CN102516077B - Method for preparing polyglycerol-co-polyethylene glycol copolymer phase-change material - Google Patents
Method for preparing polyglycerol-co-polyethylene glycol copolymer phase-change material Download PDFInfo
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- CN102516077B CN102516077B CN201110405949.6A CN201110405949A CN102516077B CN 102516077 B CN102516077 B CN 102516077B CN 201110405949 A CN201110405949 A CN 201110405949A CN 102516077 B CN102516077 B CN 102516077B
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- polyglycerol
- change material
- ester
- phase change
- vinylformic acid
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- 239000012782 phase change material Substances 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims abstract description 17
- 229920001223 polyethylene glycol Polymers 0.000 title abstract description 9
- 239000002202 Polyethylene glycol Substances 0.000 title abstract 4
- -1 acrylic acid poly glycerin ester Chemical class 0.000 claims abstract description 17
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 13
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000008367 deionised water Substances 0.000 claims abstract description 7
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 7
- 229920001577 copolymer Polymers 0.000 claims abstract description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 42
- 238000007334 copolymerization reaction Methods 0.000 claims description 30
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 28
- 229920000223 polyglycerol Polymers 0.000 claims description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 24
- 238000002360 preparation method Methods 0.000 claims description 23
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 14
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 14
- NPSSWQJHYLDCNV-UHFFFAOYSA-N prop-2-enoic acid;hydrochloride Chemical compound Cl.OC(=O)C=C NPSSWQJHYLDCNV-UHFFFAOYSA-N 0.000 claims description 14
- 150000002148 esters Chemical class 0.000 claims description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 229920001515 polyalkylene glycol Polymers 0.000 claims description 11
- 239000004160 Ammonium persulphate Substances 0.000 claims description 7
- 235000019395 ammonium persulphate Nutrition 0.000 claims description 7
- 238000004821 distillation Methods 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 239000005457 ice water Substances 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 239000003643 water by type Substances 0.000 claims description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerol Natural products OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 abstract description 4
- 239000007787 solid Substances 0.000 abstract description 3
- 238000005382 thermal cycling Methods 0.000 abstract description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 abstract description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 abstract 1
- 235000011187 glycerol Nutrition 0.000 abstract 1
- 229920002643 polyglutamic acid Polymers 0.000 description 21
- 238000002425 crystallisation Methods 0.000 description 6
- 230000008025 crystallization Effects 0.000 description 6
- 239000012071 phase Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 230000001376 precipitating effect Effects 0.000 description 4
- 230000007704 transition Effects 0.000 description 4
- 238000001816 cooling Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000010526 radical polymerization reaction Methods 0.000 description 3
- 239000007790 solid phase Substances 0.000 description 3
- 150000001263 acyl chlorides Chemical class 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000011232 storage material Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000009435 building construction Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
Landscapes
- Macromonomer-Based Addition Polymer (AREA)
- Polyethers (AREA)
Abstract
A method for preparing a polyglycerol-co-polyethylene glycol copolymer phase-change material contains the following steps of: dissolving acrylate polyethylene glycol and acrylic acid poly glycerin ester in deionized water, adding ammonium persulfate, and reacting in a constant temperature water-bath of 75 DEG C for 10-30 min to obtain the semi-IPN copolymer gel phase-change material polyglycerol-co-polyethylene glycol. The copolymer solid-solid phase-change material P(DG-co-EG) prepared in the invention has high phase change enthalpy and it can reach as high as 141.31J/g. In addition, the copolymer solid-solid phase-change material has good thermal cycling stability and thermal stability.
Description
Technical field
The present invention relates to phase-changing energy storage material technical field, be specifically related to the preparation method of a kind of polyglycerol-co-polyoxyethylene glycol [P (DG-co-EG)] copolymerization phase change material.
Background technology
Phase change material is to utilize the heat that absorbs or discharge in phase transition process to carry out the material of latent heat accumulator, has in the ability to temperature adjusting in certain limit.Phase change material have energy storage density large, hold the advantages such as exothermic process approximately constant temperature, process be easy to control; obtained good utilization in fields such as the insulations of sun power utilization, used heat and remaining pick up the heat, clothes bed clothes and building construction, and at alleviating energy crisis, improve the aspects such as energy utilization rate and brought into play important effect.
Summary of the invention
The object of the present invention is to provide the preparation method of a kind of polyglycerol-co-polyoxyethylene glycol [P (DG-co-EG)] copolymerization phase change material, and the preparation method of the raw material propylene using in preparation process acid polyglycerol ester (PDGA).
For achieving the above object, first the present invention provides the preparation method of vinylformic acid polyglycerol ester, it is characterized in that comprising the steps:
Polyglycerol is dissolved in after methylene dichloride, adds triethylamine and acrylate chloride; Under 35～55 DEG C of temperature and nitrogen protection, react 6～9 hours; After reaction finishes, the underpressure distillation at 55 DEG C of above-mentioned solution is obtained to vinylformic acid polyglycerol ester.
In aforesaid method, preferably the polyglycerol polymerization degree is 1～10.
In aforesaid method, preferably the mol ratio of polyglycerol and acrylate chloride is 1: 3～1: 12, and the mol ratio of polyglycerol and triethylamine is 1: 1～1: 6.
Adopt aforesaid method, introduce activity double key by acyl chlorides on the terminal hydroxy group of polyglycerol, obtain highly active PDGA, this PDGA can be used for preparing P (DG-co-EG) copolymerization phase change material.Comprise the steps:
1. prepare polyalkylene glycol acrylate ester: the polyoxyethylene glycol of molecular weight 2000～4000 is dissolved in after methylene dichloride, adds the triethylamine and the acrylate chloride that equate with polyoxyethylene glycol mole number; Under 35～55 DEG C of temperature and nitrogen protection, react 6～9 hours; After reaction finishes, solution is placed in to ice-water bath, adds ether, leave standstill after 5 minutes, decompress filter obtains polyalkylene glycol acrylate ester;
2. prepare copolymerization phase change material: polyalkylene glycol acrylate ester and vinylformic acid polyglycerol ester are dissolved in deionized water, add ammonium persulphate, in 75 DEG C of waters bath with thermostatic control, react 10～30min, obtain semi-intercrossing network gel copolymer phase change material polyglycerol-co-polyoxyethylene glycol.
Step of the present invention 2. in, preferably polyalkylene glycol acrylate ester (PEGA) is 1: 1～12: 1 with mole proportioning of PDGA.
Step of the present invention 2. in, the consumption of initiator system of ammonium persulfate is 1%～3% of PEGA and the two gross weight of PDGA.
The present invention introduces activity double key by acyl chlorides on the terminal hydroxy group of polyglycerol, obtain highly active vinylformic acid polyglycerol ester (PDGA), there is highly active polyalkylene glycol acrylate ester and adopt radical polymerization with same, prepared polyglycerol-co-polyoxyethylene glycol [P (DG-co-EG)] copolymerization phase change material.Research shows, P (DG-co-EG) has good solid-solid phase-change characteristic, and enthalpy of phase change reaches 141.31J/g.
Compared with other published setting phase change energy storage material and preparation method, the present invention has following advantage:
(1) the invention provides a kind of highly active vinylformic acid polyglycerol ester and preparation method thereof.
(2) the invention provides a kind of new copolymerization phase change material and preparation method thereof, copolymerization solid-solid phase transition material P (DG-co-EG) enthalpy of phase change prepared by the present invention is higher, reaches 141.31J/g.
(3) prepared copolymerization solid-solid phase transition material P (DG-co-EG) thermal cycling stability of the present invention is good.
(4) the prepared copolymerization solid-solid phase transition material P (DG-co-EG) of the present invention has good thermostability.
Brief description of the drawings
Fig. 1 is the schematic arrangement of the copolymerization phase change material for preparing of the inventive method;
Fig. 2 is the polarizing microscope picture of the copolymerization phase change material crystallization for preparing of the inventive method;
Fig. 3 is the DSC curve of the copolymerization phase change material for preparing of the inventive method;
Fig. 4 is the cooling curve of the copolymerization phase change material for preparing of the inventive method;
Fig. 5 is the thermal cycling cooling curve of the copolymerization phase change material for preparing of the inventive method;
Fig. 6 is the thermogravimetric curve of the copolymerization phase change material for preparing of the inventive method.
Embodiment
The following examples can make the present invention of those of ordinary skill in the art's comprehend, but do not limit the present invention in any way.
Embodiment 1
The preparation method of polyglycerol-co-polyoxyethylene glycol copolymerization phase change material, comprises the steps:
1. the preparation of polyalkylene glycol acrylate ester (PEGA): by the polyoxyethylene glycol PEG0.01mol of relative molecular mass 4000; triethylamine 0.01mol adds in 120ml methylene dichloride; drip again the acrylate chloride of 0.01mol; 35 DEG C are reacted after 6 hours under protection under nitrogen protection; use ether precipitating, decompress filter obtains PEGA.
2. the preparation of vinylformic acid polyglycerol ester (PDGA): by 0.01mol ten polyglycerols; triethylamine 0.01mol adds in 25ml methylene dichloride; drip the acrylate chloride of 0.12mol, 35 DEG C are reacted after 6 hours under protection under nitrogen protection again, and underpressure distillation obtains PDGA.
3. the preparation of P (DG-co-EG) copolymerization phase change material: by the PEGA of 0.001mol, the PDGA of 0.001mol is dissolved in 15ml deionized water, add the ammonium persulphate of 0.054g, in 75 DEG C of thermostat water baths, react after 10 minutes, form semi-intercrossing network copolymerization phase change material.Its structural representation is as Fig. 1.
Above-mentioned P (DG-co-EG) phase change material polarized light microscope observing is found, after PEGA and PDGA generation radical polymerization, the P (DG-co-EG) generating has dressing or micro-crosslinked molecular chain structure, fetter the crystallizing power of PEG molecular chain, in the time of P (DG-co-EG) crystallization, PEG molecular chain, as the molecule side chain of P (DG-co-EG), forms crystallization microcell, sees Fig. 2.
Research and analyse by differential heat scan calorimetric (seeing Fig. 3), P (DG-co-EG) melting enthalpy is 163.51J/g, 57.58 DEG C of melt temperatures, and crystallization enthalpy is 141.31J/g, Tc is 38.97 DEG C.Comparatively speaking, the crystallization enthalpy of this copolymerization phase change material is significantly less than melting enthalpy, and Tc is lower than melt temperature.This be because phase change monomer PEGA through with PDGA radical polymerization after, PEG molecular chain is used as a molecule side chain of multipolymer, interts between copolymerization dressing network.In the time that temperature drops to the Tc of PEG, because being subject to the molecular chain network of copolymer chain and multipolymer, PEG molecular chain fetters, and its crystallization enthalpy obviously declines compared with melting enthalpy.
Being found by cooling curve (seeing Fig. 4) research, there is temperature platform at 43.8 DEG C in the P (DG-co-EG) of different mole proportionings, and its soaking time increases with the increase of PEGA and PDGA mole of proportioning, reaches 15min.
TG curve (seeing Fig. 5) by P (DG-co-EG) is found out, the main DeR of P (DG-co-EG) occurs in 330～460 DEG C, 420 DEG C there is most degradation speed, illustrate that P (DG-co-EG) has good thermostability.
Embodiment 2
1. the preparation of PEGA: by the PEG0.01mol of 4000 relative molecular masses; triethylamine 0.01mol adds in 120ml methylene dichloride, then drips the acrylate chloride of 0.01mol, and 55 DEG C are reacted after 6 hours under protection under nitrogen protection; use ether precipitating, decompress filter obtains PEGA.
2. the preparation of PDGA: by 0.01mol ten polyglycerols, triethylamine 0.06mol adds in 25ml methylene dichloride, then drip the acrylate chloride of 0.03mol, 55 DEG C are reacted after 9 hours under protection under nitrogen protection, and underpressure distillation obtains PDGA.
3. the preparation of P (DG-co-EG) copolymerization phase change material: by the PEGA of 0.0012mol, the PDGA of 0.0001mol is dissolved in 15ml deionized water, add the ammonium persulphate of 0.148g, in thermostat water bath, react after 30 minutes, form semi-intercrossing network copolymerization phase change material.
Embodiment 3
1. the preparation of PEGA: by the PEG0.01mol of 4000 relative molecular masses; triethylamine 0.01mol adds in 120ml methylene dichloride, then drips the acrylate chloride of 0.01mol, and 35 DEG C are reacted after 9 hours under protection under nitrogen protection; use ether precipitating, decompress filter obtains PEGA.
2. the preparation of PDGA: by 0.01mol glycerol, triethylamine 0.01mol adds in 25ml methylene dichloride, then drip the acrylate chloride of 0.12mol, 55 DEG C are reacted after 9 hours under protection under nitrogen protection, and underpressure distillation obtains PDGA.
3. the preparation of P (DG-co-EG) copolymerization phase change material: by the PEGA of 0.0012mol, the PDGA of 0.0001mol is dissolved in 15ml deionized water, add the ammonium persulphate of 0.048g, in thermostat water bath, react after 15 minutes, form semi-intercrossing network copolymerization phase change material.
Embodiment 4
1. the preparation of PEGA: by the PEG0.01mol of 4000 relative molecular masses; triethylamine 0.01mol adds in 120ml methylene dichloride, then drips the acrylate chloride of 0.01mol, and 40 DEG C are reacted after 8 hours under protection under nitrogen protection; use ether precipitating, decompress filter obtains PEGA.
2. the preparation of PDGA: by 0.01mol ten polyglycerols, triethylamine 0.01mol adds in 25ml methylene dichloride, then drip the acrylate chloride of 0.03mol, 40 DEG C are reacted after 8 hours under protection under nitrogen protection, and underpressure distillation obtains PDGA.
3. the preparation of P (DG-co-EG) copolymerization phase change material: by the PEGA of 0.001mol, the PDGA of 0.001mol is dissolved in 15ml deionized water, add the ammonium persulphate of 0.054g, in thermostat water bath, react after 10 minutes, form semi-intercrossing network copolymerization phase change material.
Claims (4)
1. a preparation method for polyglycerol-co-polyoxyethylene glycol copolymerization phase change material, is characterized in that, taking vinylformic acid polyglycerol ester as raw material, comprising the steps:
1. prepare polyalkylene glycol acrylate ester: the polyoxyethylene glycol of molecular weight 2000～4000 is dissolved in after methylene dichloride, adds the triethylamine and the acrylate chloride that equate with polyoxyethylene glycol mole number; Under 35～55 DEG C of temperature and nitrogen protection, react 6～9 hours; After reaction finishes, solution is placed in to ice-water bath, adds ether, leave standstill after 5 minutes, decompress filter obtains polyalkylene glycol acrylate ester;
2. prepare vinylformic acid polyglycerol ester: polyglycerol is dissolved in after methylene dichloride, adds triethylamine and acrylate chloride; Under 35～55 DEG C of temperature and nitrogen protection, react 6～9 hours; After reaction finishes, the underpressure distillation at 55 DEG C of above-mentioned solution is obtained to vinylformic acid polyglycerol ester;
The described polyglycerol polymerization degree is 1～10;
The mol ratio of described polyglycerol and acrylate chloride is 1:3～1:12, and the mol ratio of polyglycerol and triethylamine is 1:1～1:6;
3. prepare copolymerization phase change material: the vinylformic acid polyglycerol ester that 2. the polyalkylene glycol acrylate ester that 1. step is prepared and step are prepared is dissolved in deionized water, add ammonium persulphate, in 75 DEG C of waters bath with thermostatic control, react 10～30min, obtain semi-intercrossing network gel copolymer phase change material polyglycerol-co-polyoxyethylene glycol.
2. method according to claim 1, is characterized in that step 3., and mole proportioning of polyalkylene glycol acrylate ester and vinylformic acid polyglycerol ester is 1:1～12:1.
3. method according to claim 1, is characterized in that step 3., and the consumption of ammonium persulphate is 1%～3% of polyalkylene glycol acrylate ester and the two gross weight of vinylformic acid polyglycerol ester.
4. polyglycerol-co-polyoxyethylene glycol copolymerization phase change material that as claimed in claim 1 prepared by method.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101186696A (en) * | 2006-11-17 | 2008-05-28 | 天津科技大学 | Synthesis for polyglycerol acrylate and thick oil emulsion breaking dehydration application thereof |
| CN102093552A (en) * | 2010-11-27 | 2011-06-15 | 大连工业大学 | Preparation method of phase change monomer with double-bond end groups |
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| CN101186696A (en) * | 2006-11-17 | 2008-05-28 | 天津科技大学 | Synthesis for polyglycerol acrylate and thick oil emulsion breaking dehydration application thereof |
| CN102093552A (en) * | 2010-11-27 | 2011-06-15 | 大连工业大学 | Preparation method of phase change monomer with double-bond end groups |
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