of the glucose derivative lactone to the cyclic lactone is 0: 100-100: 0, and the dosage of the cyclic lactone is not 0.
In the polymerization, the molar ratio of the glucose derivative lactone to the cyclic lactone is preferably 2.5:97.5 to 50:50, and more preferably 1:9 to 5: 5.
In the glucose derivative lactone-cyclic lactone copolymer of the present invention, the structure of the glucose derivative lactone is represented by the following formula (I):
in the formula (I), R2 group is ethanol group, 2-hydroxy-glyoxal group or 2-hydroxy-acetoxy; the value range of m is 2 and 3.
More preferably, the glucolactone derivative is glucolactone, glucurolactone or D-glucaric acid-1, 4-lactone.
In the glucose derivative lactone-cyclic lactone copolymer of the present invention, the structure of the cyclic lactone is represented by the following formula (II):
in the formula (II), the R1 group is hydrogen atom, methyl, ethyl, propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl or n-octyl. Wherein the value range of n is 1-4.
More preferably, the cyclic lactone is β -propiolactone, γ -butyrolactone, β -butyrolactone, γ -valerolactone, δ -valerolactone, e-caprolactone, γ -caprolactone, δ -caprolactone, c-heptolactone, c-pelargonilactone, δ -octalactone, γ -octalactone, c-nonalactone, c-dodecalactone, or c-undecalactone.
The invention also provides a method for preparing the glucose derivative lactone-cyclic lactone copolymer, which comprises the following steps: under the protection of inert gas, mixing the catalyst, cyclic lactone and glucose derivative lactone, heating, adding alcohol initiator and reacting.
The catalyst is a tin compound, preferably monobutyl tin oxide, di-tert-butyl tin, tetrabutyl tin, tin tetraacetate, butyltin ester, dibutyltin diacetate, triphenyltin, dibutyl dioxystannane, tri-n-butyl methoxy tin, monobutyl triisooctanoic acid tin, dibutyl triisooctanoic acid tin, dibutyltin dilaurate, stannous chloride or stannic chloride.
Wherein the ratio of the molar amount of the catalyst to the total molar amount of the cyclic lactone and the glucose derivative is 1: 4-1: 2000, preferably (1.92-220): 1000.
wherein, the alcohol initiator is organic alcohol, preferably benzyl alcohol, ethanol, ethylene glycol, diethylene glycol, glycerol, isopropanol or butanol.
Wherein the ratio of the molar amount of the catalyst to the total molar amount of the cyclic lactone and the glucose derivative is 1: 200-1: 1000, preferably (1.68-7.18): 1000.
wherein the inert gas is nitrogen or argon.
Wherein the temperature is raised to 130-170 ℃, and more preferably 140-160 ℃.
Wherein the reaction time is 4-24 hours, preferably 20-24 hours.
In the glucose derivative lactone-cyclic lactone copolymer, the melting point of a high molecular polymer can be effectively controlled by adjusting the ratio of the cyclic lactone to the glucose derivative lactone in the copolymer, and simultaneously, the action degree of hydrogen bonds among molecular chains can be adjusted by adjusting the number of hydroxyl groups, so that the crystallization property, the mechanical property and the degradation property of the copolymer are changed, and the application range of polyester is expanded.
The glucose derivative lactone-cyclic lactone copolymer has excellent nontoxicity, no irritation, good biocompatibility and good degradability, can be thoroughly decomposed into gluconic acid and 6-hydroxycaproic acid by pancreatic lipase, can be thoroughly decomposed into water and carbon dioxide by cells, and has potential prospects in biological materials and environmental materials.
Obviously, many modifications, substitutions, and variations are possible in light of the above teachings of the invention, without departing from the basic technical spirit of the invention, as defined by the following claims.
The present invention will be described in further detail with reference to the following examples. This should not be understood as limiting the scope of the above-described subject matter of the present invention to the following examples. All the technologies realized based on the above contents of the present invention belong to the scope of the present invention.
Drawings
FIG. 1 FT-IR spectra of polycaprolactone and polyglucoside
FIG. 2 FT-IR spectra of copolymers of gluconolactone and caprolactone in different ratios
FIG. 3 XRD patterns of gluconolactone and caprolactone copolymers in different proportions
FIG. 4 is a time-dependent degradation weight loss rate curve of gluconolactone and caprolactone copolymers with different proportions
FIG. 5 is a graph of pH of PBS solutions of gluconolactone and caprolactone copolymers at various ratios as a function of time
Detailed Description
In the following examples, both gluconolactone and caprolactone were commercially available and used after being dried and purified, respectively.
Example 1
The reaction process is as follows: under the nitrogen atmosphere, 49.87mL (0.5mol) of caprolactone and 0.15mL of stannous octoate/toluene solution are added into a flask, the temperature is raised to 130 ℃, 0.17mL of diethylene glycol is added, after 48 hours of reaction, the solvent is removed under vacuum, and polycaprolactone is obtained. Fourier infrared data of the product as follows from the infrared data, caprolactone polymerisation was successful. FT-IR data are shown in FIG. 1 below: v (cm)-1):3,548.60，2946.05，2866.16，1724.31。
Example 2 preparation of glucose derivative lactone-cyclic lactone polymers of the invention
The reaction process is as follows: under a nitrogen atmosphere, 49.87mL (0.45mol) of epsilon-caprolactone, 8.91g (0.05mol) of gluconolactone (gluconolactone:. epsilon. -caprolactone: 1:9), and 1.7g (0.008mol) of butylstannoic acid were heated to 140 ℃ and 0.18mL (1.8mmol) of diethylene glycol was added to react for 24 hours, thereby obtaining a copolymer of gluconolactone and caprolactone. The obtained product is from infraredThe data show that butylstannoic acid catalyzes the successful copolymerization of the glucolactone and the caprolactone. FT-IR data are shown in FIG. 2 below: v (cm)-1):3,436，3392，2946，2867，1727，1294～1185。
EXAMPLE 3 preparation of glucose derivative lactone-Cyclic lactone Polymer of the present invention
The reaction process is as follows: under an argon atmosphere, 44.33mL (0.4mol) of epsilon-caprolactone, 17.81g (0.1mol) of gluconolactone (gluconolactone: epsilon-caprolactone ═ 2:8), and 2.6g (0.012mol) of butylstannoic acid were heated to 150 ℃ and 0.15mL (2.69mmol) of ethylene glycol was added thereto to react for 12 hours, thereby obtaining a copolymer of gluconolactone and caprolactone. The product is shown in infrared data, and butyl stannic acid catalyzes glucose lactone to be successfully copolymerized with caprolactone. FT-IR data are shown in FIG. 2 below: v (cm)-1):3,384，2946，2868，1731，1294～1186。
EXAMPLE 4 preparation of glucose derivative lactone-Cyclic lactone Polymer of the present invention
The reaction process is as follows: under a nitrogen atmosphere, 38.79mL (0.35mol) of epsilon-caprolactone, 26.72g (0.15mol) of glucose lactone (glucose lactone,. epsilon. -caprolactone:. 3:7), and 3.8g (0.018mol) of butylstannoic acid were heated to 160 ℃ and 0.2mL (1.9mmol) of benzyl alcohol were added, and reacted for 20 hours to obtain a copolymer of glucose lactone and caprolactone. From the infrared data, it is seen that butylstannoic acid catalyzes the successful copolymerization of gluconolactone and caprolactone. FT-IR data are shown in FIG. 2 below: v (cm)-1):3,376，2945，2868，1731，1294～1189。
EXAMPLE 5 preparation of glucose derivative lactone-Cyclic lactone Polymer of the present invention
The reaction process is as follows: under a nitrogen atmosphere, 33.24mL (0.3mol) of ε -caprolactone, 26.72g (0.2mol) of gluconolactone (gluconolactone:. epsilon. -caprolactone: 4:6), and 1.78g (8.52mmol) of butylstannoic acid were heated to 130 ℃ and 0.2mL (3.59mmol) of ethylene glycol was added to react for 48 hours, thereby obtaining a copolymer of gluconolactone and caprolactone. From the Fourier infrared data, the butyl stannic acid catalyzes the glucose lactone to be successfully copolymerized with the caprolactone. FT-IR data are shown in FIG. 2 below: v (cm)-1):3,376，2945，2868，1731，1294～1189。
EXAMPLE 6 preparation of glucose derivative lactone-cyclic lactone polymers of the present invention
The reaction process is as follows: under a nitrogen atmosphere, 27.7mL (0.25mol) of epsilon-caprolactone, 44.54g (0.25mol) of gluconolactone (gluconolactone,. epsilon. -caprolactone:. 5:5), and 3g (0.014mol) of butylstannoic acid were heated to 140 ℃ and 0.2mL (1.99mmol) of diethylene glycol was added to the mixture to react for 24 hours, thereby obtaining a copolymer of gluconolactone and caprolactone. From the infrared data of the products obtained, it can be seen that butylstannoic acid catalyzes the successful copolymerization of gluconolactone and caprolactone. FT-IR data are shown in FIG. 2 below: v (cm)-1):3,376，2945，2868，1731，1294～1189。
Example 7 preparation of glucose derivative lactone-Cyclic lactone Polymer of the present invention
The reaction process is as follows: 50g of gluconolactone (0.28mol) and 0.6g (2.8mmol) of butylstannoic acid were dissolved in 50mL of dry toluene under a nitrogen atmosphere, the temperature was raised to 150 ℃ and 0.087mL (0.84mmol) of benzyl alcohol was added, and after 10 hours of reaction, the solvent was removed under vacuum to obtain polyglucose lactone. From the Fourier infrared data of the product, the butyl stannic acid successfully catalyzes the polymerization of the glucolactone. FT-IR data are shown in FIG. 1 below:
ν(cm-1):3,392，2930，2861，1736，1224～1026。
EXAMPLE 8 preparation of glucose derivative lactone-Cyclic lactone Polymer of the present invention
The reaction process is as follows: in a nitrogen atmosphere, 54mL (0.475mol) of ∈ -caprolactone, 0.2g (0.96mmol) of butylstannoic acid, and 2.23g (0.025mol) of gluconolactone (gluconolactone ∈ -caprolactone ═ 2.5:97.5) were put into a flask, the temperature was raised to 140 ℃, 0.2mL (3.5mmol) of ethylene glycol was added, and the reaction was carried out for 48 hours, whereby a polyglucosolide-caprolactone copolymer was obtained.
EXAMPLE 9 preparation of glucose derivative lactone-Cyclic lactone Polymer of the present invention
The reaction process is as follows: in a nitrogen atmosphere, 39mL (0.35mol) of epsilon-caprolactone, 26.72g (0.15mol) of gluconolactone (gluconolactone ∈ -caprolactone ═ 3:7) and 2.3g (0.11mol) of butylstannic acid were dissolved in 50mL of dry n-octane, the temperature was raised to 170 ℃, 0.2mL (1.9mmol) of benzyl alcohol was added, and after 4 hours of reaction, the solvent was removed in vacuo to obtain a gluconolactone-caprolactone copolymer.
Example 10
XRD test of the high molecular weight polymer obtained in examples 1 to 7 showed that the crystallinity was decreased as the content of gluconolactone was increased, and the results are shown in FIG. 3.
Example 11
The caprolactone-gluconolactone copolymer obtained in example 1-7 was immersed in a phosphate buffer solution at 37 ℃ to show a change profile of pH with time. The results are shown in FIG. 4.
The properties of the gluconolactone-cyclic lactone copolymers of the present invention are summarized in the following table:
TABLE 1 characteristic Properties of copolymers of gluconolactone and caprolactone
The experimental result shows that the copolymer of the gluconolactone and the caprolactone can be successfully prepared by the method, the adhesive reaction can not be caused, and the obtained copolymer has excellent performance and is degradable and can be prepared into in-vivo repair materials or environmental materials.
Example 12
The weight loss rate versus time curve of the phosphate buffer solution soaked with the gluconolactone and caprolactone copolymers in different ratios (0: 50,40:60,30:70,20:80,10:90,7.5:92.5,5:95,2.5:97.5,0:10, respectively) was determined as in example 8.
The results are shown in FIG. 5.
The experimental result shows that the copolymer of the gluconolactone and the caprolactone can be successfully prepared by the method, the adhesive reaction can not be caused, and the degradation rate of the finally obtained copolymer can be regulated by regulating the proportion of the gluconolactone and the caprolactone.
Comparative example
Prepared according to the method of example 1 of patent 5,531,998 to copolymerize polycaprolactone with gluconolactone, except that: the catalyst is stannous octoate, and toluene is used as a solvent under the protection of anhydrous oxygen-free inert gas, so that the adhesive reaction is finally caused, the macromolecular copolymer cannot be successfully synthesized, and the result shows that the stannous octoate cannot effectively avoid the hydroxyl adhesion caused by the glucolactone in a system.
Claims (14)
1. A process for preparing a glucose-derived lactone-cyclic lactone copolymer, characterized by: the method comprises the following steps: under the protection of inert gas, mixing a catalyst, cyclic lactone and glucose derivative lactone, heating, adding an alcohol initiator, and reacting; wherein the catalyst is butyl stannoic acid;
the molar ratio of the glucose derivative lactone to the cyclic lactone is 1: 9-5: 5.
2. The method of claim 1, wherein: the glucose derivative lactone has the following structure as shown in the formula (I):
in the formula (I), R2The group is ethanol group, 2-hydroxy-glyoxal group or 2-hydroxy-acetoxy; the value range of m is 2 and 3.
3. The method of claim 2, wherein: the glucose derivative lactone is glucolactone, glucurolactone or D-glucaric acid-1, 4-lactone.
4. The method of claim 1, wherein: the structure of the cyclic lactone is shown as the following formula (II):
in the formula (II), R1The group is hydrogen atom, methyl, ethyl, propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl or n-octyl; wherein the value range of n is 1-4.
5. The method of claim 4, wherein the cyclic lactone is β -propiolactone, γ -butyrolactone, β -butyrolactone, γ -valerolactone, δ -valerolactone, ε -caprolactone, γ -caprolactone, δ -caprolactone, propiolactone, delta-octanolide, γ -octanolide, butyrolactone, propiolactone, docosanolactone, butyrdodecanolactone, or butyrundecanolactone.
6. The method of claim 1, wherein: the ratio of the molar weight of the catalyst to the total molar weight of the cyclic lactone and the glucose derivative is 1: 4-1: 2000.
7. The method of claim 1, wherein: the ratio of the molar amount of the catalyst to the total molar amount of the cyclic lactone and the glucose derivative is (1.92-220): 1000.
8. the method of claim 1, wherein: the alcohol initiator is organic alcohol.
9. The method of claim 8, wherein: the alcohol initiator is benzyl alcohol, ethanol, ethylene glycol, diethylene glycol, glycerol, isopropanol or butanol.
10. The method of claim 1, wherein: the inert gas is nitrogen or argon.
11. The method of claim 1, wherein: the temperature is raised to 130-170 ℃.
12. The method of claim 11, wherein: the temperature is raised to 140-160 ℃.
13. The method of claim 1, wherein: the reaction time is 4-24 hours.
14. The method of claim 13, wherein: the reaction time is 20-24 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710039639.4A CN107057045B (en) | 2017-01-19 | 2017-01-19 | Glucose derivative lactone-cyclic lactone polymer and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710039639.4A CN107057045B (en) | 2017-01-19 | 2017-01-19 | Glucose derivative lactone-cyclic lactone polymer and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107057045A CN107057045A (en) | 2017-08-18 |
| CN107057045B true CN107057045B (en) | 2020-04-14 |
Family
ID=59598138
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710039639.4A Active CN107057045B (en) | 2017-01-19 | 2017-01-19 | Glucose derivative lactone-cyclic lactone polymer and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107057045B (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102015824A (en) * | 2008-03-28 | 2011-04-13 | 帝国改革有限公司 | Carbohydrate lactone polymers |
-
2017
- 2017-01-19 CN CN201710039639.4A patent/CN107057045B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102015824A (en) * | 2008-03-28 | 2011-04-13 | 帝国改革有限公司 | Carbohydrate lactone polymers |
Non-Patent Citations (4)
| Title |
|---|
| Anamaria Todea等.Biocatalytic synthesis of δ-gluconolactone andε-caprolactone copolymers.《ACTA BIOCHIMICA POLONICA》.2014,第61卷(第2期),第205-210页. * |
| Anamaria Todea等.Optimization of enzymatic ring-opening copolymerizations involving δ-gluconolactone as monomer by experimental design.《Pure Appl. Chem.》.2014,第86卷(第11期),第1781-1792页. * |
| Biocatalytic synthesis of δ-gluconolactone andε-caprolactone copolymers;Anamaria Todea等;《ACTA BIOCHIMICA POLONICA》;20140606;第61卷(第2期);第205-210页 * |
| Optimization of enzymatic ring-opening copolymerizations involving δ-gluconolactone as monomer by experimental design;Anamaria Todea等;《Pure Appl. Chem.》;20140613;第86卷(第11期);第1781-1792页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107057045A (en) | 2017-08-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US6770717B2 (en) | Sequentially ordered biodegradable lactide (glycolide or lactide/glycolide)ε-caprolactone multi-block copolymer and process for the preparation thereof | |
| Stridsberg et al. | Controlled ring-opening polymerization: polymers with designed macromolecular architecture | |
| Singh et al. | Structure-processing-property relationship of poly (glycolic acid) for drug delivery systems 1: synthesis and catalysis | |
| EP2358785B1 (en) | Process to prepare di- and multiblock copolymers. | |
| Yuan et al. | Synthesis, characterization and thermal properties of hexaarmed star-shaped poly (ε-caprolactone)-b-poly (d, l-lactide-co-glycolide) initiated with hydroxyl-terminated cyclotriphosphazene | |
| EP2268701B1 (en) | Carbohydrate lactone polymers | |
| CN106947067B (en) | Preparation method of polyester | |
| US8071690B2 (en) | Lactic acid based compositions with enhanced properties | |
| CN101815741B (en) | Method for making copolymers of lactide and a 1:4-3:6 dianhydrohexitol | |
| US6316581B1 (en) | Bioresorbable copolymers | |
| JP3408347B2 (en) | Optically active block copolymerized polyester and method for producing the same | |
| Zhao et al. | Preparation of degradable polymenthide and its elastomers from biobased menthide via organocatalyzed ring-opening polymerization and UV curing | |
| CN107057045B (en) | Glucose derivative lactone-cyclic lactone polymer and preparation method thereof | |
| JPH08127645A (en) | Block-copolymerized poly(ester-carbonate) and its production | |
| EP1641471B1 (en) | Biocompatible polymer networks | |
| KR20090059880A (en) | Preparation of copolymer containing polyesters segment via ring-opening polymerization of cyclic ester monomer in the presence of activated agent | |
| EP2647656A2 (en) | Bioresorbable and biocompatible thermoplastic elastomer having a shape memory, particularly for biomedical applications and a process for their preparation | |
| CN109096478A (en) | A kind of Aliphatic Polycarbonate Copolymers and preparation method thereof | |
| Chen et al. | Synthesis and solubility of polylactide-co-poly (amino acid) random copolymer | |
| Chen et al. | Synthesis of poly (1, 4-dioxan-2-one) catalyzed by immobilized lipase CA | |
| CN115232315B (en) | Polyglycolic acid/aliphatic polycarbonate multiblock copolymer and preparation method thereof | |
| CN111393617B (en) | Performance-adjustable thermoplastic polyester elastomer and preparation method thereof | |
| CN115232297B (en) | Polyglycolic acid/aliphatic polycarbonate triblock copolymer and preparation method thereof | |
| CN113004499B (en) | Biodegradable polyester elastomer and preparation method and application thereof | |
| KR101395357B1 (en) | Polylactic acid-polysiloxane copolymer and method of manufacturing the same |
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 |