CN1869087A - Environment response dielement intelligent gel and its preparation method - Google Patents
Environment response dielement intelligent gel and its preparation method Download PDFInfo
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- CN1869087A CN1869087A CNA2006100136308A CN200610013630A CN1869087A CN 1869087 A CN1869087 A CN 1869087A CN A2006100136308 A CNA2006100136308 A CN A2006100136308A CN 200610013630 A CN200610013630 A CN 200610013630A CN 1869087 A CN1869087 A CN 1869087A
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Abstract
An environment responsive binary intelligent gel with high hydroscopicity and swelling ratio and the response power to ambient temp and pH value is prepared from 2-acrylamide-2-methyl propanesulfonic acid and N-isopropyl acrylamide through proportional mixing, adding the mixture to the aqueous solution of N,N'- methylenediacrylamide, and polymerizing.
Description
Technical field
The present invention relates to a kind of polymer intelligent material, particularly relate to and a kind ofly have higher water-retaining capacity and swelling ratio, and have binary intelligent gel of environment-responsives such as temperature and pH value and preparation method thereof.
Background technology
Intelligent material is a kind of rising high tech tip materials, but it is meant to the environment perception and can responds and have the novel material of function ability of discovery that briefly, it has sensing, processing and an execution materials with function for a kind of.The superpolymer hydrogel is a kind of in the intelligent material, the multicomponent system that this gel is made of jointly the three-dimensional crosslinked network structure and the medium of superpolymer, a large amount of polarity, group (as amide group, carboxyl, sulfonic group etc.) such as hydrophilic are distributing on its cross-linked network, therefore, this hydrogel possess hydrophilic property.In the time of in putting it into water,, thereby make the three-dimensional network spread apart and the swelling phenomenon takes place because water molecules can be diffused in the water gel.In addition, because its crosslinking structure is to be formed by the covalent linkage with higher-strength, so it is water insoluble.Studies show that in recent years, stimulus in hydrogel environment of living in, when for example temperature, pH value, ion, electric field, medium, light, stress, magnetic field etc. change, reversible can take place for it, discontinuous hop gonosome is long-pending changes, thereby make volume that swelling or contraction take place suddenly, and the scope of swelling ratio is from several times, tens times to hundreds and thousands of times, so this hydrogel is called environmental sensitivity hydrogel or stimulating responsive hydrogel again.Because the response that intelligent superpolymer hydrogel stimulates to external world generally shows as the volume change of hop, promptly formed so-called " opening " and " pass " two states, thereby this material can be used as transmitter, power element, switch and material with memory etc. by means of this specific character and is used widely at industrial fields such as biomimetic engineering, health care, building, agricultural, textile industry, gardening.The superpolymer hydrogel is divided into monobasic monomer homopolymerization hydrogel and polynary monomer copolymerization hydrogel usually.Wherein monobasic monomer homopolymerization hydrogel is many because of the defective on monobasic monomer structure and the performance or not enoughly make the hydrogel over-all properties that is polymerized poor, so the application of polynary relatively monomer copolymerization hydrogel in a lot of fields is restricted.
The preparation method of at present the most frequently used intelligent superpolymer hydrogel mainly is chemical initiated polymerization method.Because the common technological process more complicated of this method, and restive, long reaction time, the monomer conversion and the polymerization degree are relatively low, thereby the prepared gel over-all properties that goes out is relatively poor relatively, and the result makes the intelligent of gel have a greatly reduced quality.And in recent years, the method that some novel physical initiated polymerizations prepare gel has obtained gratifying achievement, wherein mainly comprises radiation method (as gamma-rays radiation, microwave radiation, ultraviolet radiation) and optical cross-linking method etc.Wherein, low-temperature plasma initiated polymerization method is a kind ofly to utilize low-temperature plasma that reaction monomers (solid, liquid, gas mutually all can) self steam forms that reaction monomers is carried out short period of time from the several seconds by several minutes to handle and cause, and then place reaction vessels to carry out polymerization under suitable condition the monomer that is initiated, and do not need the new polymerization process of any initiator.This polymerization process adopts the method for geseous discharge to obtain low-temperature plasma usually, mainly is divided into modes such as rf electric field discharge (comprising corona discharge, glow discharge) and microwave discharge.Wherein microwave low temperature plasma is meant discharge under the microwave high-frequency rate of 2.45GHz and the special low-temperature plasma of acquisition, belong to the higher plasma body of energy, compare with the plasma body of conventional rf electric field (13.56MHz) discharge generation, it has following characteristics:
(1) microwave low temperature plasma more can increase the exciting of gas molecule, ionization and dissociation processes, the substate atom that excites is many, it exceeds an order of magnitude, plasma density big (10 to ionisation of gas and extent of dissociation than the plasma body (as the rf electric field plasma body) of other type
11～10
13), degree of ionization height (＞10%), energy is big, and is active strong, therefore is easier to take place or cause related physical, chemical reaction.
(2) can form big area, uniform plasma body; Do not have electrode in the reaction zone, can eliminate the pollution that electrode self causes, thereby be suitable for the preparation and the processing of high purity substance, and the process efficiency height.
(3) temperature of unbound electron is higher than the ionic temperature in the microwave low temperature plasma, therefore, and by the selection of suitable electromagnetic field, gaseous tension, gaseous species and the temperature range in the adjustment may command reaction zone.
(4) pressure in the reaction zone can be in very wide scope (10
-3～10
5Pa) adjust in.
(5) utilize the DISTRIBUTION OF MAGNETIC FIELD characteristics, promptly so-called " empty structure " might be enclosed in plasma body in the particular space; Also can utilize magnetic field to carry plasma body, the purpose of doing like this is to allow the processes zone separate with discharge space, thereby both has been convenient to take various corresponding technological measures, can avoid the radiation injury of plasma body again or eliminate issuable side reaction.
But do not find as yet that up to the present a kind of microwave low temperature plasma that utilizes causes AMPS/NIPA binary monomer, then prepare and have higher water-retaining capacity and swelling ratio, and have P (AMPS/NIPA) binary intelligent gel of temperature and pH value responding ability and preparation method thereof through polymerization.
Summary of the invention
In order to address the above problem, to the object of the present invention is to provide a kind ofly to have higher water-retaining capacity and swelling ratio, and have the binary intelligent gel of environment-responsives such as temperature and pH value.
It is simple that another object of the present invention provides a kind of production technique, product purity, monomer conversion and polymerization degree height, and can reduce the binary intelligent gel preparation method of discharge of poisonous waste.
In order to achieve the above object, environment response dielement intelligent gel provided by the invention be with by 2-acrylamide-2-methyl propane sulfonic acid (AMPS) and N-N-isopropylacrylamide (NIPA) with 1～8: the microwave low temperature plasma that the monomer mixture that 2～9 mol ratio is formed utilizes self gas to form causes, monomer mixture after will causing then joins and accounts for the N of monomer mixture molar weight 0.5～8% as linking agent, in N '-methylene-bisacrylamide (Bis) aqueous solution, and the gross weight that makes monomer mixture and linking agent accounts for 12～35% of aqueous solution gross weight, makes through polymerization at last.
The mol ratio preferred 3～7: 3～7 of described 2-acrylamide-2-methyl propane sulfonic acid (AMPS) and N-N-isopropylacrylamide (NIPA), N as linking agent, it is preferred 0.5～2% that N '-methylene-bisacrylamide accounts for the monomer mixture molar weight, and the gross weight of monomer mixture and linking agent accounts for aqueous solution gross weight preferred 12～25%.
Environment response dielement intelligent gel preparation method provided by the invention carries out according to the following step order:
(1) microwave low temperature plasma causes
With mol ratio is that 1～8: 2～9 2-acrylamide-2-methyl propane sulfonic acid (AMPS) and N-N-isopropylacrylamide (NIPA) monomer mix and be placed in the microwave plasma body processor cavity, close inlet mouth, close the air outlet after system is evacuated to 3Pa, make that monomeric vapour pressure rises naturally in the system, after waiting to reach 30Pa, the microwave low temperature plasma that utilizes above-mentioned monomer self gas to form under the power of 80～250W was handled 60～360 seconds monomer mixture and is caused;
(2) polyreaction
The N of monomer mixture molar weight 0.5～8% as linking agent will be accounted for, N '-methylene-bisacrylamide (Bis) and distilled water join in the container, and make the gross weight of linking agent and the above-mentioned monomer mixture that does not add as yet account for 12～35% of aqueous solution gross weight, feed nitrogen then and carry out deoxygenation, the deoxygenation time is 10 minutes, the monomer mixture that will cause joins in the container subsequently, continue inflated with nitrogen, begin to increase until reaction system viscosity, immediately that container is airtight and place 25～30 ℃ water-bath polymerization 24 hours to form gel;
(3) aftertreatment
Place distilled water to soak a week gel after the above-mentioned polymerization, change distilled water therebetween repeatedly, with abundant removal unreacted reactant and other impurity, inhale with filter paper then and remove the moisture of gel surface and to place 50 ℃ vacuum drying oven to dry to constant weight to obtain environment response dielement intelligent gel provided by the invention.
Environment response dielement intelligent gel provided by the invention is to utilize microwave low temperature plasma initiated polymerization method to be polymerized by AMPS and two monomers of NIPA, and need not to add initiator and catalyzer, it has the characteristic of PAMPS and PNIPA concurrently, both had very high water-retaining capacity and swelling ratio, have temperature and pH value responding ability again, thereby can remedy the deficiency of the equal coagel of corresponding monobasic monomer, so be a kind of novel stimuli-responsive material.This binary intelligent gel all descends to some extent in acid and alkaline condition lower volume, and stronger volumetric shrinkage phenomenon occurs in strong acid and strong base solution, thereby demonstrates good pH value susceptibility.In addition, this gel belongs to the thermal shrinkage type gel, and its swelling volume reduces with the rising of envrionment temperature, and tangible volume occurs change mutually when 39 ℃ of left and right sides, and the volume sudden change is up to hundred times, therefore has good temperature sensitivity.In addition, this preparation method have that technological process is simple, product purity is high, monomer conversion is big, polymerization time is short, the polymerization degree is big, characteristics such as energy-saving and water-saving and environmental protection.
Embodiment
The AMPS monomer that environment response dielement intelligent gel provided by the invention adopted is a kind of vinyl monomer that has sulfonic acid group, the sulfonic group that contains strong hydrophilicity in its structure, so its monobasic monomer homopolymer PAMPS has very high water-retaining capacity and the swelling ratio of Ke Da more than thousand times, the existence of sulfonic group and amide group has simultaneously determined PAMPS to have pH value susceptibility, but relative hydrophilic radical, because the effect of seeming on overall structure of its hydrophobic grouping is not outstanding, thereby on performance, do not possess temperature sensitivity, thereby become the defective place of PAMPS gel maximum.
Contain polarity amide group and hydrophobicity sec.-propyl in the NIPA monomer structure that environment response dielement intelligent gel provided by the invention adopted, the volume phase transition of its monobasic monomer homopolymer PNIPA has temperature sensitivity, it is a kind of typical thermo-responsive hydro gel, and minimum critical solution temperature is lower, only is 32.5 ℃.But because this gel belongs to the non-ionic type gel, do not contain hydrophilic radical in its structure, thus tens times less swelling ratio only had usually, thus limited of the application of this gel in a lot of fields.In addition, if adopt traditional chemical polymerization to prepare gel, residues such as initiator wherein also can influence its over-all properties.
The present invention is in conjunction with above-mentioned two kinds of monomeric structure propertiess, and utilizes microwave low temperature plasma initiated polymerization method AMPS and NIPA to be made P (AMPS/NIPA) the binary copolymerization gel of the feature structure that integrates AMPS and NIPA.This gel is a water white transparency shape solid matter, is slightly acidic, and its density changes with the different of polymerizing condition with physical strength, and its shape depends on aggregation container, if with the test tube polymerization then cylindrical.
Below in conjunction with specific embodiment environment response dielement intelligent gel provided by the invention and preparation method thereof is elaborated.
Embodiment 1:
With mol ratio 1: 1 2-acrylamide-2-methyl propane sulfonic acid (AMPS) and N-N-isopropylacrylamide (NIPA), i.e. 1.46 gram AMPS and 0.8 gram NIPA monomer mixing is placed in the microwave plasma body processor cavity, close inlet mouth, close the air outlet after system is evacuated to 3Pa, make that monomeric vapour pressure rises naturally in the system, after waiting to reach 30Pa, the microwave low temperature plasma that utilizes above-mentioned monomer self gas to form under the power of 100W was handled 120 seconds monomer mixture and is caused; I.e. 0.0218 N that restrains as linking agent of monomer mixture molar weight 1% will be accounted for, N '-methylene-bisacrylamide (Bis) and 17 gram distilled water join in the container, feed nitrogen then and carry out deoxygenation, the deoxygenation time is 10 minutes, monomer mixture with above-mentioned initiation joins in the container subsequently, this moment, the gross weight of linking agent and monomer mixture accounted for 12% of aqueous solution gross weight, continue inflated with nitrogen, begin to increase until reaction system viscosity, immediately that container is airtight and place 25 ℃ water-bath polymerization 24 hours to form gel; Place distilled water to soak a week gel after the above-mentioned polymerization, change distilled water therebetween repeatedly, with abundant removal unreacted reactant and other impurity, inhale with filter paper then and remove the moisture of gel surface and to place 50 ℃ vacuum drying oven to dry to constant weight to obtain 2.0536 grams environment response dielement intelligent gel provided by the invention.The swelling ratio of this gel in distilled water can reach 450, and transformation temperature is about 39 ℃, has good pH value susceptibility simultaneously.
Embodiment 2:
With mol ratio 1: 1 2-acrylamide-2-methyl propane sulfonic acid (AMPS) and N-N-isopropylacrylamide (NIPA), i.e. 1.46 gram AMPS and 0.8 gram NIPA monomer mixing is placed in the microwave plasma body processor cavity, close inlet mouth, close the air outlet after system is evacuated to 3Pa, make that monomeric vapour pressure rises naturally in the system, after waiting to reach 30Pa, the microwave low temperature plasma that utilizes above-mentioned monomer self gas to form under the power of 100W was handled 120 seconds monomer mixture and is caused; I.e. 0.0218 N that restrains as linking agent of monomer mixture molar weight 1% will be accounted for, N '-methylene-bisacrylamide (Bis) and 9.1272 gram distilled water join in the container, feed nitrogen then and carry out deoxygenation, the deoxygenation time is 10 minutes, monomer mixture with above-mentioned initiation joins in the container subsequently, this moment, the gross weight of linking agent and monomer mixture accounted for 20% of aqueous solution gross weight, continue inflated with nitrogen, begin to increase until reaction system viscosity, immediately that container is airtight and place 25 ℃ water-bath polymerization 24 hours to form gel; Place distilled water to soak a week gel after the above-mentioned polymerization, change distilled water therebetween repeatedly, with abundant removal unreacted reactant and other impurity, inhale with filter paper then and remove the moisture of gel surface and to place 50 ℃ vacuum chamber to dry to constant weight to obtain 2.0536 grams environment response dielement intelligent gel provided by the invention.The swelling ratio of this gel in distilled water can reach 99, and transformation temperature is about 39 ℃, has good pH value susceptibility simultaneously.
Embodiment 3:
With mol ratio 1: 9 2-acrylamide-2-methyl propane sulfonic acid (AMPS) and N-N-isopropylacrylamide (NIPA), i.e. 1.036 gram AMPS and 5.0922 gram NIPA monomers mixing are placed in the microwave plasma body processor cavity, close inlet mouth, close the air outlet after system is evacuated to 3Pa, make that monomeric vapour pressure rises naturally in the system, after waiting to reach 30Pa, the microwave low temperature plasma that utilizes above-mentioned monomer self gas to form under the power of 100W was handled 120 seconds monomer mixture and is caused; I.e. 0.0771 N that restrains as linking agent of monomer mixture molar weight 1% will be accounted for, N '-methylene-bisacrylamide (Bis) and 45.51 gram distilled water join in the container, feed nitrogen then and carry out deoxygenation, the deoxygenation time is 10 minutes, monomer mixture with above-mentioned initiation joins in the container subsequently, this moment, the gross weight of linking agent and monomer mixture accounted for 12% of aqueous solution gross weight, continue inflated with nitrogen, begin to increase until reaction system viscosity, immediately that container is airtight and place 25 ℃ water-bath polymerization 24 hours to form gel; Place distilled water to soak a week gel after the above-mentioned polymerization, change distilled water therebetween repeatedly, with abundant removal unreacted reactant and other impurity, inhale with filter paper then and remove the moisture of gel surface and to place 50 ℃ vacuum drying oven to dry to constant weight to obtain 5.5848 grams environment response dielement intelligent gel provided by the invention.The swelling ratio of this gel in distilled water can reach 158, and transformation temperature is about 35 ℃, has good pH value susceptibility simultaneously.
Embodiment 4:
With mol ratio 7: 3 2-acrylamide-2-methyl propane sulfonic acid (AMPS) and N-N-isopropylacrylamide (NIPA), i.e. 1.4504 gram AMPS and 0.3395 gram NIPA monomer mixing is placed in the microwave plasma body processor cavity, close inlet mouth, close the air outlet after system is evacuated to 3Pa, make that monomeric vapour pressure rises naturally in the system, after waiting to reach 30Pa, the microwave low temperature plasma that utilizes above-mentioned monomer self gas to form under the power of 100W was handled 120 seconds monomer mixture and is caused; I.e. 0.01542 N that restrains as linking agent of monomer mixture molar weight 1% will be accounted for, N '-methylene-bisacrylamide (Bis) and 13.24 gram distilled water join in the container, feed nitrogen then and carry out deoxygenation, the deoxygenation time is 10 minutes, monomer mixture with above-mentioned initiation joins in the container subsequently, this moment, the gross weight of linking agent and monomer mixture accounted for 12% of aqueous solution gross weight, continue inflated with nitrogen, begin to increase until reaction system viscosity, immediately that container is airtight and place 30 ℃ water-bath polymerization 24 hours to form gel; Place distilled water to soak a week gel after the above-mentioned polymerization, change distilled water therebetween repeatedly, with abundant removal unreacted reactant and other impurity, inhale with filter paper then and remove the moisture of gel surface and to place 50 ℃ vacuum drying oven to dry to constant weight to obtain 1.6248 grams environment response dielement intelligent gel provided by the invention.The swelling ratio of this gel in distilled water can reach 1000, and transformation temperature is about 65 ℃, has good pH value susceptibility simultaneously.
Embodiment 5:
With mol ratio 2: 3 2-acrylamide-2-methyl propane sulfonic acid (AMPS) and N-N-isopropylacrylamide (NIPA), be that 0.8288MPS and 0.679 gram NIPA monomer mixing are placed in the microwave plasma body processor cavity, close inlet mouth, close the air outlet after system is evacuated to 3Pa, make that monomeric vapour pressure rises naturally in the system, after waiting to reach 30Pa, the microwave low temperature plasma that utilizes above-mentioned monomer self gas to form under the power of 100W was handled 120 seconds monomer mixture and is caused; I.e. 0.0077 N that restrains as linking agent of monomer mixture molar weight 0.5% will be accounted for, N '-methylene-bisacrylamide (Bis) and 11.11 gram distilled water join in the container, feed nitrogen then and carry out deoxygenation, the deoxygenation time is 10 minutes, monomer mixture with above-mentioned initiation joins in the container subsequently, this moment, the gross weight of linking agent and monomer mixture accounted for 12% of aqueous solution gross weight, continue inflated with nitrogen, begin to increase until reaction system viscosity, immediately that container is airtight and place 25 ℃ water-bath polymerization 24 hours to form gel; Place distilled water to soak a week gel after the above-mentioned polymerization, change distilled water therebetween repeatedly, with abundant removal unreacted reactant and other impurity, inhale with filter paper then and remove the moisture of gel surface and to place 50 ℃ vacuum drying oven to dry to constant weight to obtain 1.364 grams environment response dielement intelligent gel provided by the invention.The swelling ratio of this gel in distilled water can reach 205, and transformation temperature has good pH value susceptibility simultaneously about 38 ℃.
Embodiment 6:
With mol ratio 1: 1 2-acrylamide-2-methyl propane sulfonic acid (AMPS) and N-N-isopropylacrylamide (NIPA), i.e. 1.46 gram AMPS and 0.8 gram NIPA monomer mixing is placed in the microwave plasma body processor cavity, close inlet mouth, close the air outlet after system is evacuated to 3Pa, make that monomeric vapour pressure rises naturally in the system, after waiting to reach 30Pa, the microwave low temperature plasma that utilizes above-mentioned monomer self gas to form under the power of 150W was handled 120 seconds monomer mixture and is caused; I.e. 0.0218 N that restrains as linking agent of monomer mixture molar weight 1% will be accounted for, N '-methylene-bisacrylamide (Bis) and 17 gram distilled water join in the container, feed nitrogen then and carry out deoxygenation, the deoxygenation time is 10 minutes, monomer mixture with above-mentioned initiation joins in the container subsequently, this moment, the gross weight of linking agent and monomer mixture accounted for 12% of aqueous solution gross weight, continue inflated with nitrogen, begin to increase until reaction system viscosity, immediately that container is airtight and place 25 ℃ water-bath polymerization 24 hours to form gel; Place distilled water to soak a week gel after the above-mentioned polymerization, change distilled water therebetween repeatedly, with abundant removal unreacted reactant and other impurity, inhale with filter paper then and remove the moisture of gel surface and to place 50 ℃ vacuum chamber to dry to constant weight to obtain 2.0536 grams environment response dielement intelligent gel provided by the invention.The swelling ratio of this gel in distilled water can reach 156, and transformation temperature is about 39 ℃, has good pH value susceptibility simultaneously.
Claims (3)
1, a kind of environment response dielement intelligent gel, it is characterized in that: described environment response dielement intelligent gel be with by 2-acrylamide-2-methyl propane sulfonic acid and N-N-isopropylacrylamide with 1～8: the microwave low temperature plasma that the monomer mixture that 2～9 mol ratio is formed utilizes self gas to form causes, monomer mixture after will causing then joins and accounts for the N of monomer mixture molar weight 0.5～8% as linking agent, in N '-methylene-bisacrylamide aqueous solution, and the gross weight that makes monomer mixture and linking agent accounts for 12～35% of aqueous solution gross weight, makes through polymerization at last.
2, environment response dielement intelligent gel according to claim 1, it is characterized in that: the mol ratio preferred 3～7: 3～7 of described 2-acrylamide-2-methyl propane sulfonic acid (AMPS) and N-N-isopropylacrylamide (NIPA), N as linking agent, it is preferred 0.5～2% that N '-methylene-bisacrylamide accounts for the monomer mixture molar weight, and the gross weight of monomer mixture and linking agent accounts for aqueous solution gross weight preferred 12～25%.
3, a kind of preparation method of environment response dielement intelligent gel as claimed in claim 1 is characterized in that: the preparation method of described environment response dielement intelligent gel carries out according to the following step order:
(1) microwave low temperature plasma causes
With mol ratio is that 1～8: 2～9 2-acrylamide-2-methyl propane sulfonic acid (AMPS) and N-N-isopropylacrylamide (NIPA) monomer mix and be placed in the microwave plasma body processor cavity, close inlet mouth, close the air outlet after system is evacuated to 3Pa, make that monomeric vapour pressure rises naturally in the system, after waiting to reach 30Pa, the microwave low temperature plasma that utilizes above-mentioned monomer self gas to form under the power of 80～250W was handled 60～360 seconds monomer mixture and is caused;
(2) polyreaction
The N of monomer mixture molar weight 0.5～8% as linking agent will be accounted for, N '-methylene-bisacrylamide (Bis) and distilled water join in the container, and make the gross weight of linking agent and the above-mentioned monomer mixture that does not add as yet account for 12～35% of aqueous solution gross weight, feed nitrogen then and carry out deoxygenation, the deoxygenation time is 10 minutes, the monomer mixture that will cause joins in the container subsequently, continue inflated with nitrogen, begin to increase until reaction system viscosity, immediately that container is airtight and place 25 ℃ water-bath polymerization 24 hours to form gel;
(3) aftertreatment
Place distilled water to soak a week gel after the above-mentioned polymerization, change distilled water therebetween repeatedly, with abundant removal unreacted reactant and other impurity, inhale with filter paper then and remove the moisture of gel surface and to place 50 ℃ vacuum drying oven to dry to constant weight to obtain environment response dielement intelligent gel provided by the invention.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100457797C (en) * | 2007-02-09 | 2009-02-04 | 上海大学 | Preparation for smart water gel responding microwave |
| CN102070787A (en) * | 2010-11-17 | 2011-05-25 | 哈尔滨工业大学 | Method for preparing conductive polymer gel for reinforcing steel bar corrosion electrochemical control |
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2006
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100457797C (en) * | 2007-02-09 | 2009-02-04 | 上海大学 | Preparation for smart water gel responding microwave |
| CN102070787A (en) * | 2010-11-17 | 2011-05-25 | 哈尔滨工业大学 | Method for preparing conductive polymer gel for reinforcing steel bar corrosion electrochemical control |
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