CN101230116A - Intelligent material and method for manufacturing same - Google Patents
Intelligent material and method for manufacturing same Download PDFInfo
- Publication number
- CN101230116A CN101230116A CNA2007100368969A CN200710036896A CN101230116A CN 101230116 A CN101230116 A CN 101230116A CN A2007100368969 A CNA2007100368969 A CN A2007100368969A CN 200710036896 A CN200710036896 A CN 200710036896A CN 101230116 A CN101230116 A CN 101230116A
- Authority
- CN
- China
- Prior art keywords
- base polymer
- acetalation
- enol base
- enol
- intelligent material
- 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.)
- Pending
Links
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention relates to intelligent material, namely, acetalation enol polymer which is sensitive to the temperature. The acetalation enol polymer is homopolymer or copolymer containing enol polymer monomer units. A manufacture method of the intelligent material comprises the step that the acetalation is performed to the corresponding enol polymer under the condition of acid catalysis through the aldehyde substances to obtain the acetalation enol polymer. For the intelligent material of the invention, when the temperature changes between 1 and 90 DEG C, reversible opposite phase transformation happens on the aqueous solution, the capsule, the micro-gel or the aquogel of the intelligent material, namely, when the temperature of the aqueous solution of the polymer is risen, the water soluble polymer is transformed into the water insoluble polymer; when the temperature of the gel of the polymer is risen, the swelling state is transformed into the shrinking state; when the temperature of the microcapsule of the polymer is risen, the surface of the microcapsule is shrunk and voids occurs on the surface. After the temperature is reduced, the process can return to the original state. Compared with other temperature sensitive polymer, the intelligent material of the invention has the advantages that the raw material is easy to be obtained, and the biological compatibility is good.
Description
Technical field
The present invention relates to a kind of biochemical material and manufacture method thereof, relate in particular to a kind of thermally sensitive intelligent material and manufacture method thereof.
Background technology
The polymkeric substance of temperature response is a class very big in the intelligent macromolecule material.(N-isopropylacrylamide NIPAM) is the maximum temperature sensitive polymkeric substance of research to poly N-isopropyl acrylamide, and the LCST of its aqueous solution (low critical solution temperature) is 31 ℃.Its structure and acrylamide are similar, and therefore a lot of performances are also similar with acrylamide.With the polymkeric substance of NIPAM similar, also have LCST as poly-N-isopropyl Methacrylamide, poly-N-isopropyl ethyl acrylamide, show the feature of temperature response.The LCST transition temperature of poly-N-isopropyl Methacrylamide is at 39-47 ℃, and the LCST transition temperature of poly-N-isopropyl ethyl acrylamide is at 78 ℃.But above-mentioned polyacrylamide temperature responsive polymer not only costs an arm and a leg, and monomer whose is suspicious carcinogenic substance and neurotoxin.
Except that above-mentioned acrylamide copolymer shows temperature sensitive characteristic, Vinylcaprolactam homopolymer { poly (N-vinyl caprolactam), PVCL}, poly-ethyl-methyl ether { poly (vinyl methyl ether), (methylhydroxypropylcellulose MHPC) waits polymkeric substance also to show temperature sensitive characteristic for PVME}, hydroxymethyl-propyl cellulose.
Studies show that polyvinylacetal also has temperature sensitivity, but prior art only limits to linear polyvinylacetal to the research of the temperature sensitivity of polyvinylacetal, thereby temperature sensitivity and Modulatory character are very restricted all.
Summary of the invention
Purpose of the present invention is to provide a kind of new thermally sensitive intelligent material and manufacture method thereof.
The object of the present invention is achieved like this: a kind of intelligent material, be thermally sensitive acetalation enol base polymer, described acetalation enol base polymer is the polymkeric substance that contains enol base polymer monomeric unit, and described enol base polymer monomeric unit has following structure:
Wherein, X is hydroxyl, acryl or methacryloyl; Y is methyl, ethyl, propyl group, butyl, amyl group, heptyl or phenmethyl; M, n, p, q are natural number.
Described acetalation enol base polymer is the homopolymer that contains enol base polymer monomeric unit.
Described acetalation enol base polymer is the multipolymer that contains enol base polymer monomeric unit, and comonomer is selected from a kind of in vinylformic acid, methacrylic acid, N-acrylic-amino acetate, 2-amino-ethyl methacrylic acid ester hydrochloride, diallyldimethylammonium chloride and the quaternary amine.
The polymerization degree of described enol base polymer is 250-5000, and alcoholysis degree is 60-100mol%.
Described acetalation enol base polymer is a linear contraction hydroformylation enol base polymer, and this linear contraction hydroformylation enol base polymer is water-soluble below the LCST temperature, and concentration of aqueous solution is controlled at 0.01-50wt%.
Described acetalation enol base polymer is crosslinked acetalation enol base polymer, and this crosslinked acetalation enol base polymer is a gel.
A kind of manufacture method of intelligent material makes corresponding enol base polymer acetalation obtain acetalation enol base polymer under the acid catalysis condition by aldehyde material, and concrete steps comprise:
A) preparation enol base polymer and in 60-90 ℃ water, make the 1-30wt% aqueous solution;
B) pH＜3 of usefulness acid-conditioning solution;
C) add aldehyde material, enol base polymer and aldehyde were reacted 0.5-24 hour down at 1-80 ℃, obtain reaction product acetalation enol base polymer;
D) heat up make reaction product acetalation enol base polymer precipitation or by dialysis to obtain the purified product of acetalation enol base polymer.
Described aldehyde material be selected from formaldehyde, acetaldehyde, propionic aldehyde, butyraldehyde, enanthaldehyde, phenyl aldehyde, oxalic dialdehyde, in the glutaraldehyde one or more.
The acetal degree of described enol base polymer is controlled at 0-80mol% by the consumption that changes the aldehyde of participating in acetalation.
Intelligent material of the present invention---acetalation enol base polymer is the polymkeric substance that contains enol base polymer monomeric unit, and the enol base polymer is a kind of from vinyl acetate and derivative thereof, multipolymer hydrolysis and the water-soluble polymers that obtains.It is not only cheap, and raw material is easy to get, and has favorable biological degradability, biocompatibility and good film-forming properties, toughness, becomes a kind of ideal bio-medical material day by day.As drug sustained release system, artificial cartilage material, ophthalmology, artificial cell microencapsulation, anticoagulant material, bio-medical sponge etc.
Intelligent acetalation enol base polymer of the present invention can be the multipolymer that contains vinyl alcohol units, and salt kind and concentration in the kind of the molecular weight that the LCST of its aqueous solution can be by initial enol base polymer, acetal degree, comonomer and quantity, the solution are effectively regulated and control in 1-90 ℃ of scope.
When identical degree of acetalization, the molecular weight of initial enol base polymer is big more, and the LCST of acetalation enol base polymer is low more; The initial enol base polymer of same molecular amount, LCST increases and reduces along with degree of acetalization.Many water-soluble monomers all can be used to and the copolymerization of enol base polymer, and comonomer commonly used comprises charged monomers such as vinylformic acid (AA), methacrylic acid (MAA), N-acrylic-amino acetate (N-acryloylglycine), 2-amino-ethyl methacrylic acid ester hydrochloride (2-aminoethylmethacrylate hydrochloride), diallyl dimethyl ammonium chlorine.Copolymerization not only can change LCST transition temperature, intensity and the sensitivity of polymkeric substance, but also can prepare have temperature simultaneously, the polymkeric substance of pH, ionic strength response.For example, the LCST of the unitary acetalation enol-acrylic copolymer of band carboxyl changes relevant with the pH of the aqueous solution, and carboxyl is ionized in alkaline environment, and copolymer sheet reveals higher LCST, and in the acidic medium, the LCST of multipolymer reduces.
The enol base polymer shows low critical solution temperature (LCST), promptly anti-phase temperature transition at aqueous phase after the acetalation modification.Below the LCST temperature, linear contraction hydroformylation enol base polymer is water-soluble, and to be elevated to the LCST temperature then no longer water-soluble when above when temperature, but separate from water.Usually the concentration of aqueous solution with linear contraction hydroformylation enol base polymer is controlled at 0.01-50wt%.When temperature when 1-90 ℃ changes, the linear contraction hydroformylation enol base polymer aqueous solution of temperature response takes place along with temperature raises anti-phasely to change mutually.Promptly this polymkeric substance is water-soluble when low temperature, and temperature rising post polymerization thing is separated out from water, changes insoluble polymer into by water-soluble polymers.When temperature returned to low temperature, polymkeric substance was soluble in water again, showed the reversible temperature-responsive.
Crosslinked acetalation enol base polymer gel is in the swelling state of suction below the LCST temperature, more than the LCST temperature, its gel is deviate from water, and volumetric shrinkage is dewatering state.
When temperature when 1-90 ℃ changes, volumetric shrinkage takes place in the crosslinked acetalation enol base polymer gel of temperature response along with temperature raises.Promptly this polymer gel is in the swelling state of suction when low temperature, and after temperature raise, the gel dehydration changed contraction schedule into, and volume reduces.When temperature returned to low temperature, the gel swelling that absorbs water again showed the reversible temperature-responsive.
When temperature when 1-90 ℃ changes, the crosslinked acetalation enol base polymer capsule of temperature response is along with temperature raises, capsule surface is shunk and hole occurred.When temperature returned to low temperature, the capsule surface hole disappeared, and shows the reversible temperature-responsive.
But acetalation enol base polymer is widely used high-tech sectors such as the intelligent fixedization of its high efficiency separation at molecular device, light control material, biologically active substance, enzyme and cell and medicine sustained release to the reverse response of external irritant.For example, if be assembled in medicine on the water-soluble linear contraction hydroformylation enol base polymer or when being wrapped in acetalation enol base polymer gel/capsule, when temperature was higher than its LCST phase transition temperature, its linear polymer was separated out from aqueous phase and accumulated in appointed part; Its gel/capsule shrinks, at the appointed time, appointed part discharges medicine with specified speed, reaches the raising utilization ratio of drug, reduces the purpose of medicine to the toxic side effect of health.
Embodiment
Embodiment 1
The Diisopropyl azodicarboxylate initiator that in the methanol solution of 90mol% vinyl acetate (VAc) and 10mol% diallyl dimethyl ammonium chlorine (DADMAC) mix monomer, adds 0.04wt%, 70 ℃ of following polymerizations 5 hours, preparation VAc-co-DADMAC multipolymer.Then drip the aqueous sodium hydroxide solution of 2M, make the VAc complete hydrolysis.Hydrolysate with in the HCl solution of 1M and after the dialysis 24 hours of packing in the dialysis membrane, obtain purified vinyl alcohol-diallyldimethylammonium chloride multipolymer (VA-co-DADMAC).
The concentrated hydrochloric acid that in the VA-co-DADMAC of 100g 2.5wt% aqueous copolymers solution, adds 2ml 37wt%, the cooling back drips 0.5g acetaldehyde in the ice-water bath, be warmed up to 40 ℃ of reactions 6 hours then, add the 1M aqueous sodium hydroxide solution pH=7 that neutralizes again, reaction product is packed into, and dialysis obtained purified linear contraction hydroformylation VA-co-DADMAC in 48 hours in the dialysis membrane, was a kind of intelligent material of the present invention.After tested, its LCST transition temperature in the 0.1M of the 0.5wt% NaCl aqueous solution is 37 ℃.
Embodiment 2
(polymerization degree is 1700 at the polyvinyl alcohol of 100g 2.5wt%, degree of hydrolysis is 99%) add the concentrated hydrochloric acid of 2ml 37wt% in the aqueous solution, the cooling back drips the 0.25g butyraldehyde in the ice-water bath, reaction is 6 hours under the room temperature, with in the NaOH aqueous solution of 1M and after the dialysis membrane 48h that dialyses that packs into obtain purified polyvinyl butyral acetal (PVB).PVB and polyacrylic acid (Mw=10, the 000) aqueous solution is poured on makes film on the flat board, be warming up to the film that 180 ℃ of vacuum hydro-extraction polycondensations obtain chemically crosslinked behind the film drying, be a kind of intelligent material of the present invention.After tested, the LCST transition temperature of this film is 45 ℃, when aqueous temperature is higher than 45 ℃, occurs micropore on the film; When temperature was lower than 45 ℃, micropore disappeared to reply again and is uniform thin film.
Embodiment 3
The Diisopropyl azodicarboxylate initiator that in the methanol solution of 85mol% vinyl acetate (VAc) and 15mol% vinylformic acid (AA) mix monomer, adds 0.02wt%, 70 ℃ of following polymerizations 5 hours, preparation VAc-co-AA multipolymer.Then drip the aqueous sodium hydroxide solution of 2M, make the VAc complete hydrolysis.Hydrolysate with in the HCl solution of 1M and after the dialysis 24 hours of packing in the dialysis membrane, obtain purified vinyl alcohol-acrylic copolymer (VA-co-AA).
The concentrated hydrochloric acid that in the VA-co-AA of 100g 10wt% aqueous copolymers solution, adds 2ml 37wt%, the cooling back drips 0.2g acetaldehyde and 0.2g glutaraldehyde in the ice-water bath, mix back ultrasonic degas 10min under 5 ℃, be warmed up to 40 ℃ of reactions 6 hours then, add the 1M aqueous sodium hydroxide solution pH=7 that neutralizes again, reaction product is dialysed in deionized water and is obtained purified acetalation VA-co-AA copolymer gel a week, is a kind of intelligent material of the present invention.After tested, the LCST transition temperature of this gel in the 0.2M NaCl aqueous solution is 32 ℃, is in the suction state below 32 ℃, and gel is sloughed part moisture content more than 32 ℃.
Claims (9)
1. intelligent material, it is characterized in that: described intelligent material is thermally sensitive acetalation enol base polymer, described acetalation enol base polymer is the polymkeric substance that contains enol base polymer monomeric unit, and described enol base polymer monomeric unit has following structure:
Wherein, X is hydroxyl, acryl or methacryloyl; Y is that methyl, ethyl, propyl group, butyl, amyl group, heptyl or phenmethyl m, n, p, q are natural number.
2. intelligent material as claimed in claim 1 is characterized in that: described acetalation enol base polymer is the homopolymer that contains enol base polymer monomeric unit.
3. intelligent material as claimed in claim 1, it is characterized in that: described acetalation enol base polymer is the multipolymer that contains enol base polymer monomeric unit, and comonomer is selected from a kind of in vinylformic acid, methacrylic acid, N-acrylic-amino acetate, 2-amino-ethyl methacrylic acid ester hydrochloride, diallyldimethylammonium chloride and the quaternary amine.
4. intelligent material as claimed in claim 1 is characterized in that: the polymerization degree of described enol base polymer is 250-5000, and alcoholysis degree is 60-100mol%.
5. intelligent material as claimed in claim 1, it is characterized in that: described acetalation enol base polymer is a linear contraction hydroformylation enol base polymer, this linear contraction hydroformylation enol base polymer is water-soluble below the LCST temperature, and concentration of aqueous solution is controlled at 0.01-50wt%.
6. intelligent material as claimed in claim 1 is characterized in that: described acetalation enol base polymer is crosslinked acetalation enol base polymer, and this crosslinked acetalation enol base polymer is a gel.
7. the manufacture method of an intelligent material, it is characterized in that: make corresponding enol base polymer acetalation obtain acetalation enol base polymer under the acid catalysis condition by aldehyde material, concrete steps comprise:
A) preparation enol base polymer and in 60-90 ℃ water, make the 1-30wt% aqueous solution;
B) pH＜3 of usefulness acid-conditioning solution;
C) add aldehyde material, enol base polymer and aldehyde were reacted 0.5-24 hour down at 1-80 ℃, obtain reaction product acetalation enol base polymer;
D) heat up make reaction product acetalation enol base polymer precipitation or by dialysis to obtain the purified product of acetalation enol base polymer.
8. the manufacture method of intelligent material as claimed in claim 7 is characterized in that: described aldehyde material be selected from formaldehyde, acetaldehyde, propionic aldehyde, butyraldehyde, enanthaldehyde, phenyl aldehyde, oxalic dialdehyde, in the glutaraldehyde one or more.
9. the manufacture method of intelligent material as claimed in claim 7 is characterized in that: the acetal degree of described enol base polymer is controlled at 0-80mol% by the consumption that changes the aldehyde of participating in acetalation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007100368969A CN101230116A (en) | 2007-01-26 | 2007-01-26 | Intelligent material and method for manufacturing same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007100368969A CN101230116A (en) | 2007-01-26 | 2007-01-26 | Intelligent material and method for manufacturing same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101230116A true CN101230116A (en) | 2008-07-30 |
Family
ID=39896966
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2007100368969A Pending CN101230116A (en) | 2007-01-26 | 2007-01-26 | Intelligent material and method for manufacturing same |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101230116A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111184917A (en) * | 2020-02-27 | 2020-05-22 | 福州大学 | Temperature-sensitive collagen-based hydrogel loaded with bioactive polypeptide and preparation method thereof |
| CN115838485A (en) * | 2023-02-21 | 2023-03-24 | 广东工业大学 | Temperature self-adaptive hydrogel intelligent window based on modified polyvinyl alcohol gel material |
-
2007
- 2007-01-26 CN CNA2007100368969A patent/CN101230116A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111184917A (en) * | 2020-02-27 | 2020-05-22 | 福州大学 | Temperature-sensitive collagen-based hydrogel loaded with bioactive polypeptide and preparation method thereof |
| CN111184917B (en) * | 2020-02-27 | 2021-09-28 | 福州大学 | Temperature-sensitive collagen-based hydrogel loaded with bioactive polypeptide and preparation method thereof |
| CN115838485A (en) * | 2023-02-21 | 2023-03-24 | 广东工业大学 | Temperature self-adaptive hydrogel intelligent window based on modified polyvinyl alcohol gel material |
| CN115838485B (en) * | 2023-02-21 | 2023-10-24 | 广东工业大学 | Temperature self-adaptive hydrogel intelligent window based on modified polyvinyl alcohol gel material |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Liu et al. | Preparation and swelling properties of crosslinked sodium polyacrylate | |
| CN1304441C (en) | Direct synthesis of temperate sensitive aquogel by ultraviolet radiant polymerization | |
| US20080112984A1 (en) | Novel Hydrogels Based On Polyvinyl Alcohols And Polyvinyl Alcohol Copolymers | |
| Brannon-Peppas | Preparation and characterization of crosslinked hydrophilic networks | |
| CN100556924C (en) | The preparation method of temperature and pH value valve sensitive nano microgel | |
| EP0434438B1 (en) | Hydrolytically degradable hydrophilic gels and the method for preparation thereof | |
| AU2004233805B2 (en) | Formation of strong superporous hydrogels | |
| US3931123A (en) | Hydrophilic nitrite copolymers | |
| US20070293651A1 (en) | Process for Producing Polyvinyl Acetal Resin, Polyvinyl Butyral Resin, and Process for Producing Esterified Polyvinyl Alcohol Resin | |
| CN1974608A (en) | Electronic beam radiopolymerization process of directly synthesizing temperature sensitive hydrogel | |
| JP2006523733A5 (en) | ||
| CN101608021A (en) | Preparation method of N-isopropyl acrylamide polymer compound/polyvinyl alcohol composite hydrogel and products thereof | |
| CN101891946B (en) | Enhanced biological hydrogel having DN-L structure and preparation method thereof | |
| Reddy et al. | Simultaneous and sequential micro-porous semi-interpenetrating polymer network hydrogel films for drug delivery and wound dressing applications | |
| Gürdağ et al. | Synthesis and Characterization of Novel Poly (N-isopropylacrylamide-co-N, N′-dimethylaminoethyl methacrylate sulfate) Hydrogels | |
| CN105254932A (en) | Interpenetrating network hydrogel based on alginic acid and oligopeptide and preparation method thereof | |
| CN101230116A (en) | Intelligent material and method for manufacturing same | |
| CN105175752A (en) | Multi-responsive pNIPAAm (poly(N-isopropylacrylamide))/(mPEG-g-CMCS) (methoxy polyethylene glycol-g-carboxymethyl chitosan) aquagel | |
| Pulat et al. | Fluconazole release through semi‐interpenetrating polymer network hydrogels based on chitosan, acrylic acid, and citraconic acid | |
| CN104693347A (en) | Metal ion cross-linked nanogel with zwitter-ion structure and preparing method thereof | |
| CN1212124C (en) | Preparation for injecting temperature sensitive gelatin embolism material | |
| Bell et al. | Swelling/syneresis phenomena in gel-forming interpolymer complexes | |
| Cai et al. | Poly (N-ethylacrylamide) hydrogels for lignin separation | |
| CN106492659A (en) | A kind of temperature and pH double-bang firecrackers answer PVDF semi-interpenetrating network polymer films and preparation method thereof | |
| CN101301590B (en) | Sugar-containing polymer compound film with blocked pore and preparation thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Open date: 20080730 |