CN1098882C - Biodegradable high polymer and its preparation method - Google Patents
Biodegradable high polymer and its preparation method Download PDFInfo
- Publication number
- CN1098882C CN1098882C CN98102212A CN98102212A CN1098882C CN 1098882 C CN1098882 C CN 1098882C CN 98102212 A CN98102212 A CN 98102212A CN 98102212 A CN98102212 A CN 98102212A CN 1098882 C CN1098882 C CN 1098882C
- Authority
- CN
- China
- Prior art keywords
- poly
- polyether
- lactide
- polylactide
- polycaprolactone
- 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.)
- Expired - Fee Related
Links
Landscapes
- Polyesters Or Polycarbonates (AREA)
- Materials For Medical Uses (AREA)
Abstract
本发明涉及一种具有生物降解性的聚己内酯-聚丙交酯-聚醚三元共聚物及其制法。用ε-己内酯或其衍生物同各种丙交酯或其混合物，以及烷撑氧聚醚，在催化剂异辛酸亚锡的作用和真空(低于13Pa)条件下，于110-170℃反应12-72小时，得到的聚己内酯-聚丙交酯-聚醚三元共聚物。其聚醚链段分子量可在44-22000之间调节，(聚己内酯+聚丙交酯)同聚醚的聚合单元比可在95∶5～45∶55(mol%)之间调节， 聚己内酯同聚丙交酯聚合单元比可在1∶99～99∶1(mol%)之间调节。此聚合物具有优良生物降解性能和力学性能，生物降解速度可以调节，且制备方法简易，便于生产。The invention relates to a biodegradable polycaprolactone-polylactide-polyether terpolymer and a preparation method thereof. Use ε-caprolactone or its derivatives with various lactides or their mixtures, and alkylene oxide polyether, under the action of the catalyst stannous octanoate and vacuum (less than 13Pa), at 110-170 ° C After reacting for 12-72 hours, the obtained polycaprolactone-polylactide-polyether terpolymer is obtained. The molecular weight of its polyether segment can be adjusted between 44-22000, and the polymer unit ratio of (polycaprolactone + polylactide) to polyether can be adjusted between 95:5 ~ 45:55 (mol%). The ratio of caprolactone to polylactide polymer units can be adjusted between 1:99-99:1 (mol%). The polymer has excellent biodegradability and mechanical properties, the biodegradation speed can be adjusted, and the preparation method is simple and convenient for production.
Description
The present invention relates to have polycaprolactone-polylactide-polyethers terpolymer of biological degradability and preparation method thereof.
Biodegradable polymer is to be promoted degraded by enzyme or microorganism, thereby molecular weight and molecular weight, loses intensity, so that eventual degradation or be small molecules, monomer, or become the polymer of carbonic acid gas and water.Because after utilizing biodegradable polymer as suture, nail or other medical repair materials, can utilize material degradation in vivo and metabolism voluntarily, final or be excreted, or absorbed by body, after repairing, organ needs trouble that their are taken out again thereby can exempt; Can realize that the long-term control of medicine discharges after as pharmaceutical carrier or constant release or the like with such material, so biodegradable polymer has very important and irreplaceable effect at medical field.Biodegradable polymer has crucial meaning equally for preventing the pollution of the environment, in case their price can access decline, will have immeasurable application prospect on causes such as agricultural, environmental protection.
As biodegradable polymer most important applications performance is to have suitable biodegradation rate.Therefore aliphatic polyester is the good biodegradable polymer of a class because thereby ester bond wherein can hydrolysis cause backbone breaking.Polycaprolactone had both had biological degradability as a kind of aliphatic polyester, had good drug permeability again, thereby was class bio-medical material preferably.Yet because the crystallinity of polycaprolactone is extremely strong, degree of crystallinity is very high, makes structure tightr, so wetting ability is relatively poor, biodegradation rate is very slow.(Chinese invention patent ZL92113100.3) goes up open by polycaprolactone can be reduced the crystallinity of polycaprolactone and the wetting ability of raising multipolymer with the method with polyethers copolymerization of good wetting ability and biocompatibility, reached the purpose of improving polycaprolactone multipolymer biological degradability.In view of polylactide also is a class aliphatic polyester, and has the biodegradability that is better than polycaprolactone, (Macromolecules.1986.19 such as Teyssie, 1828[U.S.]) once reported by the copolymerization of caprolactone with rac-Lactide, can make and both had good drug permeability, have the polycaprolactone-polylactide multipolymer of controllable biodegradable speed again.But this method need be used special catalyzer, the preparation condition harshness, so that the synthesis step of whole multipolymer is longer, the preparation process complexity: and the hydrophilicity of this multipolymer is still relatively poor, degradation speed is wayward.
The present invention has overcome in the prior art needs to adopt special catalyst and preparation method's harshness and hydrophilicity is poor, the uppity shortcoming of degradation speed, and provides a kind of polycaprolactone, polyethers with polylactide terpolymer and preparation method thereof.
The chemical structural formula of Biodegradable polycaprolactone one polylactide one polyethers terpolymer of the present invention is as follows:
In the formula: R=C1～C4
k＝2～10
N=4～440, n is the polyester portion polymerization degree
M=4～440, m is the polyester portion polymerization degree
P=1～500, p is the polymerized unit ratio of aliphatic polyester composition and polyether components in this multipolymer of the polyether moiety polymerization degree, i.e. (m+n): p=95: 5～45: 55 (mol%), the ratio m of two kinds of aliphatic polyester compositions: n=1: 99～99: 1 (mol%).
The preparation method of polycaprolactone one polylactide one polyethers terpolymer of the present invention adopts the method for a direct copolycondensation of step, be about to caprolactone, rac-Lactide and polyethers mixing after, in the presence of catalyzer in the direct copolycondensation of vacuum condition.Polymeric reaction temperature is 110-170 ℃, and the reaction times is 12-72 hour.
The present invention can directly use avirulent commodity stannous iso caprylate to be catalyzer, catalyst levels is 0.001～2% of the reaction mass gross weight that feeds intake, best catalyst levels is 0.005～1.0% of the reaction mass gross weight that feeds intake, and also can use butyl (tetra) titanate to be catalyzer.The biodegradation rate of multipolymer of the present invention can be by the proportioning of regulating polycaprolactone, polyethers and three components of polylactide, kind and the molecular weight of regulating polyethers, the kind of regulating polylactide is (poly--the l-rac-Lactide, poly--the d-rac-Lactide, poly--d, l-rac-Lactide and poly--l-rac-Lactide are with poly--d, the multipolymer of l-rac-Lactide) etc. multiple factor regulate.
First technical characterictic of the present invention is to adopt polyethers and the polylactide polymeric composition comprising body as polycaprolactone, can adopt different polyethers or pfpe molecule amount, adopt different polylactide and ratio thereof, make multipolymer have different crystallinity and wetting ability, to reach the purpose that changes the multipolymer biodegradation rate.
Second technical characterictic of the present invention is to use stronger polyethers of wetting ability and aliphatic polyester copolymerization, improving the wetting ability of multipolymer, thereby reach regulate multipolymer because of ester linkage hydrolyzing causes biodegradable purpose.
The 3rd technical characterictic of the present invention is to use nontoxicity, commercialization and having gone through the chemical stannous iso caprylate that can be used for medical material is a catalyzer, therefore both be beneficial to and carried out scale operation, and also be beneficial to method synthetic multipolymer thus is applied to prepare medical product.In addition, this technology also can use butyl (tetra) titanate etc. as catalyzer.
The 4th technical characterictic of the present invention is to adopt various monomers and direct synthesis of ternary multipolymer of one step of raw material, has that technology is simple, flow process short, inexpensive, the advantage that is beneficial to scale operation.
Polycaprolactone composition among the present invention is poly-ε-methyl caprolactone, poly-ε-alkyl caprolactone, and described alkyl is C
1-C
4Alkyl, any in promptly poly-ε-methyl caprolactone, ε-ethyl caprolactone, poly-ε-propyl group (or sec.-propyl) caprolactone and poly-ε-butyl (or isobutyl-) caprolactone.Any that best is in poly-epsilon-caprolactone and the poly-ε-methyl caprolactone.The polylactide composition is poly--l-rac-Lactide, poly--the d-rac-Lactide, poly--d, the l-rac-Lactide, and poly--l-rac-Lactide is with poly--d, the mixture of l-rac-Lactide.That best is poly--l-rac-Lactide and poly--d, any in the l-rac-Lactide.Polyoxyalkylene constituent can be any in the poly-alkylene oxygen polyethers such as poly-ethylene oxide,1,2-epoxyethane polyethers, poly-Sanya methylene oxygen polyethers, poly-four methylenes support oxygen polyethers.In preferably poly-ethylene oxide,1,2-epoxyethane polyethers and the poly-four methylenes support oxygen polyethers any.
Polycaprolactone-polylactide of the present invention-polyethers terpolymer has excellent biodegradability, excellent drug permeability, biocompatibility and nontoxicity, and reduces the crystallinity of polylactone, has improved the wetting ability and the biodegradation rate of multipolymer.Be a class new bio degraded macromolecular, have wide biomedical applications.The synthetic method of this multipolymer does not need special conversion unit, flow process is short, technology is simple, be convenient to suitability for industrialized production.Because the performance of copolymer products is with its ratio of components, and wherein polyethers kind and molecular weight, and the kind of rac-Lactide and changing, the therefore component and the proportioning thereof that can feed intake by control simply, the effectively performance of regulating copolymerization product easily.
Embodiment 1,
6-caprolactone 8.0 grams; l-rac-Lactide 25.0g, poly-ethylene oxide,1,2-epoxyethane polyethers (molecular weight 6000) 4.0 grams mix the back under inert atmosphere (nitrogen or argon gas) protection; add stannous iso caprylate 0.02 gram, under vacuum condition (being lower than 13Pa), reacted 50 hours then in 120 ℃.The terpolymer intrinsic viscosity [η]=1.50 (dl/g) that obtains, ratio of components (caprolactone units): (lactic acid units): (polyether units)=0.98: 5.07: 1.00 (mol%), its tensile strength of film of being cast by chloroformic solution is 53.3MPa, and extension at break is 650%.
Embodiment 2,
Operation with embodiment 1, the feed ratio that adopts is 6-caprolactone 32.0 grams, l-rac-Lactide 9.8 grams, poly-ethylene oxide,1,2-epoxyethane polyethers is 3.0 grams, the multipolymer ratio of components that obtains is (caprolactone units): (lactic acid units): (polyether units)=3.9: 1.86: 1.00 (mol%), intrinsic viscosity is 1.79dl/g, and the film tensile strength of being cast by chloroformic solution is 32.1MPa, and extension at break is 1304%.
Embodiment 3,
With the operation of embodiment 1, adopt d, l-rac-Lactide and poly-four methylenes support oxygen polyethers, temperature of reaction is 160 ℃, and the reaction times is 24 hours, and the copolymer intrinsic viscosity that obtains is 1.75dl/g,
Embodiment 4,
With the operation of embodiment 1, adopt poly-ethylene oxide,1,2-epoxyethane polyethers 6.0g, l-rac-Lactide 5.8 grams, d, l-rac-Lactide 33.50 grams, 6-caprolactone 31.20 grams are under the 0.075 gram effect of catalyzer stannous iso caprylate, in 12Pa and 150 ℃ of reactions 28 hours.This multipolymer is 40MPa by the tensile strength of film that chloroformic solution becomes, and extension at break is 1079%.
Embodiment 5,
With embodiment 1 method prepared (caprolactone units): (lactic acid units): the polycaprolactone of (poly-ethylene oxide,1,2-epoxyethane ether)=3.90: 1.86: 1.00 (mol%)-poly--l-rac-Lactide-poly-ethylene oxide,1,2-epoxyethane polyethers terpolymer, its [(caprolactone units)+(lactic acid units): (polyether units)=85.2: 14.8 (mol%), wherein (caprolactone units): (rac-Lactide unit)=67.7: 32.3 (mol%).The phosphate buffer solution of pH7.4 and 37 ℃ (under the temperature, no enzyme, the biodegradation rate when pancreatin being arranged and the esterase different condition being arranged is more as shown in Figure 1.Biological degradation is represented by the decline of polymer intrinsic viscosity.
The biodegradability of Fig. 1, polycaprolactone-polylactide-polyethers terpolymer
Copolymerization ratio of components: [caprolactone units]: [lactic acid units]: [ethylene oxide,1,2-epoxyethane unit] (mol%)=
3.90∶1.86∶1.00
Biodegradation condition pH7.4,37 ℃
-△-no enzyme condition :-zero-pancreatin (3mg/10ml);--junket enzyme (3mg/10ml) Embodiment 6,
With the method for embodiment 1 Yu proportioning, the employing butyl titanate is catalyst, the terpolymer intrinsic viscosity that obtains=1.21 (dl/g), ratio of components (caprolactone units): (lactic acid units): (polyether units)=1.25: 2.78=1.00 (mol%)
Claims (9)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98102212A CN1098882C (en) | 1998-06-03 | 1998-06-03 | Biodegradable high polymer and its preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98102212A CN1098882C (en) | 1998-06-03 | 1998-06-03 | Biodegradable high polymer and its preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1237594A CN1237594A (en) | 1999-12-08 |
| CN1098882C true CN1098882C (en) | 2003-01-15 |
Family
ID=5217208
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN98102212A Expired - Fee Related CN1098882C (en) | 1998-06-03 | 1998-06-03 | Biodegradable high polymer and its preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1098882C (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100457198C (en) * | 2003-06-25 | 2009-02-04 | 朱晓明 | Method for making degradable material of ureter bracket |
| CN100518937C (en) * | 2006-01-27 | 2009-07-29 | 浙江海正生物材料股份有限公司 | Use of stannous benzoate as catalyst |
| CN101492532B (en) * | 2006-01-27 | 2012-05-16 | 浙江海正生物材料股份有限公司 | Use of stannous benzoate as catalyst |
| WO2024123072A1 (en) * | 2022-12-06 | 2024-06-13 | 주식회사 엘지화학 | Copolymer and method for producing copolymer |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5225521A (en) * | 1991-12-31 | 1993-07-06 | E. I. Du Pont De Nemours And Company | Star-shaped hydroxyacid polymers |
| CN1087098A (en) * | 1992-11-19 | 1994-05-25 | 中国科学院化学研究所 | Biodegradable polycaprolactone polyether block polymer and preparation method thereof |
| US5550173A (en) * | 1992-11-06 | 1996-08-27 | Zeneca Limited | Polyester composition |
| EP0781309A1 (en) * | 1994-09-16 | 1997-07-02 | The Procter & Gamble Company | Biodegradable polymeric compositions and products thereof |
| WO1997034953A1 (en) * | 1996-03-19 | 1997-09-25 | The Procter & Gamble Company | Biodegradable polymeric compositions and products thereof |
-
1998
- 1998-06-03 CN CN98102212A patent/CN1098882C/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5225521A (en) * | 1991-12-31 | 1993-07-06 | E. I. Du Pont De Nemours And Company | Star-shaped hydroxyacid polymers |
| US5550173A (en) * | 1992-11-06 | 1996-08-27 | Zeneca Limited | Polyester composition |
| CN1087098A (en) * | 1992-11-19 | 1994-05-25 | 中国科学院化学研究所 | Biodegradable polycaprolactone polyether block polymer and preparation method thereof |
| EP0781309A1 (en) * | 1994-09-16 | 1997-07-02 | The Procter & Gamble Company | Biodegradable polymeric compositions and products thereof |
| WO1997034953A1 (en) * | 1996-03-19 | 1997-09-25 | The Procter & Gamble Company | Biodegradable polymeric compositions and products thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1237594A (en) | 1999-12-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4452973A (en) | Poly(glycolic acid)/poly(oxyethylene) triblock copolymers and method of manufacturing the same | |
| US4438253A (en) | Poly(glycolic acid)/poly(alkylene glycol) block copolymers and method of manufacturing the same | |
| US5321113A (en) | Copolymers of an aromatic anhydride and aliphatic ester | |
| EP1366104B1 (en) | Environmentally degradable polymeric compounds, their preparation and use as hot melt adhesive | |
| EP0832145B1 (en) | Thermoplastic biodegradable polyester, a process for the preparation thereof and articles manufactured therefrom | |
| US20030139567A1 (en) | Sequentially ordered biodegradable lactide (glycolide or lactide/glycolide)epsilon -caprolactone multi-block copolymer and process for the preparation thereof | |
| US6861503B2 (en) | Interlinked solid polyethylene glycols and copolymers thereof | |
| KR19980702244A (en) | Biodegradable polymers, methods of preparation thereof and their use for producing biodegradable molded articles | |
| JPH1053642A (en) | Absorbable polyoxaester | |
| CN101134807A (en) | Polylactic acid radical biological degradable material and method for preparing same | |
| EP0910598B1 (en) | High impact strength biodegradable material | |
| CN107522852A (en) | The biodegradable three block of bio-based of segment containing dimer acid polyester a kind of, segmented copolymer and its preparation method and application | |
| CN1133680C (en) | A kind of biodegradable ternary copolyester and its preparation method | |
| CN1098882C (en) | Biodegradable high polymer and its preparation method | |
| JP3367577B2 (en) | Acid-blocked polylactic acid | |
| AU2014237773B2 (en) | Polylactone polymers prepared from monol and diol polymerization initiators possessing two or more carboxylic acid groups | |
| CN1073582C (en) | Method of synthesis for biodegradable copolyester | |
| CN1035678C (en) | Biodegradable polycaprolactone polyether block polymer and preparing process thereof | |
| JP3374530B2 (en) | Method for producing aliphatic polyester copolymer | |
| CN1164642C (en) | Biodegradable polycarbonate/polyester/polyether terpolymer and preparation method | |
| FI102284B (en) | Elastic, biodegradable material | |
| KR100308535B1 (en) | Polyester resin composition and method for producing the same | |
| KR19980082075A (en) | Polyester resin composition and its manufacturing method | |
| FI102682B (en) | Impact resistant, biodegradable material | |
| KR19980082076A (en) | Polyester resin composition and its manufacturing method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |