CN105924640B - A method of preparing polyethylene glycol-nylon solid-solid phase change energy storage material - Google Patents
A method of preparing polyethylene glycol-nylon solid-solid phase change energy storage material Download PDFInfo
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- CN105924640B CN105924640B CN201610447482.4A CN201610447482A CN105924640B CN 105924640 B CN105924640 B CN 105924640B CN 201610447482 A CN201610447482 A CN 201610447482A CN 105924640 B CN105924640 B CN 105924640B
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- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/40—Polyamides containing oxygen in the form of ether groups
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Abstract
The present invention, which provides, a kind of prepares polyethylene glycol-nylon solid-solid phase change energy storage material method, using modified poly (ethylene glycol), lactams, anionic initiator and activator as primary raw material, it is cast in mold and is reacted after melt blending, in-situ preparation nylon during the reaction, and nylon is in net distribution in polyethylene glycol matrix, under the collective effect of Phase stracture and physics hydrogen bond, polyethylene glycol/nylon solid-solid phase change energy storage material is formed.Advantage of this approach is that obtained polyethylene glycol/nylon solid-solid phase change energy storage material quantity of heat storage is big, energy storage effect is good, reusing is good, preparation method is simple, easily controllable, is not necessarily to any solvent, not will cause environmental pollution, cost of material is lower, can be mass.
Description
Technical field
The invention belongs to this materials science fields, and in particular to a kind of to prepare polyethylene glycol-nylon solid-solid phase change energy storage material
The method of material
Background technique
The energy is the basis that the mankind depend on for existence and development, moreover, with the development of the social economy, people to natural gas,
The dependence of the natural energy sources such as petroleum, coal is increasingly reinforced.But up to the present, natural energy source has been on the verge of exhaustion, and people must not
The not energy shortage and energy crisis in face of frequently occurring.Therefore, to the effective use of the energy and energy saving people has been caused
Great attention.Then, the new material that research and development can be energy saving, becomes problem in the urgent need to address.Energy storage technology is just
It is born in this context, is to improve the effective means of energy utilization rate, and energy storage material is the basis of energy storage technology.From
Last century end starts, the research and development of the phase-changing energy storage material as energy storage material important component more and more attention has been paid to.
Phase-changing energy storage material by its course of work material phase change citation form can be divided into solid air-liquid gas, solid-liquid,
Four class of solid-solid phase change energy storage material.Wherein solid-solid phase change energy storage material is only not available for other phase-changing energy storage materials as having
Special energy storage advantage has very big practical application value, is the emphasis of current phase-changing energy storage material research and development.And in solid-solid phase change
In energy storage material, macromolecular solid solid-solid phase transition energy storage material is convenient since its phase transition temperature compares, long service life, performance are stable,
Without be subcooled and chromatography phenomenon, quantity of heat storage is big, mechanical property is preferable, convenient for processing and forming, the structural material of system can be directly used as
The features such as, it can be widely used in the every field of military and civilian, such as the storage and utilization of solar energy, thermal energy, it has also become phase
The most promising research field of change energy-storage material.
Polyethylene glycol because its phase transition temperature is suitable for, enthalpy of phase change is high, heat stagnation aftereffect is low, without mutually the features such as is separated due to it is extensive
Applied to polymer electrolyte solid-solid phase change energy storage material.Currently, the preparation method of polyethylene glycols solid-solid phase change energy storage material is main
There are chemical method and two kinds of physical method.Mainly using the method for micro- crosslinking, graft copolymerization or block copolymerization, synthesis has solid chemical method
Gu the ethylene glycol copolymer of phase transition performance, as Chinese patent CN 100436510C reports a kind of polyethylene glycol and terylene connects
The method that branch copolymerization prepares solid-solid phase change material;United States Patent (USP) US 19870055476, which is reported, utilizes cross-linked polyethylene glycol system
It is standby can energy storage temperature control textile fabric.Although chemical method can obtain high performance solid-solid phase change energy storage material, its preparation process is multiple
Miscellaneous, the solvent price used is high and recycling is difficult, the preparation cost of material is high, and the popularization of upper limit value material to a certain degree is answered
With.Polyethylene glycol is mainly blended with other polymers and prepares the composite phase change energy-storing with solid-solid phase change feature by physical method
Material.Currently, this kind of phase-changing energy storage material accounts for significant proportion in the research of macromolecular solid solid-solid phase transition energy storage material, such as China is special
Sharp CN 991160258, which is reported, obtains a kind of polyethylene glycol/cellulose composite solid solid-solid phase transition energy storage material with solution blended process;
Chinese patent CN 101230256A reports the preparation method of polyethylene glycol and epoxy resin formed composite phase-change materials.It is above-mentioned
The shortcomings that physical method, essentially consists in, and first, it needs to cause environmental pollution using a large amount of solvents;Second, multiple thermal cycle can weaken
The effect of hydrogen bond, so that the reusing of material is poor;Third, preparation process is complicated, limits its industrialization.
Technical solution:
There is provided that a kind of simple process, easily controllable, quantity of heat storage is big, storage to overcome the problems of the above-mentioned prior art
It can the good polyethylene glycol/nylon solid-solid phase change energy storage material preparation method of effect.
The present invention is achieved by the following technical scheme:
A method of preparing polyethylene glycol-nylon solid-solid phase change energy storage material, comprising the following steps:
Step 1) prepare modified poly (ethylene glycol): it will be mixed in the polyethylene glycol of melting with alkyl-blocked dose with the molar ratio of 1:2
Close, under nitrogen protection, 60-120 DEG C at a temperature of stir 30-120min, obtain modified poly (ethylene glycol).
Step 2) by the lactams of 10-70 parts by weight, the anionic initiator of 0.1-3 parts by weight and 30-90 parts by weight
Modified poly (ethylene glycol) mixing, melts 5-60min at 70-160 DEG C, adds activator 0.05-3 parts by weight, mixes 1-
Mixed product is cast in mold by 15min, and 10~60min is reacted at 140~180 DEG C.
Further to improve, the polyethylene glycol is that molecular weight is 1000-20000.
Further to improve, the weight ratio of the anionic initiator and activator is 1:10-10:1.
It is further to improve, the described alkyl-blocked dose change for alkyl monoisocyanate class or alkyl monoisothiocyanates class
Close object.
Further to improve, described alkyl-blocked dose is dodecyl isocyanate, hexadecyl isocyanate, octadecane
Based isocyanate, octadecyl isothiocyanates.
Further to improve, the lactams is butyrolactam, caprolactam, spicy inner formyl amine, one in lauric lactam
Kind or several mixtures.
Further to improve, the lactams is caprolactam.
Further to improve, the anionic initiator is the salt compounds containing lactam anion.
Further to improve, the activator is isocyanate ester compound, caprolactam class compound, acyl chloride chemical combination
One or more of mixtures of object, anhydride compound.
Compared with the prior art, the advantages of the present invention are as follows:
Alkyl-blocked modified poly (ethylene glycol) is first prepared, lactams and anionic initiator are then dissolved in modified poly- second two
It in alcohol, adds activator after mixing evenly, is cast in mold and is reacted, in reaction process, activator draws with anion
It sends out agent effect and causes lactams progress anionic ring-opening polymerization, in-situ preparation nylon.Nylon is in polyethylene glycol matrix in netted
Distribution forms polyethylene glycol/nylon solid-solid phase change energy storage material under the collective effect of this Phase stracture and physics hydrogen bond.
The advantages of preparation method is, obtained polyethylene glycol/nylon solid-solid phase change energy storage material quantity of heat storage is big, energy storage effect
Well, reusing is good, and preparation method is simple, easily controllable, is not necessarily to any solvent, not will cause environmental pollution, cost of material
It is lower, it can be mass.
Specific embodiment:
Embodiment 1
The material used in the present invention has: polyethylene glycol uses average molecular weight in the polyethylene glycol of 1000-20000
It is one or more of;Alkyl-blocked dose is the change containing an alkyl and an isocyanate groups or an isothiocyanates group
Object is closed, such as dodecyl isocyanate, hexadecyl isocyanate, octadecylisocyanate, octadecyl isothiocyanates;
Lactams is one or more of butyrolactam, caprolactam, spicy inner formyl amine, lauric lactam, preferably caprolactam;Yin from
Sub- initiator is the compound with lactam anion structure, such as sodium caprolactam, lauric lactam sodium;Activator is various
One or more of isocyanates, various acyl caprolactams, various acyl chlorides, various acid anhydrides, such as toluene di-isocyanate(TDI), second
Acyl caprolactam, chlorobenzoyl chloride, maleic anhydride.
In order to preferably be described to the present invention, applicant illustrates following examples.
Embodiment 1
In molar ratio, 2 molar parts ten are added in the polyethylene glycol that the average molecular weight of 1 molar part molten condition is 1000
Dialkyl isocyanate under nitrogen protection, persistently stirs 120min at 70 DEG C, so that modified poly (ethylene glycol) is made, it is spare;By weight
Part is measured, weighs 20 parts of caprolactams, 0.2 part of sodium caprolactam is dissolved in the modified poly (ethylene glycol) of 80 parts of molten conditions, at 70 DEG C
60min is persistently stirred, 0.3 part of maleic anhydride is added, continues to stir 15min, is cast in mold, is reacted at 140 DEG C
Polyethylene glycol/nylon solid-solid phase change energy storage material is made in 60min.
Embodiment 2
In molar ratio, 2 molar parts ten are added in the polyethylene glycol that the average molecular weight of 1 molar part molten condition is 2000
Eight alkyl isothiocyanates under nitrogen protection, persistently stir 90min at 80 DEG C, so that modified poly (ethylene glycol) is made, it is spare;It presses
Parts by weight, weigh 10 parts of caprolactams, 0.1 part of sodium caprolactam is dissolved in the modified poly (ethylene glycol) of 90 parts of molten conditions, 80
DEG C 5min is persistently stirred, add 0.05 part of toluene di-isocyanate(TDI), continued to stir 1min, be cast in mold, it is anti-at 180 DEG C
10min is answered, polyethylene glycol/nylon solid-solid phase change energy storage material is made.
Embodiment 3
In molar ratio, 2 molar parts ten are added in the polyethylene glycol that the average molecular weight of 1 molar part molten condition is 6000
Six alkyl isocyanates under nitrogen protection, persistently stir 30min at 100 DEG C, so that modified poly (ethylene glycol) is made, it is spare;By weight
Part is measured, weighs 40 parts of butyrolactams, 1 part of sodium caprolactam is dissolved in the modified poly (ethylene glycol) of 60 parts of molten conditions, is held at 100 DEG C
Continuous stirring 30min, adds 1 part of chlorobenzoyl chloride, continues to stir 10min, is cast in mold, 20min is reacted at 160 DEG C, makes
Obtain polyethylene glycol/nylon solid-solid phase change energy storage material.
Embodiment 4
In molar ratio, 2 molar parts are added in the polyethylene glycol that the average molecular weight of 1 molar part molten condition is 20000
Octadecylisocyanate under nitrogen protection, persistently stirs 60min at 160 DEG C, so that modified poly (ethylene glycol) is made, it is spare;It presses
Parts by weight, weigh 70 parts of caprolactams, 3 parts of lauric lactam sodium are dissolved in the modified poly (ethylene glycol) of 30 parts of molten conditions, 160
DEG C 30min is persistently stirred, add 3 parts of vinylcaprolactams, continued to stir 2min, be cast in mold, reacted at 180 DEG C
Polyethylene glycol/nylon solid-solid phase change energy storage material is made in 15min.
Claims (8)
1. a kind of prepare polyethylene glycol-nylon solid-solid phase change energy storage material method, which comprises the following steps:
Step 1) prepare modified poly (ethylene glycol): the polyethylene glycol of melting and the alkyl-blocked dose of molar ratio with 1:2 are mixed,
Under nitrogen protection, 60-120 DEG C at a temperature of stir 30-120min, obtain modified poly (ethylene glycol);
Step 2) by the modification of the lactams of 10-70 parts by weight, the anionic initiator of 0.1-3 parts by weight and 30-90 parts by weight
Polyethylene glycol mixing, melts 5-60min at 70-160 DEG C, adds activator 0.05-3 parts by weight, mixes 1-15min, will
Mixed product is cast to mold, and 10~60min is reacted at 140~180 DEG C, polyethylene glycol-nylon is obtained and consolidates solid phase
Change energy-storage material;
The anionic initiator is the salt compounds containing lactam anion;
The activator is isocyanate ester compound, caprolactam class compound, acyl chloride compound, anhydride compound
One or more of mixtures.
2. it is according to claim 1 it is a kind of prepare polyethylene glycol-nylon solid-solid phase change energy storage material method, feature exists
In the step 2) in, the weight summation of lactams and modified poly (ethylene glycol) is 100 parts by weight.
3. it is according to claim 1 it is a kind of prepare polyethylene glycol-nylon solid-solid phase change energy storage material method, feature exists
In the weight ratio of the anionic initiator and activator is 1:10-10:1.
4. it is according to claim 1 it is a kind of prepare polyethylene glycol-nylon solid-solid phase change energy storage material method, feature exists
In the polyethylene glycol is that molecular weight is 1000-20000.
5. it is according to claim 1 it is a kind of prepare polyethylene glycol-nylon solid-solid phase change energy storage material method, feature exists
In the described alkyl-blocked dose compound for alkyl monoisocyanate class or alkyl monoisothiocyanates class.
6. it is according to claim 1 it is a kind of prepare polyethylene glycol-nylon solid-solid phase change energy storage material method, feature exists
In described alkyl-blocked dose is dodecyl isocyanate, hexadecyl isocyanate, octadecylisocyanate, octadecane
Base isothiocyanates.
7. it is according to claim 1 it is a kind of prepare polyethylene glycol-nylon solid-solid phase change energy storage material method, feature exists
In the lactams is the mixture of one or more of butyrolactam, caprolactam, spicy inner formyl amine, lauric lactam.
8. it is according to claim 7 it is a kind of prepare polyethylene glycol-nylon solid-solid phase change energy storage material method, feature exists
In the lactams is caprolactam.
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形态稳定相变材料聚乙二醇/聚酰胺6共聚物的制备及性能;郭静等;《高分子材料科学与工程》;20090531;第25卷(第5期);第161页1实验部分 |
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