CN102516506B - Photosensitive PCL (polycaprolactone)-based copolymer and preparation method thereof - Google Patents
Photosensitive PCL (polycaprolactone)-based copolymer and preparation method thereof Download PDFInfo
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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 Polymeric Industry, increasing synthesized polymer material has been come into people's life, and the negative impact that wherein waste of non-degradable macromolecular material brings to environment is also increasing, solving day by day serious " white pollution " becomes people's question of common concern.Thereby research and development novel degradable macromolecular material, realize the regulation and control to material property, broaden application field, has important theory significance and using value.
Polycaprolactone (PCL) is a kind of hypocrystalline Linear aliphatic polyester, under room temperature, be rubbery state, it is a kind of degradable macromolecule with good thermoplasticity and forming process, can adopt extrude, product that the method such as blowing, injection and melt-spinning is made different shape, its degraded product is CO
2and H
2o, does not cause burden to human body and environment.PCL also has good medicine perviousness, biocompatibility and mechanical property simultaneously, in fields such as drug loading, organizational project, weaving, wrapping material, has wide application space.But PCL still has low melting point, the shortcoming such as poor heat resistance, degradation speed are slow, has limited its range of application.
PEG is the most frequently used hydrophilic polymer, as a kind of polyethers polymer substance, has good biocompatibility, low to the toxicity of human body, and its performance has obtained the approval of food and drug administration (FDA).As formation amphiphilic polymer that hydrophobic PCL and hydrophilic PEG are bonded together, can effectively improve the wetting property of PCL and degradation property etc.
The 4-hydroxycinnamic acid (4HCA) that the present invention is used and Caffeic acid (DHCA, coffic acid) are " the vegetalitas monomers " that a class derives from green plants, and its special molecular structure has been given its uv photosensitivity.Be introduced in PCL chain, when reservation improves the original essential property of PCL, also give the performances such as polymkeric substance ultraviolet, photoluminescence.The character such as thermal characteristics, wetting property, crystallinity and degradation property of photosensitivity PCL base co-polymer involved in the present invention all can be by regulating feed ratio and ultraviolet lighting to regulate and control.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 object 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 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 take PCL, the 4HCA of different molecular weight or the polyoxyethylene glycol (PEG) of DHCA and different molecular weight is raw material, zinc acetate or sodium acetate are catalyzer, diacetyl oxide is 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.
By proportioning, take monomer and catalyzer is placed in reactor, add solvent, under the stirring velocity of 200～400r/min, be warming up to 150～170 ℃, reaction 1-3h; Continue stir and temperature of reaction is elevated between 200～220 ℃, then after sustained reaction 6～12h, stop heating, naturally cooling; Whole polycondensation process carries out under the condition of nitrogen and lucifuge; After completion of the reaction, product is fully ground, with ethanol and deionized water fully washing respectively, finally dry at 30 ℃, obtain faint yellow or coffee-like product.
Take the PCL of different molecular weight and 4HCA during as monomer, and gained multipolymer is:
Be expressed as PCL-co-P4HCA.
Take the PCL of different molecular weight and DHCA during as monomer, and gained multipolymer is:
Be expressed as PCL-co-PDHCA.
Take PCL, the 4HCA of different molecular weight and the PEG of different molecular weight during as monomer, and gained multipolymer is:
Be expressed as PCL-co-P4HCA-b-PEG.
Take the PEG of PCL, coffic acid and different molecular weight of different molecular weight during as monomer, and gained multipolymer is:
Be expressed as PCL-co-PDHCA-b-PEG.
By characterizing methods such as infrared spectrometer, nuclear magnetic resonance analyser, ultraviolet spectrophotometer, differential scanning calorimeter, Fluorescence spectrophotometer, gel permeation chromatographs, the structure of multipolymer and performance are characterized, result shows that copolymer structure is clear and definite, and the molecular weight of multipolymer, uv photosensitivity, Photoluminescence, thermostability and degradation property all can regulate and control by controlling feed ratio and ultraviolet lighting etc.
Beneficial effect of the present invention: the prepared according to the methods of the invention photosensitivity PCL base co-polymer that has has excellent thermostability and biocompatibility, the molecular weight of multipolymer, second-order transition temperature, fusing point, degree of crystallinity, wetting property and degradation speed etc. all can, by regulating feed ratio and ultraviolet lighting to realize, be with a wide range of applications in fields such as medicine controlled releasing, organizational project, weaving, packing and agriculturals as Biodegradable material.
Accompanying drawing explanation
Fig. 1 copolymer p CL-co-P4HCA is the uv-absorbing figure under (λ=302nm) time at different ultraviolet lightings.
Fig. 2 copolymer p CL-co-P4HCA is at different ultraviolet lightings fluorogram under (λ=302nm) time.
The thermogravimetric curve figure of Fig. 3 copolymer p CL-co-P4HCA under nitrogen atmosphere.
Fig. 4 is different forms the copolymer p CL-co-P4HCA sheet material lab diagram of degrading under pH=7.4.
Embodiment
Take PCL3.42g (CL: 30mmol); 4HCA3.28g (20mmol); zinc acetate 0.110g (0.5mmol); diacetyl oxide 35ml, adds in 100ml reactor, at mixing speed, is under 200r/min, to be warming up to 160 ℃; after reaction 2h; be warming up to 200 ℃, continue stirring, isothermal reaction 7h, whole reaction is carried out under nitrogen protection and lucifuge condition.Product is fully ground, with ethanol and deionized water fully washing respectively, finally dry at 30 ℃, obtain flaxen product.Gained multipolymer is:
Be expressed as PCL-co-P4HCA.
Embodiment 2
Take PCL3.42g (CL: 30mmol), 4HCA4.92g (30mmol), zinc acetate 0.658g (3mmol), diacetyl oxide 80ml, adds in 250ml reactor, at mixing speed, is under 400r/min, to be warming up to 160 ℃, after reaction 2h, be warming up to 200 ℃, continue stirring, isothermal reaction 10h, rest part is with embodiment 1.Gained sample is through vulcanizing press hot pressing and cold pressing, and obtains multipolymer sheet material, respectively the sample before and after ultraviolet lighting has been carried out to contact angle and absorptive test, the results are shown in Table 1.
The wetting property data of table 1. multipolymer sheet material
Embodiment 3
Take PCL1.14g (CL: 10mmol); DHCA9g (50mmol); zinc acetate 0.044g (0.2mmol); diacetyl oxide 60ml, adds in 100ml reactor, at mixing speed, is under 300r/min, to be warming up to 150 ℃; after reaction 3h; be warming up to 220 ℃, stir, isothermal reaction 6h again, whole reaction is carried out under nitrogen protection and lucifuge condition.Product is fully ground, with ethanol and deionized water fully washing respectively, finally dry at 30 ℃, obtain coffee-like product.Gained multipolymer is:
Be expressed as PCL-co-PDHCA.
Embodiment 4
Take PCL2.28g (CL: 20mmol); 4HCA3.28g (20mmol); zinc acetate 0.153g (0.7mmol), diacetyl oxide 40ml, adds in 100ml reactor; at mixing speed, be under 400r/min, to be warming up to 170 ℃; after reaction 1h, dropwise add PEG (400) 0.88g (EG: 20mmol), be warming up to gradually 200 ℃; stir, isothermal reaction 12h again, whole reaction is carried out under nitrogen protection and lucifuge condition.With ethanol and deionized water fully washing respectively, then freeze-day with constant temperature at 30 ℃, obtains yellow product.Gained multipolymer is:
Be expressed as PCL-co-P4HCA-b-PEG.
Take PCL3.42g (CL: 30mmol); DHCA1.80g (10mmol); zinc acetate 0.175g (0.8mmol), diacetyl oxide 50ml, adds in 100ml reactor; at mixing speed, be under 200r/min, to be warming up to 150 ℃; after reaction 3h, dropwise add PEG (400) 0.132g (EG: 3mmol), be warming up to gradually 210 ℃; stir, isothermal reaction 10h again, whole reaction is carried out under nitrogen protection and lucifuge condition.With ethanol and deionized water fully washing respectively, then freeze-day with constant temperature at 30 ℃, obtains yellow product.Gained multipolymer is:
Be expressed as PCL-co-PDHCA-b-PEG.
Claims (7)
1. the preparation method of a photosensitivity PCL base co-polymer, it is characterized in that, take the polycaprolactone of different molecular weight as monomer 1, with 4-hydroxycinnamic acid or 3,4-dihydroxycinnamic acid is monomer 2, take anhydrous zinc acetate or sodium acetate as catalyzer, take diacetyl oxide as solvent, and the method for employing melt phase polycondensation obtains having the PCL base co-polymer of photosensitivity;
Wherein, the structural unit of monomer 1: the mol ratio of monomer 2 is 1:0.1～10, catalyzer mole dosage is 0.01～0.05 times of total monomer mole number, the quality of solvent is total monomer quality 5～10 times;
By proportioning, take monomer 1, monomer 2 and catalyzer and be placed in reactor, add solvent, under the stirring velocity of 200～400r/min, be warming up to 150～170 ℃, reaction 1-3h; Continue stir and temperature of reaction is elevated between 200～220 ℃, then after sustained reaction 6～12h, stop heating, naturally cooling; Whole polycondensation process carries out under the condition of nitrogen and lucifuge; After completion of the reaction, product is fully ground, with ethanol and deionized water fully washing respectively, finally dry at 30 ℃, obtain faint yellow or coffee-like product.
2. preparation method according to claim 1, is characterized in that, take the polycaprolactone of different molecular weight and 4-hydroxycinnamic acid during as monomer, and gained multipolymer is:
Be expressed as PCL-co-P4HCA.
3. preparation method according to claim 1, is characterized in that, take the polycaprolactone of different molecular weight and Caffeic acid during as monomer, and gained multipolymer is:
Be expressed as PCL-co-PDHCA.
4. the preparation method of a photosensitivity PCL base co-polymer, it is characterized in that, the polycaprolactone of different molecular weight of take is monomer 1,4-hydroxycinnamic acid or 3,4-dihydroxycinnamic acid is monomer 2, the polyoxyethylene glycol of different molecular weight of take is monomer 3, take anhydrous zinc acetate or sodium acetate as catalyzer, take diacetyl oxide as solvent, and the method for employing melt phase polycondensation obtains having the PCL base co-polymer of photosensitivity;
Wherein, the structural unit of monomer 1: monomer 2: the mol ratio of the structural unit of monomer 3 is 1:0.1～10:0.1～10, catalyzer mole dosage is 0.01～0.05 times of total monomer mole number, the quality of solvent is total monomer quality 5～10 times;
Monomer 1, monomer 2 and catalyzer are taken and be placed in reactor by proportioning, add solvent, under the stirring velocity of 200～400r/min, be warming up to 150～170 ℃, reaction 2-3h; By proportioning, add monomer 3 to continue stir and temperature of reaction is elevated between 200～220 ℃, then after sustained reaction 6～12h, stop heating, naturally cooling; Whole polycondensation process carries out under the condition of nitrogen and lucifuge; After completion of the reaction, product is fully ground, with ethanol and deionized water fully washing respectively, finally dry at 30 ℃, obtain faint yellow or coffee-like product.
5. preparation method according to claim 4, is characterized in that, take the polyoxyethylene glycol of polycaprolactone, 4-hydroxycinnamic acid and different molecular weight of different molecular weight during as monomer, and gained multipolymer is:
Be expressed as PCL-co-P4HCA-b-PEG.
6. preparation method according to claim 4, the polyoxyethylene glycol of polycaprolactone, Caffeic acid and different molecular weight that it is characterized in that take different molecular weight is during as monomer, and gained multipolymer is:
Be expressed as PCL-co-PDHCA-b-PEG.
7. the photosensitivity PCL base co-polymer making according to the preparation method described in any one in claim 2～6, is characterized in that, photo-crosslinking all occurs multipolymer under the UV-irradiation of 280nm; Emitting fluorescence under 380nm burst of ultraviolel, has Photoluminescence; Equal degradable under acid, alkali and neutrallty condition, and degradation speed is controlled.
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| CN105384941B (en) * | 2015-12-07 | 2018-04-13 | 江南大学 | A kind of degradable photosensitive phosphate-based copolymer |
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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 |
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