CN102492275A - Caffeic acid group polyester composition and preparation method thereof - Google Patents
Caffeic acid group polyester composition and preparation method thereof Download PDFInfo
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- CN102492275A CN102492275A CN201110406984XA CN201110406984A CN102492275A CN 102492275 A CN102492275 A CN 102492275A CN 201110406984X A CN201110406984X A CN 201110406984XA CN 201110406984 A CN201110406984 A CN 201110406984A CN 102492275 A CN102492275 A CN 102492275A
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Abstract
Provided are a caffeic acid group polyester composition and a preparation method thereof. Caffeic acid (3,4-dyhydroxy cinnamic acid) and fatty group oxyacid are used as single bodies, and the caffeic acid group polyester composition containing hydroxyapatite is prepared by adopting an in-situ polymerization method, the hydroxyapatite in the composition is dispersed evenly in a polyester matrix and is high in tensile strength. Simultaneously, compositions with different mechanical properties can be obtained by adjusting proportion of comonomer and content of the hydroxyapatite and can be applied to the field of biomedical materials. The preparation method of the caffeic acid group polyester composition is simple and practical and easy to operate.
Description
Technical field
A kind of coffee acidic group polymer blend and preparation method thereof belongs to technical field of polymer materials.
Background technology
3,4-dihydroxycinnamic acid (DHCA is commonly called as coffic acid); Mainly come from natural phant such as coffee berry, pawpaw, medically have vasodilation, improve effects such as big brain microcirculation and anti-platelet aggregation; Be a kind of very important " vegetalitas monomer ", be used as the medicine of treating disease.Coffic acid belongs to the more function group monomer, and itself and alcohol acid copolymerization can be prepared polyester, and this polyester has better biocompatibility and degradation property.Yet the mechanical property of coffic acid and alcohol acid copolymerization product is not good, and this has limited its Application Areas.
Win 40350 is the important component part of natural bone tissue, has excellent biological compatibility and biological activity, is considered to the most promising ceramic artificial tooth and artificial bone replacing material, often is used as bone alternate material.But its mechanical property is not good, and is easy crisp, poor to load carrying property, can not be suitable for the requirement of bone tissue engineer fully.
At present; Adopt the polymer-modified research of Win 40350 more (" biodegradable polymer/hydroxyapatite composite material progress ", polymer circular, 2009; The 4th phase; 58-63), with Win 40350 and the compound preparation polymkeric substance/apatite composite material of polymkeric substance, the physical and mechanical properties of this material and the biocompatibility of osseous tissue increase.Yet interface adhesion difference between Win 40350 and polymer materials matrix and Win 40350 disperse the inhomogeneous bottleneck that this type of material mechanical performance further improves that becomes in polymeric matrix.
Summary of the invention
Coffic acid 3; The 4-dihydroxycinnamic acid contains two hydroxyls and a carboxylic acid functional; Itself and the aliphatic hydroxyl acid polyester that (comprising 3-hydroxy-propionic acid, 7-hydroxyl enanthic acid, 10-hydroxydecanoic acid, 10-hydroxyl-2-decylenic acid, terminal hydroxy group laurostearic acid), copolymerization obtained; Because the number of hydroxyl is more than the carboxylic acid functional number in the reaction monomers, so, a large amount of hydroxyls still contained in the polyester.As everyone knows; Hydroxyapatite surface also contains abundant hydroxyl; If it is Win 40350 and coffic acid polyester is compound; The interface adhesion difference and the Win 40350 that will overcome between Win 40350 and polymer materials matrix disperse problems such as inhomogeneous in polymeric matrix, increase substantially the mechanical property of polymer materials.
Based on above reason, the inventor has developed a kind of coffee acidic group polymer blend that contains Win 40350 through situ aggregation method.Win 40350 is uniformly dispersed in the coffee acid based polyester in the said composition, and its tensile strength is high.
In preparation caffeic acid composition process of the present invention, the processing that Win 40350 need not carry out any prior art just can be uniformly dispersed in the coffee acid based polyester, the simple easy handling of technology.
Therefore, the purpose of this invention is to provide the coffee acidic group polymer blend that contains Win 40350, it has good tensile.
Another object of the present invention provides said preparation of compositions method.
A kind of coffee acidic group polymer blend of the present invention is characterized in that including in this kind polymer blend the following component of blend: coffee acid based polyester and Win 40350; The weight ratio of Win 40350 and coffee acid based polyester is (0.5～150): 100, preferred (2～100): 100, more preferably (5～80): 100; The coffee acid based polyester is obtained by coffic acid and aliphatic hydroxyl acid copolymerization, and coffic acid is 1 with the sour mol ratio of aliphatic hydroxyl: (0.1～5), preferred 1: (0.2～4), more preferably 1: (0.4～3); Aliphatic hydroxyl acid can be at least a in 3-hydroxy-propionic acid, 7-hydroxyl enanthic acid, 10-hydroxydecanoic acid, 10-hydroxyl-2-decylenic acid, the terminal hydroxy group laurostearic acid.
Compsn is catalyzer with the sodium acetate among the present invention, and diacetyl oxide is a solvent, adopts the progressively method acquisition of polycondensation of original position; Its concrete grammar is: catalyst consumption is the 1mol% of coffic acid amount; The consumption of solvent is 5～10 times of total monomer weight, takes by weighing coffic acid, aliphatic hydroxyl acid, Win 40350, solvent and catalyzer by proportioning and places reactor drum, after stirring makes monomer be dissolved in solvent; With mixing solutions ultra-sonic dispersion 30～60min; Continue to stir 10min, be warming up to 140～160 ℃ again, reaction 1-2h; Under agitation be warmed up to then between 190～200 ℃, behind sustained reaction 6～12h, stop heating again, cooling; Whole progressively polycondensation process is carried out under the condition of nitrogen and lucifuge; After reaction finishes, obtain polymer blend through washing, purifying.
Beneficial effect of the present invention: Win 40350 is uniformly dispersed in polyester matrix in the coffee acidic group polymer blend of the present invention; Its tensile strength is high; Simultaneously, can also obtain the compsn of different mechanical properties through adjustment comonomer proportioning and Win 40350 content; Said composition can be used for biomedical materials field.
The preparation method of coffee acidic group polymer blend provided by the present invention is simple, easy handling.
The subordinate list explanation
Fig. 1 is the section SEM scintigram of embodiment 2.Circular white portion is the Win 40350 particle among the figure, and visible Win 40350 particle is uniformly dispersed in polymeric matrix.
Embodiment
Comparative example 1
Take by weighing coffic acid 90g (0.5mol), terminal hydroxy group laurostearic acid 64.8g (0.3mol), sodium acetate 0.45g (5mmol); Diacetyl oxide 1.2L joins in the 2L reaction kettle, under agitation is warming up to 140 ℃; Behind the reaction 1h; Be warming up to 190 ℃ gradually, stirring, isothermal reaction 6h, entire reaction is carried out under nitrogen protection and lucifuge condition.Reactant is with deionized water wash twice, and redeposition twice in ethanol, at 30 ℃ of following freeze-day with constant temperature, obtains polymerisate then.Gained coffic acid acid based polyester carries out hot pressing and colds pressing through vulcanizing press, carries out cutting preparation standard batten again, carries out the tensile property test.Its result sees table 1.
Embodiment 1
Take by weighing coffic acid 90g (0.5mol), terminal hydroxy group laurostearic acid 64.8g (0.3mol), sodium acetate 0.45g (5mmol), diacetyl oxide 1.3L; Win 40350 15.5g joins in the 2L reaction kettle, after stirring makes monomer be dissolved in solvent, with mixing solutions ultra-sonic dispersion 30min; Continue to stir 10min, be warming up to 140 ℃ again, behind the reaction 1h; Be warming up to 190 ℃ gradually, stirring, isothermal reaction 6h, entire reaction is carried out under nitrogen protection and lucifuge condition.Reactant is with deionized water wash twice, and redeposition twice in ethanol, at 30 ℃ of following freeze-day with constant temperature, obtains polymerisate then.Gained coffic acid acid based polyester compsn carries out hot pressing and colds pressing through vulcanizing press, carries out cutting preparation standard batten again, carries out the tensile property test.Its result sees table 1.
Embodiment 2
Except described Win 40350 add-on is the 31g, all the other conditions are all identical with embodiment 1.Gained coffic acid acid based polyester compsn carries out the tensile property test through hot-forming preparation standard batten.Its result sees table 1.
Embodiment 3
Except described Win 40350 add-on is the 46.5g, all the other conditions are all identical with embodiment 1.Gained coffic acid acid based polyester compsn carries out the tensile property test through hot-forming preparation standard batten.Its result sees table 1.
Table 1
Comparative example 2
Take by weighing coffic acid 18g (0.1mol), 7-hydroxyl enanthic acid 73g (0.5mol), sodium acetate 0.09g (1mmol); Diacetyl oxide 1.1L joins in the 2L reaction kettle, under agitation is warming up to 160 ℃; Behind the reaction 1h; Be warming up to 200 ℃ gradually, stirring, isothermal reaction 10h, entire reaction is carried out under nitrogen protection and lucifuge condition.Reactant is with deionized water wash twice, and redeposition twice in ethanol, at 30 ℃ of following freeze-day with constant temperature, obtains polymerisate then.Gained coffic acid acid based polyester carries out hot pressing and colds pressing through vulcanizing press, carries out cutting preparation standard batten again, carries out the tensile property test.Its result sees table 2.
Embodiment 4
Take by weighing coffic acid 18g (0.1mol), 7-hydroxyl enanthic acid 73g (0.5mol), sodium acetate 0.09g (1mmol), diacetyl oxide 1.1L; Win 40350 9.1g joins in the 2L reaction kettle, after stirring makes monomer be dissolved in solvent, with mixing solutions ultra-sonic dispersion 30min; Continue to stir 10min, be warming up to 160 ℃ again, behind the reaction 1h; Be warming up to 200 ℃ gradually, stirring, isothermal reaction 10h, entire reaction is carried out under nitrogen protection and lucifuge condition.Reactant is with deionized water wash twice, and redeposition twice in ethanol, at 30 ℃ of following freeze-day with constant temperature, obtains polymerisate then.Gained coffic acid acid based polyester compsn carries out hot pressing and colds pressing through vulcanizing press, carries out cutting preparation standard batten again, carries out the tensile property test.Its result sees table 2.
Embodiment 5
Except described Win 40350 add-on is the 27.3g, all the other conditions are all identical with embodiment 4.Gained coffic acid acid based polyester compsn carries out the tensile property test through hot-forming preparation standard batten.Its result sees table 2.
Embodiment 6
Except described Win 40350 add-on is the 63.7g, all the other conditions are all identical with embodiment 4.Gained coffic acid acid based polyester compsn carries out the tensile property test through hot-forming preparation standard batten.Its result sees table 2.
Table 2
Comparative example 3
Take by weighing coffic acid 144g (0.8mol), 10-hydroxyl-2-decylenic acid 18.8g (0.1mol), sodium acetate 0.72g (8mmol); Diacetyl oxide 1.2L joins in the reaction kettle, under agitation is warming up to 140 ℃; Behind the reaction 2h; Be warming up to 190 ℃ gradually, stirring, isothermal reaction 8h, entire reaction is carried out under nitrogen protection and lucifuge condition.Reactant is with deionized water wash twice, and redeposition twice in ethanol, at 30 ℃ of following freeze-day with constant temperature, obtains polymerisate then.Gained coffic acid acid based polyester carries out hot pressing and colds pressing through vulcanizing press, carries out cutting preparation standard batten again, carries out the tensile property test.Its result sees table 3.
Embodiment 7
Take by weighing coffic acid 144g (0.8mol), 10-hydroxyl-2-decylenic acid 18.8g (0.1mol), sodium acetate 0.72g (8mmol), diacetyl oxide 1.2L; Win 40350 8.14g joins in the 2L reaction kettle, after stirring makes monomer be dissolved in solvent, with mixing solutions ultra-sonic dispersion 30min; Continue to stir 10min, under agitation be warming up to 140 ℃, behind the reaction 2h; Be warming up to 190 ℃ gradually, stirring, isothermal reaction 8h, entire reaction is carried out under nitrogen protection and lucifuge condition.Reactant is with deionized water wash twice, and redeposition twice in ethanol, at 30 ℃ of following freeze-day with constant temperature, obtains polymerisate then.Gained coffic acid acid based polyester carries out hot pressing and colds pressing through vulcanizing press, carries out cutting preparation standard batten again, carries out the tensile property test.Its result sees table 3.
Embodiment 8
Except described Win 40350 add-on is the 16.3g, all the other conditions are all identical with embodiment 7.Gained coffic acid acid based polyester compsn carries out the tensile property test through hot-forming preparation standard batten.Its result sees table 3.
Embodiment 9
Except described Win 40350 add-on is the 32.6g, all the other conditions are all identical with embodiment 7.Gained coffic acid acid based polyester compsn carries out the tensile property test through hot-forming preparation standard batten.Its result sees table 3.
Table 3
Claims (3)
1. a coffee acidic group polymer blend is characterized in that containing following component: coffee acid based polyester and Win 40350; The weight ratio of Win 40350 and coffee acid based polyester is (0.5～150): 100, preferred (2～100): 100, more preferably (5～80): 100; The coffee acid based polyester is obtained by coffic acid and aliphatic hydroxyl acid copolymerization, and coffic acid is 1 with the sour mol ratio of aliphatic hydroxyl: (0.1～5), preferred 1: (0.2～4), more preferably 1: (0.4～3).
2. coffee acidic group polymer blend according to claim 1 is characterized in that with the sodium acetate being catalyzer, and diacetyl oxide is a solvent, adopts progressively polycondensation method acquisition of original position; Concrete preparation method is: catalyst consumption is the 1mol% of coffic acid amount, and the consumption of solvent is 5～10 times of total monomer weight, takes by weighing coffic acid, aliphatic hydroxyl acid, Win 40350, solvent and catalyzer by proportioning and places reactor drum; After stirring makes monomer be dissolved in solvent,, continue to stir 10min with mixing solutions ultra-sonic dispersion 30～60min; Be warming up to 140～160 ℃ again, reaction 1-2h under agitation is warmed up between 190～200 ℃ then; Behind sustained reaction 6～12h, stop heating, cooling; Whole progressively polycondensation process is carried out under the condition of nitrogen and lucifuge, after reaction finishes, obtains polymer blend through washing, purifying.
3. according to the described coffee acidic group of claim 1～2 polymer blend, its tensile strength is high, simultaneously, can also obtain the compsn of different mechanical properties through adjustment comonomer proportioning and Win 40350 content, and said composition is used for biomedical materials field.
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| CN201110406984XA CN102492275A (en) | 2011-12-09 | 2011-12-09 | Caffeic acid group polyester composition and preparation method thereof |
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| CN201110406984XA CN102492275A (en) | 2011-12-09 | 2011-12-09 | Caffeic acid group polyester composition and preparation method thereof |
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Citations (2)
| 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 |
| CN101787115A (en) * | 2009-12-28 | 2010-07-28 | 江南大学 | Method for preparing photoactive ternary amphiphilic polyester |
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- 2011-12-09 CN CN201110406984XA patent/CN102492275A/en active Pending
Patent Citations (2)
| 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 |
| CN101787115A (en) * | 2009-12-28 | 2010-07-28 | 江南大学 | Method for preparing photoactive ternary amphiphilic polyester |
Non-Patent Citations (1)
| Title |
|---|
| 李海东等: "PVA/HA复合水凝胶的制备及性能研究", 《长春工业大学学报（自然科学版）》 * |
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Application publication date: 20120613 |