CN101608021B - Preparation method of N-isopropyl acrylamide polymer/polyvinyl alcohol composite hydrogel and product thereof - Google Patents
Preparation method of N-isopropyl acrylamide polymer/polyvinyl alcohol composite hydrogel and product thereof Download PDFInfo
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Abstract
The invention discloses a preparation method of N-isopropyl acrylamide polymer/polyvinyl alcohol composite hydrogel and a product thereof. The preparation method comprises the following steps: evenly mixing N-isopropyl acrylamide polymer solution having mass fraction of 0.5-1.5% with polyvinyl alcohol solution having mass fraction of 5-20% according to a mass ratio of 0.5-1.5:1, then slowly adding a crosslinking agent which is equivalent to 1-5% of the mass of the mixed liquor obtained, evenly stirring, and keeping standing for 8-24 hours to obtain the N-isopropyl acrylamide polymer/polyvinyl alcohol composite hydrogel. The N-isopropyl acrylamide polymer is a homopolymer of N-isopropyl acrylamide or a copolymer of the N-isopropyl acrylamide and acrylic ester or methacrylate. The preparation method is characterized by simple operation and low cost, and the obtained product is characterized by good temperature sensitivity, stable morphology, not easy leakage and better mechanical property, and has wide application prospect in the intelligent light-control energy-saving material field.
Description
Technical field
The present invention relates to a kind of preparation method of temperature sensitive hydrogel and the product that makes thereof, particularly the preparation method of N-isopropyl acrylamide polymer compound/polyvinyl alcohol composite hydrogel and the product that makes thereof.
Background technology
Building energy conservation is not only the economic problems that reduce energy consumption, and is the grand strategy problem of human kind sustainable development.95% is highly energy-consuming building in China's existing building, and more than 27% of total energy consumption of the building energy consumption account whole nation occupies first of all kinds of energy consumptions, and the unit building energy consumption is 3 times of developed country under the homoclime condition.Therefore, advance building energy conservation very urgent with all strength.
Go along with sb. to guard him greatly in the parts influencing the door and window of building energy consumption, body of wall, roofing, ground four, the heat-insulating property of door and window is the poorest, and its energy consumption accounts for 40%～50% of building enclosure parts total energy consumption.Therefore, strengthening the thermal and insulating performance of door and window, reduce the door and window energy consumption, is the important step of improving the indoor thermal environment quality and improving the building energy conservation level.
Intelligent aqueous gel capable is a kind of hydrophilic but be not dissolved in the crosslink polymer network of water, stimulates (as temperature, pressure, electric field, magnetic field, light, pH value or ionic strength etc.) can perception and respond by swelling and contraction for the small physical chemistry of environment.Poly N-isopropyl acrylamide (PNIPA) hydrogel is a kind of temperature sensitive hydrogel that is widely studied, and lowest critical solution temperature (LCST) is 33 ℃.When envrionment temperature was lower than this temperature, poly N-isopropyl acrylamide hydrogel water absorption and swelling, hydrogel were water white transparency; When envrionment temperature was higher than this temperature, the poly N-isopropyl acrylamide hydrogel shrank dehydration and takes place to change mutually, and hydrogel changes gonorrhoea into by water white transparency.N-N-isopropylacrylamide (NIPA) has temperature sensitivity equally with the copolymer aquagel of acrylate or methacrylic ester, and LCST can regulate and control in 18～33 ℃ by the structure and the ratio that change comonomer.Therefore, N-isopropyl acrylamide polymer compound hydrogel can be used as the intelligent dimming material and is used to make the energy-saving glass door and window, thereby reaches light modulation, thermoregulated effect, reduces the door and window energy consumption.But N-isopropyl acrylamide polymer compound hydrogel is a kind of viscous aqueous solution, and the form instability is leaked easily, and poor mechanical property, should not directly make the energy-saving glass door and window.
Polyvinyl alcohol (PVA) hydrogel has snappiness, be easy to moulding, advantage such as have no side effect, and is used widely at biomedical sector.
Summary of the invention
In view of this, one of purpose of the present invention is to provide a kind of preparation method of N-isopropyl acrylamide polymer compound/polyvinyl alcohol composite hydrogel, and is easy and simple to handle, with low cost; Two of purpose of the present invention is to provide a kind of product that adopts this method to make, and not only has good temperature sensitivity, and form stable, the difficult leakage, and mechanical property is better.
For achieving the above object, in a first aspect of the present invention, a kind of preparation method of N-isopropyl acrylamide polymer compound/polyvinyl alcohol composite hydrogel is provided, with massfraction is that 0.5%～1.5% the N-isopropyl acrylamide polymer compound aqueous solution and massfraction are that 5%～20% polyvinyl alcohol water solution is 0.5～1.5 according to mass ratio: 1 mixes, slowly add the linking agent that is equivalent to above-mentioned mixed solution quality 1%～5% again, stir, left standstill 8～24 hours, and promptly got N-isopropyl acrylamide polymer compound/polyvinyl alcohol composite hydrogel;
The homopolymer that described N-isopropyl acrylamide polymer compound is the N-N-isopropylacrylamide or the multipolymer of N-N-isopropylacrylamide and acrylate or methacrylic ester.
Further, described acrylate is methyl acrylate, ethyl propenoate or butyl acrylate; Described methacrylic ester is methyl methacrylate, Jia Jibingxisuanyizhi or butyl methacrylate;
Further, the mass ratio of N-N-isopropylacrylamide and acrylate is 1: 0.03～0.15 in the multipolymer of described N-N-isopropylacrylamide and acrylate; The mass ratio of N-N-isopropylacrylamide and methacrylic ester is 1: 0.03～0.15 in the multipolymer of described N-N-isopropylacrylamide and methacrylic ester;
Further, the polymerization degree of described polyvinyl alcohol is 1000～10000;
Further, the massfraction of the described N-isopropyl acrylamide polymer compound aqueous solution is 0.6%～1.2%; The massfraction of described polyvinyl alcohol water solution is 8%～15%;
Further, the massfraction of the described N-isopropyl acrylamide polymer compound aqueous solution is 0.8%～1.0%; The massfraction of described polyvinyl alcohol water solution is 9%～12%;
Further, the mass ratio of described N-isopropyl acrylamide polymer compound solution and polyvinyl alcohol solution is 1: 1;
Further, described linking agent is organic crosslinking agent or inorganic crosslinking agent, and described organic crosslinking agent is made up of the acidic mixed aqueous solution of dialdehyde or diphenol or polyphenol, methyl alcohol, glacial acetic acid and the vitriol oil; Described inorganic crosslinking agent is made up of the alkaline aqueous solution of borax or boric acid;
Further, described organic crosslinking agent is made up of the acidic mixed aqueous solution of glutaraldehyde, methyl alcohol, glacial acetic acid and the vitriol oil: it is 5% solution that the glutaraldehyde dilute with water of 5 parts by volume is made volume fraction; It is 50% solution that the methyl alcohol dilute with water of 20 parts by volume is made volume fraction; It is 10% solution that the glacial acetic acid dilute with water of 2 parts by volume is made volume fraction; It is 20% solution that the vitriol oil dilute with water of 2 parts by volume is made volume fraction; Above-mentioned 4 kinds of solution are mixed, promptly.
In a second aspect of the present invention, the product that provides the preparation method that adopts described N-isopropyl acrylamide polymer compound/polyvinyl alcohol composite hydrogel to make.
Beneficial effect of the present invention is: the present invention makes composite aquogel with N-isopropyl acrylamide polymer compound and polyvinyl alcohol under the effect of linking agent, easy and simple to handle, with low cost; The gained composite aquogel has good temperature sensitivity, and stable in properties can repeat transparent-reversible change process of gonorrhoea heat and reach more than ten thousand times; The LCST scope is wide, and is adjustable between 18～33 ℃; The visible light transmissivity difference of clear state and gonorrhoea attitude is big, surpasses 70%; And form stable, the difficult leakage has mechanical property and stretch-proof ability preferably; Have wide practical use in intelligent dimming energy-saving material field, can be made into intelligent dimming energy-saving glass pad pasting or be used to prepare intelligent dimming energy-saving glass door and window as the core of laminated glass, when summer temp is higher, play the sunshading and heat-insulating effect, reduce room temp, reduce energy consumption for cooling; Competent daylighting in the holding chamber reduced electric consumption on lighting and heating energy consumption when temperature was low in the winter time.
Embodiment
In order to make the purpose, technical solutions and advantages of the present invention clearer, below the preferred embodiments of the present invention are described in detail.
The preparation of embodiment 1, poly N-isopropyl acrylamide/polyvinyl alcohol composite hydrogel
It is 5% solution that the glutaraldehyde dilute with water of 5mL is made volume fraction; It is 50% solution that the methyl alcohol dilute with water of 20mL is made volume fraction; It is 10% solution that the glacial acetic acid dilute with water of 2mL is made volume fraction; It is 20% solution that the vitriol oil dilute with water of 2mL is made volume fraction; Above-mentioned 4 kinds of solution are mixed, promptly get organic crosslinking agent;
With the 10g massfraction is that 1% the poly N-isopropyl acrylamide aqueous solution and 10g massfraction are that 10% polyvinyl alcohol 1799 (mean polymerisation degree is 1750 ± 50) aqueous solution is even, drip the 0.5g organic crosslinking agent again, stir, left standstill 24 hours, and promptly got poly N-isopropyl acrylamide/polyvinyl alcohol composite hydrogel.
After testing, the LCST of gained composite aquogel is 33.2 ℃; Thickness is that the clear state of composite aquogel film of 1mm and the visible light transmissivity difference of gonorrhoea attitude are 87%.
The preparation of embodiment 2, poly-(N-N-isopropylacrylamide-methyl acrylate)/polyvinyl alcohol composite hydrogel
According to embodiment 1 described method, substitute poly N-isopropyl acrylamide with poly-(N-N-isopropylacrylamide-methyl acrylate), make poly-(N-N-isopropylacrylamide-methyl acrylate)/polyvinyl alcohol composite hydrogel.
After testing, with the composite aquogel that (N-N-isopropylacrylamide-methyl acrylate) makes that gathers of different monomers mass ratio, its LCST is as shown in table 1; Thickness is the composite aquogel film of 1mm, and the visible light transmissivity difference of its clear state and gonorrhoea attitude is as shown in table 1.
The performance of table 1, the composite aquogel that makes with poly-(the N-N-isopropylacrylamide-methyl acrylate) of different monomers mass ratio
The preparation of embodiment 3, poly-(N-N-isopropylacrylamide-ethyl propenoate)/polyvinyl alcohol composite hydrogel
According to embodiment 1 described method, substitute poly N-isopropyl acrylamide with poly-(N-N-isopropylacrylamide-ethyl propenoate), make poly-(N-N-isopropylacrylamide-ethyl propenoate)/polyvinyl alcohol composite hydrogel.
After testing, with the composite aquogel that (N-N-isopropylacrylamide-ethyl propenoate) makes that gathers of different monomers mass ratio, its LCST is as shown in table 2; Thickness is the composite aquogel film of 1mm, and the visible light transmissivity difference of its clear state and gonorrhoea attitude is as shown in table 2.
The performance of table 2, the composite aquogel that makes with poly-(the N-N-isopropylacrylamide-ethyl propenoate) of different monomers mass ratio
The preparation of embodiment 4, poly-(N-N-isopropylacrylamide-butyl acrylate)/polyvinyl alcohol composite hydrogel
According to embodiment 1 described method, substitute poly N-isopropyl acrylamide with poly-(N-N-isopropylacrylamide-butyl acrylate), make poly-(N-N-isopropylacrylamide-butyl acrylate)/polyvinyl alcohol composite hydrogel.
After testing, adopt the composite aquogel that (N-N-isopropylacrylamide-butyl acrylate) makes that gathers of different monomers mass ratio, its LCST is as shown in table 3; Thickness is the composite aquogel film of 1mm, and the visible light transmissivity difference of its clear state and gonorrhoea attitude is as shown in table 3.
The performance of table 3, the composite aquogel that makes with poly-(the N-N-isopropylacrylamide-butyl acrylate) of different monomers mass ratio
The preparation of embodiment 5, poly-(N-N-isopropylacrylamide-methyl methacrylate)/polyvinyl alcohol composite hydrogel
According to embodiment 1 described method, substitute poly N-isopropyl acrylamide with poly-(N-N-isopropylacrylamide-methyl methacrylate), make poly-(N-N-isopropylacrylamide-methyl methacrylate)/polyvinyl alcohol composite hydrogel.
After testing, with the composite aquogel that (N-N-isopropylacrylamide-methyl methacrylate) makes that gathers of different monomers mass ratio, its LCST is as shown in table 4; Thickness is the composite aquogel film of 1mm, and the visible light transmissivity difference of its clear state and gonorrhoea attitude is as shown in table 4.
The performance of table 4, the composite aquogel that makes with poly-(the N-N-isopropylacrylamide-methyl methacrylate) of different monomers mass ratio
The preparation of embodiment 6, poly-(N-N-isopropylacrylamide-Jia Jibingxisuanyizhi)/polyvinyl alcohol composite hydrogel
According to embodiment 1 described method, substitute poly N-isopropyl acrylamide with poly-(N-N-isopropylacrylamide-Jia Jibingxisuanyizhi), make poly-(N-N-isopropylacrylamide-Jia Jibingxisuanyizhi)/polyvinyl alcohol composite hydrogel.
After testing, with the composite aquogel that (N-N-isopropylacrylamide-Jia Jibingxisuanyizhi) makes that gathers of different monomers mass ratio, its LCST is as shown in table 5; Thickness is the composite aquogel film of 1mm, and the visible light transmissivity difference of its clear state and gonorrhoea attitude is as shown in table 5.
The performance of table 5, the composite aquogel that makes with poly-(the N-N-isopropylacrylamide-Jia Jibingxisuanyizhi) of different monomers mass ratio
The preparation of embodiment 7, poly-(N-N-isopropylacrylamide-butyl methacrylate)/polyvinyl alcohol composite hydrogel
According to embodiment 1 described method, substitute poly N-isopropyl acrylamide with poly-(N-N-isopropylacrylamide-butyl methacrylate), make poly-(N-N-isopropylacrylamide-butyl methacrylate)/polyvinyl alcohol composite hydrogel.
After testing, adopt the composite aquogel that (N-N-isopropylacrylamide-butyl methacrylate) makes that gathers of different monomers mass ratio, its LCST is as shown in table 6; Thickness is the composite aquogel film of 1mm, and the visible light transmissivity difference of its clear state and gonorrhoea attitude is as shown in table 6.
The performance of table 6, the composite aquogel that makes with poly-(the N-N-isopropylacrylamide-butyl methacrylate) of different monomers mass ratio
In the present invention, linking agent can be organic crosslinking agent, also can be inorganic crosslinking agent.Organic crosslinking agent preferably is made up of the dialdehyde (oxalic dialdehyde, mda, suceinic aldehyde, glutaraldehyde etc.) or the acidic mixed aqueous solution of diphenol (Resorcinol, pyrocatechol, 2,4-resorcylic acid etc.) or polyphenol (Phloroglucinol, gallic acid etc.), methyl alcohol, glacial acetic acid and the vitriol oil; Most preferably form by the acidic mixed aqueous solution of glutaraldehyde, methyl alcohol, glacial acetic acid and the vitriol oil.Inorganic crosslinking agent preferably is made up of the alkaline aqueous solution of borax or boric acid, can adopt following method preparation: with 5.0g borax and 0.2g sodium hydroxide 100mL deionized water dissolving, perhaps, with 6.0g boric acid and 1.0g sodium hydroxide 100mL deionized water dissolving, promptly get inorganic crosslinking agent.
With reference to embodiment 1～7, with massfraction is 0.5%～1.5% (to be preferably 0.6%～1.2%, be more preferred from 0.8%～1.0%, the best is 1.0%) N-isopropyl acrylamide polymer compound solution and massfraction be 5%～20% (to be preferably 8%～15%, be more preferred from 9%～12%, the best is 10%) polyvinyl alcohol (polymerization degree is 1000～10000) solution be (to be preferably 0.7～1.3: 1 at 0.5～1.5: 1 according to mass ratio, be more preferred from 0.8～1.2: 1, the best is 1: 1) mix, slow again adding is equivalent to above-mentioned mixed solution quality 1%～5% and (is preferably 1.5%～4%, be more preferred from 2%～3%, the best is 2.5%) the organic or inorganic linking agent, stir, leave standstill 8～24 hours (being preferably 12～24 hours), can make N-isopropyl acrylamide polymer compound/polyvinyl alcohol composite hydrogel.
The gained composite aquogel has good temperature sensitivity, and stable in properties can repeat transparent-reversible change process of gonorrhoea heat and reach more than ten thousand times; The LCST scope is wide, and is adjustable between 18～33 ℃; The visible light transmissivity difference of clear state and gonorrhoea attitude is big, surpasses 70%; Form is similar to jelly, and is stable, the difficult leakage, and mechanical property is preferably arranged.The composite aquogel that adopts organic crosslinking agent to make is compared with the composite aquogel that adopts inorganic crosslinking agent to make, the visible light transmissivity difference of the LCST of the two, clear state and gonorrhoea attitude is basic identical, the composite aquogel stretch-proof ability that adopts organic crosslinking agent to make is strong, can be used to prepare intelligent dimming energy-saving glass pad pasting; Though the composite aquogel stretch-proof ability that adopts inorganic crosslinking agent to make is not so good as the former, cost of material is lower, and the core that can be used as laminated glass is used to prepare the energy-conservation laminated glass window of intelligent dimming.
Explanation is at last, above embodiment is only unrestricted in order to technical scheme of the present invention to be described, although by invention has been described with reference to the preferred embodiments of the present invention, but those of ordinary skill in the art is to be understood that, can make various changes to it in the form and details, and the spirit and scope of the present invention that do not depart from appended claims and limited.
Claims (9)
1.N-the preparation method of isopropyl acrylamide polymer compound/polyvinyl alcohol composite hydrogel, it is characterized in that: with massfraction is that 0.5%～1.5% the N-isopropyl acrylamide polymer compound aqueous solution and massfraction are that 5%～20% polyvinyl alcohol water solution is 0.5～1.5 according to mass ratio: 1 mixes, slowly add the linking agent that is equivalent to above-mentioned mixed solution quality 1%～5% again, stir, left standstill 8～24 hours, and promptly got N-isopropyl acrylamide polymer compound/polyvinyl alcohol composite hydrogel;
The homopolymer that described N-isopropyl acrylamide polymer compound is the N-N-isopropylacrylamide or the multipolymer of N-N-isopropylacrylamide and acrylate or methacrylic ester;
Described linking agent is organic crosslinking agent or inorganic crosslinking agent, and described organic crosslinking agent is made up of the acidic mixed aqueous solution of dialdehyde or diphenol or polyphenol, methyl alcohol, glacial acetic acid and the vitriol oil; Described inorganic crosslinking agent is made up of the alkaline aqueous solution of borax or boric acid.
2. the preparation method of N-isopropyl acrylamide polymer compound/polyvinyl alcohol composite hydrogel according to claim 1 is characterized in that: described acrylate is methyl acrylate, ethyl propenoate or butyl acrylate; Described methacrylic ester is methyl methacrylate, Jia Jibingxisuanyizhi or butyl methacrylate.
3. the preparation method of N-isopropyl acrylamide polymer compound/polyvinyl alcohol composite hydrogel according to claim 2 is characterized in that: the mass ratio of N-N-isopropylacrylamide and acrylate is 1: 0.03～0.15 in the multipolymer of described N-N-isopropylacrylamide and acrylate; The mass ratio of N-N-isopropylacrylamide and methacrylic ester is 1: 0.03～0.15 in the multipolymer of described N-N-isopropylacrylamide and methacrylic ester.
4. the preparation method of N-isopropyl acrylamide polymer compound/polyvinyl alcohol composite hydrogel according to claim 1 is characterized in that: the polymerization degree of described polyvinyl alcohol is 1000～10000.
5. the preparation method of N-isopropyl acrylamide polymer compound/polyvinyl alcohol composite hydrogel according to claim 1 is characterized in that: the massfraction of the described N-isopropyl acrylamide polymer compound aqueous solution is 0.6%～1.2%; The massfraction of described polyvinyl alcohol water solution is 8%～15%.
6. the preparation method of N-isopropyl acrylamide polymer compound/polyvinyl alcohol composite hydrogel according to claim 5 is characterized in that: the massfraction of the described N-isopropyl acrylamide polymer compound aqueous solution is 0.8%～1.0%; The massfraction of described polyvinyl alcohol water solution is 9%～12%.
7. the preparation method of N-isopropyl acrylamide polymer compound/polyvinyl alcohol composite hydrogel according to claim 1 is characterized in that: the mass ratio of the described N-isopropyl acrylamide polymer compound aqueous solution and polyvinyl alcohol water solution is 1: 1.
8. the preparation method of N-isopropyl acrylamide polymer compound/polyvinyl alcohol composite hydrogel according to claim 1 is characterized in that: described organic crosslinking agent is made up of the acidic mixed aqueous solution of glutaraldehyde, methyl alcohol, glacial acetic acid and the vitriol oil: it is 5% solution that the glutaraldehyde dilute with water of 5 parts by volume is made volume fraction; It is 50% solution that the methyl alcohol dilute with water of 20 parts by volume is made volume fraction; It is 10% solution that the glacial acetic acid dilute with water of 2 parts by volume is made volume fraction; It is 20% solution that the vitriol oil dilute with water of 2 parts by volume is made volume fraction; Above-mentioned 4 kinds of solution are mixed, promptly.
9. the product that adopts the preparation method of the described N-isopropyl acrylamide polymer of claim 1 compound/polyvinyl alcohol composite hydrogel to make.
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