CN105482430B - A kind of method that utilization sol-gal process prepares polyethylene glycol phase-change material - Google Patents

A kind of method that utilization sol-gal process prepares polyethylene glycol phase-change material Download PDF

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CN105482430B
CN105482430B CN201510838982.6A CN201510838982A CN105482430B CN 105482430 B CN105482430 B CN 105482430B CN 201510838982 A CN201510838982 A CN 201510838982A CN 105482430 B CN105482430 B CN 105482430B
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peg
added
certain amount
phase
polyethylene glycol
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CN105482430A (en
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张平
张丽
王峰
康明
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Southwest University of Science and Technology
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Southwest University of Science and Technology
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/02—Materials undergoing a change of physical state when used
    • C09K5/06—Materials undergoing a change of physical state when used the change of state being from liquid to solid or vice versa
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation

Abstract

The present invention discloses a kind of polyethylene glycol（PEG）Phase-change material and preparation method thereof.The composite phase-change material has phosphorus, nitrogen, three kinds of elements of silicon, with graphite oxide, cyanuric trichloride, and organophosphor chloride compounds and amino silicone and PEG are raw material, and the compound PEG phase-change materials of a kind of phosphorous, nitrogen, silicon are prepared using sol-gal process.Phase-change material of the present invention causes PEG can be while realizing raising heat-resisting ability, leak-preventing ability in same framework material；PEG addition can be with flexible and changeable simultaneously；And obtained framework material can add in high polymer material the fire resistance for improving material.

Description

A kind of method that utilization sol-gal process prepares polyethylene glycol phase-change material
Technical field
The present invention relates to a kind of method that utilization sol-gal process prepares high thermal stability PEG phase-change materials, belong to phase transformation Material Field.
Background technology
So-called phase-change material, is exactly that material can absorb energy when environment temperature is higher than the fusing point of material, on the contrary then discharge Energy.The energy of a large amount of forms by latent heat phase-changing energy storage material can store being reused, such as sun Can, geothermal energy and the heat energy that industrially wastes etc..Polyethylene glycol（PEG）Because it has suitable phase transition temperature, no supercooling Phenomenon, nontoxic, high latent heat, and the advantages of good chemical stability, so that as the focus studied instantly.
But, PEG is easily revealed in phase transition process, and the capacity of heat transmission is low and makes it in actual applications the shortcomings of inflammability It is restricted.The capillary attraction of the superfine utilization aerosil hole of Zheng, using chemical graft and sol-gal process point PEG/SiO2 composite phase-change materials are not prepared for（South China Science ＆ Engineering University, 2013）；Chongyun Wang etc. are using three kinds of differences The expanded graphite of pore structure, activated carbon, ordered mesoporous carbon material is prepared into composite phase-change material with PEG respectively, for porous material The selection of material proposes experimental according to (Solar Energy Materials and Solar Cells, 2012,105: 21-26).But the latent heat of phase-change material can be reduced as skeletal support material from inorganic material, influence the energy storage of material Energy.Phase-change material can also be by the use of high-molecular organic material as matrix material, but organic material in actual applications inflammable Property limits it and used many.Therefore, the fire resistance for improving material is particularly important.Preparing collection resistance now Combustion, heat conduction, energy storage still lacks cost-effective method in terms of the PEG composites of one.
Silicon substrate fire retardant is acknowledged as preferable halogen-free flame retardants (Polymer Degradation and Stability, 2009, 94:465-495), and siloxanes can be formed multifunctionality material such as catalyst carrier, it is porous Material and fire retardant (Angewandte Chemie International Edition, 2006,45: 3216-3251). Therefore, if there is siloxanes in flame-retardant composition contained by material, the material is expected to turn into the composite for being adapted to stored energy application（Simultaneously Possess the heat resistance of inorganic material and the compatibility of organic material）.
The content of the invention
The invention provides a kind of high thermal stability PEG phase change composite materials.Wherein skeleton structure type is as follows：（Wherein G generations Epoxy graphite lamellar structure）
R is Cl, NH in formula2, or for can with amino react group such as：Phosphoryl chloride phosphorus oxychloride, carboxyl, isocyanates, many ethene Polyamines, polyamide, polyetheramine, phenolic aldehyde amine, epoxy radicals, sulfonic group etc.；
R ' is phenyl or chlorine;R 〞 are oxygen or sulphur.
The present invention also provides a kind of high thermal stability PEG phase change composite material preparation methods, specifically includes following steps：
（1）Using GO as raw material, DMF is added（DMF）, dichloro is added dropwise under normal temperature while stirring sub- Sulfone, then heats to 50 ~ 80 DEG C, thionyl chloride is centrifuged off after 12 ~ 24h, then wash many with chloroform dried in advance Secondary, last 50 ~ 80 DEG C of drying obtain intermediate I；
（2）Cyanuric trichloride（CAC）It is scattered in the acetone and deionized water through refrigeration, is sufficiently stirred for, keeps solution temperature Between 0 ~ 5 DEG C, ammoniacal liquor is added dropwise（Time for adding is controlled in 20 ~ 40min）, react and filtered after 30 ~ 60min, obtain product 2- The chloro- 1,3,5- triazines of amino -4,6- two（ADCT）That is intermediate II；
（3）A certain amount of intermediate I and intermediate II are scattered in DMF solution, are added after triethylamine, at 70 ~ 90 DEG C 24 ~ 30h is mixed, finally intermediate III is obtained with ethanol and the deionized water centrifuge washing of refrigeration；
（4）The acetone through refrigeration is added into intermediate III, deionized water is added dropwise ammoniacal liquor using separatory funnel, dripped 70 ~ 90 DEG C of 1 ~ 2h of reaction are warming up to after finishing, last 70 ~ 90 DEG C of drying obtain intermediate IV；
（5）A certain amount of triethylamine and diphenylphosphoryl dichloro is added in three-necked flask and passes to nitrogen protection.By centre Body IV is scattered in a certain amount of chloroform, is added dropwise in three-necked flask.Mix after 24 ~ 36h and add at room temperature A certain amount of aminopropyl triethoxysilane（KH550）, 50 ~ 60 DEG C are warming up to after stirring 2 ~ 5h, 3 ~ 5h of stirring is remixed, finally Centrifugation obtains intermediate V；
（6）A certain amount of polyethylene glycol（2000~4000）（PEG）It is dissolved in a certain amount of deionized water, stirs at room temperature Mix 2 ~ 3h.Intermediate V is scattered in a certain amount of absolute ethyl alcohol, and the PEG aqueous solution is slowly dropped to after 1 ~ 5min of ultrasound In, add a certain amount of 28% NH after mixing 24 ~ 36h under normal temperature3·H2O, be warming up to after 50 ~ 60 DEG C and be stirred for 24 ~ 36h, is realized using sol-gal process during this and coats PEG into the loose structure of framework material, final mixture Beaker is transferred to, 60 ~ 70 DEG C of drying to constant weights obtain compound PEG phase-change materials.
Advantages of the present invention：
（1）PEG can realize raising heat-resisting ability, leak-preventing ability simultaneously in same framework material；
（2）Obtained framework material can add in high polymer material the fire resistance for improving material；
（3）PEG addition can be with flexible and changeable.
As seen from Figure 1,3438cm-1It is nearby O-H stretching vibration peak, 2960cm-1And 2850cm-1Nearby respectively For-CH3- and-CH2- antisymmetric stretching vibration absworption peak and symmetrical stretching vibration absworption peak, 1630cm-1And 1440cm-1Near Respectively-CH3- and-CH2- deformation vibration the absworption peak, 1261cm-1It is nearby P=O stretching vibration absworption peak, 1029cm-1Near For P-O-C stretching vibration absworption peak, 924cm-1It is nearby P-N absworption peak, 694cm-1Nearby inhaled for P-C stretching vibration Receive peak, 1110cm-1It is nearby Si-O-Si stretching vibration absworption peak, 806cm-1Nearby inhaled for the deformation vibration of triazine ring skeleton Receive peak.Above-mentioned data illustrate the characteristic IR absorbance peaks that there is framework material in the molecular structure.
Brief description of the drawings
Fig. 1 is the infared spectrum of the framework material of the embodiment of the present invention 2.
Embodiment
The present invention can be further illustrated in conjunction with the embodiments
Embodiment 1
Weigh the GO 0.20g prepared in advance to be placed in 250ml three-necked flasks, 1ml N, N- dimethyl are added thereto Formamide (DMF), unlatching is slowly stirred, and 50ml thionyl chlorides are slowly added dropwise to above-mentioned system with constant pressure funnel（SOCl2）, Then heat to 70 DEG C of reaction 24h, obtained reaction product intermediate I；
Weigh in the 250ml flasks that 4.00g CAC are placed under condition of ice bath, the 50ml acetone through refrigeration is slowly added to successively With 50ml deionized waters, uniform suspension is formed after magnetic agitation, 0 DEG C is kept in the process.It is by 100ml concentration again 1mol/L ammoniacal liquor is slowly dropped to the help of dropping funel in above-mentioned suspension, keeps 0 ~ 5 DEG C of reaction 30min.By Filter, is washed and 50 DEG C are dried to obtain product ADCT i.e. intermediate II；
Intermediate I in the presence of 50mlDMF and 669ul triethylamines, is heated to 85 DEG C of stirring reaction 30h with intermediate II Obtain intermediate III；
Add the 35ml acetone through refrigeration into intermediate III, 40ml deionized waters, 60ml concentration, which is then slowly added dropwise, is 85 DEG C of reaction 1h are warming up to after 1mol/L ammoniacal liquor, completion of dropping, last 85 DEG C of drying obtain intermediate IV；
200ul triethylamines and 10ml chloroforms are added in 250ml three-necked flasks and pass to nitrogen protection, add 200ul diphenylphosphoryl dichloros.Intermediate IV is scattered in 50ml chloroforms, is slowly added into dropwise in three-necked flask.Room Temperature lower mix adds 670ul KH550 and 400ul triethylamines after 24h, be warming up to 50 DEG C after stirring 2h, close nitrogen, then 3h is mixed, finally centrifugation obtains intermediate V；
0.10g PEG2000 are dissolved in 20ml deionized waters, and 2h is stirred at room temperature.It is anhydrous that intermediate V is scattered in 20ml In ethanol, and it is slowly dropped to after ultrasound 1min in the PEG aqueous solution, the ammonia that 1ml 28% is added after 24h is mixed under normal temperature Water, is warming up to after 60 DEG C and is stirred for 24h, and final mixture is transferred to beaker, and 60 DEG C of drying to constant weights obtain PEG composites.Institute The enthalpy change value for obtaining composite is 88.12J/g.
Embodiment 2
Intermediate V is prepared according to the method and consumption in embodiment 1；
0.15g PEG2000 are dissolved in 20ml deionized waters, and 2h is stirred at room temperature.It is anhydrous that intermediate V is scattered in 20ml In ethanol, and it is slowly dropped to after ultrasound 1min in the PEG aqueous solution, the ammonia that 1ml 28% is added after 24h is mixed under normal temperature Water, is warming up to after 60 DEG C and is stirred for 24h, and final mixture is transferred to beaker, and 60 DEG C of drying to constant weights obtain PEG composites.Institute The enthalpy change value for obtaining composite is 102.1J/g.
Embodiment 3
Intermediate V is prepared according to the method and consumption in embodiment 1；
0.20g PEG2000 are dissolved in 20ml deionized waters, and 2h is stirred at room temperature.It is anhydrous that intermediate V is scattered in 20ml In ethanol, and it is slowly dropped to after ultrasound 1min in the PEG aqueous solution, the ammonia that 1ml 28% is added after 24h is mixed under normal temperature Water, is warming up to after 60 DEG C and is stirred for 24h, and final mixture is transferred to beaker, and 60 DEG C of drying to constant weights obtain PEG composites.Institute The enthalpy change value for obtaining composite is 63.19J/g.

Claims (2)

1. one kind prepares polyethylene glycol using sol-gal process（PEG）The method of phase-change material, it is characterised in that utilize KH550 Hydrolytic process, while PEG is coated in the pore structure of framework material, wherein framework material structure is as follows：
G represents oxidized graphite flake Rotating fields in formula, and R is Cl, NH2, or for that can include with the group of amino reaction：Phosphoryl chloride phosphorus oxychloride, One kind in carboxyl, isocyanates, polyethylene polyamine, polyamide, polyetheramine, phenolic aldehyde amine, epoxy radicals, sulfonic group；R ' is phenyl Or chlorine;R 〞 are oxygen or sulphur.
2. the method that a kind of utilization sol-gal process as claimed in claim 1 prepares PEG phase-change materials, it is characterised in that its Step is：
（1）Using GO as raw material, DMF is added（DMF）, thionyl chloride is added dropwise while stirring under normal temperature, so After be warming up to 50 ~ 80 DEG C, be centrifuged off thionyl chloride after 12 ~ 24h, then washed repeatedly, most with chloroform dried in advance 50 ~ 80 DEG C of drying obtain intermediate I afterwards；
（2）Cyanuric trichloride（CAC）It is scattered in the acetone and deionized water through refrigeration, is sufficiently stirred for, keeps solution temperature 0 ~ 5 Between DEG C, then ammoniacal liquor is added dropwise into the dispersion soln of above-mentioned cyanuric trichloride, the time that the ammoniacal liquor is added dropwise is 20 ~ 40min, reaction Filtered after 30 ~ 60min, obtain the chloro-1,3,5-triazines of product 2- amino -4,6- bis-（ADCT）That is intermediate II；
（3）A certain amount of intermediate I and intermediate II are scattered in DMF solution, are added after triethylamine, are mixed at 70 ~ 90 DEG C 24 ~ 30h is stirred, finally intermediate III is obtained with ethanol and the deionized water centrifuge washing of refrigeration；
（4）The acetone through refrigeration is added into intermediate III, deionized water is added dropwise after ammoniacal liquor, completion of dropping using separatory funnel 70 ~ 90 DEG C of 1 ~ 2h of reaction are warming up to, last 70 ~ 90 DEG C of drying obtain intermediate IV；
（5）A certain amount of triethylamine and diphenylphosphoryl dichloro is added in three-necked flask and passes to nitrogen protection；By intermediate IV It is scattered in a certain amount of chloroform, is added dropwise in three-necked flask；Mix after 24 ~ 36h and added necessarily at room temperature The aminopropyl triethoxysilane of amount（KH550）, 50 ~ 60 DEG C are warming up to after stirring 2 ~ 5h, 3 ~ 5h of stirring is remixed, finally centrifuges Obtain intermediate V；
（6）A certain amount of polyethylene glycol（PEG）It is dissolved in a certain amount of deionized water, 2 ~ 3h is stirred at room temperature；Intermediate V It is scattered in a certain amount of absolute ethyl alcohol, and is slowly dropped to after 1 ~ 5min of ultrasound in the PEG aqueous solution, is mixed under normal temperature A certain amount of ammoniacal liquor is added after 24 ~ 36h, 24 ~ 36h is stirred for after being warming up to 50 ~ 60 DEG C, sol-gal process is utilized during this Realize and coat PEG into the loose structure of framework material, final mixture is transferred to beaker, 60 ~ 70 DEG C of drying to constant weights are obtained To compound PEG phase-change materials, the molecular weight of the polyethylene glycol is 2000 ~ 20000.
CN201510838982.6A 2015-11-27 2015-11-27 A kind of method that utilization sol-gal process prepares polyethylene glycol phase-change material Expired - Fee Related CN105482430B (en)

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