CN102382267B - Method for preparing interpenetrating network intelligent hydrogel by adopting frontal polymerization - Google Patents
Method for preparing interpenetrating network intelligent hydrogel by adopting frontal polymerization Download PDFInfo
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- CN102382267B CN102382267B CN 201110235721 CN201110235721A CN102382267B CN 102382267 B CN102382267 B CN 102382267B CN 201110235721 CN201110235721 CN 201110235721 CN 201110235721 A CN201110235721 A CN 201110235721A CN 102382267 B CN102382267 B CN 102382267B
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Abstract
A method for preparing interpenetrating network intelligent hydrogel by adopting frontal polymerization belongs to the technical field of functional high-polymer material preparation. The specific process is as follows: sensitive monomer, cross-linking agent, initiator and linear polymer are dissolved into dimethylsulfoxide or dimethylformamide solvent, the solution is added into a cylindrical polymerizer in certain size, one end of the reactor is heated to initiate polymerization reaction, the heat source is then removed, the polymerization heat produced by the reaction is utilized to initiate reaction layer by layer until the monomer in the whole reactor is completely polymerized, the product is taken out and immersed in deionized water, and after drying, the interpenetrating network intelligent hydrogel is obtained. The method has the advantages that: the process is simple, energy consumption is low, moreover, the structure of the prepared interpenetrating network intelligent hydrogel is uniform, the strength of the water-saturated hydrogel can reach 600KPa.
Description
Technical field
The invention belongs to the functional high molecule material preparing technical field, particularly a kind of method that adopts the ripple polymerization to prepare the interpenetrating(polymer)networks intelligent aqueous gel capable.
Background technology
Intelligent aqueous gel capable is that a class is stimulated by the small physics and chemistry of external environment, such as temperature, pH value, salt concn, light, electric field, chemical substance etc., the macromolecule hydrogel that obviously changes will occur in himself character, also often is called as sensitive hydrogel and stimuli responsive hydrogel.The These characteristics of intelligent aqueous gel capable makes its high-technology field such as intelligent immobilization, artificial muscle and light control material at drug controllable release, molecular separation, chemical transformation device, chemical storage device, memory switch, sensor, enzyme and cell that broad research and application prospect be arranged.
The drawbacks limit that the intelligent aqueous gel capable gel-strength is low its practical application, for improving the gel-strength of intelligent aqueous gel capable, Chinese scholars has been carried out many-sided research, find that two or more polymkeric substance forms the interpenetrating(polymer)networks intelligent aqueous gel capable by the network entanglement, can improve the mechanical property of hydrogel; Simultaneously, the peculiar interaction energy that forces of interpenetrating(polymer)networks impels two kinds to have difference in functionality or the very large stable combination of polymer formation of performance difference, from and realize the complementation of function between the component or performance.
In the preparation process of traditional interpenetrating(polymer)networks intelligent aqueous gel capable, polyreaction occurs simultaneously at each position of reactor, can discharge simultaneously a large amount of reaction heat concerning thermopositive reaction.Sudden and violent poly-for fear of generation, reaction must be carried out under low monomer and initiator concentration, therefore needs long-time continuous heating ability synthetic product.Yet long-time polymerization easily causes out of phase separation and segregation in the polymkeric substance, affects homogeneity and the use properties of product structure.Although the report that adopts photopolymerization technique to prepare the interpenetrating(polymer)networks intelligent aqueous gel capable is also arranged, is subject to the dimensional thickness of material and the restriction of photopermeability.
Consider that ripple polymerization process medium wave temperature is high, the reaction times is short, be conducive to moving freely and activating of linear polymeric, so two kinds of polymkeric substance easily run through mutually, mutually tangle, thereby improve both consistency and stability of system.Therefore, this patent provides a kind of method for preparing interpenetrating net polymer with the ripple polymerization technique.
Ripple polymerization be otherwise known as Frontal Polymerization or frontal polymerization refer to utilize the heat release of chemical reaction self with a kind of polymerization process of conversion of monomer for polymkeric substance.Monomer is initiated rear polymerization reaction take place, discharges heat of polymerization; After thermal source was withdrawn, heat of polymerization spread towards periphery, caused contiguous monomer generation polymerization, emitted more reaction heat, formed narrow thermal reaction area, was called heat wave; If thermosteresis is little, heat wave can certainly be sent to the unreacted zone and progressively spread, until the whole polymerizations of all raw materials.
The ripple polymerization has been used to prepare the full interpenetrating net polymer of Functionally Graded Materials, thermochromism matrix material, epoxy-amine resin and radically curing diacrylate, but finds that not yet the ripple polymerization prepares the report of interpenetrating(polymer)networks intelligent aqueous gel capable material at present.
Summary of the invention
The object of the present invention is to provide a kind of method that adopts the ripple polymerization to prepare the interpenetrating(polymer)networks intelligent aqueous gel capable, solved the problem that the polymerization time that prior art exists is grown, is separated, energy consumption is high.
Technical scheme of the present invention realizes in the following manner:
(1) sensitive monomer and linking agent are dissolved in the organic solvent by a certain percentage, are made into homogeneous solution, linking agent N, the mass ratio of N '-methylene-bisacrylamide and sensitive monomer are 0.2: 100～1.6: 100;
(2) then add linear polymer, stir, the add-on of linear polymer is 5～20 % by weight of sensitive monomer; Adding at last initiator mixes;
(3) mix in the rear immigration polymerizer; To the heating of polymerizer one end, initiated polymerization;
(4) after the reaction beginning, withdraw thermal source, the heat that polyreaction itself produces continues initiated polymerization, until the whole polymerizations of all raw materials obtain work in-process to the unreacted regional diffusion;
(5) work in-process obtain the interpenetrating(polymer)networks intelligent aqueous gel capable through washing, drying after the pulverizing.
As preferred technical scheme, described sensitive monomer is temperature-sensitive monomer NIPA, N, the acid of N '-DMAA or pH sensitive monomer acrylic or methacrylic, the perhaps mixture of aforementioned two kinds of monomers, described sensitive monomer concentration is 35～70 % by weight.
As preferred technical scheme, described organic solvent is methyl-sulphoxide or dimethyl formamide.
As preferred technical scheme, described initiator is Diisopropyl azodicarboxylate, azo two eyeball in different heptan, isopropyl benzene
A kind of in hydrogen peroxide, the benzoyl peroxide, initiator is 0.5～2 % by weight of sensitive monomer consumption.
As preferred technical scheme, described linear polymer is a kind of in Polyvinylpyrolidone (PVP), methylcellulose gum, polyacrylic acid, the polyacrylamide.
Described polymerizer diameter is 50～150mm, the cylindrical polymerizer of high 1000mm.
Take foregoing as the basis, under the prerequisite that does not break away from basic fundamental thought of the present invention, according to ordinary skill knowledge and the means of this area, modification, replacement or the change of various ways can also be arranged to its content.
The invention has the advantages that: adopt the ripple polymerization technique to prepare interpenetration network hydrogel, reaction is carried out under high monomer and initiator concentration, and reaction is fast, temperature is high, but establishment is separated, obtain the product of even structure, gel-strength reached as high as 600Kpa when water absorption and swelling was saturated; Reaction process does not need the extraneous heat supply that continues, and energy consumption is low.
Embodiment
Embodiment below by the embodiment form, foregoing of the present invention is described in further detail again, but this should be interpreted as that following each embodiment is the restriction to the related scope of the above-mentioned theme of the present invention, all technology that realizes based on foregoing of the present invention all belong to scope of the present invention.
Embodiment 1
With N, N '-methylene-bisacrylamide linking agent and NIPA monomer are dissolved in the methyl-sulphoxide organic solvent by 0.2: 100 mass ratio, are made into homogeneous solution, and monomer concentration is 70%; Then add linear polyethylene and the pyrrolidone K30 of monomer mass 20%, stir; The Diisopropyl azodicarboxylate initiator that adds at last monomer consumption 2%, mixing rear immigration diameter is 50mm, in the cylindrical polymerizer of high 1000mm; To the heating of reactor one end, initiated polymerization; After the reaction beginning, withdraw thermal source, the heat that polyreaction itself produces continues initiated polymerization, until the whole polymerizations of all raw materials to the unreacted regional diffusion; Work in-process are through washing, and drying obtains the finished product after the pulverizing.
Embodiment 2
With linking agent N, N '-methylene-bisacrylamide and temperature sensitive monomer N, N '-DMAA is dissolved in the dimethyl formamide organic solvent by 0.5: 100 mass ratio, is made into homogeneous solution, and monomer concentration is 60%; Then add the linear polyacrylic acid of monomer mass 16%, stir; The 2,2'-Azobis(2,4-dimethylvaleronitrile) initiator that adds at last monomer consumption 1.6%, mixing rear immigration diameter is 80mm, in the cylindrical polymerizer of high 1000mm; To the heating of reactor one end, initiated polymerization; After the reaction beginning, withdraw thermal source, the heat that polyreaction itself produces continues initiated polymerization, until the whole polymerizations of all raw materials to the unreacted regional diffusion; Work in-process are through washing, and drying obtains the finished product after the pulverizing.
Embodiment 3
With N, N '-methylene-bisacrylamide linking agent and pH sensitive monomer vinylformic acid are dissolved in the methyl-sulphoxide organic solvent by 0.8: 100 mass ratio, are made into homogeneous solution, and monomer concentration is 50%; Then add linear polyethylene and the pyrrolidone K30 of monomer mass 12%, stir; The isopropyl benzene hydroperoxide initiator that adds at last monomer consumption 1.2%, mixing rear immigration diameter is 100mm, in the cylindrical polymerizer of high 1000mm; To the heating of reactor one end, initiated polymerization; After the reaction beginning, withdraw thermal source, the heat that polyreaction itself produces continues initiated polymerization, until the whole polymerizations of all raw materials to the unreacted regional diffusion; Work in-process are through washing, and drying obtains the finished product after the pulverizing.
Embodiment 4
With N, N '-methylene-bisacrylamide linking agent and pH sensitive monomer methacrylic acid are dissolved in the dimethyl formamide organic solvent by 1.2: 100 mass ratio, are made into homogeneous solution, and monomer concentration is 40%; Then add the linear polyacrylamide of monomer mass 8%, stir; The benzoyl peroxide initiator that adds at last monomer consumption 1.0%, mixing rear immigration diameter is 120mm, in the cylindrical polymerizer of high 1000mm; To the heating of reactor one end, initiated polymerization; After the reaction beginning, withdraw thermal source, the heat that polyreaction itself produces continues initiated polymerization, until the whole polymerizations of all raw materials to the unreacted regional diffusion; Work in-process are through washing, and drying obtains the finished product after the pulverizing.
Embodiment 5
Monomer NIPA, methacrylic acid are dissolved in the dimethyl formamide organic solvent in any proportion, and monomer concentration is 35%, linking agent N, and N '-methylene-bisacrylamide and mix monomer are made into homogeneous solution with 1.6: 100 mass ratio; Then add the linear methylcellulose gum of monomer mass 5%, stir; The Diisopropyl azodicarboxylate initiator that adds at last monomer consumption 0.5%, mixing rear immigration diameter is 150mm, in the cylindrical polymerizer of high 1000mm; To the heating of reactor one end, initiated polymerization; After the reaction beginning, withdraw thermal source, the heat that polyreaction itself produces continues initiated polymerization, until the whole polymerizations of all raw materials to the unreacted regional diffusion; Work in-process are through washing, and drying obtains the finished product after the pulverizing.
Claims (2)
1. method that adopts the ripple polymerization to prepare the interpenetrating(polymer)networks intelligent aqueous gel capable, it is characterized in that: processing step is:
(1) sensitive monomer and linking agent are dissolved in the organic solvent by a certain percentage, are made into homogeneous solution, linking agent N, the mass ratio of N '-methylene-bisacrylamide and sensitive monomer are 0.2: 100～1.6: 100;
(2) then add linear polymer, stir, the add-on of linear polymer is 5～20 % by weight of sensitive monomer; Adding at last initiator mixes;
(3) mix in the rear immigration polymerizer; To the heating of polymerizer one end, initiated polymerization;
(4) after the reaction beginning, withdraw thermal source, the heat that polyreaction itself produces continues initiated polymerization, until the whole polymerizations of all raw materials obtain work in-process to the unreacted regional diffusion;
(5) work in-process obtain the interpenetrating(polymer)networks intelligent aqueous gel capable through washing, drying after the pulverizing;
Described sensitive monomer is temperature-sensitive monomer NIPA, N, the acid of N '-DMAA or pH sensitive monomer acrylic or methacrylic, and the perhaps mixture of aforementioned two kinds of monomers, described sensitive monomer concentration is 35～70 % by weight;
Described organic solvent is methyl-sulphoxide or dimethyl formamide;
Described initiator is a kind of in Diisopropyl azodicarboxylate, azo two eyeball in different heptan, isopropyl benzene hydroperoxide, the benzoyl peroxide, and initiator is 0.5～2 % by weight of sensitive monomer consumption;
Described linear polymer is a kind of in Polyvinylpyrolidone (PVP), methylcellulose gum, polyacrylic acid, the polyacrylamide.
2. method according to claim 1, it is characterized in that: described polymerizer diameter is 50～150mm, the cylindrical polymerizer of high 1000mm.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1974608A (en) * | 2006-11-24 | 2007-06-06 | 清华大学 | Electronic beam radiopolymerization process of directly synthesizing temperature sensitive hydrogel |
| CN101712736A (en) * | 2009-11-20 | 2010-05-26 | 北京科技大学 | Method for preparing fast responsive temperature-sensitive hydrogel by adopting frontal polymerization technology |
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| CN1974608A (en) * | 2006-11-24 | 2007-06-06 | 清华大学 | Electronic beam radiopolymerization process of directly synthesizing temperature sensitive hydrogel |
| CN101712736A (en) * | 2009-11-20 | 2010-05-26 | 北京科技大学 | Method for preparing fast responsive temperature-sensitive hydrogel by adopting frontal polymerization technology |
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