CN102219974B - Organic intelligent glass with performance of heat storage and heat release and preparation method thereof - Google Patents
Organic intelligent glass with performance of heat storage and heat release and preparation method thereof Download PDFInfo
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Abstract
The invention discloses organic intelligent glass with the performance of heat storage and heat release and a preparation method thereof. In the organic intelligent glass, polymethylmethacrylate is taken as a matrix material, and polyethylene glycol is taken as an intelligent heat storage and release material, wherein the addition amount of the polyethylene glycol is 10 to 30 percent based on that of the matrix material. The preparation method comprises the following steps of: mixing the polyethylene glycol, a polymethylmethacrylate monomer and an initiator, performing pre-polymerization by thermal initiation at a high temperature, pouring into a die, and polymerizing and demolding to obtain a finished product. The preparation method is simple, the added polyethylene glycol serving as a heat storage material is non-toxic and harmless, and cannot pollute an environment, and a production process is mature, so the organic intelligent glass is easy to produce and synthesize and is used on a large scale. The organic intelligent glass can be applied to temperature regulating fabrics and building materials.
Description
One, technical field
The present invention relates to material of construction of a kind of efficient energy-saving energy-consumption and preparation method thereof, specifically a kind of organic intelligent glass with heat accumulation exothermicity and preparation method thereof.
Two, background technology
According to statistics, China's building energy consumption has reached 30% in social total energy consumption, along with the expansion of Chinese Urbanization scale, the propelling of city-building, and the raising of living standards of the people, building energy consumption will cumulative year after year.China in 1996 building year consumes 3.3 hundred million tons of standard coals, accounts for 24% of energy consumption total amount, has reached 3.76 hundred million tons to calendar year 2001, account for that total amount consumes 27.6%, annual growth is 5/1000ths.According to prediction, China will be within shorter time in future, and building energy consumption will rise to more than 35%.The situation of domestic present energy scarcity will be faced with formidable challenges.In recent years south China and North China frequently power cuts to limit consumption beaten alarm bell to us.Current, building energy conservation has become the common key subjects of paying close attention in countries in the world, is the particularly important leverage of the rapid growth of China's economy of the sustainable development of socio-economy.
The power saving of window is the problem that at first must consider in the building energy conservation.Building ten go along with sb. to guard him greatly (door and window, body of wall, roofing and ground) in the parts, the energy consumption of door and window is about 4 times of body of wall, 5 times of roofing, more than 20 times of ground accounts for more than 50% of architectural exterior-protecting construction energy consumption.
Western developed country is carried out Building Energy-saving Work from 20 century 70s, obtained so far very outstanding effect.The power-saving technology of window has also obtained considerable progress, and that Energy Saving Windows presents is multi-functional, the development trend of hi-tech.People to the functional requirement of window from simple printing opacity, keep out the wind, keep off the rain energy-conservation, comfortable, adjust lighting quantity etc. flexibly, technically from using common sheet glass to using hollow heat insulation technology (double glazing) and various high performance adiabatic masking techniques (heat-reflecting glass etc.).At present, developed country has begun to develop the energy-saving glass window that the next generation has " intellectuality ", is called for short smart window, and this smart window can change according to envrionment conditions or people's will and penetrates indoor sunshine amount, realizes energy-conservation to greatest extent.With regard to present total situation, Energy Saving Windows also is not widely applied in China.The one, the Building Energy-saving Work of China is started late, and corresponding rules are complete not enough, and whole people's awareness of saving energy is also strong not; The 2nd, China's Energy Saving Windows technology is perfect not, and cost is higher, and market is difficult to accept.But with regard to the experience in developed country and area, the application of Energy Saving Windows is the important step of building energy conservation, all can be widely adopted sooner or later.According to the rough estimates of the American National door and window evaluation council (NFRC), can save 30% heating and refrigeration expense between the use year of Energy Saving Windows.The America and Europe, the building more than 90% has adopted double glazing at present, and 40% glass has been brought into use the Low-E double glazing in the building.
Yet, the demand of people's gegenschein radiation in practical situation, along with weather and season, even different time on the same day and changing.When weather was warmmer, we wished that the solar thermal energy radiation of trying one's best few enters indoor; When it cyclostrophic was cool, we wished that solar thermal energy radiation as much as possible enters indoor.Certainly, adopt mechanical shading system to achieve the goal.If but set about from glass itself, make can automatically regulating with temperature of glass, should be a kind of more advanced reasonable approach, Here it is so-called intelligent type energy saving window, abbreviation smart window.Intelligent characteristics will be important symbols of Energy Saving Windows of future generation.The appearance of smart window indicates people's further going deep into and propelling building energy conservation.The realization of smart window can have various ways.These smart window mainly rely on the film that is deposited on the window glass, under some physical factor (such as light, electricity or heat) excites the optical property of film are changed, thereby realize the adjusting to sun power irradiation.The smart window of these Discoloration mechanisms all can realize sunlight adjusting in various degree, but cut both ways.For example, electrochromism can be changed to low transmission continuously from high permeability, and switch efficiency is higher, but complex manufacturing technology and need the power supply voltage supply, system cost is higher, and present small-scale application is on high-grade vehicle glass; Photochromicly can change optical property (such as sun glasses) by illumination simply, but can't be applicable to float glass process at present, if what play discoloration is the organic plastics layer, the weather resistance of material is again a problem; The gas-discoloration Energy Saving Windows is a focus of current research, and this Energy Saving Windows can realize variable color by the hydrogen hydrogen gas mixture, and maximum sharp point is that it can be combined with the solar hydrogen making technology; Another kind method then is to add phase-change heat-storage material in window glass, absorb heat energy superfluous in daytime and when need night, discharge, thereby can alleviate the contradiction of energy supply and demand on time-space, therefore in the society of the current outstanding energy and environmental problem, phase change material receives much concern.
Phase-change heat-storage material comprises inorganics and organism two large classes.Most inorganic phase-changing materials have corrodibility, and have the shortcoming that cold-peace is separated in phase transition process, affect its use.And organic phase change material does not in use just have above-mentioned shortcoming, and stable chemical nature, low price, so practical application maximum be organic phase change material.Polyoxyethylene glycol is as a kind of common intelligent organic phase-change heat accumulating, has advantages of nontoxic, nonirritant and with many organic matter components good intermiscibility arranged.Simultaneously, the polyoxyethylene glycol of different molecular weight has different transformation temperatures and stores thermal energy larger, can well be used for building energy saving field.Therefore, thus it is a kind of new selection of present building energy conservation that this intelligence of polyoxyethylene glycol is stored that hot material and this high strength of PMMA, high transparent material be combined with each other as the substitute of window-glass in the existing building.
Three, summary of the invention
The present invention aims to provide a kind of organic intelligent glass with heat accumulation exothermicity and preparation method thereof, to reach energy-conservation purpose.The technical issues that need to address are to find a kind of phase-change heat-storage material to make itself and body material have good consistency.
Technical solution problem of the present invention adopts following technical scheme:
The characteristics that the present invention has the organic intelligent glass of heat accumulation exothermicity are: described organic intelligent glass is as body material take polymethylmethacrylate, polyoxyethylene glycol is that intelligence is stored hot material, and wherein the addition of polyoxyethylene glycol is the 10-30% of body material quality.
The characteristics that the present invention has the organic intelligent glass of heat accumulation exothermicity also are: the number-average molecular weight of described polyoxyethylene glycol is 600-20000.
Preparation method's the characteristics that the present invention has the organic intelligent glass of heat accumulation exothermicity are: at first polyoxyethylene glycol, methyl methacrylate monomer and initiator mixed, and the pre-polymerization of high temperature thermal initiation, through filling with mould, polymerization and the demoulding get product again; Described initiator is azo-bis-isobutyl cyanide or benzoyl peroxide.
Preparation method's the characteristics that the present invention has the organic intelligent glass of heat accumulation exothermicity are to operate according to the following steps:
Polyoxyethylene glycol, methyl methacrylate and initiator are mixed, and in 70-90 ℃ of heating in water bath prepolymerization, when solution system viscosity reaches 0.8-1.0Pas, stopped heating also is cooled to room temperature and namely gets performed polymer after the sealing; Described performed polymer is poured in the mould, in 35-45 ℃ of curing reaction 24-30 hour, subsequently at 95-105 ℃ of thermal treatment 1-2 hour, be cooled to after the room temperature demoulding and namely get and have the pmma material that intelligence is stored heat after the sealing;
The addition of described initiator is the 0.01-0.1% of body material quality.
Preparation method's the characteristics that the present invention has the organic intelligent glass of heat accumulation exothermicity also are: solidification value is 40 ℃, and thermal treatment temp is 100 ℃.
As a kind of novel energy-saving building materials, it is simple that present method has preparation, is easy to the advantages such as production cost is low.The thickness of window-glass can be by adjusting the total amount of monomer, and thermal storage performance then can be adjusted by proportioning between adjustment monomer and the heat accumulating.
Compared with the prior art, beneficial effect of the present invention is embodied in:
1, heat accumulating polyoxyethylene glycol during the present invention evenly distributes in polymethylmethacrylate, thereby give the characteristics of building glass material Intelligent heat storage, namely when room temp is higher, the polyoxyethylene glycol that synthetic glass mixes can and store unnecessary heat absorption, in case Indoor Temperature is spent and low just can have been discharged the energy of storage, thereby greatly reduce the consumption of the energy.
2, the control thermal characteristics of organic intelligent glass of the present invention can be controlled by the molecular weight of adjusting polyoxyethylene glycol and with the polymer monomer proportioning.The control thermal characteristics of namely controlling hot material can be controlled, therefore, and the building glass material that can obtain being fit to by optimizing reaction conditions.
3, the present invention can also be as heat insulating material formed for food product pack, the fields such as fabric.
4, preparation method of the present invention is simple, and the heat accumulating polyoxyethylene glycol of interpolation is nontoxic, can not give environment, and production technique is ripe, is easy to produce synthetic and large-scale the use.
Four, description of drawings
Fig. 1 is the optical photograph of the organic intelligent glass for preparing of the present invention.
Fig. 2 is the optical photograph of the organic intelligent glass of the different PEG 20000 additions that prepare of the present invention.
Fig. 3 is the optical photograph of organic intelligent glass of the polyoxyethylene glycol of the interpolation different molecular weight for preparing of the present invention.
Fig. 4 be the different Macrogol 2000 additions that prepare of the present invention organic intelligent glass store thermal characteristics figure.
Fig. 5 be the interpolation different molecular weight for preparing of the present invention polyoxyethylene glycol organic intelligent glass store thermal characteristics figure.
Fig. 6 is the XRD spectra of the organic intelligent glass for preparing of the present invention.
Five, embodiment
Embodiment 1:
The organic intelligent glass that has the heat accumulation exothermicity in the present embodiment is take polymethylmethacrylate as body material, and polyoxyethylene glycol is that intelligence is stored hot material, and wherein the number-average molecular weight of polyoxyethylene glycol is 2000, and transformation temperature is 41-46 ℃.
The organic intelligent glass that has the heat accumulation exothermicity in the present embodiment prepares by the following method:
Methyl methacrylate 25g, polyoxyethylene glycol 2.5g and the initiator benzoyl peroxide 25mg of newly distillation are added in the Erlenmeyer flask, steam enters in the Erlenmeyer flask when preventing pre-polymerization, wrap one deck preservative film at bottleneck after shaking up, tighten with rubber ring again, sealing is rear in 70-90 ℃ of heating in water bath prepolymerization, when solution system viscosity reaches 0.8-1.0Pas, stopped heating and be cooled to room temperature obtains performed polymer to stop polyreaction immediately; The gained performed polymer is poured in the mould, be careful when filling with mould, do not make prepolymer intermediate formation bubble, and entirely do not fill, slightly stay one section space, in order to avoid prepolymer expanded by heating and overflowing, then with preservative film mould is sealed, make prepolymer and air isolated, sealing is rear in 40 ℃ of curing reaction 24-30 hours, subsequently at 100 ℃ of thermal treatment 1-2 hours, be cooled to after the room temperature demoulding and namely get and have the pmma material that intelligence is stored heat.
Embodiment 2:
The organic intelligent glass that has the heat accumulation exothermicity in the present embodiment is take polymethylmethacrylate as body material, and polyoxyethylene glycol is that intelligence is stored hot material, and wherein the number-average molecular weight of polyoxyethylene glycol is 2000, and transformation temperature is 41-46 ℃.
The organic intelligent glass that has the heat accumulation exothermicity in the present embodiment prepares by the following method:
Methyl methacrylate 25g, polyoxyethylene glycol 5g and the initiator benzoyl peroxide 5mg of newly distillation are added in the Erlenmeyer flask, steam enters in the Erlenmeyer flask when preventing pre-polymerization, wrap one deck preservative film at bottleneck after shaking up, tighten with rubber ring again, sealing is rear in 70-90 ℃ of heating in water bath prepolymerization, when solution system viscosity reaches 0.8-1.0Pas, stopped heating and be cooled to room temperature obtains performed polymer to stop polyreaction immediately; The gained performed polymer is poured in the mould, be careful when filling with mould, do not make prepolymer intermediate formation bubble, and entirely do not fill, slightly stay one section space, in order to avoid prepolymer expanded by heating and overflowing, then with preservative film mould is sealed, make prepolymer and air isolated, sealing is rear in 45 ℃ of curing reaction 24-30 hours, subsequently at 105 ℃ of thermal treatment 1-2 hours, be cooled to after the room temperature demoulding and namely get and have the pmma material that intelligence is stored heat.
Embodiment 3:
The organic intelligent glass that has the heat accumulation exothermicity in the present embodiment is take polymethylmethacrylate as body material, and polyoxyethylene glycol is that intelligence is stored hot material, and wherein the number-average molecular weight of polyoxyethylene glycol is 2000, and transformation temperature is 41-46 ℃.
The organic intelligent glass that has the heat accumulation exothermicity in the present embodiment prepares by the following method:
Methyl methacrylate 25g, polyoxyethylene glycol 7.5g and the initiator benzoyl peroxide 10mg of newly distillation are added in the Erlenmeyer flask, steam enters in the Erlenmeyer flask when preventing pre-polymerization, wrap one deck preservative film at bottleneck after shaking up, tighten with rubber ring again, sealing is rear in 70-90 ℃ of heating in water bath prepolymerization, when solution system viscosity reaches 0.8-1.0Pas, stopped heating and be cooled to room temperature obtains performed polymer to stop polyreaction immediately; The gained performed polymer is poured in the mould, be careful when filling with mould, do not make prepolymer intermediate formation bubble, and entirely do not fill, slightly stay one section space, in order to avoid prepolymer expanded by heating and overflowing, then with preservative film mould is sealed, make prepolymer and air isolated, sealing is rear in 35 ℃ of curing reaction 24-30 hours, subsequently at 95 ℃ of thermal treatment 1-2 hours, be cooled to after the room temperature demoulding and namely get and have the pmma material that intelligence is stored heat.
Embodiment 4:
The organic intelligent glass that has the heat accumulation exothermicity in the present embodiment is take polymethylmethacrylate as body material, and polyoxyethylene glycol is that intelligence is stored hot material, and wherein the number-average molecular weight of polyoxyethylene glycol is 2000, and transformation temperature is 41-46 ℃.
Have the preparation method of organic intelligent glass of heat accumulation exothermicity in the present embodiment with embodiment 1, the addition of different is polyoxyethylene glycol is 6.0g, and the initiator of interpolation is azo-bis-isobutyl cyanide, and addition is 15mg.
Embodiment 5:
The organic intelligent glass that has the heat accumulation exothermicity in the present embodiment is take polymethylmethacrylate as body material, and polyoxyethylene glycol is that intelligence is stored hot material, and wherein the number-average molecular weight of polyoxyethylene glycol is 600, and transformation temperature is 18-22 ℃.
Have the preparation method of organic intelligent glass of heat accumulation exothermicity in the present embodiment with embodiment 1, the addition of different is polyoxyethylene glycol is 5.0g, and the initiator of interpolation is azo-bis-isobutyl cyanide, and addition is 20mg.
Embodiment 6:
The organic intelligent glass that has the heat accumulation exothermicity in the present embodiment is take polymethylmethacrylate as body material, and polyoxyethylene glycol is that intelligence is stored hot material, and wherein the number-average molecular weight of polyoxyethylene glycol is 20000, and transformation temperature is 60-62 ℃.
Have the preparation method of organic intelligent glass of heat accumulation exothermicity in the present embodiment with embodiment 1, the addition of different is polyoxyethylene glycol is 5.0g, and the initiator of interpolation is azo-bis-isobutyl cyanide, and addition is 2.5mg.
Fig. 1 is the optical photograph of the organic intelligent glass for preparing of the present invention.As can be seen from Figure 1, the Intelligent heat storage glass of the present invention's preparation is higher in the visible region transparency, compare with common synthetic glass, its transparency does not have too large variation, illustrate when doping one timing, the transparency change of Intelligent heat storage glass is little, subsequent experimental find when polyoxyethylene glycol doping mark up to 20% the time, the transparency of Intelligent heat storage glass is still better.
Fig. 2 is the optical photograph of the organic intelligent glass of the different polyoxyethylene glycol additions that prepare of the present invention.As can be seen from Figure 2, along with the increase of doping polyoxyethylene glycol amount, the transparency of intelligent glass descends to some extent, gradually by transparent become opaque.Explanation is along with the increase of doping, and polyoxyethylene glycol descends to some extent in the dispersiveness of polymethyl methacrylate, and the image of reuniting increases.
Fig. 3 is the optical photograph of organic intelligent glass of the polyoxyethylene glycol of the interpolation different molecular weight for preparing of the present invention.As can be seen from Figure 3, along with the increase of doping molecular weight polyethylene glycol, the transparency of intelligent glass also descends to some extent, and this dispersiveness that polyoxyethylene glycol also has been described also by certain decline agglomeration has occured.
The synthetic glass that Fig. 4 and Fig. 5 have illustrated the polyoxyethylene glycol that mixed has in corresponding temperature range and well stores thermal characteristics.Fig. 4 be different Macrogol 2000 additions organic intelligent glass store thermal characteristics figure, along with the addition of Macrogol 2000 increases to 30% from 10%, the thermal characteristics of storing of synthetic glass rises thereupon.Fig. 4 has shown by the amount that changes the peg molecule that mixes in the synthetic glass can regulate and control the heat energy power of storing in the synthetic glass.Fig. 5 be different polyoxyethylene glycol number-average molecular weight organic intelligent glass store thermal characteristics figure, along with the polyoxyethylene glycol number-average molecular weight increases to 20000 from 600, the hot temperature of storing of synthetic glass also changes thereupon, is about 18～22 ℃, the synthetic glass heat absorption heat accumulation temperature of doping Macrogol 2000 such as the synthetic glass heat absorption heat accumulation temperature of doping Polyethylene Glycol-600 and is about 41～46 ℃, the synthetic glass heat absorption heat accumulation temperature of doping PEG 20000 and is about 60～62 ℃.Fig. 5 has shown by changing the molecular weight polyethylene glycol that mixes in the synthetic glass can regulate and control the temperature that undergoes phase transition when hot of storing in the synthetic glass.
Fig. 6 is the XRD figure spectrum of polyoxyethylene glycol in the organic intelligent glass for preparing of the present invention, has characterized crystal formation, the degree of crystallinity of phase change material.Fig. 6 has illustrated that polyoxyethylene glycol exists with solid form in the intelligent synthetic glass when low temperature, along with the temperature corresponding XRD peak that raises disappears, polyoxyethylene glycol is solid-liquid phase change in the intelligent synthetic glass.
Claims (2)
1. preparation method with organic intelligent glass of heat accumulation exothermicity is characterized in that: at first polyoxyethylene glycol, methyl methacrylate monomer and initiator mixed, and the pre-polymerization of high temperature thermal initiation, through filling with mould, polymerization and the demoulding get product again; Described initiator is Diisopropyl azodicarboxylate or benzoyl peroxide; Described high temperature is 70-90 ℃;
Described organic intelligent glass is take polymethylmethacrylate as body material, and polyoxyethylene glycol is that intelligence is stored hot material, and wherein the addition of polyoxyethylene glycol is the 10-30% of body material quality; The number-average molecular weight of described polyoxyethylene glycol is 600-20000;
Specifically according to the following steps operation:
Polyoxyethylene glycol, methyl methacrylate and initiator are mixed, and in 70-90 ℃ of heating in water bath prepolymerization, when solution system viscosity reaches 0.8-1.0Pas, stopped heating also is cooled to room temperature and namely gets performed polymer after the sealing; Described performed polymer is poured in the mould, in 35-45 ℃ of curing reaction 24-30 hour, subsequently at 95-105 ℃ of thermal treatment 1-2 hour, be cooled to after the room temperature demoulding and namely get and have the pmma material that intelligence is stored heat after the sealing;
The addition of described initiator is the 0.01-0.1% of body material quality.
2. preparation method according to claim 1, it is characterized in that: solidification value is 40 ℃, thermal treatment temp is 100 ℃.
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| CN104407454A (en) * | 2014-12-22 | 2015-03-11 | 常熟市赛蒂镶嵌玻璃制品有限公司 | Thermochromism glass |
| KR20190091548A (en) | 2016-12-14 | 2019-08-06 | 아르끄마 프랑스 | Air gap control composition for carbonyl-containing monomer polymerization |
| CN107267122A (en) * | 2017-06-01 | 2017-10-20 | 苏州三拓冷链技术有限公司 | A kind of production technology for phase-change accumulation energy module of shaping |
| CN108020009A (en) * | 2017-12-16 | 2018-05-11 | 常熟市久昇电器有限公司 | A kind of high-intensity hollow glass refrigerator doors |
| CN108050754A (en) * | 2017-12-16 | 2018-05-18 | 常熟市久昇电器有限公司 | A kind of heat-insulation and heat-preservation hollow glass refrigerator doors |
| CN109251276A (en) * | 2018-10-22 | 2019-01-22 | 湖北科技学院 | A kind of dynamic lithium battery temperature control polyethylene glycol groups phase-changing energy storage material and its preparation method |
| CN109504351B (en) * | 2018-12-20 | 2021-03-26 | 大连理工大学 | Polyether-based composite phase change energy storage material and preparation method thereof |
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| EP1308434B1 (en) * | 2001-11-01 | 2006-03-15 | Nippon Shokubai Co., Ltd. | (Meth)acryloyl group-containing compound and method for producing the same |
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| 刘国勤,黄芳,关春龙,朱贺,彭进,张琳琪,夏绍灵,王春华.PMMA/PEG共混物形态和热性质的研究.《广州化工》.2007,第35卷(第1期), * |
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