CN105601954A - Preparation method of biological friendly hydrogel with excellent rebound resilience - Google Patents
Preparation method of biological friendly hydrogel with excellent rebound resilience Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/075—Macromolecular gels
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
- C08L29/02—Homopolymers or copolymers of unsaturated alcohols
- C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2329/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2329/02—Homopolymers or copolymers of unsaturated alcohols
- C08J2329/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2471/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
- C08J2471/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Abstract
The invention relates to a preparation method of biological friendly hydrogel with excellent rebound resilience. The hydrogel is formed through a repeated freezing method by introducing octa-ammonium polyhedral oligomeric silsesquioxane and hydroxyl-terminated polyhedral oligomeric silsesquioxane in PVA-PEG gel. The hydrogel has excellent mechanical strength and biocompatibility, the preparation process is simple, and the preparation method can be used for the field of tissue engineering.
Description
Technical field
The invention belongs to the preparation method of hydrogel, particularly relate to a kind of excellent resilience, good biocompatibility and machineThe preparation method of the hydrogel of tool performance.
Background technology
High-molecular gel refers to the system of macromolecular compound and the solvent composition of three-dimensional net structure, macromolecule whereinWith Van der Waals force, chemical bonding force, physics is wound around power, the connections such as hydrogen bond force. Because it is a kind of three-dimensional network stereochemical structure, thereforeIt can not be by dissolution with solvents, is dispersed in solvent simultaneously and can keeps certain shape. Although solvent can not be by three-dimensional netted knotThe macromolecule dissolution of structure, but in macromolecular compound, solvophilic group part can be made macromolecule molten by solvent actionSwollen, this is also the reason that forms high-molecular gel.
Biological medicine gel, taking the control of the simulation to tissue and performance as ultimate aim, to the biology of gelCompatibility, degradability, mechanical property, cell or albumen adhesion, controlled drug release, special selective etc. proposed very highRequirement. In recent years, the synthetic and natural macromolecular of multiple difference is used to the research in this field. Synthetic material is as PLA (PLA),Polyurethane (PU), polyethylene glycol (PEG) etc. has all been used as tissue engineering material and has used. Current biological medicine is also deposited with gelSignificantly not enough, the most outstanding is that its mechanical property is poor, cannot meet for the mould of tissue that has higher-strength requirementPlan demand. How improving the mechanical strength with biocompatibility gel is problem demanding prompt solution. In common high strengthIn gel preparation preparation, three kinds of mode typical cases the most, as dual network gel, topological structure gel and nano-composite gel, whereinNano-composite gel is for adding different nano-substances if clay, imvite etc. are as crosslinking agent or reinforcing agent, and its method is simple, effectFruit significantly, is considered to the preparation method of optimal high-strength gel.
Polyhedral oligomeric silsesquioxane (Polyhedraloligomericsilsesquioxane, POSS) isA novel organic-inorganic nano particle, synthetic first in nineteen forty-six. Propping up at the Air Force Research Laboratory in 1991Hold down, Lichtenhan etc. have prepared a series of POSS with functional group, and use it for high molecular modification. POSS'sGeneral molecular formula is (RSiO1.5)8, the R in formula is organic substituent, can be inertia group and the second such as H, alkyl, arylThiazolinyl, amino isoreactivity group, simultaneously molecule has inorganic skeleton and molecular dimension between 1 ~ 3nm. Inertia group can increaseThe compatibility of large POSS and polymer; Active group can react with polymer or polymer monomer by chemical modification.Owing to thering is these characteristics, so POSS has been a great concern once coming out. And be used to the modification of polymer. And it is nearNian Lai, POSS has been widely used in biological field, and finds to have extraordinary biocompatibility. Meanwhile, POSS is also transportedFor hydrogel be used to improve gel mechanical property, separate swelling speed or by functional introducing hydrogel. AdoptPOSS hybridized hydrogel still has very large development space. In research, POSS added the research of gel to be all limited to the side at POSS in the pastIn chain, introduce reactive group and introduce in gel by reaction as two keys, epoxide group etc., and because most POSS is mono-Body is oil-soluble, only can introduce in gel by the reaction of organic phase, and POSS skewness in gel, cause it poly-Thereby collection has affected the performance of gel, has limited its application.
In the present invention, be matrix gel by the PEG taking freezing polymerization, introducing and matrix have better compatible thereinProperty and interactional POSS particle, obtained POSS hybrid gel. This gel has good mechanical strength, especially hasExcellent resilience. Because of the good biocompatibility that POSS itself has, the potential bioengineering that applies to of this gel eases upRelease field.
Summary of the invention
The object of the invention is the preparation method for a kind of hydrogel is provided, especially provide one to there is better mechanicsThe preparation method of the hydrogel of performance, excellent resilience and biocompatibility.
The object of the invention is to be achieved through the following technical solutions:
One has the friendly hydrogel preparation method of excellent elastic biology, and its preparation process is:
(1) configuration of pre-polymerization liquid: configuration is dissolved with the aqueous solution of finite concentration polyvinyl alcohol (PVA), polyethylene glycol (PEG), at itIn slowly add eight ammonium cage shape silsesquioxanes (Oa-POSS), after stirring, ultrasonic concussion 20min, even to solutionTransparent, after add terminal hydroxy group POSS compound, high-speed stirred after 10 minutes ultrasonic concussion 20min even to system, obtain pre-polymerizationLiquid A.
In pre-polymerization liquid A, the mass concentration of PVA in the aqueous solution between 15%-30%, the quality of PEG in the aqueous solutionConcentration is between 2%-5%, and the consumption of terminal hydroxy group POSS compound is between the 3-6% of PVA quality, eight ammonium cage shape sesquialtersThe consumption of siloxanes is between the 2%-4% of PVA.
(2) pre-polymerization fluid-tight is closed as put into-80 degree liquid nitrogen chilling after container 30 minutes, be transferred under-20 degree environment coldFreeze 24 hours, after be moved to room temperature (20 degree) and thaw for lower 12 hours, repeat above chilling-freeze-thaw process and repeat 5 times.
(3) gel is taken out from container and repeatedly alternately soak unconjugated to remove in gel with deionized water and acetoneMonomer, after obtain final gel with deionized water rinsing with the acetone of removing completely in gel.
Further, the degree of polymerization of described polyvinyl alcohol is between 400-3000, and alcoholysis degree is greater than 98%.
Further, the molecular weight of PEG of the present invention is between 2000-6000.
Further, terminal hydroxy group POSS compound of the present invention is the POSS particle that end group has one or more hydroxyls, is twoPlant i.e. 1, the 2-PropanediollsobutylPOSS(1 of POSS particle, 2-propylene glycol butyl ether POSS) and TMPDiollsobutylPOSS(trimethylolpropane-isobutyl group propane diols POSS) in a kind of or both arbitrary proportion is mixedClose, both molecular structural formulas are as follows:
TMPDiollsobutylPOSS：
R=isobutyl(isobutyl group)
1,2-PropanediollsobutylPOSS：
R=isobutyl(isobutyl group)
Eight ammonium cage shape silsesquioxanes (OaPOSS) of the present invention are hydrophilic monomer, and this POSS monomer is because have a large amount ofThe existence of ammonium, has monomer good water-soluble. Its structural formula is as follows:
Further, described three kinds of different POSS particles all can adopt HybridPlastics to buy product.
Further, the hydrogen between the hydroxyl of the moulding of this gel based on producing in freeze-thaw process between PVA, PEG groupKey active force.
Further, described three kinds of POSS particles are at synthetic effect difference, TMPDiollsobutylPOSS and 1, the 2-of being of gelPropanediollsobutylPOSS, because of the existence of end group diol bond, can mutually do with PVA, PEG matrix in building-up processWith, by freeze-thaw process implementation Hydrogenbond so that POSS particle is combined with strand closely and is realized winding, with realityNow good mechanical property and resilience. Meanwhile, eight ammonium cage shape silsesquioxanes have significantly hydrophilic-lipophile, canEffectively improve the dispersion of terminal hydroxy group POSS in matrix.
Further, prepared gel has good mechanical property and resilience.
In the time that gel swelling rate is 7 times, its hot strength between 64.5-112.5Kpa, elongation at break betweenBetween 267.6%-442.7%, be not compressed to 90% brokenly, be stretched to 300% with interior resilience completely;
In the time that gel swelling rate is 10 times, its hot strength is between 51.6-98.2Kpa, and elongation at break is between 254.3%-Between 474.2%, be not compressed to 90% brokenly, be stretched to 300% with interior resilience completely. While being stretched to 400%, length returns back to formerThe 105%-110% of gel length.
Detailed description of the invention
Below in conjunction with the detailed description of the invention of specific embodiment form, foregoing of the present invention is remake further in detailSet forth, be the restriction to the related scope of the above-mentioned theme of the present invention but should not be construed as following each embodiment, all based on the present inventionThe technology that foregoing is realized all belongs to the scope of the invention.
Embodiment 1
One has the friendly hydrogel preparation method of excellent elastic biology, and its preparation process is:
(1) configuration of pre-polymerization liquid: configuration is dissolved with the aqueous solution of finite concentration PVA, PEG, slowly adds therein eight ammonium cagesShape silsesquioxane (Oa-POSS), ultrasonic concussion 20min after stirring, to solution homogeneous transparent, after add terminal hydroxy group POSSCompound, high-speed stirred after 10 minutes ultrasonic concussion 20min even to system, obtain pre-polymerization liquid A.
In pre-polymerization liquid A, the mass concentration of PVA in the aqueous solution is that the mass concentration of 20%, PEG in the aqueous solution is 3%, endThe consumption of hydroxyl POSS compound is that the consumption of 5%, eight ammonium cage shape silsesquioxane of PVA quality is PVA 3%.
(2) pre-polymerization fluid-tight is closed as put into-80 degree liquid nitrogen chilling after container 30 minutes, be transferred under-20 degree environment coldFreeze 24 hours, after be moved to room temperature (20 degree) and thaw for lower 12 hours, repeat above chilling-freeze-thaw process and repeat 5 times.
(3) gel is taken out from container and repeatedly alternately soak unconjugated to remove in gel with deionized water and acetoneMonomer, after obtain final gel with deionized water rinsing with the acetone of removing completely in gel.
The degree of polymerization of described polyvinyl alcohol is 800, and alcoholysis degree is greater than 98%.
The molecular weight of described PEG is 5000.
Described terminal hydroxy group POSS compound is 1,2-PropanediollsobutylPOSS and TMPDiollsobutylPOSSEqual proportion is mixed.
When the present embodiment gel swelling rate is 7 times, its hot strength is 82.6Kpa, and elongation at break is between 358.4%,Be not compressed to 90% brokenly, be stretched to 300% with interior resilience completely;
When gel swelling rate is 10 times, its hot strength is 68.5Kpa, and elongation at break is between 329.6%, is compressed to 90% notFragmentation, is stretched to 300% with interior resilience completely. While being stretched to 400%, length returns back to 106.5% of former gel length.
Embodiment 2
One has the friendly hydrogel preparation method of excellent elastic biology, and its preparation process is:
(1) configuration of pre-polymerization liquid: configure the certain density PEG aqueous solution, slowly add therein eight ammonium cage shape sesquialter siliconOxygen alkane (OaPOSS), ultrasonic concussion 20min after stirring, to solution homogeneous transparent, after add terminal hydroxy group POSS compound, heightIt is even to system that speed stirs after 10 minutes ultrasonic concussion 20min, obtains pre-polymerization liquid A.
In pre-polymerization liquid A, the mass concentration of PVA in the aqueous solution is that the mass concentration of 25%, PEG in the aqueous solution is 3.5%,The consumption of terminal hydroxy group POSS compound is that the consumption of 4.5%, eight ammonium cage shape silsesquioxane of PVA quality is PVA2.5%。
(2) pre-polymerization fluid-tight is closed as put into-80 degree liquid nitrogen chilling after container 30 minutes, be transferred under-20 degree environment coldFreeze 24 hours, after be moved to room temperature (20 degree) and thaw for lower 12 hours, repeat above chilling-freeze-thaw process and repeat 5 times.
(3) gel is taken out from container and repeatedly alternately soak unconjugated to remove in gel with deionized water and acetoneMonomer, after obtain final gel with deionized water rinsing with the acetone of removing completely in gel.
The degree of polymerization of described polyvinyl alcohol is 800, and alcoholysis degree is greater than 98%.
The molecular weight of described PEG is 4000.
Described terminal hydroxy group POSS compound is TMPDiollsobutylPOSS.
Prepared gel has good mechanical property and resilience.
In the time that gel swelling rate is 7 times, its hot strength is 72.3Kpa, and elongation at break is 321.5%, is compressed to 90%Not broken, be stretched to 300% with interior resilience completely;
In the time that gel swelling rate is 10 times, its hot strength is 56.3Kpa, and elongation at break is 288.5%, is compressed to 90% and does not breakBroken, between tension failure, all can recoil to original length.
Claims (4)
1. have the friendly hydrogel preparation method of excellent elastic biology, its preparation process is:
(1): the configuration of pre-polymerization liquid: configuration is dissolved with the aqueous solution of finite concentration polyvinyl alcohol (PVA), polyethylene glycol (PEG), existWherein slowly add eight ammonium cage shape silsesquioxanes (Oa-POSS), after stirring, ultrasonic concussion 20min, equal to solutionEven transparent, after add terminal hydroxy group POSS compound, high-speed stirred after 10 minutes ultrasonic concussion 20min even to system, obtain pre-Poly-liquid A;
In pre-polymerization liquid A, the mass concentration of PVA in the aqueous solution between 15%-30%, the mass concentration of PEG in the aqueous solutionBetween 2%-5%, the consumption of terminal hydroxy group POSS compound is between the 3-6% of PVA quality, eight ammonium cage shape silsesquioxanesThe consumption of alkane is between the 2%-4% of PVA;
(2): pre-polymerization fluid-tight is closed as put into-80 degree liquid nitrogen chilling after container 30 minutes, be transferred under-20 degree environment freezing 24Hour, after be moved to room temperature (20 degree) and thaw for lower 12 hours, repeat above chilling-freeze-thaw process and repeat 5 times;
(3): gel is taken out from container with deionized water and acetone and repeatedly alternately soaked to remove unconjugated list in gelBody, after obtain final gel with deionized water rinsing with the acetone of removing completely in gel.
2. one as claimed in claim 1 has the friendly hydrogel preparation method of excellent elastic biology, it is characterized in that:The degree of polymerization of described polyvinyl alcohol is between 400-3000, and alcoholysis degree is greater than 98%.
3. one as claimed in claim 1 has the friendly hydrogel of excellent elastic biology, it is characterized in that: described PEGMolecular weight between 2000-6000.
4. one as claimed in claim 1 has the friendly hydrogel of excellent elastic biology, it is characterized in that: described end hydroxylBase POSS compound is 1,2-PropanediollsobutylPOSS(1,2-propylene glycol butyl ether POSS) and TMPDiollsobutylPOSS(trimethylolpropane-isobutyl group propane diols POSS) in a kind of or both arbitrary proportion mix.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107118373A (en) * | 2017-05-27 | 2017-09-01 | 湖北大学 | A kind of POSS PEG hybridized hydrogels, its preparation method and application |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102219938A (en) * | 2010-04-15 | 2011-10-19 | 江南大学 | Preparation method of hydrophobically modified sodium alginate |
| CN103087088A (en) * | 2011-10-28 | 2013-05-08 | 江南大学 | Preparation and applications of novel alkyl cage silsesquioxane nanometer hybrid |
| CN105237925A (en) * | 2015-11-05 | 2016-01-13 | 南京理工大学 | Nanometer bacterial cellulose\polyvinyl alcohol\polyethylene glycol porous composite hydrogel |
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- 2016-01-28 CN CN201610058569.2A patent/CN105601954A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102219938A (en) * | 2010-04-15 | 2011-10-19 | 江南大学 | Preparation method of hydrophobically modified sodium alginate |
| CN103087088A (en) * | 2011-10-28 | 2013-05-08 | 江南大学 | Preparation and applications of novel alkyl cage silsesquioxane nanometer hybrid |
| CN105237925A (en) * | 2015-11-05 | 2016-01-13 | 南京理工大学 | Nanometer bacterial cellulose\polyvinyl alcohol\polyethylene glycol porous composite hydrogel |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107118373A (en) * | 2017-05-27 | 2017-09-01 | 湖北大学 | A kind of POSS PEG hybridized hydrogels, its preparation method and application |
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Application publication date: 20160525 |