CN106916461A - A kind of preparation of phase-changing energy storage material - Google Patents
A kind of preparation of phase-changing energy storage material Download PDFInfo
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- CN106916461A CN106916461A CN201510990382.1A CN201510990382A CN106916461A CN 106916461 A CN106916461 A CN 106916461A CN 201510990382 A CN201510990382 A CN 201510990382A CN 106916461 A CN106916461 A CN 106916461A
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/28—Treatment by wave energy or particle radiation
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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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/14—Peroxides
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/541—Silicon-containing compounds containing oxygen
- C08K5/5425—Silicon-containing compounds containing oxygen containing at least one C=C bond
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- 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
- C09K5/063—Materials absorbing or liberating heat during crystallisation; Heat storage materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2391/00—Characterised by the use of oils, fats or waxes; Derivatives thereof
- C08J2391/06—Waxes
-
- 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
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3045—Sulfates
Abstract
The invention belongs to new material research and development field, and in particular to a kind of phase-changing energy storage material and its preparation and application.Phase-changing energy storage material of the present invention, its raw material contains the component of following parts by weight：The weight portion of sodium sulphate 10~50；The weight portion of crosslinking agent 5~20；The weight portion of paraffin 40~70；The weight portion of water 10~25；The weight portion of curing agent 1~4；The weight portion of cumyl peroxide 0.5~1.0；The weight portion of dibutyl tin laurate 0.5~1.0.The phase-changing energy storage material has the advantages that phase transition temperature is suitable, thermal conductivity factor is larger and energy storage density is high.
Description
Technical field
The invention belongs to new material research and development field, and in particular to a kind of phase-changing energy storage material and preparation method thereof.
Background technology
Phase-changing energy storage material is, using latent heat ability of the material in phase transition process, to store or release energy.The reason of energy storage material
Have very early by basis, external advanced country begins to research the sixties early in twentieth century, and China is then in the eighties
Just start the research of phase-changing energy storage material.Phase-changing energy storage material species is various, can be divided into according to its phase transformation mode：It is solid-solid, solid
- liquid, liquid-gas, solid-gas phase-changing energy storage material.According to material composition, it is divided into inorganic phase-changing energy storage material, the storage of organic class phase transformation
Can material and composite phase-change energy storage material.Inorganic phase-changing energy storage material be mainly crystallization water fuse salt, metal and its alloy,
Fluoride and mineral matter etc..Organic storage material is mainly macromolecular material class, such as aromatic hydrocarbon, aliphatic hydrocarbon, aldoketones.
Composite class can be proportioning between inorganic energy storage material combine, can be being combined with machine between organic energy storage material,
It is probably that proportioning between organic energy storage material and inorganic energy storage material is combined.Development by theoretic research and in practice,
The energy storage feature of various types of materials general orientation or apparent.The characteristics of such as mineral-type materials energy storage：Using scope is wide, heat conduction
Coefficient is big, heat of fusion is larger, energy storage density is big, general in neutral, cheap etc..Easily there is surfusion simultaneously, i.e.,
Do not crystallized when material condensation is to " condensation point ", and just start crystallization when need to arrive " condensation point " a certain temperature once.Also easily go out
Now it is separated, i.e., when heating makes saline mixture become inorganic salts, salt and the crystallization water are separated, and generation precipitation is sunken to bottom.Have
Good moldability during machine class ergastic substances solid-state, it is not easy to occur being separated and surfusion, the corrosivity of material is small, Performance comparision
Stabilization, small toxicity, low cost.But there is also the spies such as thermal conductivity factor is small, readily volatilized, energy storage density is small, danger coefficient is higher
Point.Composite may draw both advantages, but technique is relatively typically more complicated and relatively costly etc..
In CN 103059818A：Paraffin has that heat storage capacity is big, phase transition temperature as traditional solid-liquid type phase-changing energy storage material
Change with the change of relative molecular mass, have good thermal circulation performance and steady with heat storage capacity stabilization, transformation behavior
Fixed, abundance, it is cheap the characteristics of.Paraffin is mixed by linear paraffin, with the increase of chain, fusing point
Increase with heat of fusion, its fusing point is -12~75 DEG C, heat of fusion is 150~250J/g.Many national applications by paraffin
Journal of Sex Research is used as one of Main way for developing phase-changing energy storage material.In the action oriented research of paraffin, can using paraffin emulsifier
So that successfully paraffin phase change material to be emulsified.The emulsifying agent that this respect is used can be divided into two major classes：Ionic emulsifying agent and nonionic
Type emulsifying agent.Wherein, ionic emulsifying agent is divided into anionic emulsifier, cationic emulsifier and amphoteric emulsifying agent again.
The hydrophilic radical of the anionic emulsifier is anion, and the hydrophilic group being connected with hydrophobic group when it is dissolved in water is anion.Root
Different according to anion concrete structure can be divided into carboxylic acid type, sulfuric ester salt form, sulfonate type and phosphate type again.Institute
The hydrophilic radical of cationic emulsifier is stated for cation, different according to cationic structure concrete structure can be divided into quaternary amine again
Type and amine salt type.Cationic emulsifier has the advantages that not being afraid of hard water and acid, but because its is expensive, it is less individually to make
With.
The present invention is based on above-mentioned understanding, is further improved.By add inorganic energy storage material improved in paraffin paraffin melt
Point is low, and thermal conductivity factor is small, the low feature of energy storage density.
The content of the invention
The shortcoming of prior art in view of the above, it is an object of the invention to provide a kind of phase-changing energy storage material and its prepare with should
With the phase-changing energy storage material has the advantages that phase transition temperature is suitable, thermal conductivity factor is larger and energy storage density is high.
In order to achieve the above objects and other related objects, the present invention is adopted the following technical scheme that：
The first aspect of the present invention provides a kind of phase-changing energy storage material, and its raw material contains the component of following parts by weight：Sodium sulphate
10~50 weight portions；The weight portion of crosslinking agent 5~20；The weight portion of paraffin 40~70；The weight portion of water 10~25；Curing agent 1~
4 weight portions；The weight portion of cumyl peroxide 0.5~1.0；The weight portion of dibutyl tin laurate 0.5~1.0.
Preferably, the crosslinking agent is selected from any one or more in VTES, di-isopropylbenzene hydroperoxide
Combination.
The VTES can be obtained by commercially available approach, for example, can use A151 VTESs
Or A171 vinyltrimethoxy silanes.
Preferably, the molecular weight ranges of the paraffin are 2000~10000.
Preferably, the curing agent is selected from any one or more in m-phenylene diamine (MPD), diaminodiphenyl-methane, dibenamine base ether
Combination.
The second aspect of the present invention, still further provides a kind of method for preparing foregoing phase-changing energy storage material, comprise the following steps：
(1) paraffin is mixed with crosslinking agent, prepares paraffin prepolymer；
(2) step (1) gained paraffin prepolymer is mixed with aqueous sodium persulfate solution, adds curing agent solidification to obtain final product phase transformation
Energy storage material.
Preferably, in step (1), after mixing, paraffin performed polymer is prepared under ultraviolet light.
Preferably, in step (1), after mixing, then mixing 6h prepares paraffin performed polymer at 90 DEG C.
Preferably, in step (2), mixed using agitator under the conditions of 100~120 DEG C during mixing, the rotating speed of agitator is
1800rpm, continues 3h.
Preferably, in step (2), logical nitrogen is solidified after adding curing agent.
The third aspect of the present invention, additionally provides purposes of the foregoing phase-changing energy storage material in energy storage and domain of control temperature.
Compared with prior art, the invention has the advantages that：
It is inorganic organic so as to prepare together with inorganic phase-changing material is compound to organic phase change material paraffin by the method being crosslinked
Phase-change material, it is a kind of inorganic organic hybridization phase-changing energy storage material, and Inorganic phase change energy storage material can be overcome to be subcooled and be separated
Shortcoming, while the less shortcoming of organic phase change energy storage material thermal conductivity factor can also be overcome.Described inorganic organic hybridization phase transformation storage
Energy material can be used for the fields such as house constant temperature, solar water heater, heat accumulation and electronic thermostatic.Prepare solid-solid phase-change energy-storage material,
And inorganic salts used and paraffin are all environmentally friendly materials.The method technique is easy, nontoxic, non-environmental-pollution, raw
Produce low cost.Using the energy storage material obtained by the method for preparing phase-changing energy storage material that the present invention is provided, with the reversible phase of solid-solid
Become energy storage property, phase transition temperature is suitable, and between 50-100 DEG C, enthalpy of phase change is high, in 150J/g, hot energy storage density is big, nothing is oozed
Leakage, without phase separation, can be recycled, without container encapsulation, have good value in energy storage and domain of control temperature.
Specific embodiment
The present invention is expanded on further with reference to specific embodiment, it should be appreciated that these embodiments be merely to illustrate the present invention and without
In limiting the scope of the invention.
Embodiments of the present invention are illustrated below by way of specific instantiation, those skilled in the art can be as disclosed by this specification
Content understand other advantages of the invention and effect easily.The present invention can also add by way of a different and different embodiment
To implement or apply, the various details in this specification can also be based on different viewpoints and application, without departing from essence of the invention
Various modifications or alterations are carried out under god.
Embodiment 1
The phase-changing energy storage material of the present embodiment, its raw material contains the component of following parts by weight：The weight portion of sodium sulphate 30；A151
The weight portion of VTES 10；The weight portion of paraffin (molecular weight 2000) 50；The parts by weight of water 10；Isophthalic
The parts by weight of diamines 4；0.5 part of cumyl peroxide；The weight portion of dibutyl tin laurate 0.5.
Preparation method：By the weight portion of paraffin (molecular weight 2000) 50, with crosslinking agent A151 VTESs 10
Weight portion is in the weight portion of graft initiator DCP cumyl peroxides 0.5, the weight of grafting catalysts dibutyl tin laurate 0.5
The lower mixing of amount part effect, under ultraviolet light, mixes 6h at 90 DEG C, prepares paraffin performed polymer.Then, the stone that will be formed
Wax performed polymer is uniformly mixed with the weight portion of sodium sulphate 30 (adding water 10 parts) at 120 DEG C in high speed agitator, stirring
Device rotating speed is set to 2000rpm, after continuing 3h, adds the weight portion of curing agent m-phenylene diamine (MPD) 4 and solidifies at low temperature, and system may be selected
The method of the logical nitrogen of cryogen carries out low-temperature setting.Solidification completion obtains final product desired phase-changing energy storage material.
Embodiment 2
The phase-changing energy storage material of the present embodiment, its raw material contains the component of following parts by weight：The weight portion of sodium sulphate 40；
The weight portion of crosslinking agent A171 vinyl trimethoxies silicon 5；The weight portion of paraffin (molecular weight 3000) 40；The weight of water 15
Part；The weight portion of diaminodiphenyl-methane 3；The weight portion of cumyl peroxide 0.8；The weight portion of dibutyl tin laurate 0.8.
Preparation method：By the weight portion of paraffin (molecular weight 3000) 40, with the weight of crosslinking agent A171 vinyl trimethoxies silicon 5
Number is in the weight portion of graft initiator DCP cumyl peroxides 0.8, the weight of grafting catalysts dibutyl tin laurate 0.8
The lower mixing of part effect, under ultraviolet light, mixes 6h at 90 DEG C, prepares paraffin performed polymer.Then the paraffin that will be formed is pre-
Aggressiveness is uniformly mixed with the weight portion of sodium sulphate 40 (adding water 15 parts) at 110 DEG C in high speed agitator, and agitator turns
Speed is set to 2300rpm, after continuing 3h, adds the weight portion of curing agent diaminodiphenyl-methane 3 and solidifies at low temperature, may be selected
The method of the logical nitrogen of refrigerant carries out low-temperature setting.Solidification completion obtains final product desired phase-changing energy storage material.
Embodiment 3
The phase-changing energy storage material of the present embodiment, its raw material contains the component of following parts by weight：The weight portion of sodium sulphate 50；
The weight portion of crosslinking agent di-isopropylbenzene hydroperoxide 15；The weight portion of paraffin (molecular weight 4000) 60；The weight portion of water 25；Gu
The weight portion of agent dibenamine base ether 3；The weight portion of cumyl peroxide 1.0；The weight portion of dibutyl tin laurate 1.0.
Preparation method：By the weight portion of paraffin (molecular weight 4000) 60, exist with the weight portion of crosslinking agent di-isopropylbenzene hydroperoxide 15
The weight portion of graft initiator DCP cumyl peroxides 1.0, the effect of the weight portion of grafting catalysts dibutyl tin laurate 1.0
Lower mixing, under ultraviolet light, 6h is mixed at 90 DEG C, prepares paraffin performed polymer.Then the paraffin performed polymer for being formed is existed
It is uniformly mixed in high speed agitator with the weight portion of sodium sulphate 50 (adding water 25 parts) at 100 DEG C, agitator speed is set to
1800rpm, after continuing 3h, adds the weight portion of curing agent dibenamine base ether 3 and solidifies at low temperature, and the logical nitrogen of refrigerant may be selected
The method of gas carries out low-temperature setting.Solidification completion obtains final product desired phase-changing energy storage material.
Embodiment 4
The phase-changing energy storage material of the present embodiment, its raw material contains the component of following parts by weight：The weight portion of sodium sulphate 10；
The weight portion of crosslinking agent A151 vinyl triethoxyls silicon 10；The weight portion of paraffin (molecular weight 5000) 70；The weight of water 20
Part；The weight portion of curing agent dibenamine base ether 5；The weight portion of cumyl peroxide 1.0；The weight portion of dibutyl tin laurate 1.0.
Preparation method：By the weight portion of paraffin (molecular weight 5000) 70, with the weight of crosslinking agent A151 vinyl triethoxyls silicon 10
Amount part is in the weight portion of graft initiator DCP cumyl peroxides 1.0, the weight of grafting catalysts dibutyl tin laurate 1.0
The lower mixing of part effect, under ultraviolet light, mixes 6h at 90 DEG C, prepares paraffin performed polymer.Then the paraffin that will be formed is pre-
Aggressiveness is uniformly mixed with the weight portion of sodium sulphate 10 (adding water 20 parts) at 110 DEG C in high speed agitator, and agitator turns
Speed is set to 1800rpm, after continuing 3h, adds the weight portion of curing agent dibenamine base ether 5 and solidifies at low temperature, and refrigeration may be selected
The method of the logical nitrogen of agent carries out low-temperature setting.Solidification completion obtains final product desired phase-changing energy storage material.
Embodiment 5
The phase-changing energy storage material of the present embodiment, its raw material contains the component of following parts by weight：The weight portion of sodium sulphate 20；Crosslinking agent
The weight portion of A151 vinyl triethoxyls silicon 20；The weight portion of paraffin (molecular weight 10000) 50；The weight portion of water 10；Gu
The weight portion of agent dibenamine base ether 1；The weight portion of cumyl peroxide 1.0；The weight portion of dibutyl tin laurate 1.0.
Preparation method：By the weight portion of paraffin (molecular weight 10000) 50, with crosslinking agent A151 vinyl triethoxyls silicon 20
Weight portion is in the weight portion of graft initiator DCP cumyl peroxides 1.0, the weight of grafting catalysts dibutyl tin laurate 1.0
The lower mixing of amount part effect, under ultraviolet light, mixes 6h at 90 DEG C, prepares paraffin performed polymer.Then the paraffin that will be formed
Performed polymer is uniformly mixed, agitator with the weight portion of sodium sulphate 20 (adding water 10 parts) at 120 DEG C in high speed agitator
Rotating speed is set to 1800rpm, after continuing 3h, adds the weight portion of curing agent dibenamine base ether 1 and solidifies at low temperature, and system may be selected
The method of the logical nitrogen of cryogen carries out low-temperature setting.Solidification completion obtains final product desired phase-changing energy storage material.
Embodiment 6
Above-described embodiment 1-5 is prepared into resulting materials, experimental results is carried out as follows：
In sum, a kind of obtained phase-changing energy storage material has larger thermal conductivity factor and energy storage density in the present invention, so,
The present invention effectively overcomes various shortcoming of the prior art and has high industrial utilization.
The above-described embodiments merely illustrate the principles and effects of the present invention, not for the limitation present invention.It is any to be familiar with this skill
The personage of art all can carry out modifications and changes under without prejudice to spirit and scope of the invention to above-described embodiment.Therefore, such as
Those of ordinary skill in the art completed under without departing from disclosed spirit and technological thought all etc.
Effect modifications and changes, should be covered by claim of the invention.
Claims (10)
1. a kind of phase-changing energy storage material, its raw material contains the component of following parts by weight：The weight portion of sodium sulphate 10~50；Crosslinking agent 5~
20 weight portions；The weight portion of paraffin 40~70；The weight portion of water 10~25；The weight portion of curing agent 1~4；Peroxidating two
The weight portion of isopropylbenzene 0.5~1.0；The weight portion of dibutyl tin laurate 0.5~1.0.
2. phase-changing energy storage material according to claim 1, it is characterised in that the crosslinking agent be selected from VTES,
The combination of any one or more in di-isopropylbenzene hydroperoxide.
3. phase-changing energy storage material according to claim 1, it is characterised in that the molecular weight ranges of the paraffin are 2000~
10000。
4. phase-changing energy storage material according to claim 1, it is characterised in that the curing agent is selected from m-phenylene diamine (MPD), diaminourea two
The combination of any one or more in phenylmethane, dibenamine base ether.
5. a kind of method for preparing the phase-changing energy storage material as described in Claims 1 to 4 any claim, comprises the following steps：
(1) paraffin is mixed with crosslinking agent, cumyl peroxide, dibutyl tin laurate, prepares paraffin performed polymer；
(2) step (1) gained paraffin performed polymer is mixed with aqueous sodium persulfate solution, adds curing agent solidification to obtain final product phase-changing energy storage material.
6. method according to claim 5, it is characterised in that in step (1), after mixing, prepares under ultraviolet light
Paraffin performed polymer.
7. method according to claim 5, it is characterised in that in step (1), after mixing, then mix 6h at 90 DEG C
Prepare paraffin performed polymer.
8. method according to claim 5, it is characterised in that in step (2), adopted under the conditions of 100~120 DEG C during mixing
Mixed with agitator, the rotating speed of agitator is 1800rpm, continues 3h.
9. method according to claim 5, it is characterised in that in step (2), to add and lead to nitrogen after curing agent and solidified.
10. purposes of the phase-changing energy storage material in energy storage and domain of control temperature as described in Claims 1 to 4 any claim.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201510990382.1A CN106916461A (en) | 2015-12-24 | 2015-12-24 | A kind of preparation of phase-changing energy storage material |
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| CN201510990382.1A CN106916461A (en) | 2015-12-24 | 2015-12-24 | A kind of preparation of phase-changing energy storage material |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112143462A (en) * | 2020-10-27 | 2020-12-29 | 中国矿业大学 | Composite phase change material taking polystyrene with siloxy functional group as support material, and preparation method and application thereof |
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Application publication date: 20170704 |