CN104788684B - A kind of preparation method of difunctional brush solid-solid phase change energy storage material - Google Patents
A kind of preparation method of difunctional brush solid-solid phase change energy storage material Download PDFInfo
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Abstract
The present invention relates to a kind of preparation method of difunctional brush solid-solid phase change energy storage material, concretely comprise the following steps：First, using surfactant- free emulsion polymerization and the crosslinking nano polystyrene microballoon that SSS prepares surface hydroxylation is added（PS‑OH）；Then under nitrogen protection, using the method for graft copolymerization by poly glycol monomethyl ether（MPEG）Pass through 4,4 ' methyl diphenylene diisocyanates（MDI）It is grafted on above-mentioned PS OH, obtains with waterproof effect and the adjustable difunctional brush solid-solid phase change energy storage material of phase transition temperature, enthalpy of phase change.This method technique is simple, easily-controllable；The phase transition temperature and enthalpy of phase change of obtained phase-change material are adjustable, heat endurance is good, particle diameter is small.The phase-change material can be applied in mortar and concrete, with good insulation, waterproof effect.
Description
Technical field
Present invention relates particularly to a kind of preparation side with waterproof and the difunctional brush solid-solid phase-change energy-storage material of energy storage
Method, the phase transition temperature and enthalpy of phase change of prepared phase-change material are adjustable, available for building materials fields such as building mortar and concrete.
Background technology
With the increasingly raising of China's economy growth level, the consumption to the energy is also increasing.Therefore, how to develop new
The energy and effectively using the existing energy turn into industrial development important topic.Energy storage can solve energy supply and demand in the time
Spatially unmatched contradiction.Phase-changing energy storage material, during its thing phase change, can absorb heat or to ring from environment
Heat is released in border, so as to reach energy storage and discharge and regulation energy requirement and the purpose for supplying mismatch.Phase-change accumulation energy skill
Art is to the exploitation of the energy and rationally using significant, and solid-solid phase transition material is due to no liquid, gas in phase transition process
Produce, it is nontoxic, corrosion-free, pollution-free and the coefficient of expansion is small, obtain extensive concern.
In solid-solid phase transition material, macromolecule class phase transformation material is big with its quantity of heat storage, easy processing shaping, in the absence of supercooling,
Precipitation and the advantage of distillation phenomenon, can be directly used as the structural material of system, as most promising phase-change material.It is high
Molecule solid-solid phase transition material is broadly divided into two classes：One class is high molecular crosslink resin, such as crosslinked polyolefin, crosslined polyacetal
Class, another kind of is graft copolymer, such as cellulose graft copolymer, polyester quasi-graft copolymer, polystyrene graft copolymer,
Silane grafted copolymers.Graft copolymer be one kind it is dystectic it is high molecular on the basis of, using another on chemical bonding
The macromolecule of low melting point forms polymer as side chain.During heating, be first low melting point macromolecule side chain occur from crystalline state to
The phase in version of amorphous state.Although in amorphous state, due to being grafted on dystectic main chain, losing free mobility,
So remaining in that solid forms.Therefore, this kind of phase-change material is reached using the phase in version of the macromolecule side chain of low melting point
The purpose of energy storage.
Polyethylene glycol (PEG) is by (CH2-CH2-O)nThe long chain macromolecule of structure composition, it is simple in construction, easily crystallize, be
The more perfect a kind of macromolecule solid-liquid phase change material studied at present.Polyethylene glycol has enthalpy of phase change big, and phase transition temperature is normal
The advantages of in warm scope.By controlling the size of molecular weight that its phase transition performance can be adjusted, required enthalpy of phase change is obtained
And phase transition temperature, molecule chain end is hydroxyl, and reaction can be chemically modified as active group.Poly glycol monomethyl ether
（MPEG）It is, with methyl blocking, to there is-CH2-CH2One end of-O- compositions carries the long chain macromolecule of hydroxyl.When its molecular weight is higher
When, it is easy to crystallize and with higher enthalpy of phase change.Polyethylene glycol and poly glycol monomethyl ether are grafted on using grafting copolymerization process
Research on certain skeletal support material is also wide.The A of patent of invention CN 103524707 disclose a kind of phase transition temperature can
The preparation method of the comb copolymer solid-solid phase-change energy-storage material of tune, using the method for graft copolymerization by poly glycol monomethyl ether
It is grafted to by triisocyanate on polyethylene glycol and obtains the adjustable pectination phase-changing energy storage material of phase transition temperature and enthalpy of phase change.King
The gorgeous autumn（The preparation of PET/MPEG solid-solid phase-change energy-storage materials and performance study, Guangdong chemical industry, 18 phases in 2014）Deng with poly- to benzene
Dioctyl phthalate second diester（PET）For framework material, MPEG is phase-change material, in toluene di-isocyanate(TDI) and dibutyl tin dilaurate
PET/MPEG solid-solid phase transition materials are prepared under effect, the material is with MPEG content increase, enthalpy of phase change increase.Jiang Zhenhua（It is poly-
Glycol monoethyl ether（MPEG）/ polyvinyl alcohol（PVA）The synthesis of macromolecule solid-solid phase transition material and performance, institution of higher education's chemistry
Journal, 10 phases in 2004）Deng using graft copolymerization to synthesize using PVA as main chain, poly glycol monomethyl ether is the solid-solid phase of side chain
Become material, solve the solubility problem of polyethylene glycol/polyvinyl alcohol.Pei Yuling（Poly glycol monomethyl ether solid-solid phase change material
Synthesis and performance test, Beijing Institute of Clothing Tech's journal, 4 phases in 2010）Deng using MPEG as soft segment, with 4,4- diphenyl methanes
Isocyanates（MDI）, neopentyl glycol（NPG）The polyurethane solid-solid phase-change material that phase transition temperature is low, enthalpy of phase change is high has been synthesized for hard section
Material.
And above-mentioned technique study is changed only for soft segment MPEG enthalpy of phase change, heat endurance and deliquescent aspect
Enter, the phase-change material of synthesis is generally comb shaped structure, and feature is single.And by MPEG be grafted on nano grade polymer microballoon with
The method for preparing the phase-changing energy storage material for having waterproof and energy storage bi-functional concurrently has not been reported.
The invention provides a kind of preparation side with waterproof and the difunctional brush solid-solid phase-change energy-storage material of energy storage
Method, and preparation technology is simple, easily-controllable, process environmental protection, applies in construction material or other energy storage materials, can table
Reveal excellent waterproof and phase-change accumulation energy performance.
The content of the invention
This hair provides a kind of preparation method of difunctional brush solid-solid phase-change energy-storage material, is prepared by this method
The phase transition temperature of phase-changing energy storage material, enthalpy of phase change are adjustable, realize the multifunction of phase-change material, solve building materials wall etc.
Thermal-insulating waterproof two fold problem.
To realize this target, the present invention is first with surfactant- free emulsion polymerization and adds SSS and prepares table
The hydroxylated crosslinking nano polystyrene microballoon in face（PS-OH）, and with the method for graft copolymerization by poly glycol monomethyl ether
（MPEG）Pass through 4,4 '-methyl diphenylene diisocyanate（MDI）It is grafted on PS-OH, obtains phase transition temperature and enthalpy of phase change is equal
Adjustable difunctional brush phase-changing energy storage material.
Specifically, preparation method of the invention comprises the following steps：
（1）Hydroxylating crosslinking nano polystyrene microballoon（PS-OH）Preparation：Each material is pressed necessarily in this step
Mass ratio is added, and first, when reactor being heated into 60 DEG C under nitrogen protection, styrene is added into reactor（St）、
Deionized water（H2O）, sodium hydroxide（NaOH）, sodium acid carbonate（NaHCO3）, stirring mixing；Temperature of charge reaches in question response kettle
At 70 DEG C, cross-linker divinylbenzene is added（DVB）；Initiator potassium persulfate is added at 75 DEG C（KPS）；Benzene second is added at 85 DEG C
Alkene sodium sulfonate（NaSS）, and react 4~5 hours at this temperature；It is eventually adding hydroxyethyl methacrylate（HEMA）Continue anti-
Reaction solution is taken out after answering 3~5 hours, hydroxylating crosslinking nano polystyrene microballoon is obtained through centrifugation, drying and grinding（PS-
OH）.
（2）By 4,4 '-methyl diphenylene diisocyanate（MDI）It is dissolved in solvent, obtains 4,4 '-diphenyl methane two is different
Cyanic acid ester solution；By poly glycol monomethyl ether（MPEG）It is dissolved in solvent, obtains poly glycol monomethyl ether solution.
（3）Under nitrogen protection, by the step（2）In poly glycol monomethyl ether solution be added in reactor, side
Stirring side is heated to adding the step at 70 DEG C（2）In 4,4 '-methyl diphenylene diisocyanate solution, and isothermal reaction
4~10 hours, obtain the poly glycol monomethyl ether with special end group（MPEG-NCO）Solution.
（4）By the step（1）In obtained hydroxylating crosslinking nano polystyrene microballoon（PS-OH）It is scattered in solvent
In, and it is added to the step（3）In the obtained poly glycol monomethyl ether with special end group（MPEG-NCO）In solution,
Reacted 8~20 hours under the conditions of 70~85 DEG C under nitrogen protection, obtain the nanoparticle copolymer solution with brush-like structure.
（5）By the step（4）In obtain nanoparticle copolymer solution filtration washing, vacuum drying, it is then natural
Room temperature is cooled to, it is polished to obtain difunctional brush solid-solid phase-change energy-storage material（PS-MPEG）.
Preferably, the step（1）In each material ratio be styrene, deionized water, sodium hydroxide, sodium acid carbonate
Mass ratio is（27~100）:400:0.04:0.04, divinylbenzene is the 1%~6% of styrene quality, and potassium peroxydisulfate is benzene second
The 1.8% of alkene quality, SSS is the 1%~2% of styrene quality, and hydroxyethyl methacrylate is styrene quality
5%~13%.
Preferably, poly glycol monomethyl ether in the preparation method（MPEG）Molecular weight be 550~5000.
Preferably, the step（2）Middle poly glycol monomethyl ether（MPEG）Mass ratio with solvent is 1:（5.7~9）, 4,
The mass ratio of 4 '-methyl diphenylene diisocyanate and solvent is 1:（5.7~9）.
Preferably, 4,4 '-methyl diphenylene diisocyanate in the step (3)（MDI）And poly glycol monomethyl ether
（MPEG）Mol ratio be 1:（1~1.8）.
Preferably, in the step (4) PS-OH and the mass ratio of solvent is 1:（5.7~9）.
Preferably, the step（4）In have special end group poly glycol monomethyl ether（MPEG-NCO）Handed over hydroxylating
Join nanoscale polystyrene microsphere（PS-OH）The two contained hydroxyl mol ratio is 1:（1~2）.
Preferably, solvent used in the preparation method is N, N '-dimethylformamide（DMF）, acetone, in toluene
Any one.
The present invention controls the hydroxyl grafting density of polystyrene microsphere by different material proportions, thus control it is solid-
The grafting density of poly glycol monomethyl ether on solid-solid phase transition energy storage material, realizes phase transition temperature and the phase transformation of solid-solid phase transition material
Enthalpy it is adjustable；Alternatively, it is also possible to change the molecular weight of poly glycol monomethyl ether, so as to realize the phase alternating temperature of solid-solid phase transition material
Degree is adjustable with enthalpy of phase change.
The positive effect of the present invention
Add the polystyrene microsphere particle diameter prepared after SSS with emulsifier-free emulsion polymerization smaller, so that with
It is that phase-changing energy storage material prepared by matrix reaches nanoscale, and the introducing of hydroxyethyl methacrylate allows microballoon as anti-
Water mortar modifier.By adjusting the molecular weight and grafting density of poly glycol monomethyl ether, phase transition temperature and enthalpy of phase change can be made
It is adjustable, so that a series of phase-change materials for meeting different demands are made.So the solid-solid phase transition material prepared is caused to possess waterproof
With energy storage bi-functional, and the poly glycol monomethyl ether strand undergone phase transition is grafted on polystyrene microsphere, overcomes phase
Become the defect of material easy to leak, performance is stable.Whole preparation technology is simple to operation, obtains product directly using without secondary envelope
Dress and parcel, it is with low cost, it is environment-friendly.
Embodiment
With reference to several specific embodiments of the invention, the invention will be further described, but protection scope of the present invention
Be not limited thereto, any one skilled in the art in the range of the technology of the present invention, can readily occur in change or
Replace, should all be included within the scope of the present invention.Therefore, protection scope of the present invention should be with the protection model of claim
Enclose and be defined.
The grafting density of hydroxyethyl methacrylate is by power spectrum in the nano-grade hydroxy crosslinked polystyrene microsphere of preparation
Analysis（EDS）Measure, it is close by changing grafting of the content of hydroxyethyl methacrylate and cross-linker divinylbenzene to hydroxyl
Degree is regulated and controled.The Hydrodynamic diameter of polymer microballoon is determined by laser particle analyzer.Obtained difunctional solid-solid phase-change
Energy storage material is by differential scanning calorimeter（DSC）Test phase-change accumulation energy performance.
Embodiment 1
1. the preparation of solid-solid phase-change energy-storage material
（1）Hydroxylating crosslinking nano polystyrene microballoon（PS-OH）Preparation：Each quality of material compares St:H2O:NaOH:
NaHCO3=100:400:0.04:0.04, DVB is that 6%, KPS of St amounts is that 1.8%, NaSS of St amounts is 1.6%, HEMA of St amounts
For the 13% of St amounts.First, when reactor being heated into 60 DEG C under nitrogen protection, 100g St, 400g are added into reactor
H2O、0.04g NaOH、0.04g NaHCO3, stirring mixing；When temperature of charge reaches 70 DEG C in question response kettle, 6g DVB are added；
1.8g KPS are added at 75 DEG C；1.6g NaSS are added at 85 DEG C, and are reacted 5 hours at this temperature；It is eventually adding 13g HEMA
Continue to take out reaction solution after reacting 5 hours, obtain PS-OH through centrifugation, drying and grinding, PS-OH hydroxyl grafting density is
0.65mmol/g, average grain diameter are 85nm.
（2）By 0.25g MDI（0.001mol）2.25g is dissolved in by dry DMF solvent, stirring and concentration being made
For 10wt% MDI solution；By 6g MPEG（0.0012mol, molecular weight 5000）54g is dissolved in by dry DMF solvent, stirring
Mix the uniform MPEG solution that concentration is made for 10wt%.The mol ratio of MDI and MPEG in both solution are 1:1.2.
（3）Under nitrogen protection, by the step（2）In MPEG solution be added in reactor, heat while stirring
The step is added during to 70 DEG C（2）In MDI solution, and isothermal reaction 10 hours obtains the poly- second two with special end group
Alcohol monomethyl ether（MPEG-NCO）Solution.
（4）By step described in 1.54g（1）In obtained PS-OH 13.86g be dispersed in ultrasonic wave dry DMF solvent
Central, concentration is 10wt%, is then added to the step（3）In in obtained MPEG-NCO solution（MPEG-NCO and PS-OH
Middle hydroxyl mol ratio is 1:1）, reacted 8 hours under the conditions of 70 DEG C under nitrogen protection, obtain the nanometer with brush-like structure micro-
Ball copolymer solution.
（5）By the step（4）In obtain nanoparticle copolymer solution filtration washing, vacuum drying, it is then natural
Room temperature is cooled to, it is polished to obtain difunctional brush solid-solid phase-change energy-storage material（PS-MPEG）.
2. solid-solid phase-change energy-storage material application test
Using DSC test PS-MPEG melting temperature be 63.3 DEG C, melting enthalpy be 155.8J/g.It is configured to PS-MPEG
Cement mortar, proportioning（In mass ratio）For cement: PS-MPEG:Aggregate:Water reducer:Defoamer=1:0.1:3:0.005:
0.002, according to《Inorganic leak-stopping material GB 23440-2009》Tested, the impermeability pressure of mortar specimen is 2.0MPa.
Concrete outcome is shown in Table 1.
Embodiment 2
1. the preparation of solid-solid phase-change energy-storage material
（1）Step in PS-OH preparation be the same as Example 1（1）.
（2）By 0.25g MDI（0.001mol）1.84g is dissolved in by dry DMF solvent, stirring and concentration being made
For 12wt% MDI solution；By 2.66g MPEG（0.0014mol, molecular weight 1900）It is dissolved in 19.51g molten by dry DMF
In agent, stir the MPEG solution for being made that concentration is 12wt%.The mol ratio of MDI and MPEG in both solution are 1:
1.4。
（3）Under nitrogen protection, by the step（2）In MPEG solution be added in reactor, heat while stirring
The step is added during to 70 DEG C（2）In MDI solution, and isothermal reaction 6 hours obtains the polyethylene glycol with special end group
Monomethyl ether（MPEG-NCO）Solution.
（4）By step described in 2.31g（1）In obtained PS-OH 16.94g be dispersed in ultrasonic wave dry DMF solvent
Central, concentration is 12wt%, is then added to the step（3）In in obtained MPEG-NCO solution（MPEG-NCO and PS-OH
Middle hydroxyl mol ratio is 1:1.5）, reacted 10 hours under the conditions of 75 DEG C under nitrogen protection, obtain receiving with brush-like structure
Meter Wei Qiu copolymer solutions.
（5）By the step（4）In obtain nanoparticle copolymer solution filtration washing, vacuum drying, it is then natural
Room temperature is cooled to, it is polished to obtain difunctional brush solid-solid phase-change energy-storage material（PS-MPEG）.
2. solid-solid phase-change energy-storage material application test
Using DSC test PS-MPEG melting temperature be 45.6 DEG C, melting enthalpy be 133.7J/g.It is configured to PS-MPEG
Cement mortar, proportioning（In mass ratio）For cement: PS-MPEG:Aggregate:Water reducer:Defoamer=1:0.1:3:0.005:
0.002, according to《Inorganic leak-stopping material GB 23440-2009》Tested, the impermeability pressure of mortar specimen is 1.9MPa.
Concrete outcome is shown in Table 1.
Embodiment 3
1. the preparation of solid-solid phase-change energy-storage material
（1）Step in PS-OH preparation be the same as Example 1（1）.
（2）By 0.25g MDI（0.001mol）2.25g is dissolved in by dry toluene solvant, stirring, it is dense to be made
Spend the MDI solution for 10wt%；By 1g MPEG（0.001mol, molecular weight 1000）It is dissolved in toluene solvants of the 9g by drying,
Stir the MPEG solution for being made that concentration is 10wt%.The mol ratio of MDI and MPEG in both solution are 1:1.
（3）Under nitrogen protection, by the step（2）In MPEG solution be added in reactor, heat while stirring
The step is added during to 70 DEG C（2）In MDI solution, and isothermal reaction 8 hours obtains the polyethylene glycol with special end group
Monomethyl ether（MPEG-NCO）Solution.
（4）By step described in 2.77g（1）In obtained PS-OH that 24.93g dry toluenes are dispersed in ultrasonic wave is molten
Among agent, concentration is 10wt%, is then added to the step（3）In in obtained MPEG-NCO solution（MPEG-NCO and PS-
Hydroxyl mol ratio is 1 in OH:1.8）, react 15 hours, obtain with brush-like structure under the conditions of 80 DEG C under nitrogen protection
Nanoparticle copolymer solution.
（5）By the step（4）In obtain nanoparticle copolymer solution filtration washing, vacuum drying, it is then natural
Room temperature is cooled to, it is polished to obtain difunctional brush solid-solid phase-change energy-storage material（PS-MPEG）.
2. solid-solid phase-change energy-storage material application test
Using DSC test PS-MPEG melting temperature be 33.2 DEG C, melting enthalpy be 96.5J/g.It is configured to PS-MPEG
Cement mortar, proportioning（In mass ratio）For cement: PS-MPEG:Aggregate:Water reducer:Defoamer=1:0.1:3:0.005:
0.002, according to《Inorganic leak-stopping material GB 23440-2009》Tested, the impermeability pressure of mortar specimen is 2.0MPa.
Concrete outcome is shown in Table 1.
Embodiment 4
1. the preparation of solid-solid phase-change energy-storage material
（1）Step in PS-OH preparation be the same as Example 1（1）.
（2）By 0.25g MDI（0.001mol）1.67g is dissolved in by dry toluene solvant, stirring, it is dense to be made
Spend the MDI solution for 13wt%；By 0.825g MPEG（0.0015mol, molecular weight 550）5.52g is dissolved in by dry toluene
In solvent, stir the MPEG solution for being made that concentration is 13wt%.The mol ratio of MDI and MPEG in both solution are 1:
1.5。
（3）Under nitrogen protection, by the step（2）In MPEG solution be added in reactor, heat while stirring
The step is added during to 70 DEG C（2）In MDI solution, and isothermal reaction 9 hours obtains the polyethylene glycol with special end group
Monomethyl ether（MPEG-NCO）Solution.
（4）By step described in 2.15g（1）In obtained PS-OH that 14.39g dry toluenes are dispersed in ultrasonic wave is molten
Among agent, concentration is 13wt%, is then added to the step（3）In in obtained MPEG-NCO solution（MPEG-NCO and PS-
Hydroxyl mol ratio is 1 in OH:1.4）, react 20 hours, obtain with brush-like structure under the conditions of 85 DEG C under nitrogen protection
Nanoparticle copolymer solution.
（5）By step（4）Obtained reaction product carries out filtration washing, and then vacuum drying places and naturally cool to room
Obtained after temperature, grinding with difunctional brush solid-solid phase-change energy-storage material（PS-MPEG）.
2. solid-solid phase-change energy-storage material application test
Using DSC test PS-MPEG melting temperature be 20.5 DEG C, melting enthalpy be 79.8J/g.It is configured to PS-MPEG
Cement mortar, proportioning（In mass ratio）For cement: PS-MPEG:Aggregate:Water reducer:Defoamer=1:0.1:3:0.005:
0.002, according to《Inorganic leak-stopping material GB 23440-2009》Tested, the impermeability pressure of mortar specimen is 2.0MPa.
Concrete outcome is shown in Table 1.
Embodiment 5
1. the preparation of solid-solid phase-change energy-storage material
（1）Hydroxylating crosslinking nano polystyrene microballoon（PS-OH）Preparation：Each quality of material compares St:H2O:NaOH:
NaHCO3=100:400:0.04:0.04, DVB is that 1%, KPS of St amounts is that 1.8%, NaSS of St amounts is that 2%, HEMA of St amounts is
The 5% of St amounts.First, when reactor being heated into 60 DEG C under nitrogen protection, 100g St, 400g are added into reactor
H2O、0.04g NaOH、0.04g NaHCO3, stirring mixing；When temperature of charge reaches 70 DEG C in question response kettle, 1g DVB are added；
1.8g KPS are added at 75 DEG C；2.0g NaSS are added at 85 DEG C, and are reacted 5 hours at this temperature；It is eventually adding 5g HEMA
Continue to take out reaction solution after reacting 4 hours, obtain PS-OH through centrifugation, drying and grinding, PS-OH hydroxyl grafting density is
0.38mmol/g, average grain diameter are 75nm.
（2）By 0.25g MDI（0.001mol）1.43g is dissolved in by dry acetone solvent, stirring, it is dense to be made
Spend the MDI solution for 15wt%；By 1.6g MPEG（0.0016mol, molecular weight 1000）It is dissolved in 9.07g molten by dry acetone
In agent, stir the MPEG solution for being made that concentration is 15wt%.The mol ratio of MDI and MPEG in both solution are 1:
1.6。
（3）Under nitrogen protection, by the step（2）In MPEG solution be added in reactor, heat while stirring
The step is added during to 70 DEG C（2）In MDI solution, and isothermal reaction 4 hours obtains the polyethylene glycol with special end group
Monomethyl ether（MPEG-NCO）Solution.
（4）By step described in 4.21g（1）In obtained PS-OH that 23.86g dry acetones are dispersed in ultrasonic wave is molten
Among agent, concentration is 15wt%, is then added to the step（3）In in obtained MPEG-NCO solution（MPEG-NCO and PS-
Hydroxyl mol ratio is 1 in OH:1.6）, react 18 hours, obtain with brush-like structure under the conditions of 75 DEG C under nitrogen protection
Nanoparticle copolymer solution.
（5）By the step（4）In obtain nanoparticle copolymer solution filtration washing, vacuum drying, it is then natural
Room temperature is cooled to, it is polished to obtain difunctional brush solid-solid phase-change energy-storage material（PS-MPEG）.
2. solid-solid phase-change energy-storage material application test
Using DSC test PS-MPEG melting temperature be 31.3 DEG C, melting enthalpy be 90.2J/g.It is configured to PS-MPEG
Cement mortar, proportioning（In mass ratio）For cement: PS-MPEG:Aggregate:Water reducer:Defoamer=1:0.1:3:0.005:
0.002, according to《Inorganic leak-stopping material GB 23440-2009》Tested, the impermeability pressure of mortar specimen is 1.9MPa.
Concrete outcome is shown in Table 1.
Embodiment 6
1. the preparation of solid-solid phase-change energy-storage material
（1）Hydroxylating crosslinking nano polystyrene microballoon（PS-OH）Preparation：Each quality of material compares St:H2O:NaOH:
NaHCO3=80:400:0.04:0.04, DVB is that 5%, KPS of St amounts is that 1.8%, NaSS of St amounts is that 1.8%, HEMA of St amounts is
The 10% of St amounts.First, when reactor being heated into 60 DEG C under nitrogen protection, 80g St, 400g are added into reactor
H2O、0.04g NaOH、0.04g NaHCO3, stirring mixing；When temperature of charge reaches 70 DEG C in question response kettle, 4g DVB are added；
1.44g KPS are added at 75 DEG C；1.44g NaSS are added at 85 DEG C, and are reacted 4 hours at this temperature；It is eventually adding 8g
HEMA continues to take out reaction solution after reacting 3 hours, obtains PS-OH through centrifugation, drying and grinding, PS-OH hydroxyl grafting density is
0.45mmol/g, average grain diameter are 80nm.
（2）By 0.25g MDI（0.001mol）1.54g is dissolved in by dry acetone solvent, stirring, it is dense to be made
Spend the MDI solution for 14wt%；By 1.8g MPEG（0.0018mol, molecular weight 1000）11.06g is dissolved in by dry acetone
In solvent, stir the MPEG solution for being made that concentration is 14wt%.The mol ratio of MDI and MPEG in both solution are 1:
1.8。
（3）Under nitrogen protection, by the step（2）In MPEG solution be added in reactor, heat while stirring
The step is added during to 70 DEG C（2）In MDI solution, and isothermal reaction 5 hours obtains the polyethylene glycol with special end group
Monomethyl ether（MPEG-NCO）Solution.
（4）By step described in 3.4g（1）In obtained PS-OH be dispersed in ultrasonic wave 20.52g dryings acetone it is molten
Among agent, concentration is 14wt%, is then added to the step（3）In in obtained MPEG-NCO solution（MPEG-NCO and PS-
Hydroxyl mol ratio is 1 in OH:1.5）, react 15 hours, obtain with brush-like structure under the conditions of 70 DEG C under nitrogen protection
Nanoparticle copolymer solution.
（5）By the step（4）In obtain nanoparticle copolymer solution filtration washing, vacuum drying, it is then natural
Room temperature is cooled to, it is polished to obtain difunctional brush solid-solid phase-change energy-storage material（PS-MPEG）.
2. solid-solid phase-change energy-storage material application test
Using DSC test PS-MPEG melting temperature be 32.1 DEG C, melting enthalpy be 95.4J/g.It is configured to PS-MPEG
Cement mortar, proportioning（In mass ratio）For cement: PS-MPEG:Aggregate:Water reducer:Defoamer=1:0.1:3:0.005:
0.002, according to《Inorganic leak-stopping material GB 23440-2009》Tested, the impermeability pressure of mortar specimen is 2.0MPa.
Concrete outcome is shown in Table 1.
Embodiment 7
1. the preparation of solid-solid phase-change energy-storage material
（1）Hydroxylating crosslinking nano polystyrene microballoon（PS-OH）Preparation：Each quality of material compares St:H2O:NaOH:
NaHCO3=27:400:0.04:0.04, DVB is that 3%, KPS of St amounts is that 1.8%, NaSS of St amounts is that 1%, HEMA of St amounts is St
The 8% of amount.First, when reactor being heated into 60 DEG C under nitrogen protection, 27g St, 400g H are added into reactor2O、
0.04g NaOH、0.04g NaHCO3, stirring mixing；When temperature of charge reaches 70 DEG C in question response kettle, 0.81g DVB are added；
0.486g KPS are added at 75 DEG C；0.27g NaSS are added at 85 DEG C, and are reacted 4 hours at this temperature；It is eventually adding 2.16g
HEMA continues to take out reaction solution after reacting 5 hours, obtains PS-OH through centrifugation, drying and grinding, PS-OH hydroxyl grafting density is
0.58mmol/g, average grain diameter are 82nm.
（2）By 0.25g MDI（0.001mol）1.43g is dissolved in by dry DMF solvent, stirring and concentration being made
For 15wt% MDI solution；By 1.5g MPEG（0.0015mol, molecular weight 1000）8.5g is dissolved in by dry DMF solvent
In, stir the MPEG solution for being made that concentration is 15wt%.The mol ratio of MDI and MPEG in both solution are 1:1.5.
（3）Under nitrogen protection, by the step（2）In MPEG solution be added in reactor, heat while stirring
The step is added during to 70 DEG C（2）In MDI solution, and isothermal reaction 7 hours obtains the polyethylene glycol with special end group
Monomethyl ether（MPEG-NCO）Solution.
（4）By step described in 1.43g（1）In obtained PS-OH 8.10g be dispersed in ultrasonic wave dry DMF solvent
Central, concentration is 15wt%, is then added to the step（3）In in obtained MPEG-NCO solution（MPEG-NCO and PS-OH
Middle hydroxyl mol ratio is 1:1.2）, reacted 20 hours under the conditions of 80 DEG C under nitrogen protection, obtain receiving with brush-like structure
Meter Wei Qiu copolymer solutions.
（5）By the step（4）In obtain nanoparticle copolymer solution filtration washing, vacuum drying, it is then natural
Room temperature is cooled to, it is polished to obtain difunctional brush solid-solid phase-change energy-storage material（PS-MPEG）.
2. solid-solid phase-change energy-storage material application test
Using DSC test PS-MPEG melting temperature be 34.5 DEG C, melting enthalpy be 98.5J/g.It is configured to PS-MPEG
Cement mortar, proportioning（In mass ratio）For cement: PS-MPEG:Aggregate:Water reducer:Defoamer=1:0.1:3:0.005:
0.002, according to《Inorganic leak-stopping material GB 23440-2009》Tested, the impermeability pressure of mortar specimen is 2.0MPa.
Concrete outcome is shown in Table 1.
The performance of difunctional brush solid-solid phase-change energy-storage material prepared by each embodiment of table 1
Claims (8)
1. a kind of preparation method of difunctional brush solid-solid phase-change energy-storage material, it is characterised in that this method comprises the following steps：
（1）The preparation of hydroxylating crosslinking nano polystyrene microballoon (PS-OH)：Each material adds by a certain percentage in this step
Enter, first, when reactor being heated into 60 DEG C under nitrogen protection, styrene, deionized water, hydroxide are added into reactor
Sodium, sodium acid carbonate, stirring mixing；When temperature of charge reaches 70 DEG C in question response kettle, cross-linker divinylbenzene is added；At 75 DEG C
Add initiator potassium persulfate；SSS is added at 85 DEG C, and is reacted 4~5 hours at this temperature；It is eventually adding first
Base hydroxy-ethyl acrylate continues to take out reaction solution after reacting 3~5 hours, and PS-OH is obtained through centrifugation, drying and grinding；
（2）4,4 '-methyl diphenylene diisocyanate is dissolved in solvent, 4 are obtained, 4 '-methyl diphenylene diisocyanate is molten
Liquid；Poly glycol monomethyl ether is dissolved in solvent, poly glycol monomethyl ether solution is obtained；
（3）Under nitrogen protection, by the step（2）In poly glycol monomethyl ether solution be added in reactor, side stirring
While being heated to adding the step at 70 DEG C（2）In 4,4 '-methyl diphenylene diisocyanate solution, and isothermal reaction 4~
10 hours, obtain MPEG-NCO solution；
（4）Will be by the step（1）In obtained PS-OH be scattered in solvent, and be added to the step（3）In obtain
In MPEG-NCO solution, reacted 8~20 hours under the conditions of 70~85 DEG C under nitrogen protection, obtain receiving with brush-like structure
Meter Wei Qiu copolymer solutions；
（5）By the step（4）In obtain nanoparticle copolymer solution filtration washing, vacuum drying, then natural cooling
It is polished to obtain solid-solid phase-change energy-storage material to room temperature.
2. preparation method according to claim 1, it is characterised in that：The step（1）In each material ratio be benzene second
Alkene, deionized water, sodium hydroxide, the mass ratio of sodium acid carbonate are（27~100）:400:0.04:0.04, divinylbenzene is benzene
The 1%~6% of Ethylene mass, potassium peroxydisulfate is the 1.8% of styrene quality, and SSS is the 1%~2% of styrene quality,
Hydroxyethyl methacrylate is the 5%~13% of styrene quality.
3. preparation method according to claim 1, it is characterised in that：The relative molecular mass of the poly glycol monomethyl ether
For 550~5000.
4. preparation method according to claim 1, it is characterised in that：The step（2）In poly glycol monomethyl ether with
The mass ratio of solvent is 1:（5.7~9）, 4, the mass ratio of 4 '-methyl diphenylene diisocyanate and solvent is 1:（5.7~9）.
5. preparation method according to claim 1, it is characterised in that：4 in the step (3), 4 '-diphenyl methane two
The mol ratio of isocyanates and poly glycol monomethyl ether is 1:（1~1.8）.
6. preparation method according to claim 1, it is characterised in that：The quality of PS-OH and solvent in the step (4)
Than for 1:（5.7~9）.
7. preparation method according to claim 1, it is characterised in that：MPEG-NCO and PS-OH bis- in the step (4)
Hydroxyl mol ratio contained by person is 1:（1~2）.
8. the preparation method according to any one claim in claim 1 to 7, it is characterised in that：The solvent is
Any one in N, N '-dimethylformamide, acetone, toluene.
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