CN112062906B - Preparation method of nuclear shell structure environment response type polymer - Google Patents
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
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- C08J2351/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
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- C08J2429/00—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
- C08J2429/02—Homopolymers or copolymers of unsaturated alcohols
- C08J2429/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
Abstract
The invention relates to a preparation method of a nuclear shell structure environment response type polymer. The invention adopts hydrophobic monomers, polyvinyl alcohol, azobenzene derivatives and the like as main reaction raw materials, prepares a photoresponse type polymer by a method of graft polymerization, crosslinking esterification and composite assembly, namely, the hydrophobic monomers are graft polymerized firstly, then the polyvinyl alcohol is crosslinked under the action of a crosslinking agent and then esterified with the azobenzene derivatives to obtain esterified hydrogel, and finally the photoresponse type polymer is obtained by composite assembly. According to the invention, the photoresponse type polymer is successfully prepared by wrapping the polymer with the polyvinyl alcohol crosslinked esterified hydrogel to form the core-shell structure, the reaction process is convenient, controllable, simple and efficient, the effects of excellent environmental response, intelligent conversion and the like are shown, the requirements of long service life, high durability and the like of the concrete material are met, and the method has good market prospect and application value.
Description
Technical Field
The invention relates to the technical field of photoresponse polymers for cement concrete, in particular to a specific preparation method for synthesizing an environment-responsive polymer by firstly carrying out graft polymerization on hydrophobic monomers and then compounding and assembling the hydrophobic monomers and hydrogel crosslinked with polyvinyl alcohol.
Background
The concrete has the characteristics of high compressive strength, low cost, easy forming and the like, is a building material with the largest consumption at present, and is widely applied to basic facilities and structural engineering of railways, ports, roads, bridges and the like. However, the concrete material itself has disadvantages such as high brittleness and poor volume stability, and the occurrence of shrinkage and cracks is inevitable. The concrete shrinkage refers to a phenomenon that the volume of concrete is reduced during the setting and hardening process, and includes chemical shrinkage, plastic shrinkage, self-shrinkage, temperature shrinkage, drying shrinkage, carbonization shrinkage and the like, wherein the influence of the drying shrinkage and the self-shrinkage on the performance of the concrete is most significant. In the process of drying and shrinking the concrete, the moisture in the gaps, the coarse holes, the capillary holes and the gel holes of the concrete is gradually lost, and the shrinkage stress of the capillary holes is continuously increased to induce volume shrinkage and the generation of macro cracks. This not only affects the appearance of the building, but also adversely affects the safety and durability of the building structure, and is the root cause of the reduction in the service life of the building.
The environmental response type polymer has responsiveness and sensitivity to external environment in specific environment, and is a hot spot in the research field of high molecular science and surface interface chemistry nowadays. By utilizing the molecular structure design, the modification and the cutting can be effectively carried out on macromolecules with different structural forms, so that the polymer has multiple functional groups and functional effects at the same time, and the method becomes an important means for designing and synthesizing the environment response type polymer at present. The environmental response type polymer is one of the important branches of the intelligent functional polymer, has attracted more and more intensive research interests of researchers, and is increasingly an important research object in the frontier field.
The hydrogel polymer has unique three-dimensional network stereo structure and hydrophilic chemical property, so that the hydrogel polymer is a potential material for modifying synthetic environment response polymers. Therefore, the designed and modified hydrogel polymer with the environmental response characteristic is wrapped with the functional substance to form the composite material with the shape of a core-shell structure, and the multifunctional characteristics and the functional characteristics can be realized. The hydrogel polymer is applied to concrete materials, and the effect on the concrete is intelligently regulated and controlled through the response of the external environment, so that the performance of the concrete is improved, the functional modification and application range of the hydrogel polymer are enriched, and the hydrogel polymer has remarkable development potential and application prospect.
Patent CN104030596B (published: 2015, 6, and 17) reports an environment-friendly pollution-free alkali-free anti-crack concrete polymer, which comprises 35-66% of fly ash, 8-18% of polypropylene short fiber, 2-18% of polyethylene glycol, 3-17% of methacrylic acid, 2-15% of calcium formate, 3-16% of neopentyl glycol and 0.2-0.8% of sodium dodecyl benzene sulfonate. The method has the advantages of simple feeding mode and easily controlled production conditions, and the produced alkali-free anti-cracking concrete polymer with low alkali content and low doping amount can effectively reduce the shrinkage of concrete, inhibit non-load cracks and improve the durability of the concrete, and has better social benefit and economic benefit. However, the polymer prepared by the method is simple physical blending, cannot realize polymer functionalization through molecular structure design, does not embody the concept of 'environmental response', and cannot spontaneously and intelligently control the effect of reducing and cracking in a specific environment.
Patent CN102030872A (published: 2011, 04, 27) reports a preparation method of comb polymer for concrete, which is prepared by polymerizing monomer a (ether macromonomer containing unsaturated double bond), monomer B ((meth) acrylic acid or its salt), monomer C (alkoxy polyether (meth) acrylate), and monomer D (maleic anhydride mono-or diester) through radical copolymerization reaction under the action of initiator. The reaction process of the invention is easy to control, good shrinkage reducing effect can be achieved by mixing the concrete with lower mixing amount, and the defect of strength reduction caused by the traditional shrinkage reducing component is overcome. However, the synthesis process of the invention still belongs to the traditional concrete admixture synthesis technology, and the improvement of the volume stability and the durability of the concrete is not realized by designing a synthesis environment response polymer and a modified hydrogel compounding mode.
Patent CN106632925A (published: 2017, 5, month and 10) reports a preparation method and application of a chitosan temperature-sensitive block copolymer, wherein chitosan and an acetic anhydride solution react to obtain acetylated chitosan, a chain transfer agent, a catalyst and a dehydrating agent are added to react to obtain a RAFT reagent of the chitosan, and then NIPAM and an initiator are added to perform RAFT polymerization reaction to obtain the chitosan temperature-sensitive block copolymer CS-g-NIPAM. The invention adopts an activity controllable polymerization RAFT method, the reaction is stable and does not implode, and the obtained polymerization product CS-g-NIPAM has narrow molecular weight distribution and good environmental response characteristic. However, the method disclosed by the invention has the disadvantages of harsh requirements on catalysts and reaction conditions, complex production process and high polymerization cost, and does not apply the environmental response characteristic to the research field of improving the performance of concrete.
The polymers or their blends described in most patents exhibit good shrinkage crack resistance properties in concrete. However, the above preparation methods all have some disadvantages, and researchers still mostly adopt a simple multi-component physical mixing or follow the traditional concrete admixture copolymerization mode, and do not consider the combination of the polymer environmental response characteristic and the concrete performance improvement. The existing environment response type polymer is not used for reference in the field of polymers for cement concrete, and the real regulation and control of the application performance of the concrete can be realized based on the molecular structure design of the polymer and the method of hydrogel environment response modification and structure compounding. Therefore, the adsorption type hydrophobic polymer is combined with the modified hydrogel through the assembly form of the core-shell structure by utilizing the molecular structure innovation, the inhibition of concrete shrinkage is realized through the intelligent environmental response behavior, the method has wide development space and industrial production value, and no report is found at home and abroad about the research.
Disclosure of Invention
The invention aims to provide a preparation process of a nuclear shell structure environment response type polymer. The method comprises the steps of firstly grafting and polymerizing hydrophobic monomers to obtain an adsorption type hydrophobic polymer, then crosslinking polyvinyl alcohol under the action of a crosslinking agent, esterifying the crosslinked polyvinyl alcohol and azobenzene derivatives to obtain esterified hydrogel, and finally carrying out composite assembly to obtain the photoresponse type polymer with excellent performance. Based on the advantage of intelligent hydrogel composite assembly, the invention innovatively introduces photoresponsive groups on the surface of the hydrogel and assembles the photoresponsive groups and the adsorption type hydrophobic polymer into a core-shell structure, so that the hydrogel responds under the action of ultraviolet irradiation, and simultaneously, the hydrophobic polymer is adsorbed on the surface of cement particles to inhibit the concrete shrinkage effect, thereby enriching the application of hydrogel chemical modification and composite assembly thereof in the field of cement concrete. The environment response type polymer synthesized by the method is different from the traditional hydrogel, the environment response release function of the polymer can realize intelligent regulation and control of polymer adsorption, and the polymer shows more excellent action effect and wider development prospect than the traditional polymer material for cement concrete.
The invention provides a preparation method of a nuclear shell structure environment response type polymer, which prepares a photoresponse type polymer material by a method of firstly graft polymerizing hydrophobic monomers and then carrying out composite assembly on the hydrophobic monomers and hydrogel obtained by crosslinking and esterifying polyvinyl alcohol, and comprises the following conditions and steps:
(1) graft polymerization: adding a hydrophobic monomer and an organic solvent into a reactor, stirring and heating to 60-90 ℃, filling nitrogen for 3-5 times, deoxidizing for 10-30 minutes repeatedly, sealing, adding a molecular weight regulator, adding an acid solution of cerium ammonium salt with the mass fraction of 20-40%, stirring for 5-15 minutes, adding an aqueous solution of glucose derivatives with the mass fraction of 40-80%, reacting for 1-6 hours at constant temperature, cooling to 20-40 ℃, adding an alkaline solution with the mass fraction of 10-50% for neutralizing until the pH value is 6-8, removing the solvent by reduced pressure distillation, and adding an aqueous solution of an emulsifier with the mass fraction of 5-30% to obtain a polymer emulsion;
(2) and (3) crosslinking reaction: adding polyvinyl alcohol and deionized water into a reactor, stirring, heating to 70-90 ℃, introducing nitrogen to purge for 5-20 minutes, adding a cross-linking agent, stirring and reacting for 1-2 hours, pouring the mixed solution into a mould, cooling to 20-40 ℃, carrying out cross-linking reaction for 24-60 hours, then demoulding, and washing with deionized water for 3-5 times to obtain hydrogel;
(3) esterification reaction: adding an azobenzene derivative and an organic solvent into a reactor, adding the product hydrogel obtained in the step (2), adding a catalyst, stirring for 5-20 minutes, adding a water-carrying agent when the temperature is raised to 60-80 ℃, continuously raising the temperature to 90-120 ℃ to perform esterification reaction, separating water obtained by the reaction while reacting, vacuumizing after reacting for 2-10 hours to remove the water-carrying agent, cooling to 20-40 ℃, distilling under reduced pressure to remove the solvent, and washing with deionized water for 3-5 times to obtain esterified hydrogel;
(4) and (3) composite assembly: adding the esterified hydrogel obtained in the step (3) into the polymer emulsion obtained in the step (1), soaking for 6-12 hours, adding a flocculant aqueous solution with the mass fraction of 10% -40%, stirring for 20-50 minutes, washing with deionized water for 5-8 times, and then drying in vacuum to obtain the photoresponse polymer;
(5) and (3) response process: and (4) doping the photoresponse polymer obtained in the step (4) into fresh concrete, uniformly stirring, and irradiating by using ultraviolet light for 24-60 hours after 0.5-24 hours to generate photoresponse and generate a corresponding application performance effect.
The hydrophobic monomer in the step (1) is one or more of styrene, phenylisopropylene, vinyl toluene, phenylpropylene, methyl methacrylate, ethyl methacrylate and butyl methacrylate; the organic solvent in the step (1) is dimethyl sulfoxide, 1, 4-dioxane or dimethylformamide, and the mass ratio of the dosage to the hydrophobic monomer in the step (1) is 3-10: 1; the molecular weight regulator in the step (1) is isopropanol, n-dodecyl mercaptan or isooctyl 3-mercaptopropionate, and the molar ratio of the dosage of the molecular weight regulator to the hydrophobic monomer in the step (1) is 0.1-0.5: 1; the acid solution of cerium ammonium salt in the step (1) is nitric acid solution of cerium ammonium nitrate or sulfuric acid solution of cerium ammonium sulfate, and the molar ratio of the dosage of cerium ammonium salt to the hydrophobic monomer in the step (1) is 0.005-0.15: 1; the glucose derivative in the step (1) is one or more of gluconic acid, sodium gluconate, potassium gluconate, glucaric acid and D-glucuronic acid, and the molar ratio of the dosage to the hydrophobic monomer in the step (1) is 0.2-1: 1; the solute of the alkaline solution in the step (1) is sodium hydroxide, potassium hydroxide, ethylenediamine or triethylamine; the emulsifier in the step (1) is sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, sodium stearate or dodecyl diphenyl etherThe mass ratio of the amount of sodium disulfonate to the hydrophobic monomer in the step (1) is 0.03-0.08: 1; the mass of the deionized water in the step (2) is 25-80% of that of the polyvinyl alcohol in the step (2); the cross-linking agent in the step (2) is glutaraldehyde, boric acid, epichlorohydrin or terephthalaldehyde, and the mass ratio of the dosage of the cross-linking agent to the polyvinyl alcohol in the step (2) is 0.02-0.05: 1; the azobenzene derivative in the step (3) is azobenzene-4-benzoic acid or 4-dimethylamine azobenzene-4-carboxylic acid; the organic solvent in the step (3) is dimethyl sulfoxide, 1, 4-dioxane or dimethylformamide, and the mass ratio of the dosage of the organic solvent to the azobenzene derivative in the step (3) is 3-10: 1; the catalyst in the step (3) is p-toluenesulfonic acid, phosphoric acid or sulfamic acid, and the dosage of the catalyst is 1.5-10% of the sum of the mass of the azobenzene derivative in the step (3) and the mass of the hydrogel in the step (2); the water-carrying agent in the step (3) is cyclohexane, benzene or toluene, and the using amount of the water-carrying agent is 8-30% of the sum of the mass of the azobenzene derivative in the step (3) and the mass of the hydrogel in the step (2); the mass ratio of the esterified hydrogel to the polymer emulsion in the step (4) is 1: 10-20; the flocculating agent in the step (4) is ferric sulfate, aluminum sulfate, sodium chloride or calcium chloride, and the mass ratio of the dosage to the hydrophobic monomer in the step (1) is 0.1-0.3: 1; the mass ratio of the photoresponse polymer in the step (5) to the cementing material in the fresh concrete is 0.01-0.1: 1; the wavelength range of the ultraviolet light in the step (5) is 360-395 nm; the ultraviolet light intensity in the step (5) is 80-120mW/cm2。
The molecular structural formula of the polymer obtained in step (1) of the method of the present invention is as follows:
wherein R is1Is carboxyl, aldehyde or methylene hydroxyl; r2Hydrogen, sodium or potassium; r3Is hydrogen or methyl; r is4Is phenyl, carbomethoxy, carbethoxy, carbomethoxy, benzyl or o-tolyl;
wherein n is a positive integer representing the number of repeating units of each branch in the polymer, and n is in the range of 15 to 120.
Compared with the prior art, the method of the invention has the following beneficial effects:
1. based on the advantages of intelligent hydrogel composite assembly, the invention obtains the adsorption type hydrophobic polymer through hydrophobic monomer graft polymerization, then the polyvinyl alcohol is crosslinked under the action of a crosslinking agent and esterified with azobenzene derivatives to obtain the esterified hydrogel, and finally the photoresponse type polymer is obtained through composite assembly.
2. The invention discloses a novel functional polymer for concrete, which is characterized in that the intelligent hydrogel is a material capable of making corresponding intelligent response by contacting with the stimulation of the external environment, so that the property of the self structure or swelling characteristic is changed, and the required functional efficacy is exerted.
3. The invention creatively designs the assembly of the environment-responsive modified hydrogel and the core-shell structure of the adsorption type hydrophobic polymer, the synthetic product is a material which is composed of hydrophilic polymer cross-linked chains and contains a large number of environment-responsive groups, the three-dimensional network structure of the material can play a skeleton role, the void change is spontaneously generated under the action of the external ultraviolet light, the substances in the core-shell are regulated and released to be quickly anchored on the surfaces of cement particles in concrete slurry, a compact polymer adsorption layer is formed, the hydrophobic water retention effect is realized, and the technical advantages are obvious.
4. Compared with the traditional method, the synthesis method has the advantages of common and easily-obtained raw materials required by the reaction, simple and controllable synthesis process, conventional synthesis processes of esterification reaction, polymerization reaction, composite assembly and other steps, no need of special operation or expensive auxiliary agents, no special requirement on equipment, enrichment of the preparation method of the functional polymer for synthesizing the concrete, high efficiency, convenience, controllable molecular weight, high molecular design degree and the like, easy realization of industrial production, and remarkable popularization potential and application value.
5. The synthesized nuclear shell structure environment response type polymer shows intelligent and efficient response behavior under the action of ultraviolet light, the hydrogel polymer system is stable in state and strong in adaptability, the controlled release capability is not influenced by factors such as system ion concentration, the concrete material can show good effects of inhibiting shrinkage and resisting water absorption under a low mixing amount, the concrete material shows consistent regularity at different ages, and the hydrogel polymer has excellent performance indexes, is beneficial to driving technical innovation and optimizing upgrading, and has good economic benefit and application prospect.
Drawings
Fig. 1 is a graph showing the change in the encapsulation efficiency of examples 1 to 6.
Fig. 2 is a graph showing the change in the amount of the carrier in examples 1 to 6.
Fig. 3 is a graph showing transmittance changes before and after ultraviolet light irradiation in examples 1 to 6.
FIG. 4 is a graph showing the change in water absorption of concrete in comparative example and examples 1 to 6.
Detailed Description
The present invention will be described in further detail with reference to examples, but the practice of the present invention is not limited thereto.
Example 1
Adding 30g of methyl methacrylate and 300g of 1, 4-dioxane into a reactor, stirring and heating to 60 ℃, filling nitrogen, repeatedly deoxidizing for 20 minutes for 5 times, sealing, adding 18.18g of isooctyl 3-mercaptopropionate, adding 2.74g of nitric acid solution of 30 mass percent of ammonium ceric nitrate, stirring for 10 minutes, adding 19.4g of D-glucuronic acid aqueous solution with 60 mass percent, reacting for 4 hours at constant temperature, cooling to 20 ℃, adding 10 mass percent of sodium hydroxide solution for neutralizing to pH 7, distilling under reduced pressure to remove solvent, adding 4g of mass percent of sodium hydroxide, and stirring30% of sodium dodecyl sulfate aqueous solution to obtain polymer emulsion; adding 40g of polyvinyl alcohol and 10g of deionized water into a reactor, stirring and heating to 70 ℃, introducing nitrogen to purge for 20 minutes, adding 1.2g of epoxy chloropropane, stirring and reacting for 2 hours, pouring the mixed solution into a mould, cooling to 20 ℃, carrying out crosslinking reaction for 60 hours, then demoulding, and washing with deionized water for 5 times to obtain hydrogel; adding 30g of azobenzene-4-benzoic acid and 240g of dimethyl sulfoxide into a reactor, adding 30g of hydrogel and 1.2g of p-toluenesulfonic acid, stirring for 10 minutes, adding 12g of cyclohexane when the temperature is raised to 60 ℃, continuously raising the temperature to 90 ℃ to perform esterification reaction, separating water obtained by the reaction while reacting, vacuumizing after reacting for 10 hours to remove cyclohexane, cooling to 20 ℃, carrying out reduced pressure distillation to remove the solvent, and washing with deionized water for 5 times to obtain esterified hydrogel; adding 5g of esterified hydrogel into 100g of polymer emulsion, soaking for 6 hours, adding 15g of aqueous solution of ferric sulfate with the mass fraction of 20%, stirring for 45 minutes, washing with deionized water for 7 times, and drying in vacuum to obtain the photoresponse polymer; 1192.1g of photoresponsive polymer were incorporated into 23842g of fresh concrete and stirred homogeneously, after 24 hours with an intensity of 90mW/cm at a wavelength of 365nm2The ultraviolet light irradiates for 48 hours, and then the photoresponse can be generated and the corresponding application performance effect can be generated.
Example 2
Firstly, adding 30g of styrene and 90g of dimethyl sulfoxide into a reactor, stirring and heating to 70 ℃, filling nitrogen for 3 times, deoxidizing for 30 minutes, sealing, adding 5.19g of isopropanol, then adding 79.05g of nitric acid solution of ammonium ceric nitrate with the mass fraction of 20%, stirring for 12 minutes, then adding 24.23g of gluconic acid aqueous solution with the mass fraction of 70%, reacting for 2 hours at constant temperature, cooling to 20 ℃, adding 50% of sodium hydroxide solution with the mass fraction, neutralizing until the pH value is 7, removing the solvent by reduced pressure distillation, and then adding 9g of aqueous solution of sodium dodecyl sulfate with the mass fraction of 10%, thus obtaining polymer emulsion; adding 40g of polyvinyl alcohol and 24g of deionized water into a reactor, stirring, heating to 90 ℃, introducing nitrogen for purging for 5 minutes, adding 1.6g of terephthalaldehyde, stirring for reacting for 2 hours, pouring the mixed solution into a mold, and coolingDemoulding after the crosslinking reaction is carried out for 48 hours at the temperature of 20 ℃, and washing for 4 times by using deionized water to obtain hydrogel; adding 30g of 4-dimethylaminoazobenzene-4-carboxylic acid and 90g of 1, 4-dioxane into a reactor, adding 30g of hydrogel and 4.8g of phosphoric acid, stirring for 20 minutes, adding 6g of benzene when the temperature is raised to 70 ℃, continuously raising the temperature to 120 ℃ for esterification reaction, separating water obtained by the reaction while reacting, vacuumizing after reacting for 8 hours to remove benzene, cooling to 20 ℃, distilling under reduced pressure to remove the solvent, and washing with deionized water for 5 times to obtain esterified hydrogel; adding 5g of esterified hydrogel into 100g of polymer emulsion, soaking for 10 hours, adding 10g of aqueous solution of ferric sulfate with the mass fraction of 30%, stirring for 50 minutes, washing for 6 times by using deionized water, and then drying in vacuum to obtain the photoresponse polymer; 1181g of photoresponsive polymer is mixed into 23620g of fresh concrete and evenly stirred, and after 2 hours, the mixture is used for mixing with 80mW/cm of light intensity with the wavelength of 360nm2The ultraviolet light irradiates for 60 hours, and then the photoresponse can be generated and the corresponding application performance effect can be generated.
Example 3
Firstly, adding 30g of vinyl toluene and 150g of dimethylformamide into a reactor, stirring and heating to 80 ℃, filling nitrogen, repeatedly deoxidizing for 20 minutes, sealing, adding 27.71g of 3-isooctyl mercaptopropionate, adding 6.98g of nitric acid solution of ammonium ceric nitrate with the mass fraction of 20%, stirring for 5 minutes, adding 104.1g of gluconic acid aqueous solution with the mass fraction of 40%, reacting for 6 hours at constant temperature, cooling to 40 ℃, adding ethylenediamine solution with the mass fraction of 30% to neutralize until the pH value is 6, removing the solvent by reduced pressure distillation, and adding 12g of sodium stearate aqueous solution with the mass fraction of 20% to obtain polymer emulsion; adding 40g of polyvinyl alcohol and 32g of deionized water into a reactor, stirring, heating to 80 ℃, introducing nitrogen for purging for 12 minutes, adding 2g of glutaraldehyde, stirring for reacting for 2 hours, pouring the mixed solution into a mold, cooling to 40 ℃, carrying out crosslinking reaction for 60 hours, then demolding, and washing with deionized water for 5 times to obtain hydrogel; adding 30g of 4-dimethylaminoazobenzene-4-carboxylic acid and 150g of dimethylformamide into a reactor, adding 30g of hydrogel and 0.9g of sulfamic acid, stirring for 5 minutes, adding 18g of toluene when the temperature is increased to 80 ℃, and continuously heatingCarrying out esterification reaction at 110 ℃, separating water obtained in the reaction while reacting, vacuumizing to remove toluene after reacting for 8 hours, cooling to 40 ℃, distilling under reduced pressure to remove the solvent, and washing with deionized water for 5 times to obtain esterified hydrogel; adding 5g of esterified hydrogel into 50g of polymer emulsion, soaking for 12 hours, adding 30g of aqueous solution of sodium chloride with the mass fraction of 20%, stirring for 20 minutes, washing with deionized water for 8 times, and drying in vacuum to obtain a photoresponse polymer; 1204.4g of a photoresponsive polymer are admixed to 24088g of fresh concrete and stirred homogeneously, after 20 hours at 395nm with an intensity of 120mW/cm2The ultraviolet light irradiates for 30 hours, and then the photoresponse can be generated and the corresponding application performance effect can be generated.
Example 4
Firstly, adding 30g of phenylisoprene and 240g of 1, 4-dioxane into a reactor, stirring and heating to 60 ℃, filling nitrogen, repeatedly deoxidizing for 10 minutes for 5 times, sealing, adding 5.14g of n-dodecyl mercaptan, then adding 5.93g of nitric acid solution of 30 mass percent of ammonium ceric nitrate, stirring for 8 minutes, adding 55.42g of 50 mass percent sodium gluconate aqueous solution, reacting for 5 hours at constant temperature, cooling to 35 ℃, adding 20 mass percent potassium hydroxide solution for neutralizing until the pH value is 8, removing the solvent by reduced pressure distillation, and then adding 6g of 25 mass percent sodium dodecyl benzene sulfonate aqueous solution to obtain polymer emulsion; adding 40g of polyvinyl alcohol and 20g of deionized water into a reactor, stirring and heating to 70 ℃, introducing nitrogen for purging for 10 minutes, adding 0.8g of glutaraldehyde, stirring for reacting for 2 hours, pouring the mixed solution into a mold, cooling to 35 ℃, carrying out crosslinking reaction for 48 hours, then demolding, and washing with deionized water for 3 times to obtain hydrogel; adding 30g of azobenzene-4-benzoic acid and 180g of dimethylformamide into a reactor, adding 30g of hydrogel and 3g of sulfamic acid, stirring for 10 minutes, adding 12g of toluene when the temperature is raised to 70 ℃, continuously raising the temperature to 120 ℃ to perform esterification reaction, separating water obtained by the reaction while reacting, vacuumizing to remove the toluene after reacting for 5 hours, cooling to 35 ℃, carrying out reduced pressure distillation to remove the solvent, and washing with deionized water for 5 times to obtain esterified hydrogel; 5g of esterified hydrogel are added to 75g of polymer emulsionSoaking the solution for 6 hours, adding 22.5g of an aqueous solution of aluminum sulfate with the mass fraction of 40%, stirring for 30 minutes, washing with deionized water for 5 times, and then drying in vacuum to obtain a photoresponse polymer; 1196.3g of a photoresponsive polymer were incorporated into 23926g of fresh concrete and stirred homogeneously, after 10 hours with an intensity of 110mW/cm at a wavelength of 365nm2The ultraviolet light irradiates for 24 hours, and then the photoresponse can be generated and the corresponding application performance effect can be generated.
Example 5
Firstly, adding 30g of phenylpropylene and 90g of dimethylformamide into a reactor, stirring and heating to 90 ℃, filling nitrogen, repeatedly deoxidizing for 30 minutes for 5 times, sealing, adding 11.08g of isooctyl 3-mercaptopropionate, adding 17.8g of sulfuric acid solution of 25 mass percent of ammonium cerium sulfate, stirring for 15 minutes, adding 53.39g of aqueous solution of glucaric acid with the mass percent of 80 percent, reacting for 3 hours at constant temperature, cooling to 30 ℃, adding 25 mass percent of triethylamine solution, neutralizing until the pH value is 7, removing the solvent by reduced pressure distillation, and adding 30g of aqueous solution of 5 mass percent of sodium dodecyl diphenyl ether disulfonate to obtain polymer emulsion; adding 40g of polyvinyl alcohol and 12g of deionized water into a reactor, stirring and heating to 90 ℃, introducing nitrogen to purge for 15 minutes, adding 0.8g of terephthalaldehyde, stirring and reacting for 1 hour, pouring the mixed solution into a mold, cooling to 30 ℃, carrying out crosslinking reaction for 24 hours, then demolding, and washing with deionized water for 5 times to obtain hydrogel; adding 30g of 4-dimethylaminoazobenzene-4-carboxylic acid and 300g of 1, 4-dioxane into a reactor, adding 30g of hydrogel and 6g of phosphoric acid, stirring for 20 minutes, adding 15g of cyclohexane when the temperature is raised to 60 ℃, continuously raising the temperature to 100 ℃ for esterification reaction, separating water obtained by the reaction while reacting, vacuumizing after reacting for 5 hours to remove cyclohexane, cooling to 30 ℃, distilling under reduced pressure to remove a solvent, and washing with deionized water for 5 times to obtain esterified hydrogel; adding 5g of esterified hydrogel into 50g of polymer emulsion, soaking for 10 hours, adding 90g of aqueous solution of calcium chloride with the mass fraction of 10%, stirring for 35 minutes, washing with deionized water for 8 times, and drying in vacuum to obtain the photoresponse polymer; 1206g of photoresponsive polymer was incorporated into 24120g of fresh concrete and homogenizedStirring for 10 hr, and measuring with 375nm wavelength intensity of 80mW/cm2The ultraviolet light irradiates for 24 hours, and then the photoresponse can be generated and the corresponding application performance effect can be generated.
Example 6
Firstly, adding 30g of ethyl methacrylate and 210g of dimethyl sulfoxide into a reactor, stirring and heating to 80 ℃, filling nitrogen for repeatedly removing oxygen for 10 minutes, sealing, adding 6.32g of isopropanol, then adding 28.85g of nitric acid solution of ammonium ceric nitrate with the mass fraction of 40%, stirring for 12 minutes, then adding 51.58g of gluconic acid aqueous solution with the mass fraction of 50%, reacting for 6 hours at constant temperature, cooling to 35 ℃, adding 10% of potassium hydroxide solution with the mass fraction of 10% for neutralizing until the pH value is 7, removing the solvent by reduced pressure distillation, and then adding 10.5g of aqueous solution of sodium stearate with the mass fraction of 20% to obtain polymer emulsion; adding 40g of polyvinyl alcohol and 16g of deionized water into a reactor, stirring and heating to 70 ℃, introducing nitrogen to purge for 20 minutes, adding 2g of boric acid, stirring and reacting for 1 hour, pouring the mixed solution into a mold, cooling to 35 ℃, performing crosslinking reaction for 24 hours, then demolding, and washing with deionized water for 5 times to obtain hydrogel; adding 30g of azobenzene-4-benzoic acid and 210g of dimethyl sulfoxide into a reactor, adding 30g of hydrogel and 3.6g of p-toluenesulfonic acid, stirring for 15 minutes, adding 4.8g of cyclohexane when the temperature is raised to 80 ℃, continuously raising the temperature to 120 ℃ for esterification reaction, separating water obtained by the reaction while reacting, vacuumizing after reacting for 5 hours to remove cyclohexane, cooling to 35 ℃, carrying out reduced pressure distillation to remove the solvent, and washing with deionized water for 5 times to obtain esterified hydrogel; adding 5g of esterified hydrogel into 75g of polymer emulsion, soaking for 12 hours, adding 15g of aqueous solution of sodium chloride with the mass fraction of 20%, stirring for 30 minutes, washing with deionized water for 8 times, and drying in vacuum to obtain a photoresponse polymer; 1215.6g of a photoresponsive polymer are admixed with 24312g of fresh concrete and stirred homogeneously, after 12 hours with an intensity of 90mW/cm at 395nm, using a wavelength of 395nm2The ultraviolet light irradiates for 24 hours, and then the photoresponse can be generated and the corresponding application performance effect can be generated.
The implementation effect is as follows:
the encapsulation efficiency is shown in fig. 1, the amount of carrier is shown in fig. 2, and the optical response of the transmittance is shown in fig. 3. As can be seen from fig. 3, the transmittance is significantly reduced after the ultraviolet light irradiation, which indicates that the environment-responsive polymer can generate the environment response under the ultraviolet light irradiation, and the released adsorption-type hydrophobic polymer shows stronger hydrophobicity.
1. Water absorption of concrete
The concrete material composition ratio is shown in table 1, and the flexural anchoring content for fixing the synthesized environment responsive polymer of the present invention is 5% of the cement amount. The comparative example used was a concrete to which no environment-responsive polymer was added, and the proportions of the remaining components were unchanged.
TABLE 1 concrete mix proportion (kg/m)3)
| Cement | Fly ash | Mineral powder | Sand | Stone (stone) | Water (I) | Water reducing agent | Environmentally responsive polymers |
| 223 | 72 | 65 | 845 | 1050 | 162 | 0.6％ | 5％ |
As can be seen from fig. 4, the environmental response polymer can generate environmental response under the condition of ultraviolet light irradiation, and the released adsorption type hydrophobic polymer obviously reduces the water absorption rate, can effectively reduce the entrance of external moisture, and is beneficial to improving the durability of concrete.
2. Shrinkage reducing effect of concrete
The shrinkage test results of the concrete prepared according to table 1 are shown in table 2, the flexural strength of the environmental response polymer synthesized by the invention is fixed to 5% of the cement amount, the used comparative example is the concrete without the environmental response polymer, and the proportions of the other components are not changed.
TABLE 2 concrete shrinkage test results
| Polymer and method of making same | The mixing amount is% | 1d[×10-4] | 7d[×10-4] | 14d[×10-4] | 28d[×10-4] |
| Comparative example | 0 | -1.32 | -4.20 | -6.03 | -8.91 |
| Example 1 | 5 | -0.12 | -2.28 | -3.71 | -5.87 |
| Example 2 | 5 | -0.91 | -3.76 | -5.02 | -6.50 |
| Example 3 | 5 | -0.34 | -3.42 | -4.07 | -6.23 |
| Example 4 | 5 | -0.09 | -1.67 | -3.28 | -4.96 |
| Example 5 | 5 | -1.01 | -3.70 | -5.23 | -7.10 |
| Example 6 | 5 | -0.52 | -3.61 | -4.20 | -6.02 |
As can be seen from table 2, the environmental response polymer synthesized by the example of the present invention can significantly inhibit the shrinkage of concrete, and the environmental response polymer achieves the shrinkage reduction effect by releasing the adsorption type hydrophobic polymer under the irradiation of ultraviolet light, which is different from the action mechanism of typical concrete polymers. As can be seen from the shrinkage results in Table 2, the environmental response polymers synthesized in the examples of the present invention can effectively reduce the drying shrinkage of concrete, and the shrinkage of 1d, 7d, 14d and 28d is better than that of the comparative examples.
Claims (3)
1. The preparation method of the nuclear shell structure environment response type polymer is characterized in that:
(1) graft polymerization: adding a hydrophobic monomer and an organic solvent into a reactor, stirring and heating to 60-90 ℃, filling nitrogen, repeatedly deoxidizing for 10-30 minutes for 3-5 times, sealing, adding a molecular weight regulator, adding an acid solution of cerium ammonium salt with the mass fraction of 20-40%, stirring for 5-15 minutes, adding an aqueous solution of glucose derivatives with the mass fraction of 40-80%, reacting for 1-6 hours at a constant temperature, cooling to 20-40 ℃, adding an alkaline solution with the mass fraction of 10-50% to neutralize to a pH value of 6-8, removing the solvent by reduced pressure distillation, and adding an aqueous solution of an emulsifier with the mass fraction of 5-30%, thereby obtaining a polymer emulsion;
(2) and (3) crosslinking reaction: adding polyvinyl alcohol and deionized water into a reactor, stirring, heating to 70-90 ℃, introducing nitrogen, purging for 5-20 minutes, adding a cross-linking agent, stirring and reacting for 1-2 hours, pouring the mixed solution into a mould, cooling to 20-40 ℃, demoulding after the cross-linking reaction is carried out for 24-60 hours, and washing with deionized water for 3-5 times to obtain hydrogel;
(3) esterification reaction: adding an azobenzene derivative and an organic solvent into a reactor, adding the product hydrogel obtained in the step (2), adding a catalyst, stirring for 5-20 minutes, adding a water-carrying agent when the temperature is raised to 60-80 ℃, continuously raising the temperature to 90-120 ℃ to perform esterification reaction, separating water obtained by the reaction while reacting, vacuumizing after reacting for 2-10 hours to remove the water-carrying agent, cooling to 20-40 ℃, distilling under reduced pressure to remove the solvent, and washing with deionized water for 3-5 times to obtain esterified hydrogel;
(4) and (3) composite assembly: adding the esterified hydrogel obtained in the step (3) into the polymer emulsion obtained in the step (1), soaking for 6-12 hours, adding a flocculant aqueous solution with the mass fraction of 10% -40%, stirring for 20-50 minutes, washing with deionized water for 5-8 times, and then drying in vacuum to obtain the photoresponse polymer;
wherein, the hydrophobic monomer in the step (1) is one or more of styrene, phenylisopropylene, vinyl toluene, phenylpropylene, methyl methacrylate, ethyl methacrylate and butyl methacrylate; the organic solvent in the step (1) is dimethyl sulfoxide, 1, 4-dioxane or dimethylformamide, and the mass ratio of the dosage to the hydrophobic monomer in the step (1) is 3-10: 1; the molecular weight regulator in the step (1) is isopropanol, n-dodecyl mercaptan or isooctyl 3-mercaptopropionate, and the molar ratio of the dosage of the molecular weight regulator to the hydrophobic monomer in the step (1) is 0.1-0.5: 1; the acid solution of cerium ammonium salt in the step (1) is nitric acid solution of cerium ammonium nitrate or sulfuric acid solution of cerium ammonium sulfate, and the molar ratio of the dosage of cerium ammonium salt to the hydrophobic monomer in the step (1) is 0.005-0.15: 1; the glucose derivative in the step (1) is one or more of gluconic acid, sodium gluconate, potassium gluconate, glucaric acid and D-glucuronic acid, and the molar ratio of the dosage to the hydrophobic monomer in the step (1) is 0.2-1: 1; the solute of the alkaline solution in the step (1) is sodium hydroxide, potassium hydroxide, ethylenediamine or triethylamine; the emulsifier in the step (1) is sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, sodium stearate or sodium dodecyl diphenyl ether disulfonate, and the mass ratio of the dosage of the emulsifier to the hydrophobic monomer in the step (1) is 0.03-0.08: 1; the mass of the deionized water in the step (2) is 25-80% of that of the polyvinyl alcohol in the step (2); the cross-linking agent in the step (2) is glutaraldehyde, boric acid, epichlorohydrin or terephthalaldehyde, and the mass ratio of the dosage of the cross-linking agent to the polyvinyl alcohol in the step (2) is 0.02-0.05: 1; the azobenzene derivative in the step (3) is azobenzene-4-benzoic acid or 4-dimethylamine azobenzene-4-carboxylic acid; the organic solvent in the step (3) is dimethyl sulfoxide, 1, 4-dioxane or dimethylformamide, and the mass ratio of the dosage of the organic solvent to the azobenzene derivative in the step (3) is 3-10: 1; the catalyst in the step (3) is p-toluenesulfonic acid, phosphoric acid or sulfamic acid, and the dosage of the catalyst is 1.5-10% of the sum of the mass of the azobenzene derivative in the step (3) and the mass of the hydrogel in the step (2); the water-carrying agent in the step (3) is cyclohexane, benzene or toluene, and the using amount of the water-carrying agent is 8-30% of the sum of the mass of the azobenzene derivative in the step (3) and the mass of the hydrogel in the step (2); the mass ratio of the esterified hydrogel to the polymer emulsion in the step (4) is 1: 10-20; the flocculating agent in the step (4) is ferric sulfate, aluminum sulfate, sodium chloride or calcium chloride, and the mass ratio of the dosage to the hydrophobic monomer in the step (1) is 0.1-0.3: 1.
2. The method of claim 1, wherein the polymer of step (1) has the following molecular formula:
wherein R is1Is carboxyl, aldehyde or methylene hydroxyl; r2Hydrogen, sodium or potassium; r3Is hydrogen or methyl; r4Is phenyl, carbomethoxy, carbethoxy, carbomethoxy, benzyl or o-tolyl;
wherein n is a positive integer representing the number of repeat units in each branch of the polymer, and n is in the range of 15 to 120.
3. Use of a photoresponsive polymer obtainable by the process according to claim 1, characterized in that: the photoresponse polymer obtained in the step (4) is doped into fresh concrete and is uniformly stirred, and after 0.5-24 hours, ultraviolet light is used for irradiating for 24-60 hours, so that photoresponse can be generated; the mass ratio of the photoresponse polymer to the cementing material in the fresh concrete is 0.01-0.1: 1; the wavelength range of the ultraviolet light is 360-395 nm; the ultraviolet light intensity is 80-120mW/cm2。
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| CN1526747A (en) * | 2003-09-24 | 2004-09-08 | 天津工业大学 | Environment responding aquogel copolymer and its prepn |
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| CN107936268A (en) * | 2017-12-11 | 2018-04-20 | 长春工业大学 | A kind of preparation method of the tough hydrogel of the crosslinked environment sensitive of nucleocapsid microgel |
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| CN1526747A (en) * | 2003-09-24 | 2004-09-08 | 天津工业大学 | Environment responding aquogel copolymer and its prepn |
| CN102351459A (en) * | 2011-07-15 | 2012-02-15 | 清华大学 | Preparation method of sustained-release water reducer microcapsule |
| CN102633960A (en) * | 2012-04-01 | 2012-08-15 | 华东理工大学 | Multi-environmental-sensitivity triblock copolymer and preparation method and application thereof |
| CN105440190A (en) * | 2015-12-23 | 2016-03-30 | 北京科技大学 | Preparation method of multi-responsiveazobenzene functionalized polymer |
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