CN104788684A - Preparation method of double-function brush-like solid-solid phase-change energy storage material - Google Patents
Preparation method of double-function brush-like solid-solid phase-change energy storage material Download PDFInfo
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Abstract
The invention relates to a preparation method of a double-function brush-like solid-solid phase-change energy storage material, which comprises the following steps: adding sodium p-styrenesulfonate to prepare surface-hydroxylated crosslinked nano polystyrene microspheres (PS-OH) by soap-free emulsion polymerization; and in a nitrogen protective atmosphere, grafting polyethyleneglycol monomethyl ether (MPEG) onto the PS-OH through 4,4'-diphenylmethane diisocyanate (MDI) by graft copolymerization to obtain the double-function brush-like solid-solid phase-change energy storage material with waterproof effect and adjustable phase-change temperature and phase-change enthalpy. The method is simple and controllable in technique. The obtained phase-change material has the advantages of adjustable phase-change temperature and phase-change enthalpy, favorable heat stability and small particle size. The phase-change material is applicable to mortar and concrete, and has favorable thermal-insulation and waterproof effects.
Description
Technical field
The present invention is specifically related to a kind of preparation method with waterproof and the bifunctional brush solid-solid phase-change energy-storage material of energy storage, and the transformation temperature of prepared phase change material and enthalpy of phase change are all adjustable, can be used for the building materials field such as building mortar and concrete.
Background technology
Along with the raising day by day of China's economy growth level, also increasing to the consumption of the energy.Therefore, how to develop the new energy and effectively utilize the existing energy to become the important topic of industrial development.Energy storage can solve energy supply and demand unmatched contradiction over time and space.Phase-changing energy storage material, in its thing phase change process, can absorb heat or release heat in environment from environment, thus reaches the object of energy storage and release and adjusting energy demand and supply mismatch.Phase change energy storage technology to the exploitation of the energy and Appropriate application significant, and solid-solid phase transition material produces due to absence of liquid in phase transition process, gas, nontoxic, corrosion-free, pollution-free and the coefficient of expansion is little, obtains extensive concern.
In solid-solid phase transition material, high score subclass phase change material is large with its quantity of heat storage, easy machine-shaping, do not exist cold, separate out and the advantage of distillation phenomenon, directly can be used as the structured material of system, become the most promising phase change material.Polymer solid-solid phase transition material is mainly divided into two classes: a class is high molecular crosslink resin, as crosslinked polyolefin, crosslined polyacetal class, another kind of is graft copolymer, as cellulose graft copolymer, polyester graft copolymer, polystyrene graft copolymer, silane grafted copolymers.Graft copolymer is on the dystectic high molecular basis of one, utilizes the polymer of another kind of low melting point on chemical bonding as side chain, forms polymkeric substance.During heating, be first the phase in version of polymer side chain generation from crystalline state to amorphous state of low melting point.Although be in amorphous state, owing to being grafted on dystectic main chain, lose free-flowing property, so still keep solid form.Therefore, this kind of phase change material utilizes the phase in version of the polymer side chain of low melting point to reach the object of energy storage.
Polyoxyethylene glycol (PEG) is by (CH
2-CH
2-O)
nthe long chain macromolecule of structure composition, structure is simple, easy crystallization, is comparatively perfect a kind of polymer solid-liquid phase change material of research at present.It is large that polyoxyethylene glycol has enthalpy of phase change, the transformation temperature advantage such as within the scope of normal temperature.Can be regulated its phase transition performance by the size controlling molecular weight, obtain required enthalpy of phase change and transformation temperature, molecule chain end is hydroxyl, can be used as active group and carries out chemical modification reaction.Poly glycol monomethyl ether (MPEG) is with methyl blocking, has-CH
2-CH
2one end that-O-forms is with the long chain macromolecule of hydroxyl.When its molecular weight is higher, is easy to crystallization and there is higher enthalpy of phase change.The research utilizing grafting copolymerization process polyoxyethylene glycol and poly glycol monomethyl ether to be grafted on certain skeletal support material is also more extensive.Patent of invention CN 103524707 A discloses the preparation method of the adjustable comb copolymer solid-solid phase-change energy-storage material of a kind of transformation temperature, utilizes the method for graft copolymerization to be grafted to by triisocyanate by poly glycol monomethyl ether and polyoxyethylene glycol obtains transformation temperature and all adjustable pectination phase-changing energy storage material of enthalpy of phase change.Wang Yanqiu (preparation of PET/MPEG solid-solid phase-change energy-storage material and performance study, Guangdong chemical industry, 18 phases in 2014) etc. with polyethylene terephthalate (PET) for framework material, MPEG is phase change material, PET/MPEG solid-solid phase transition material has been prepared under the effect of tolylene diisocyanate and dibutyl tin dilaurate, this material increases with the content of MPEG, and enthalpy of phase change increases.Jiang Zhenhua (the synthesis and characteries of poly glycol monomethyl ether (MPEG)/polyvinyl alcohol (PVA) polymer solid-solid phase transition material; SCI; 10 phases in 2004) etc. adopt graft copolymerization to have synthesized take PVA as main chain; poly glycol monomethyl ether is the solid-solid phase transition material of side chain, solves the solubility problem of polyoxyethylene glycol/polyvinyl alcohol.Pei Yuling (the synthesis and characteries test of poly glycol monomethyl ether solid-solid phase change material, Beijing Institute of Clothing Tech's journal, 4 phases in 2010) etc. be soft section with MPEG, with 4,4-ditan, isocyanic ester (MDI), neopentyl glycol (NPG) have synthesized the urethane solid-solid phase transition material that transformation temperature is low, enthalpy of phase change is high for hard section.
And above-mentioned technique study only improves for the enthalpy of phase change of soft section of MPEG, thermostability and deliquescent aspect, the phase change material of synthesis mostly is comb shaped structure, and functional single.And MPEG is grafted to the method that nano grade polymer microballoon has the phase-changing energy storage material of waterproof and energy storage bi-functional concurrently with preparation and have not been reported.
The invention provides a kind of preparation method with waterproof and the bifunctional brush solid-solid phase-change energy-storage material of energy storage, and preparation technology simply, is easily controlled, process environmental protection, is applied in construction material or other energy storage material, can show excellent waterproof and phase-change accumulation energy performance.
Summary of the invention
This preparation method providing a kind of difunctional brush solid-solid phase-change energy-storage material, transformation temperature, the enthalpy of phase change of the phase-changing energy storage material prepared by the method are all adjustable, achieve the multifunction of phase change material, solve the thermal-insulating waterproof two fold problem of building materials body of wall etc.
For realizing this goal, first the present invention utilizes surfactant-free emulsion polymerization and adds the crosslinking nano polystyrene microballoon (PS-OH) that Sodium styrene sulfonate prepares surface hydroxylation, and by the method for graft copolymerization by poly glycol monomethyl ether (MPEG) by 4,4 '-diphenylmethanediisocyanate (MDI) is grafted on PS-OH, obtains transformation temperature and all adjustable difunctional brush phase-changing energy storage material of enthalpy of phase change.
Particularly, preparation method of the present invention comprises the steps:
(1) preparation of hydroxylation crosslinking nano polystyrene microballoon (PS-OH): each material adds by certain mass ratio in this step; first; when under nitrogen protection reactor being heated to 60 DEG C, in reactor, add vinylbenzene (St), deionized water (H
2o), sodium hydroxide (NaOH), sodium bicarbonate (NaHCO
3), be uniformly mixed; When temperature of charge reaches 70 DEG C in question response still, add cross-linker divinylbenzene (DVB); Initiator potassium persulfate (KPS) is added when 75 DEG C; Add Sodium styrene sulfonate (NaSS) when 85 DEG C, and react 4 ~ 5 hours at this temperature; Finally add hydroxyethyl methylacrylate (HEMA) to continue reaction and take out reaction solution after 3 ~ 5 hours, obtain hydroxylation crosslinking nano polystyrene microballoon (PS-OH) through centrifugal, drying and grinding.
(2) 4,4 '-diphenylmethanediisocyanate (MDI) is dissolved in solvent, obtains 4,4 '-diphenylmethanediisocyanate solution; Poly glycol monomethyl ether (MPEG) is dissolved in solvent, obtains poly glycol monomethyl ether solution.
(3) under nitrogen protection; poly glycol monomethyl ether solution in described step (2) is joined in reactor; 4 in described step (2) are added when being heated to 70 DEG C while stirring; 4 '-diphenylmethanediisocyanate solution; and isothermal reaction 4 ~ 10 hours, obtain poly glycol monomethyl ether (MPEG-NCO) solution with special end group.
(4) hydroxylation crosslinking nano polystyrene microballoon (PS-OH) obtained in described step (1) is scattered in solvent; and join in poly glycol monomethyl ether (MPEG-NCO) solution with special end group obtained in described step (3); react 8 ~ 20 hours under 70 ~ 85 DEG C of conditions under nitrogen protection, obtain the Nano microsphere copolymer solution with brush structure.
(5) by obtain in described step (4) Nano microsphere copolymer solution filtration washing, vacuum-drying, then naturally cool to room temperature, through grinding after obtain difunctional brush solid-solid phase-change energy-storage material (PS-MPEG).
Preferably, in described step (1), the ratio of each material is vinylbenzene, the mass ratio of deionized water, sodium hydroxide, sodium bicarbonate is (27 ~ 100): 400:0.04:0.04, Vinylstyrene is 1% ~ 6% of vinylbenzene quality, Potassium Persulphate is 1.8% of vinylbenzene quality, Sodium styrene sulfonate is 1% ~ 2% of vinylbenzene quality, and hydroxyethyl methylacrylate is 5% ~ 13% of vinylbenzene quality.
Preferably, in described preparation method, the molecular weight of poly glycol monomethyl ether (MPEG) is 550 ~ 5000.
Preferably, in described step (2), poly glycol monomethyl ether (MPEG) is 1:(5.7 ~ 9 with the mass ratio of solvent), 4, the mass ratio of 4 '-diphenylmethanediisocyanate and solvent is 1:(5.7 ~ 9).
Preferably, in described step (3) 4, the mol ratio of 4 '-diphenylmethanediisocyanate (MDI) and poly glycol monomethyl ether (MPEG) is 1:(1 ~ 1.8).
Preferably, the PS-OH in described step (4) and the mass ratio of solvent are 1:(5.7 ~ 9).
Preferably, poly glycol monomethyl ether (MPEG-NCO) and the two contained hydroxyl mol ratio of hydroxylation crosslinking nano polystyrene microballoon (PS-OH) in described step (4) with special end group are 1:(1 ~ 2).
Preferably, solvent used in described preparation method is any one in N, N '-dimethyl formamide (DMF), acetone, toluene.
The present invention controls the hydroxyl grafting density of polystyrene microsphere by different material proportions, thus controls the grafting density of the poly glycol monomethyl ether on solid-solid phase-change energy-storage material, realizes the transformation temperature of solid-solid phase transition material and the adjustable of enthalpy of phase change; In addition, also can change the molecular weight of poly glycol monomethyl ether, thus realize the transformation temperature of solid-solid phase transition material and the adjustable of enthalpy of phase change.
positively effect of the present invention
The polystyrene microsphere particle diameter prepared with emulsifier-free emulsion polymerization after adding Sodium styrene sulfonate is less, thus make to reach nano level with its phase-changing energy storage material prepared by matrix, the introducing of hydroxyethyl methylacrylate makes microballoon can as waterproof mortar properties-correcting agent.By regulating the molecular weight of poly glycol monomethyl ether and grafting density, can make transformation temperature and enthalpy of phase change adjustable, thus the phase change material of obtained a series of satisfied different demand.Make the solid-solid phase transition material prepared possess waterproof and energy storage bi-functional like this, and the poly glycol monomethyl ether molecular chain undergone phase transition is grafted on polystyrene microsphere, overcomes the defect of phase change material easy to leak, stable performance.Whole preparation technology is simple to operation, obtains product and directly uses without the need to secondary encapsulation and parcel, with low cost, environmental friendliness.
Embodiment
Below in conjunction with several specific embodiment of the present invention, the invention will be further described; but protection scope of the present invention is not limited thereto; anyly be familiar with those skilled in the art within the scope of the technology of the present invention; change can be expected easily or replace, all should be encompassed within protection scope of the present invention.Therefore, protection scope of the present invention should be as the criterion with the protection domain of claim.
In the nano-grade hydroxy crosslinked polystyrene microsphere of preparation, the grafting density of hydroxyethyl methylacrylate is recorded by energy spectrum analysis (EDS), is regulated and controled by the grafting density of content to hydroxyl changing hydroxyethyl methylacrylate and cross-linker divinylbenzene.The Hydrodynamic diameter of polymer microballoon is measured by laser particle analyzer.Obtained difunctional solid-solid phase-change energy-storage material tests phase-change accumulation energy performance by differential scanning calorimeter (DSC).
embodiment 1
1. the preparation of solid-solid phase-change energy-storage material
(1) preparation of hydroxylation crosslinking nano polystyrene microballoon (PS-OH): each quality of material compares St:H
2o:NaOH:NaHCO
3=100:400:0.04:0.04, DVB be St amount 6%, KPS be St amount 1.8%, NaSS be St amount 1.6%, HEMA be St amount 13%.First, when under nitrogen protection reactor being heated to 60 DEG C, in reactor, 100g St, 400g H is added
2o, 0.04g NaOH, 0.04g NaHCO
3, be uniformly mixed; When temperature of charge reaches 70 DEG C in question response still, add 6g DVB; 1.8g KPS is added when 75 DEG C; Add 1.6g NaSS when 85 DEG C, and react 5 hours at this temperature; Finally add 13g HEMA to continue reaction and take out reaction solution after 5 hours, obtain PS-OH through centrifugal, drying and grinding, the hydroxyl grafting density of PS-OH is 0.65mmol/g, median size is 85nm.
(2) by 0.25g MDI(0.001mol) be dissolved in 2.25g in the DMF solvent of super-dry, stir and make the MDI solution that concentration is 10wt%; By 6g MPEG(0.0012mol, molecular weight 5000) be dissolved in 54g in the DMF solvent of super-dry, stir and make the MPEG solution that concentration is 10wt%.The mol ratio of MDI and the MPEG in these two kinds of solution is 1:1.2.
(3) under nitrogen protection; MPEG solution in described step (2) is joined in reactor; the MDI solution in described step (2) is added when being heated to 70 DEG C while stirring, and isothermal reaction 10 hours, obtain poly glycol monomethyl ether (MPEG-NCO) solution with special end group.
(4) the PS-OH ultrasonic wave obtained in step described in 1.54g (1) is dispersed in the middle of the dry DMF solvent of 13.86g; concentration is 10wt%; then join (in MPEG-NCO and PS-OH, hydroxyl mol ratio is 1:1) in the MPEG-NCO solution obtained in described step (3); react 8 hours under 70 DEG C of conditions under nitrogen protection, obtain the Nano microsphere copolymer solution with brush structure.
(5) by obtain in described step (4) Nano microsphere copolymer solution filtration washing, vacuum-drying, then naturally cool to room temperature, through grinding after obtain difunctional brush solid-solid phase-change energy-storage material (PS-MPEG).
2. solid-solid phase-change energy-storage material application testing
The melt temperature utilizing DSC to test PS-MPEG is 63.3 DEG C, melting enthalpy is 155.8J/g.Sand-cement slurry is mixed with PS-MPEG, proportioning (in mass ratio) is cement: PS-MPEG: aggregate: water reducer: defoamer=1:0.1:3:0.005:0.002, test according to " inorganic leak-stopping material GB 23440-2009 ", the impermeability pressure of mortar specimen is 2.0MPa.Concrete outcome is in table 1.
embodiment 2
1. the preparation of solid-solid phase-change energy-storage material
(1) preparation of PS-OH is with the step (1) in embodiment 1.
(2) by 0.25g MDI(0.001mol) be dissolved in 1.84g in the DMF solvent of super-dry, stir and make the MDI solution that concentration is 12wt%; By 2.66g MPEG(0.0014mol, molecular weight 1900) be dissolved in 19.51g in the DMF solvent of super-dry, stir and make the MPEG solution that concentration is 12wt%.The mol ratio of MDI and the MPEG in these two kinds of solution is 1:1.4.
(3) under nitrogen protection; MPEG solution in described step (2) is joined in reactor; the MDI solution in described step (2) is added when being heated to 70 DEG C while stirring, and isothermal reaction 6 hours, obtain poly glycol monomethyl ether (MPEG-NCO) solution with special end group.
(4) the PS-OH ultrasonic wave obtained in step described in 2.31g (1) is dispersed in the middle of the dry DMF solvent of 16.94g; concentration is 12wt%; then join (in MPEG-NCO and PS-OH, hydroxyl mol ratio is 1:1.5) in the MPEG-NCO solution obtained in described step (3); react 10 hours under 75 DEG C of conditions under nitrogen protection, obtain the Nano microsphere copolymer solution with brush structure.
(5) by obtain in described step (4) Nano microsphere copolymer solution filtration washing, vacuum-drying, then naturally cool to room temperature, through grinding after obtain difunctional brush solid-solid phase-change energy-storage material (PS-MPEG).
2. solid-solid phase-change energy-storage material application testing
The melt temperature utilizing DSC to test PS-MPEG is 45.6 DEG C, melting enthalpy is 133.7J/g.Sand-cement slurry is mixed with PS-MPEG, proportioning (in mass ratio) is cement: PS-MPEG: aggregate: water reducer: defoamer=1:0.1:3:0.005:0.002, test according to " inorganic leak-stopping material GB 23440-2009 ", the impermeability pressure of mortar specimen is 1.9MPa.Concrete outcome is in table 1.
embodiment 3
1. the preparation of solid-solid phase-change energy-storage material
(1) preparation of PS-OH is with the step (1) in embodiment 1.
(2) by 0.25g MDI(0.001mol) be dissolved in 2.25g in the toluene solvant of super-dry, stir and make the MDI solution that concentration is 10wt%; By 1g MPEG(0.001mol, molecular weight 1000) be dissolved in 9g in the toluene solvant of super-dry, stir and make the MPEG solution that concentration is 10wt%.The mol ratio of MDI and the MPEG in these two kinds of solution is 1:1.
(3) under nitrogen protection; MPEG solution in described step (2) is joined in reactor; the MDI solution in described step (2) is added when being heated to 70 DEG C while stirring, and isothermal reaction 8 hours, obtain poly glycol monomethyl ether (MPEG-NCO) solution with special end group.
(4) the PS-OH ultrasonic wave obtained in step described in 2.77g (1) is dispersed in the middle of 24.93g dry toluene solvent; concentration is 10wt%; then join (in MPEG-NCO and PS-OH, hydroxyl mol ratio is 1:1.8) in the MPEG-NCO solution obtained in described step (3); react 15 hours under 80 DEG C of conditions under nitrogen protection, obtain the Nano microsphere copolymer solution with brush structure.
(5) by obtain in described step (4) Nano microsphere copolymer solution filtration washing, vacuum-drying, then naturally cool to room temperature, through grinding after obtain difunctional brush solid-solid phase-change energy-storage material (PS-MPEG).
2. solid-solid phase-change energy-storage material application testing
The melt temperature utilizing DSC to test PS-MPEG is 33.2 DEG C, melting enthalpy is 96.5J/g.Sand-cement slurry is mixed with PS-MPEG, proportioning (in mass ratio) is cement: PS-MPEG: aggregate: water reducer: defoamer=1:0.1:3:0.005:0.002, test according to " inorganic leak-stopping material GB 23440-2009 ", the impermeability pressure of mortar specimen is 2.0MPa.Concrete outcome is in table 1.
embodiment 4
1. the preparation of solid-solid phase-change energy-storage material
(1) preparation of PS-OH is with the step (1) in embodiment 1.
(2) by 0.25g MDI(0.001mol) be dissolved in 1.67g in the toluene solvant of super-dry, stir and make the MDI solution that concentration is 13wt%; By 0.825g MPEG(0.0015mol, molecular weight 550) be dissolved in 5.52g in the toluene solvant of super-dry, stir and make the MPEG solution that concentration is 13wt%.The mol ratio of MDI and the MPEG in these two kinds of solution is 1:1.5.
(3) under nitrogen protection; MPEG solution in described step (2) is joined in reactor; the MDI solution in described step (2) is added when being heated to 70 DEG C while stirring, and isothermal reaction 9 hours, obtain poly glycol monomethyl ether (MPEG-NCO) solution with special end group.
(4) the PS-OH ultrasonic wave obtained in step described in 2.15g (1) is dispersed in the middle of 14.39g dry toluene solvent; concentration is 13wt%; then join (in MPEG-NCO and PS-OH, hydroxyl mol ratio is 1:1.4) in the MPEG-NCO solution obtained in described step (3); react 20 hours under 85 DEG C of conditions under nitrogen protection, obtain the Nano microsphere copolymer solution with brush structure.
(5) reaction product that step (4) obtains is carried out filtration washing, vacuum-drying, then place and naturally cool to room temperature, after grinding, obtain that there is bifunctional brush solid-solid phase-change energy-storage material (PS-MPEG).
2. solid-solid phase-change energy-storage material application testing
The melt temperature utilizing DSC to test PS-MPEG is 20.5 DEG C, melting enthalpy is 79.8J/g.Sand-cement slurry is mixed with PS-MPEG, proportioning (in mass ratio) is cement: PS-MPEG: aggregate: water reducer: defoamer=1:0.1:3:0.005:0.002, test according to " inorganic leak-stopping material GB 23440-2009 ", the impermeability pressure of mortar specimen is 2.0MPa.Concrete outcome is in table 1.
embodiment 5
1. the preparation of solid-solid phase-change energy-storage material
(1) preparation of hydroxylation crosslinking nano polystyrene microballoon (PS-OH): each quality of material compares St:H
2o:NaOH:NaHCO
3=100:400:0.04:0.04, DVB be St amount 1%, KPS be St amount 1.8%, NaSS be St amount 2%, HEMA be St amount 5%.First, when under nitrogen protection reactor being heated to 60 DEG C, in reactor, 100g St, 400g H is added
2o, 0.04g NaOH, 0.04g NaHCO
3, be uniformly mixed; When temperature of charge reaches 70 DEG C in question response still, add 1g DVB; 1.8g KPS is added when 75 DEG C; Add 2.0g NaSS when 85 DEG C, and react 5 hours at this temperature; Finally add 5g HEMA to continue reaction and take out reaction solution after 4 hours, obtain PS-OH through centrifugal, drying and grinding, the hydroxyl grafting density of PS-OH is 0.38mmol/g, median size is 75nm.
(2) by 0.25g MDI(0.001mol) be dissolved in 1.43g in the acetone solvent of super-dry, stir and make the MDI solution that concentration is 15wt%; By 1.6g MPEG(0.0016mol, molecular weight 1000) be dissolved in 9.07g in the acetone solvent of super-dry, stir and make the MPEG solution that concentration is 15wt%.The mol ratio of MDI and the MPEG in these two kinds of solution is 1:1.6.
(3) under nitrogen protection; MPEG solution in described step (2) is joined in reactor; the MDI solution in described step (2) is added when being heated to 70 DEG C while stirring, and isothermal reaction 4 hours, obtain poly glycol monomethyl ether (MPEG-NCO) solution with special end group.
(4) the PS-OH ultrasonic wave obtained in step described in 4.21g (1) is dispersed in the middle of 23.86g dry acetone solvent; concentration is 15wt%; then join (in MPEG-NCO and PS-OH, hydroxyl mol ratio is 1:1.6) in the MPEG-NCO solution obtained in described step (3); react 18 hours under 75 DEG C of conditions under nitrogen protection, obtain the Nano microsphere copolymer solution with brush structure.
(5) by obtain in described step (4) Nano microsphere copolymer solution filtration washing, vacuum-drying, then naturally cool to room temperature, through grinding after obtain difunctional brush solid-solid phase-change energy-storage material (PS-MPEG).
2. solid-solid phase-change energy-storage material application testing
The melt temperature utilizing DSC to test PS-MPEG is 31.3 DEG C, melting enthalpy is 90.2J/g.Sand-cement slurry is mixed with PS-MPEG, proportioning (in mass ratio) is cement: PS-MPEG: aggregate: water reducer: defoamer=1:0.1:3:0.005:0.002, test according to " inorganic leak-stopping material GB 23440-2009 ", the impermeability pressure of mortar specimen is 1.9MPa.Concrete outcome is in table 1.
embodiment 6
1. the preparation of solid-solid phase-change energy-storage material
(1) preparation of hydroxylation crosslinking nano polystyrene microballoon (PS-OH): each quality of material compares St:H
2o:NaOH:NaHCO
3=80:400:0.04:0.04, DVB be St amount 5%, KPS be St amount 1.8%, NaSS be St amount 1.8%, HEMA be St amount 10%.First, when under nitrogen protection reactor being heated to 60 DEG C, in reactor, 80g St, 400g H is added
2o, 0.04g NaOH, 0.04g NaHCO
3, be uniformly mixed; When temperature of charge reaches 70 DEG C in question response still, add 4g DVB; 1.44g KPS is added when 75 DEG C; Add 1.44g NaSS when 85 DEG C, and react 4 hours at this temperature; Finally add 8g HEMA to continue reaction and take out reaction solution after 3 hours, obtain PS-OH through centrifugal, drying and grinding, the hydroxyl grafting density of PS-OH is 0.45mmol/g, median size is 80nm.
(2) by 0.25g MDI(0.001mol) be dissolved in 1.54g in the acetone solvent of super-dry, stir and make the MDI solution that concentration is 14wt%; By 1.8g MPEG(0.0018mol, molecular weight 1000) be dissolved in 11.06g in the acetone solvent of super-dry, stir and make the MPEG solution that concentration is 14wt%.The mol ratio of MDI and the MPEG in these two kinds of solution is 1:1.8.
(3) under nitrogen protection; MPEG solution in described step (2) is joined in reactor; the MDI solution in described step (2) is added when being heated to 70 DEG C while stirring, and isothermal reaction 5 hours, obtain poly glycol monomethyl ether (MPEG-NCO) solution with special end group.
(4) the PS-OH ultrasonic wave obtained in step described in 3.4g (1) is dispersed in the middle of the acetone solvent of 20.52g drying; concentration is 14wt%; then join (in MPEG-NCO and PS-OH, hydroxyl mol ratio is 1:1.5) in the MPEG-NCO solution obtained in described step (3); react 15 hours under 70 DEG C of conditions under nitrogen protection, obtain the Nano microsphere copolymer solution with brush structure.
(5) by obtain in described step (4) Nano microsphere copolymer solution filtration washing, vacuum-drying, then naturally cool to room temperature, through grinding after obtain difunctional brush solid-solid phase-change energy-storage material (PS-MPEG).
2. solid-solid phase-change energy-storage material application testing
The melt temperature utilizing DSC to test PS-MPEG is 32.1 DEG C, melting enthalpy is 95.4J/g.Sand-cement slurry is mixed with PS-MPEG, proportioning (in mass ratio) is cement: PS-MPEG: aggregate: water reducer: defoamer=1:0.1:3:0.005:0.002, test according to " inorganic leak-stopping material GB 23440-2009 ", the impermeability pressure of mortar specimen is 2.0MPa.Concrete outcome is in table 1.
embodiment 7
1. the preparation of solid-solid phase-change energy-storage material
(1) preparation of hydroxylation crosslinking nano polystyrene microballoon (PS-OH): each quality of material compares St:H
2o:NaOH:NaHCO
3=27:400:0.04:0.04, DVB be St amount 3%, KPS be St amount 1.8%, NaSS be St amount 1%, HEMA be St amount 8%.First, when under nitrogen protection reactor being heated to 60 DEG C, in reactor, 27g St, 400g H is added
2o, 0.04g NaOH, 0.04g NaHCO
3, be uniformly mixed; When temperature of charge reaches 70 DEG C in question response still, add 0.81g DVB; 0.486g KPS is added when 75 DEG C; Add 0.27g NaSS when 85 DEG C, and react 4 hours at this temperature; Finally add 2.16g HEMA to continue reaction and take out reaction solution after 5 hours, obtain PS-OH through centrifugal, drying and grinding, the hydroxyl grafting density of PS-OH is 0.58mmol/g, median size is 82nm.
(2) by 0.25g MDI(0.001mol) be dissolved in 1.43g in the DMF solvent of super-dry, stir and make the MDI solution that concentration is 15wt%; By 1.5g MPEG(0.0015mol, molecular weight 1000) be dissolved in 8.5g in the DMF solvent of super-dry, stir and make the MPEG solution that concentration is 15wt%.The mol ratio of MDI and the MPEG in these two kinds of solution is 1:1.5.
(3) under nitrogen protection; MPEG solution in described step (2) is joined in reactor; the MDI solution in described step (2) is added when being heated to 70 DEG C while stirring, and isothermal reaction 7 hours, obtain poly glycol monomethyl ether (MPEG-NCO) solution with special end group.
(4) the PS-OH ultrasonic wave obtained in step described in 1.43g (1) is dispersed in the middle of the dry DMF solvent of 8.10g; concentration is 15wt%; then join (in MPEG-NCO and PS-OH, hydroxyl mol ratio is 1:1.2) in the MPEG-NCO solution obtained in described step (3); react 20 hours under 80 DEG C of conditions under nitrogen protection, obtain the Nano microsphere copolymer solution with brush structure.
(5) by obtain in described step (4) Nano microsphere copolymer solution filtration washing, vacuum-drying, then naturally cool to room temperature, through grinding after obtain difunctional brush solid-solid phase-change energy-storage material (PS-MPEG).
2. solid-solid phase-change energy-storage material application testing
The melt temperature utilizing DSC to test PS-MPEG is 34.5 DEG C, melting enthalpy is 98.5J/g.Sand-cement slurry is mixed with PS-MPEG, proportioning (in mass ratio) is cement: PS-MPEG: aggregate: water reducer: defoamer=1:0.1:3:0.005:0.002, test according to " inorganic leak-stopping material GB 23440-2009 ", the impermeability pressure of mortar specimen is 2.0MPa.Concrete outcome is in table 1.
the performance of the difunctional brush solid-solid phase-change energy-storage material prepared by each embodiment of table 1
Claims (8)
1. a preparation method for difunctional brush solid-solid phase-change energy-storage material, is characterized in that the method comprises the steps:
(1) preparation of hydroxylation crosslinking nano polystyrene microballoon (PS-OH): each material adds by a certain percentage in this step, first, when under nitrogen protection reactor being heated to 60 DEG C, in reactor, add vinylbenzene, deionized water, sodium hydroxide, sodium bicarbonate, be uniformly mixed; When temperature of charge reaches 70 DEG C in question response still, add cross-linker divinylbenzene; Initiator potassium persulfate is added when 75 DEG C; Add Sodium styrene sulfonate when 85 DEG C, and react 4 ~ 5 hours at this temperature; Finally add hydroxyethyl methylacrylate continuation reaction and take out reaction solution after 3 ~ 5 hours, obtain PS-OH through centrifugal, drying and grinding;
(2) 4,4 '-diphenylmethanediisocyanate is dissolved in solvent, obtains 4,4 '-diphenylmethanediisocyanate solution; Poly glycol monomethyl ether is dissolved in solvent, obtains poly glycol monomethyl ether solution;
(3) under nitrogen protection, poly glycol monomethyl ether solution in described step (2) is joined in reactor, 4 in described step (2) are added when being heated to 70 DEG C while stirring, 4 '-diphenylmethanediisocyanate solution, and isothermal reaction 4 ~ 10 hours, obtain MPEG-NCO solution;
(4) will be scattered in solvent by the PS-OH obtained in described step (1), and join in the MPEG-NCO solution obtained in described step (3), react 8 ~ 20 hours under 70 ~ 85 DEG C of conditions under nitrogen protection, obtain the Nano microsphere copolymer solution with brush structure;
(5) by obtain in described step (4) Nano microsphere copolymer solution filtration washing, vacuum-drying, then naturally cool to room temperature, through grinding after obtain solid-solid phase-change energy-storage material.
2. preparation method according to claim 1, it is characterized in that: in described step (1), the ratio of each material is vinylbenzene, the mass ratio of deionized water, sodium hydroxide, sodium bicarbonate is (27 ~ 100): 400:0.04:0.04, Vinylstyrene is 1% ~ 6% of vinylbenzene quality, Potassium Persulphate is 1.8% of vinylbenzene quality, Sodium styrene sulfonate is 1% ~ 2% of vinylbenzene quality, and hydroxyethyl methylacrylate is 5% ~ 13% of vinylbenzene quality.
3. preparation method according to claim 1, is characterized in that: the relative molecular mass of described poly glycol monomethyl ether is 550 ~ 5000.
4. preparation method according to claim 1, is characterized in that: the poly glycol monomethyl ether in described step (2) and the mass ratio of solvent are 1:(5.7 ~ 9), 4, the mass ratio of 4 '-diphenylmethanediisocyanate and solvent is 1:(5.7 ~ 9).
5. preparation method according to claim 1, is characterized in that: in described step (3) 4, and the mol ratio of 4 '-diphenylmethanediisocyanate and poly glycol monomethyl ether is 1:(1 ~ 1.8).
6. preparation method according to claim 1, is characterized in that: the PS-OH in described step (4) and the mass ratio of solvent are 1:(5.7 ~ 9).
7. preparation method according to claim 1, is characterized in that: the hydroxyl mol ratio contained by both MPEG-NCO and the PS-OH in described step (4) is 1:(1 ~ 2).
8. according to the preparation method in claim 1 to 7 described in any one claim, it is characterized in that: described solvent is any one in N, N '-dimethyl formamide, acetone, toluene.
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| CN108251064A (en) * | 2017-12-30 | 2018-07-06 | 沈阳化工研究院有限公司 | A kind of preparation method of modified attapulgite phase-changing energy storage material |
| CN108251064B (en) * | 2017-12-30 | 2020-06-02 | 沈阳化工研究院有限公司 | Preparation method of modified attapulgite phase change energy storage material |
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| CN115160578B (en) * | 2022-06-24 | 2023-09-29 | 纯钧新材料(深圳)有限公司 | Solid-solid phase change material for data center, preparation method and cooling liquid thereof |
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