CN101230256B - Method for preparing polyethylene glycol and epoxy resin formed composite phase-change materials - Google Patents
Method for preparing polyethylene glycol and epoxy resin formed composite phase-change materials Download PDFInfo
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- CN101230256B CN101230256B CN2008100256385A CN200810025638A CN101230256B CN 101230256 B CN101230256 B CN 101230256B CN 2008100256385 A CN2008100256385 A CN 2008100256385A CN 200810025638 A CN200810025638 A CN 200810025638A CN 101230256 B CN101230256 B CN 101230256B
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Abstract
The invention discloses a preparation method of polyethylene glycol and epoxy resin shaping composite phase change material. The invention includes the following steps of (1) adding polyethylene glycol and epoxy resin into a reaction container, adding the mixture liquid of firming agent and accelerant after polyethylene glycol is completely dissolved and is dispersed evenly with the epoxy resin; (2) defoaming the mixture obtained from step (1) in vaccum, pouring the mixture into a die applied with parting agent, transferring the die into an oven for solidification and moulding for 24-48 hours, then cooling the die until demoulding. The materials proportions are that epoxy resin condensate is 10 to 50 percent, polyethyleneglycol is 50 to 90 percent; the contents of the firming agent and the accelerant respectively account for 8 to 40 percent and 1 to10 percent of the epoxy resin. The composite phase change material of the invention not only has large potential heat and excellent energy accumulating effect, but also has good figuration performance and high stability.
Description
Technical field
The present invention relates to thermal energy storage and utilize material, the preparation method of particularly a kind of polyoxyethylene glycol and epoxy resin formed composite phase-change materials.
Background technology
Phase change material discharges or the absorption latent heat of phase change in its phase transition process, thereby reaches energy storage and release and alleviate the unbalance contradiction of energy supply and demand, is with a wide range of applications.Mushy stage takes place and transforms in the tradition phase change material when fusion, must use special container to be encapsulated, and this not only increases production cost, and has reduced heat transfer efficiency.Phase change material and propping material (skeleton) are carried out composite modified (comprising physics, chemical modification), utilize its physical entanglement or chemically crosslinked effect, can make phase change material before and after phase transformation, keep original shape (solid-state), promptly form so-called shaping phase-change material, can effectively address the above problem.Polyoxyethylene glycol (PEG) is that a class enthalpy of phase change is higher, the thermal hysteresis effect is low, nothing is separated and the phase-changing energy storage material of transformation temperature a wider range.In its solid-liquid phase change process, there is liquid phase to produce.Pass through chemical modification, as utilize PEG terminal hydroxy group and Cellulose diacetate, polyvinyl alcohol, end-functional groups such as NCO polyurethane prepolymer that copolyreaction takes place, form shape phase change material admittedly-fixedly, such material is owing to the chemical bonding effect of skeleton polymer to PEG, and its enthalpy of phase change and transformation temperature reduce.By physically modified, as PEG being adsorbed in polymer fiber surfaces such as polypropylene, polyester, filamentary material with " temperature regulation " function.PEG and polypropylene (PP), PEG and polyacrylamide (PAM) etc. are similarly arranged.Such material use be physical action between two components, therefore, less to PEG enthalpy of phase change, transformation temperature influence.But in the above-mentioned physical modification method, mainly have the deficiency of two aspects: the polarity difference of (1) superpolymer powder and PEG makes it be difficult to homodisperse in melting process; (2) melting process all is to carry out being higher than more than the propping material Tc, and the hot rerum natura of PEG is exerted an influence.
Summary of the invention
The present invention is directed to that existing phase change material exists in melting process be difficult to homodisperse and to problems such as the hot rerum natura of polyoxyethylene glycol exert an influence, but provide that a kind of shape stability is good, heat storage capacity is high, the preparation method of the polyoxyethylene glycol of stable performance machine-shaping and epoxy resin formed composite phase-change materials.
The present invention can be achieved by the following technical programs: the preparation method of a kind of polyoxyethylene glycol and epoxy resin formed composite phase-change materials comprises the steps:
(1) polyoxyethylene glycol, Resins, epoxy are joined in the reaction vessel, after treating that polyoxyethylene glycol dissolves fully and being uniformly dispersed with Resins, epoxy, the mixed solution that adds solidifying agent and promotor;
(2) step (1) obtains mixture and remove bubble under vacuum, pours in the mould that scribbles releasing agent, and mould is transferred to curing molding in the baking oven, is cooled to the room temperature demoulding.
In the present invention, in the step (1), described polyoxyethylene glycol number-average molecular weight is 1000～10000, and the number average molecule number is that 2000～6000 polyoxyethylene glycol and number average molecule number are that 8000～10000 polyoxyethylene glycol is by 0.5～1/1 mixed effect the best;
In the step (1), described Resins, epoxy is selected bisphenol A type epoxy resin for use, and its oxirane value is in 0.3～0.6 scope, and its consumption accounts for 10～50% weight of amount of the mixture, and 15～30% weight that epoxy resin content accounts for amount of the mixture in the gel are optimum range; Bisphenol A type epoxy resin is selected one or more among E51, E44, the E31 for use;
In the step (1), described solidifying agent is selected amine curing agent for use, and its consumption is 8～40% weight of content of epoxy resin, and the consumption of best effect is to account for 20～30% of content of epoxy resin; Described amine curing agent is selected diethylenetriamine, triethylene tetramine, tetraethylene pentamine for use, one or more in dimethylaminopropylamine, diethylaminopropylamine, trimethylhexamethylenediamine, the polyoxypropylene diamine.
In the step (1), describedly be used to reduce the solidification value of amine curing agent and the promotor of time is selected tertiary amines for use, 2, one or more in 4,6 three (dimethylamino methyl) phenol (DMP-30), the benzyldimethylamine (DMBA), its consumption is 1～10% weight of content of epoxy resin, and optimum amount is 3～6% of a content of epoxy resin.
In the step (2), the 24～48h that finalizes the design in 60 ℃ of baking ovens is cooled to the room temperature demoulding then.
Compared with prior art, the present invention has the following advantages:
One, composite phase-change material latent heat amount of the present invention is big, accumulation of energy is effective;
Two, composite phase-change material setting performance of the present invention is good, and in figuration composite phase-changing material, support matrix content just had the effect that formalizes preferably at 15% o'clock;
Three, composite phase-change material of the present invention stability is high, because Resins, epoxy is high temperature resistant, corrosion-resistant support matrix, stability itself is strong, when composite, because of spatial network restriction and hydrogen bond action, has increased pining down mutually of the two with polyoxyethylene glycol.
Description of drawings
Fig. 1 is that the composite phase-change material that the inventive method prepares carries out thermo-mechanical analysis figure;
Fig. 2 is composite phase-change material hot-fluid-temperature variation that the inventive method prepares;
Fig. 3 is that the composite phase-change material that the inventive method prepares carries out the thermal weight loss test result.
Embodiment
Below in conjunction with embodiment the specific embodiment of the present invention is described in detail.
Principle of work of the present invention is as follows: by homodisperse polyoxyethylene glycol (PEG) and bisphenol A type epoxy resin (EP), under solidifying agent, promotor effect, crosslinking reaction takes place, form network structure, PEG makes stopping composition, is dispersed in the network, and the free movement of PEG crystallization segment is produced restriction; Simultaneously, (OH) ether is (O-) with polyoxyethylene glycol terminal hydroxy group (CH for the hydroxyl of Resins, epoxy
2-form stronger hydrogen bond between OH), further strengthened both interactions, thereby polyoxyethylene glycol can be embedded into firmly in the epoxy networks, when a solid liquid phase transition took place, the polyoxyethylene glycol liquid that can not leaked out from skeleton.
Embodiment 1
Under the room temperature, in the 1.5L Erlenmeyer flask, adding 200g trade mark E51, oxirane value are 0.6 epoxy resin liquid, under the powerful stirring of numerical control stirrer, slowly add polyoxyethylene glycol (PEG4000/PEG8000=1/1) powder 900g, treat its all the dissolving back and with the EP homodisperse after, add the 40%D230 solidifying agent that accounts for the EP amount respectively and the mixed solution of 10%DMP-30 promotor, continue to stir, until all mixing.Reaction mixture is outgased under vacuum, when no longer including the bubble generation in the reaction solution, be poured in the mould that scribbles releasing agent and preheating, mould is transferred to curing molding 48h in 60 ℃ of baking ovens, be cooled to the room temperature demoulding and get figuration composite phase-changing material.
Above-mentioned composite phase-change material is carried out thermo-mechanical analysis as shown in Figure 1: for polyethylene glycol samples, in the hot melt process, take place to change mutually, 69.89 ℃ of its initial melt temperatures, maximum melting rate (429.9 μ m/ ℃) is at 78.61 ℃, its deformation quantity (6449 μ m) equals the length of the preceding sample of phase transformation, the i.e. whole fusions of sample substantially.And for the PEG/EP sample, because the formation of three-dimensional net structure, and the physical crosslinking between alcoholic extract hydroxyl group and the epoxy polar group, make PEG be limited among the EP firmly.Although in heat-processed, taken place to change mutually, shown the melting behavior different with PEG.The initial melt temperature of PEG/EP sample rises to 79.29 ℃, and maximum melting rate is located at 100.46 ℃, and its numerical value is-374.8 μ m ℃
-1, contrast PEG, its melting rate reduces, and deformation quantity is also much smaller, only is 473.0 μ m, is 0.73% of PEG deformation quantity.As seen, even in the temperature that exceeds more than the PEG fusing point, still can keep PEG not trickle from matrix material, show excellent setting performance, promptly sample still remains the solid-solid phase change on the macroscopic view more than the fusing point of PEG.
Resins, epoxy further can be obtained a result by polarized light microscope observing to the setting effect of polyoxyethylene glycol: for the polyoxyethylene glycol product, in the time of 30 ℃, demonstrate the spherocrystal crystalline orientation, present tangible cross frosting phenomenon, illustrate that PEG is a sphaerocrystal under the normal temperature.Matrix material PEG/EP still has frosting phenomenon, shows that PEG/EP still exists with crystal habit at normal temperatures, but because the cross-linked network of EP has influenced PEG crystalline regularity, causes PEG crystallization imperfection, and its spherocrystal crystalline orientation weakens.When being warmed up to (68 ℃) when reaching near the fusing point (65 ℃), polyoxyethylene glycol all dissolves, and produces bubble.After adding setting composition Resins, epoxy, even in the temperature that exceeds polyoxyethylene glycol fusing point nearly 15 ℃ (80 ℃), phase change material is converted into amorphous state by crystal form, the frosting phenomenon completely dissolve, but do not occur the trickling of liquid PEG in the polarizing microscope picture, illustrate that the EP as carrier has played good setting effect.
Polyoxyethylene glycol and epoxy resin formed composite phase-change materials can be seen by Electronic Speculum: the phase change material polyoxyethylene glycol is evenly distributed in the cross-linked network structure of Resins, epoxy, Resins, epoxy as carrier with its coating, fixing.Because epoxy resin cured product has good thermotolerance, cohesiveness and mechanical property, when polyoxyethylene glycol undergoes phase transition the storage of carrying out energy and discharges, the cross-linked network of Resins, epoxy plays the framework effect of supporting constraint, makes this matrix material show as solid-solid phase change on macroscopic view.
Polyoxyethylene glycol and polyoxyethylene glycol and epoxy resin formed composite phase-change materials hot-fluid-temperature variation be as shown in Figure 2: the polyoxyethylene glycol phase change material has quite high heat storage capacity (186.7J/g), and transformation temperature is 61.28 ℃.After compound, the melting enthalpy of figuration composite phase-changing material still higher (132.4J/g), PEG/EP changes mutually 54～68 ℃ of generations.Show that moving into of Resins, epoxy has been the setting effect.But Resins, epoxy adds, and makes the polyoxyethylene glycol crystallization produce defective, thereby the latent heat of phase change of figuration composite phase-changing material reduces, transformation temperature (60.32 ℃) slightly descends.
Above-mentioned polyoxyethylene glycol and epoxy resin formed composite phase-change materials are carried out the thermal weight loss test result as shown in Figure 3: along with temperature raises, sample quality is constant substantially, and the decomposition or the volatilization of component do not take place.Just begin weightlessness during to 330 ℃, sample constant weight after 470 ℃.Hence one can see that, and composite phase-change material PEG/EP decomposition temperature is very high, fine at its transformation temperature scope internal stability, and be difficult for volatilization and decompose, be the good phase change material of a kind of thermostability.
Under the room temperature, in the 1L Erlenmeyer flask, adding 100g trade mark E44, oxirane value are 0.3 epoxy resin liquid, under the powerful stirring of numerical control stirrer, slowly add polyoxyethylene glycol (PEG4000/PEG10000=1/1) powder 100g, treat its all the dissolving back and with the EP homodisperse after, add the 8%D230 solidifying agent that accounts for the EP amount respectively and the mixed solution of 1%DMP-30 promotor, continue to stir, until all mixing.Reaction mixture is outgased under vacuum, when no longer including the bubble generation in the reaction solution, be poured in the mould that scribbles releasing agent and preheating, mould is transferred to curing molding 24h in 60 ℃ of baking ovens, be cooled to the room temperature demoulding and get figuration composite phase-changing material.
Embodiment 3
Under the room temperature, in the 1.5L Erlenmeyer flask, adding 100g trade mark E31, oxirane value are 0.5 epoxy resin liquid, under the powerful stirring of numerical control stirrer, slowly add polyoxyethylene glycol (PEG4000/PEG8000=1/1) powder 500g, treat its all the dissolving back and with the EP homodisperse after, add the 30%D230 solidifying agent that accounts for the EP amount respectively and the mixed solution of 5%DMP-30 promotor, continue to stir, until all mixing.Reaction mixture is outgased under vacuum, when no longer including the bubble generation in the reaction solution, be poured in the mould that scribbles releasing agent and preheating, mould is transferred to curing molding 36h in 60 ℃ of baking ovens, be cooled to the room temperature demoulding and get figuration composite phase-changing material.
Under the room temperature, in the 1.5L Erlenmeyer flask, adding 100g trade mark E44, oxirane value are 0.4 epoxy resin liquid, under the powerful stirring of numerical control stirrer, slowly add polyoxyethylene glycol (PEG1000/PEG6000=1/1) powder 200g, treat its all the dissolving back and with the EP homodisperse after, add the 25%D230 solidifying agent that accounts for the EP amount respectively and the mixed solution of 6%DMP-30 promotor, continue to stir, until all mixing.Reaction mixture is outgased under vacuum, when no longer including the bubble generation in the reaction solution, be poured in the mould that scribbles releasing agent and preheating, mould is transferred to curing molding 30h in 60 ℃ of baking ovens, be cooled to the room temperature demoulding and get figuration composite phase-changing material.
Embodiment 5
Extracting epoxy resin cured article content accounts for below 10% or below 55% respectively, and other operational condition is identical with embodiment 1.The result shows: when epoxy resin cured product content 10% is following, the capillary adsorption in Resins, epoxy duct and with the sub-chain motion of polyoxyethylene glycol hydrogen bond action when being not enough to offset the polyoxyethylene glycol fusion, will fusion leak out, the composite phase-change material bad mechanical strength that obtains simultaneously, cracked easily, promptly can not well formalize.When epoxy resin content 55% is above, too strong to the restriction of polyoxyethylene glycol, its crystallization segment havoc, its melting enthalpy significantly reduces.When epoxy resin content 35%, its melting enthalpy has only 29.95J/g.Therefore, epoxy resin cured product content is in 10～50% scopes.Effect is preferably 10～30%, has both had setting effect preferably, and very high fusion potential heat value is arranged again.
Claims (5)
1. the preparation method of polyoxyethylene glycol and epoxy resin formed composite phase-change materials is characterized in that comprising the steps:
(1) polyoxyethylene glycol, Resins, epoxy are joined in the reaction vessel, after treating that polyoxyethylene glycol dissolves fully and being uniformly dispersed with Resins, epoxy, the mixed solution that adds solidifying agent and promotor; Described polyoxyethylene glycol number-average molecular weight is 1000～10000; Described Resins, epoxy is selected bisphenol A type epoxy resin for use, and its oxirane value is in 0.3～0.6 scope, and its consumption accounts for 10～50% weight of amount of the mixture; Described solidifying agent is selected amine curing agent for use, and its consumption is 8～40% weight of content of epoxy resin; Described promotor is selected tertiary amines for use, and its consumption is 1～10% weight of content of epoxy resin;
(2) step (1) obtains mixture and remove bubble under vacuum, pours in the mould that scribbles releasing agent, and mould is transferred to curing molding in the baking oven, is cooled to the room temperature demoulding.
2. method according to claim 1 is characterized in that bisphenol A type epoxy resin selects more than one among E51, E44, the E31 for use.
3. method according to claim 1, it is characterized in that described amine curing agent selects diethylenetriamine, triethylene tetramine, tetraethylene pentamine for use, more than one in dimethylaminopropylamine, diethylaminopropylamine, trimethylhexamethylenediamine, the polyoxypropylene diamine.
4. method according to claim 1 is characterized in that in the step (1), and described tertiary amines is more than one in 2,4,6 three (dimethylamino methyl) phenol, the benzyldimethylamine.
5. method according to claim 1 is characterized in that in the step (2) that the 24～48h that finalizes the design is cooled to the room temperature demoulding then in 60 ℃ of baking ovens.
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| CN111378250B (en) * | 2020-04-10 | 2022-05-03 | 南通大学 | Epoxy resin composite shape-stabilized phase change material and preparation method and application thereof |
| CN114058190A (en) * | 2020-08-04 | 2022-02-18 | 中国科学院大连化学物理研究所 | Crystallization-controllable shape-stabilized epoxy phase change material and preparation method thereof |
| CN114437380B (en) * | 2020-10-30 | 2023-08-15 | 中国石油化工股份有限公司 | Modified fully-vulcanized powder rubber, preparation method thereof and epoxy resin composition thereof |
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| CN1079109C (en) * | 1999-09-08 | 2002-02-13 | 中国科学院广州化学研究所 | Reticular solid-solid phase change material and its preparing process |
| CN1966571A (en) * | 2005-11-16 | 2007-05-23 | 宁波大学 | Preparation method of epoxy resin base micron to nano grade pore gelatin |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1079109C (en) * | 1999-09-08 | 2002-02-13 | 中国科学院广州化学研究所 | Reticular solid-solid phase change material and its preparing process |
| CN1966571A (en) * | 2005-11-16 | 2007-05-23 | 宁波大学 | Preparation method of epoxy resin base micron to nano grade pore gelatin |
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