CN102516506A - Photosensitive PCL (polycaprolactone)-based copolymer and preparation method thereof - Google Patents
Photosensitive PCL (polycaprolactone)-based copolymer and preparation method thereof Download PDFInfo
- Publication number
- CN102516506A CN102516506A CN2011103745671A CN201110374567A CN102516506A CN 102516506 A CN102516506 A CN 102516506A CN 2011103745671 A CN2011103745671 A CN 2011103745671A CN 201110374567 A CN201110374567 A CN 201110374567A CN 102516506 A CN102516506 A CN 102516506A
- Authority
- CN
- China
- Prior art keywords
- pcl
- monomer
- different molecular
- molecular weight
- preparation
- 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.)
- Granted
Links
- 0 CC(*OC1=CC[C@@](C=CC(*)=O)C=C1O*)=O Chemical compound CC(*OC1=CC[C@@](C=CC(*)=O)C=C1O*)=O 0.000 description 1
Images
Landscapes
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention relates to a photosensitive PCL (polycaprolactone)-based copolymer and a preparation method thereof and belongs to the field of function materials. According to the invention, the photosensitive PCL-based copolymer is prepared by using polycaprolactone (PCL), 4-hydroxycinnamic acid (4HCA) or 3, 4-dihydroxycinnamic acid (caffeic acid, DHCA) with different molecular weights and polyethylene glycol (PEG) with different molecular weights as the raw materials, using anhydrous zinc acetate or sodium acetate as a catalyst and using acetic anhydride as a solvent through adopting a melt phase polycondensation method. The performances such as thermal stability, melting point, crystallinity, glass transition temperature, wettability and degradation velocity of the copolymer can be regulated and controlled by controlling the composition and the conditions, such as UV (ultraviolet) illumination, of the copolymer. The copolymer has photoluminescence property, physiological compatibility and degradability and can be widely applied to the fields of drug controlled release, tissue engineering, textile, packaging and agriculture.
Description
Technical field
A kind of photosensitivity PCL base co-polymer and preparation method thereof belongs to technical field of functional polymer preparation.
Background technology
Fast development along with polymer industry; Increasing synthesized polymer material has been come into people's life; And wherein the waste of non-degradable macromolecular material is also increasing to the negative impact that environment brings, and solving serious day by day " white pollution " becomes people's question of common concern.Thereby research and development novel degradable macromolecular material, realize regulation and control to material property, widen Application Areas, have important significance for theories and using value.
Polycaprolactone (PCL) is a kind of hypocrystalline molded lines property aliphatic polyester; Be rubbery state under the room temperature; Be a kind of degradable macromolecule with good thermal plasticity and forming process property, can adopt extrude, product that method such as blowing, injection and melt-spinning is processed different shape, its degraded product is CO
2And H
2O does not cause burden to human body and environment.PCL also has excellent drug perviousness, biocompatibility and mechanical property simultaneously, has wide application space in fields such as drug loading, organizational project, weaving, wrapping material.But PCL still has lower melting point, and poor heat resistance, degradation speed wait shortcoming slowly, have limited its range of application.
PEG is the most frequently used hydrophilic polymer, as a kind of polyethers polymer substance, has excellent biological compatibility, and is low to the toxicity of human body, and its performance has obtained the approval of food and drug administration (FDA).Like formation amphiphilic polymer that hydrophobic PCL and hydrophilic PEG are bonded together, can effectively improve wellability and degradation property of PCL etc.
The 4-hydroxycinnamic acid (4HCA) and 3 that the present invention is used, 4-dihydroxycinnamic acid (DHCA, coffic acid) are one type " vegetalitas monomers " of deriving from green plants, and its specific molecule structure has been given its uv photosensitivity.Be introduced in the PCL chain, when reservation improves the original essential property of PCL, also give performances such as polymkeric substance ultraviolet, pl-.The character such as thermal property, wellability, crystallinity and degradation property of photosensitivity PCL base co-polymer involved in the present invention all can be regulated and control through regulating feed ratio and ultraviolet lighting.This PCL base co-polymer with photosensitivity can be widely used in medicine controlled releasing, organizational project, weaving, packing and agriculture field.
Summary of the invention
The purpose of this invention is to provide a kind of photosensitivity PCL base co-polymer and preparation method thereof, adopt melt-polycondensation that functional 4HCA and DHCA are introduced in the PCL main polymer chain, obtain having the uv photosensitivity PCL base co-polymer of degradability.
Technical scheme of the present invention: a kind of preparation method of photosensitivity PCL base co-polymer; Directly PCL, 4HCA or DHCA and the different molecular weight polyethylene glycol (PEG) with different molecular weight is raw material; Zinc acetate or sodium acetate are catalyzer; Diacetyl oxide is a solvent, adopts the method for melt phase polycondensation to obtain having photosensitivity PCL base co-polymer;
Proportioning is: the structural unit of monomer 1 (PCL of different molecular weight): monomer 2 (4HCA or DHCA): the mol ratio of the structural unit of monomer 3 (PEG of different molecular weight) is 1: 0.1～10: 0.1～10; Catalyst levels is 0.01～0.05 times of total monomer mole number; The quality of solvent is 5～10 times of total monomer quality.
Take by weighing monomer and catalyzer places reactor drum by proportioning, add solvent, under the stirring velocity of 200～400r/min, be warming up to 150～170 ℃, reaction 1-3h; Continue to stir and temperature of reaction is elevated between 200～220 ℃, behind sustained reaction 6～12h, stop heating, naturally cooling again; Whole polycondensation process carries out under the condition of nitrogen and lucifuge; After reaction finishes, product is fully ground, dry under 30 ℃ at last with ethanol and deionized water difference thorough washing, get faint yellow or coffee-like product.
When being monomer with the PCL of different molecular weight and 4HCA, the gained multipolymer is:
Be expressed as PCL-co-P4HCA.
When being monomer with the PCL of different molecular weight and DHCA, the gained multipolymer is:
Be expressed as PCL-co-PDHCA.
When being monomer with the PEG of PCL, 4HCA and the different molecular weight of different molecular weight, the gained multipolymer is:
Be expressed as PCL-co-P4HCA-b-PEG.
When being monomer with the PEG of PCL, coffic acid and the different molecular weight of different molecular weight, the gained multipolymer is:
Table does not become PCL-co-PDHCA-b-PEG.
Characterize through the structure and the performance of characterizing methods such as IR, NMR, ultraviolet spectrophotometer, DSC, fluorescence spectrophotometry appearance, gel permeation chromatograph multipolymer; The result shows that copolymer structure is clear and definite, and the molecular weight of multipolymer, uv photosensitivity, pl-property, thermostability and degradation property all can be regulated and control through control feed ratio and ultraviolet lighting etc.
Beneficial effect of the present invention: the photosensitivity PCL base co-polymer that has prepared according to the methods of the invention has excellent thermostability and biocompatibility; The molecular weight of multipolymer, second-order transition temperature, fusing point, percent crystallinity, wellability and degradation speed etc. all can be realized through regulating feed ratio and ultraviolet lighting, be with a wide range of applications in fields such as medicine controlled releasing, organizational project, weaving, packing and agriculturals as Biodegradable material.
Description of drawings
Fig. 1 copolymer p CL-co-P4HCA is at different ultraviolet lightings (the uv-absorbing spectrogram under the time of λ=302nm).
(λ=302nm) is fluorogram under the time at different ultraviolet lightings for Fig. 2 copolymer p CL-co-P4HCA.
The thermogravimetric curve figure of Fig. 3 copolymer p CL-co-P4HCA under nitrogen atmosphere.
Fig. 4 is different to form the copolymer p CL-co-P4HCA sheet material lab diagram of under pH=7.4, degrading.
Embodiment
Embodiment 1
Take by weighing PCL3.42g (CL:30mmol), 4HCA3.28g (20mmol), zinc acetate 0.110g (0.5mmol); Diacetyl oxide 35ml adds in the 100ml reactor drum, is to be warming up to 160 ℃ under the 200r/min at mixing speed; Behind the reaction 2h; Be warming up to 200 ℃, continue stirring, isothermal reaction 7h, entire reaction is carried out under nitrogen protection and lucifuge condition.Product is fully ground, dry under 30 ℃ at last with ethanol and deionized water difference thorough washing, get flaxen product.The gained multipolymer is:
Be expressed as PCL-co-P4HCA.
Embodiment 2
Take by weighing PCL3.42g (CL:30mmol), 4HCA4.92g (30mmol), zinc acetate 0.658g (3mmol); Diacetyl oxide 80ml adds in the 250ml reactor drum, is to be warming up to 160 ℃ under the 400r/min at mixing speed; Behind the reaction 2h; Be warming up to 200 ℃, continue stirring, isothermal reaction 10h, rest part is with embodiment 1.The gained sample is through vulcanizing press hot pressing and cold pressing, and obtains multipolymer sheet material, respectively the sample before and after the ultraviolet lighting has been carried out contact angle and absorptive test, and the result sees table 1.
The wellability data of table 1. multipolymer sheet material
Embodiment 3
Take by weighing PCL1.14g (CL:10mmol), DHCA9g (50mmol), zinc acetate 0.044g (0.2mmol); Diacetyl oxide 60ml adds in the 100ml reactor drum, is to be warming up to 150 ℃ under the 300r/min at mixing speed; Behind the reaction 3h; Be warming up to 220 ℃, stir, isothermal reaction 6h again, entire reaction is carried out under nitrogen protection and lucifuge condition.Product is fully ground, dry under 30 ℃ at last with ethanol and deionized water difference thorough washing, get coffee-like product.The gained multipolymer is:
Be expressed as PCL-co-PDHCA.
Embodiment 4
Take by weighing PCL2.28g (CL:20mmol), 4HCA3.28g (20mmol), zinc acetate 0.153g (0.7mmol); Diacetyl oxide 40ml adds in the 100ml reactor drum, is to be warming up to 170 ℃ under the 400r/min at mixing speed; Behind the reaction 1h, dropwise add PEG (400) 0.88g (EG:20mmol), be warming up to 200 ℃ gradually; Stir, isothermal reaction 12h again, entire reaction is carried out under nitrogen protection and lucifuge condition.With ethanol and deionized water difference thorough washing,, get yellow product then at 30 ℃ of following freeze-day with constant temperature.The gained multipolymer is:
Be expressed as PCL-co-P4HCA-b-PEG.
Embodiment 5
Take by weighing PCL3.42g (CL:30mmol), DHCA1.80g (10mmol), zinc acetate 0.175g (0.8mmol); Diacetyl oxide 50ml adds in the 100ml reactor drum, is to be warming up to 150 ℃ under the 200r/min at mixing speed; Behind the reaction 3h, dropwise add PEG (400) 0.132g (EG:3mmol), be warming up to 210 ℃ gradually; Stir, isothermal reaction 10h again, entire reaction is carried out under nitrogen protection and lucifuge condition.With ethanol and deionized water difference thorough washing,, get yellow product then at 30 ℃ of following freeze-day with constant temperature.The gained multipolymer is:
Be expressed as PCL-co-PDHCA-b-PEG.
Claims (7)
1. photosensitivity PCL base co-polymer and preparation method thereof; It is characterized in that polycaprolactone (PCL), 4-hydroxycinnamic acid (4HCA) or 3 with different molecular weight; (coffic acid DHCA) is monomer to the 4-dihydroxycinnamic acid, and anhydrous zinc acetate or sodium acetate are catalyzer; Diacetyl oxide is a solvent, the PCL base co-polymer that the method for employing melt phase polycondensation has obtained having photosensitivity.
Proportioning is: the structural unit of monomer 1 (PCL of different molecular weight): the mol ratio of monomer 2 (4HCA or DHCA) is 1: 0.1～10; Catalyst levels is 0.01～0.05 times of total monomer mole number; The quality of solvent is 5～10 times of total monomer quality;
Take by weighing monomer and catalyzer places reactor drum by proportioning, add solvent, under the stirring velocity of 200～400r/min, be warming up to 150～170 ℃, reaction 1-3h; Continue to stir and temperature of reaction is elevated between 200～220 ℃, behind sustained reaction 6～12h, stop heating, naturally cooling again; Whole polycondensation process carries out under the condition of nitrogen and lucifuge; After reaction finishes, product is fully ground, dry under 30 ℃ at last with ethanol and deionized water difference thorough washing, get faint yellow or coffee-like product.
2. preparation method according to claim 1, when it is characterized in that being monomer with the PCL of different molecular weight and 4HCA, the gained multipolymer is:
Be expressed as PCL-co-P4HCA.
3. preparation method according to claim 1, when it is characterized in that being monomer with the PCL of different molecular weight and DHCA, the gained multipolymer is:
Be expressed as PCL-co-PDHCA.
4. photosensitivity PCL base co-polymer and preparation method thereof; It is characterized in that polycaprolactone (PCL), 4-hydroxycinnamic acid (4HCA) or 3 with different molecular weight; The 4-dihydroxycinnamic acid (coffic acid, DHCA) and different molecular weight polyethylene glycol (PEG) be monomer, anhydrous zinc acetate or sodium acetate are catalyzer; Diacetyl oxide is a solvent, the PCL base co-polymer that the method for employing melt phase polycondensation has obtained having photosensitivity.
Proportioning is: the structural unit of monomer 1 (PCL of different molecular weight): monomer 2 (4HCA or DHCA): the mol ratio of the structural unit of monomer 3 (PEG of different molecular weight) is 1: 0.1～10: 0.1～10; Catalyst levels is 0.01～0.05 times of total monomer mole number; The quality of solvent is 5～10 times of total monomer quality;
Monomer 1, monomer 2 and catalyzer are taken by weighing and place reactor drum by proportioning, add solvent, under the stirring velocity of 200～400r/min, be warming up to 150～170 ℃, reaction 2-3h; Add monomer 3 by proportioning and continue to stir and temperature of reaction is elevated between 200～220 ℃, behind sustained reaction 6～12h, stop heating, naturally cooling again; Whole polycondensation process carries out under the condition of nitrogen and lucifuge; After reaction finishes, product is fully ground, dry under 30 ℃ at last with ethanol and deionized water difference thorough washing, get faint yellow or coffee-like product.
5. preparation method according to claim 4, when the PEG that it is characterized in that PCL, 4HCA and different molecular weight with different molecular weight was monomer, the gained multipolymer was:
Be expressed as PCL-co-P4HCA-b-PEG.
6. preparation method according to claim 4, when the PEG that it is characterized in that PCL, DHCA and different molecular weight with different molecular weight was monomer, the gained multipolymer was:
Be expressed as PCL-co-PDHCA-b-PEG.
7. the photosensitivity PCL base co-polymer that makes according to the arbitrary described preparation method of claim 2～6 is characterized in that multipolymer all photo-crosslinking can take place under the UV-irradiation of 280nm; But emitting fluorescence under the 380nm burst of ultraviolel has pl-property; Equal degradable under acid, alkali and neutrallty condition, and degradation speed is controlled.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110374567.1A CN102516506B (en) | 2011-11-23 | 2011-11-23 | Photosensitive PCL (polycaprolactone)-based copolymer and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110374567.1A CN102516506B (en) | 2011-11-23 | 2011-11-23 | Photosensitive PCL (polycaprolactone)-based copolymer and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102516506A true CN102516506A (en) | 2012-06-27 |
| CN102516506B CN102516506B (en) | 2014-05-07 |
Family
ID=46287605
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110374567.1A Expired - Fee Related CN102516506B (en) | 2011-11-23 | 2011-11-23 | Photosensitive PCL (polycaprolactone)-based copolymer and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102516506B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104860827A (en) * | 2015-04-08 | 2015-08-26 | 中国石油大学(华东) | Photosensitive carboxylic acid molecule and preparation thereof, and application of photosensitive carboxylic acid molecule in drug sustained release |
| CN105384941A (en) * | 2015-12-07 | 2016-03-09 | 江南大学 | Degradable photosensitive phosphate copolymers |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101544749A (en) * | 2009-04-28 | 2009-09-30 | 江南大学 | Preparation method for biodegradable fluorescent polyester multipolymer |
| JP2010220746A (en) * | 2009-03-23 | 2010-10-07 | Terumo Corp | Ionizing radiation resistant material |
| CN102093540A (en) * | 2010-11-18 | 2011-06-15 | 江南大学 | Ricinoleic acid-based elastomer |
-
2011
- 2011-11-23 CN CN201110374567.1A patent/CN102516506B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010220746A (en) * | 2009-03-23 | 2010-10-07 | Terumo Corp | Ionizing radiation resistant material |
| CN101544749A (en) * | 2009-04-28 | 2009-09-30 | 江南大学 | Preparation method for biodegradable fluorescent polyester multipolymer |
| CN102093540A (en) * | 2010-11-18 | 2011-06-15 | 江南大学 | Ricinoleic acid-based elastomer |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104860827A (en) * | 2015-04-08 | 2015-08-26 | 中国石油大学(华东) | Photosensitive carboxylic acid molecule and preparation thereof, and application of photosensitive carboxylic acid molecule in drug sustained release |
| CN104860827B (en) * | 2015-04-08 | 2016-11-23 | 中国石油大学(华东) | Heliosensitivity carboxylic acid molecules, the application being prepared in medicament slow release |
| CN105384941A (en) * | 2015-12-07 | 2016-03-09 | 江南大学 | Degradable photosensitive phosphate copolymers |
| CN105384941B (en) * | 2015-12-07 | 2018-04-13 | 江南大学 | A kind of degradable photosensitive phosphate-based copolymer |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102516506B (en) | 2014-05-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US11530294B2 (en) | Polylactic acid composite and use thereof | |
| CN101649045B (en) | Biodegradable polyester-polyester segmented copolymer, preparation method and application thereof | |
| JP5285834B2 (en) | Method for producing polylactic acid | |
| CN106957514B (en) | PBAT base biodegradation composite material with high water vapor barrier property | |
| CN101328259B (en) | Preparation of biodegradable fermentation organic acid ployester | |
| US6933335B1 (en) | Thermoplastic polymer blend produced from thermoplastic starch and method for the production thereof | |
| CN106519311B (en) | A kind of thermoplastic starch-polyvinyl alcohol anti-fog thin film and preparation method thereof | |
| AU2018357174B2 (en) | Polylactic acid composite material and application thereof | |
| CN1974660A (en) | Process for producing aliphatic polyester composition | |
| CN102675577B (en) | Long-chain branched polylactic resin and preparation method and application thereof | |
| JP2005187626A (en) | Manufacturing process of polylactic acid stereo complex body | |
| CN106084697A (en) | A kind of lactic acid composite material having heat-resisting and mechanical property concurrently and preparation method thereof | |
| JP2004161802A (en) | Biodegradable polyester resin composition and method for producing the same | |
| JP5175421B2 (en) | Stereocomplex polylactic acid and method for producing the same | |
| CN104804388A (en) | Preparation method of high molecular weight polylactic acid material with high stereo-compound content | |
| JP2006028336A (en) | Method for producing polylactic acid block copolymer | |
| CN103172855B (en) | A kind of Lactic acid-amino acid copolyester amide and preparation method thereof | |
| CN102206406B (en) | Method for preparing transparent heat-resistance polylactic acid modification material | |
| CN102516506B (en) | Photosensitive PCL (polycaprolactone)-based copolymer and preparation method thereof | |
| CN106188534B (en) | A kind of polyamide and preparation method thereof, polyamide material prepared therefrom | |
| CN105694007B (en) | A kind of new preparation method of star polylactic acid co-glycolic acid | |
| CN109825016A (en) | A kind of biodegrade PVA stretch wrap film and preparation method thereof | |
| CN101225222B (en) | Polylactic acid as well as derivative composite material and preparation method thereof | |
| CN106751568B (en) | A kind of antibacterial PBAT/PLA composite membranes and preparation method thereof | |
| CN114685958A (en) | Modified preparation method of polylactic acid material |
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 | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Application publication date: 20120627 Assignee: Wuxi Orinko New Material Co., Ltd. Assignor: Jiangnan University Contract record no.: 2015990000149 Denomination of invention: Photosensitive PCL (polycaprolactone)-based copolymer and preparation method thereof Granted publication date: 20140507 License type: Exclusive License Record date: 20150331 |
|
| LICC | Enforcement, change and cancellation of record of contracts on the licence for exploitation of a patent or utility model | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20140507 Termination date: 20161123 |