CN109897601A - A kind of polyurethane phase-change material and its preparation method and application - Google Patents
A kind of polyurethane phase-change material and its preparation method and application Download PDFInfo
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- CN109897601A CN109897601A CN201910118336.0A CN201910118336A CN109897601A CN 109897601 A CN109897601 A CN 109897601A CN 201910118336 A CN201910118336 A CN 201910118336A CN 109897601 A CN109897601 A CN 109897601A
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- polyethylene glycol
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Abstract
The invention belongs to chemical materials synthesis technical fields, more particularly to a kind of polyurethane phase-change material and its preparation method and application, the polyurethane phase-change material is prepared from the following raw materials: polyethylene glycol, alcohols chain extender, diisocyanate, catalyst and chain terminating agent, based on the percentage composition of raw material gross weight, wherein polyethylene glycol 75-85%, catalyst 0.01-0.5%, the chain terminating agent accounts for the 0.5-3.5% of polyethylene glycol quality, the isocyanate groups molar ratio in hydroxyl summation and the diisocyanate in hydroxyl and alcohols chain extender in the polyethylene glycol is 0.93-0.99；Polyurethane phase-change material prepared by the present invention is solid-solid phase-change energy-storage material, phase transition process volume change is small, no liquid generates, chemical stability is good, and polyurethane phase-change material phase transition temperature prepared by the present invention is 20-45 DEG C, for comfort zone human-acceptable, the phase transition temperature demand of apparel textile under the conditions of Different climate can be met, realize the energy-storage function of apparel textile.
Description
Technical field
The invention belongs to chemical materials synthesis technical fields more particularly to a kind of polyurethane phase-change material and preparation method thereof
And application.
Background technique
China is an energy consumption big country, and there is an urgent need to the reasonable utilizations and distribution to the energy.With the development of science and technology,
Demand of the mankind to the energy increasingly increases, but be not still to the utilization rate of the energy simultaneously it is very high, there is very big wastes, thus
Cause the supply of the energy gradually nervous.Therefore, how to develop the new energy and improve its utilization rate have become it is very tight
Urgent problem.Since the supply and demand of the energy has very strong time dependence in many cases, in order to reasonably utilize
It, people often need temporary unused energy storage to allow it to release again when needed.Phase-change material conduct
Energy storage carrier can be improved the utilization rate of the energy, alleviate the problem of energy shortage, has been widely used the system in refrigerator and air-conditioning
Cold and cold-storage, the automatic constant-temperature of intelligent building, the energy storage in application of solar energy and switching technology and daily necessities field.
Polyurethane phase-changing energy storage material is a kind of also in the material of exploitation, it is to utilize the fuel factor in substance phase transition process
Realize the storage and release of energy, and liquid does not occur in phase transition process, is a kind of transformation from solid to solid.In addition to general
Outside the advantages that logical phase-change material energy storage density is big, storage, exothermic process approximation isothermal, process is easy to control, polyurethane phase-change accumulation energy material
Material is also with the excellent machinability and mechanical property of high molecular material.The validity of phase-change material depends on its temperature range
And enthalpy of phase change, different applications need different phase transition temperatures, such as solar power generation, it is desirable that 90 DEG C or more of high temperature phase
Become material, the phase-change material for apparel textile is different according to the weather of application region, and phase transition temperature difference is such as used for
When harsh climate, 15-30 DEG C should be, be used to when temperature climate be 25-37 DEG C, be used to when big amount of exercise or hot climate be 32-
42℃.High molecular weight polyethylene glycol system or the micro- glue of polyurethane energy storage are generally used to the research of polyurethane phase-change material at present
Capsule material, super branched polyurethane material, although enthalpy of phase change is higher, phase transition temperature is also higher simultaneously, and generally greater than 45 DEG C, and institute
Costly with cost of material, there is also the problem of machine-shaping difficulty, be not suitable for being applied to apparel textile field.
Summary of the invention
In order to solve the above-mentioned technical problem the present invention provides a kind of polyurethane phase-change material and its preparation method and application.
The technical scheme to solve the above technical problems is that a kind of polyurethane phase-change material, by following raw material system
At: polyethylene glycol, alcohols chain extender, diisocyanate, catalyst and chain terminating agent, based on the percentage composition of raw material gross weight,
Wherein polyethylene glycol 75-85%, catalyst 0.01-0.5%, the chain terminating agent account for the 0.5-3.5% of polyethylene glycol quality, institute
The hydroxyl summation stated in hydroxyl and alcohols chain extender in polyethylene glycol is rubbed with the isocyanate groups in the diisocyanate
You are than being 0.93-0.99.Further, the molecular weight polyethylene glycol is 250-2000g/mol, just lower than this range enthalpy of phase change
Can be relatively low, in addition it is exactly current polyurethane that higher than this range enthalpy of phase change meeting height but phase transition temperature, rheological temperature etc., which can also increase,
It is usually to limit molecular weight polyethylene glycol to be greater than 2000 in the patent document of phase-change material, generally pursues high enthalpy of phase change, and this is specially
Using the polyethylene glycol preparation phase transition temperature lower than 2000 molecular weight, lower, enthalpy of phase change is suitable for demand in terms of being suitble to clothes to benefit
' 20-45 DEG C of phase transition temperature of polyurethane phase-change material prepared by the present invention, be comfort temperature model human-acceptable to phase-change material
Enclose ', it is the starting point of this patent.
Further, the alcohols chain extender is 1,3-PD, 1,4-butanediol, 2- methyl-1,3-propanediol, 3 methyl-
The mixture of one or more of 1,5- pentanediol and neopentyl glycol.
Further, the diisocyanate is methyl diphenylene diisocyanate, hexamethylene diisocyanate, toluene two
One or more of isocyanates, naphthalene diisocyanate, benzene dimethylene diisocyanate and paraphenylene diisocyanate are mixed
Close object.
Further, the catalyst is dibutyl tin dilaurate, stannous octoate, Mono-n-butyltin, triethylene two
The mixture of one or more of amine, tetramethyl butane diamine, zinc octoate and zinc naphthenate.
Further, the chain terminating agent is 1- hexadecanol, 1- octadecanol, glycol monoethyl ether, propylene glycol monomethyl ether
With the mixture of one or more of poly glycol monomethyl ether.
The present invention provides a kind of preparation method of polyurethane phase-change material, includes the following steps: to expand polyethylene glycol, alcohols
Chain agent and chain terminating agent are decompressed to -0.09MPa~-0.1MPa dehydration 2-4h at 100-120 DEG C, make moisture content 0-
250ppm is cooled to 70-80 DEG C, and catalyst and diisocyanate is added, is stirred to react under the mixing speed of 500-1500rpm
15-200s, obtained material are poured into 100-120 DEG C of curing 10-20h in pallet and obtain polyurethane phase-change material after cooling；
Based on the percentage composition of raw material gross weight, wherein polyethylene glycol 75-85%, catalyst 0.01-0.5%, the chain
Terminator accounts for the 0.5-3.5% of polyethylene glycol quality, the hydroxyl summation in the hydroxyl and alcohols chain extender in the polyethylene glycol
It is 0.93-0.99 with the isocyanate groups molar ratio in the diisocyanate.
The present invention provides a kind of preparation method of polyurethane phase-change material, includes the following steps: polyethylene glycol in 100-
It is decompressed to -0.09MPa~-0.1MPa dehydration 2-4h at 120 DEG C, makes moisture content down to 0-250ppm, is cooled to 70-80
DEG C, diisocyanate is added, is stirred to react 2-3h for 80-90 DEG C under the mixing speed of 500-800rpm, obtains performed polymer, then plus
Enter catalyst, chain terminating agent and alcohols chain extender, is stirred to react 5- for 80-90 DEG C under the mixing speed of 500-1500rpm
20min, resulting material are poured into 100-120 DEG C of curing 10-20h in pallet and obtain polyurethane phase-change material after cooling；
Based on the percentage composition of raw material gross weight, wherein polyethylene glycol 75-85%, catalyst 0.01-0.5%, the chain
Terminator accounts for the 0.5-3.5% of polyethylene glycol quality, the hydroxyl summation in the hydroxyl and alcohols chain extender in the polyethylene glycol
It is 0.93-0.99 with the isocyanate groups molar ratio in the diisocyanate.
Application of the polyurethane phase-change material in apparel textile field prepared by the present invention.
The beneficial effects of the present invention are: polyurethane phase-change material prepared by the present invention is solid-solid phase-change energy-storage material, phase transformation
Process volume change is small, and no liquid generates, and chemical stability is good, and polyurethane phase-change material phase transition temperature prepared by the present invention
20-45 DEG C, it is comfort zone human-acceptable, the phase transition temperature need of apparel textile under the conditions of Different climate can be met
It asks, realizes the energy-storage function of apparel textile.
Specific embodiment
The principles and features of the present invention are described below, and the given examples are served only to explain the present invention, is not intended to limit
Determine the scope of the present invention.
Embodiment 1
Polyethylene glycol 500g, 1,4- butanediol 24.99g, positive octadecyl alcolol 3.9g that molecular weight is 1800g/mol are added anti-
It answering in device, -0.09MPa dehydration 2.5h is decompressed at 110 DEG C, sample detection moisture content 200ppm is cooled to 70 DEG C,
Stannous octoate 0.13g is added；Then methyl diphenylene diisocyanate 141.67g is added into reactor, in stirring for 500rpm
It mixes and is stirred to react 35s under speed, obtained material is poured into 120 DEG C of curing 16h in pallet and obtains polyurethane phase transformation after cooling
Material, performance are as shown in table 1 below.
Embodiment 2
The polyethylene glycol 400 g that molecular weight is 1600g/mol is added in reactor and is decompressed to -0.095MPa at 120 DEG C
Dehydration 2h, sample detection moisture content 150ppm, is cooled to 80 DEG C；Hexamethylene diisocyanate is added into device
80.6g is stirred to react 2.5h for 85 DEG C under the mixing speed of 600rpm, obtains base polyurethane prepolymer for use as；Then monobutyl is aoxidized
Tin 0.5g, glycol monoethyl ether 8.0g, 2- methyl-1,3-propanediol 19.4g are added in the reactor for filling performed polymer,
Lower 85 DEG C of the mixing speed of 850rpm are stirred to react 10min；Resulting material will finally be reacted and be poured into 120 DEG C of curings in pallet
15h obtains polyurethane phase-change material, performance is as shown in table 1 below after cooling.
Embodiment 3
Reaction is added in polyethylene glycol 656g, neopentyl glycol 24.80g, positive hexadecanol 15g that molecular weight is 1500g/mol
In device, it is decompressed to -0.09MPa dehydration 3h, sample detection moisture content 180ppm at 115 DEG C, is cooled to 75 DEG C, is added
Dibutyl tin dilaurate 0.8g；Then hexamethylene diisocyanate 119.2g is added into reactor, in stirring for 700rpm
It mixes and is stirred to react 85s under speed, obtained material is poured into 110 DEG C of curing 18h in pallet and obtains polyurethane phase transformation after cooling
Material, performance are as shown in table 1 below.
Embodiment 4
Polyethylene glycol 680g, 1,4- butanediol 3.12g, poly glycol monomethyl ether 23g that molecular weight is 1000g/mol are added
Enter in reactor, -0.095MPa dehydration 2h is decompressed at 115 DEG C, sample detection moisture content 150ppm is cooled to 80
DEG C, triethylenediamine 0.96g is added；Then hexamethylene diisocyanate 124.88g is added into reactor, in 900rpm
Mixing speed under be stirred to react 150s, resulting material is poured into 110 DEG C of curing 18h in pallet and obtains polyurethane phase after cooling
Become material, performance is as shown in table 1 below.
Embodiment 5
By molecular weight be 800g/mol polyethylene glycol 36g, molecular weight be 1900g/mol polyethylene glycol 324g, 1,4-
Butanediol 16.35g, positive octadecyl alcolol 5.35g are added in reactor, and -0.1MPa dehydration 2h is decompressed at 110 DEG C, sample
Moisture content 160ppm is detected, is cooled to 80 DEG C, stannous octoate 0.11g is added；Then diphenyl methane is added into reactor
Diisocyanate 68.09g, is stirred to react 65s under the mixing speed of 1000rpm, resulting material be poured into pallet 115 DEG C it is ripe
Change 16h and obtains polyurethane phase-change material, performance is as shown in table 1 below after cooling.
Table 1
Melting temperature reflects phase transition temperature, and melting enthalpy reflects enthalpy of phase change, by data in table 1 as it can be seen that present invention gained
Polyurethane phase-change material phase transition temperature is below 45 DEG C, in comfort zone human-acceptable, and the equal > 50J/ of enthalpy of phase change
G, while flow starting temperature is lower than 140 DEG C, is able to carry out low temperature process use, can meet the application in apparel textile field.
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all in spirit of the invention and
Within principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of polyurethane phase-change material, which is characterized in that based on the percentage composition of raw material gross weight, be prepared from the following raw materials:
Polyethylene glycol accounts for 75-85%, and catalyst accounts for 0.01-0.5%, and the chain terminating agent accounts for the 0.5-3.5% of polyethylene glycol quality, institute
The hydroxyl summation stated in hydroxyl and alcohols chain extender in polyethylene glycol is rubbed with the isocyanate groups in the diisocyanate
You are than being 0.93-0.99.
2. a kind of polyurethane phase-change material according to claim 1, which is characterized in that the molecular weight polyethylene glycol is 250-
2000g/mo l。
3. a kind of polyurethane phase-change material according to claim 1, which is characterized in that the alcohols chain extender is 1,3- the third two
One or more of alcohol, 1,4- butanediol, 2- methyl-1,3-propanediol, 3 methyl-1s, 5- pentanediol and neopentyl glycol mix
Close object.
4. a kind of polyurethane phase-change material according to claim 1, which is characterized in that the diisocyanate is diphenylmethyl
Alkane diisocyanate, hexamethylene diisocyanate, toluene di-isocyanate(TDI), naphthalene diisocyanate, two isocyanide of phenylenedimethylidyne
The mixture of one or more of acid esters and paraphenylene diisocyanate.
5. a kind of polyurethane phase-change material according to claim 1, which is characterized in that the catalyst is two fourth of tin dilaurate
One of Ji Xi, stannous octoate, Mono-n-butyltin, triethylenediamine, tetramethyl butane diamine, zinc octoate and zinc naphthenate
Or several mixture.
6. a kind of polyurethane phase-change material according to claim 1, which is characterized in that the chain terminating agent is 1- hexadecane
The mixing of one or more of alcohol, 1- octadecanol, glycol monoethyl ether, propylene glycol monomethyl ether and poly glycol monomethyl ether
Object.
7. a kind of preparation method of polyurethane phase-change material, which comprises the steps of: expand polyethylene glycol, alcohols
Chain agent and chain terminating agent are decompressed to -0.09MPa~-0.1MPa dehydration 2-4h at 100-120 DEG C, make moisture content 0-
250ppm is cooled to 70-80 DEG C, and catalyst and diisocyanate is added, and stirs under the mixing speed of 500-1500rpm anti-
15-200s is answered, obtained material obtains polyurethane phase-change material after cooling in 100-120 DEG C of curing 10-20h；
Based on the percentage composition of raw material gross weight, wherein polyethylene glycol 75-85%, catalyst 0.01-0.5%, the chain termination
Agent accounts for the 0.5-3.5% of polyethylene glycol quality, hydroxyl summation and institute in the hydroxyl and alcohols chain extender in the polyethylene glycol
Stating the isocyanate groups molar ratio in diisocyanate is 0.93-0.99.
8. a kind of preparation method of polyurethane phase-change material, which comprises the steps of: by polyethylene glycol in 100-
It is decompressed to -0.09MPa~-0.1MPa dehydration 2-4h at 120 DEG C, makes moisture content down to 0-250ppm, is cooled to 70-
80 DEG C, diisocyanate is added, is stirred to react 2-3h for 80-90 DEG C under the mixing speed of 500-800rpm, obtains performed polymer, then
Catalyst, chain terminating agent and alcohols chain extender is added, is stirred to react 5- for 80-90 DEG C under the mixing speed of 500-1500rpm
20min, resulting material obtain polyurethane phase-change material after cooling in 100-120 DEG C of curing 10-20h；
Based on the percentage composition of raw material gross weight, wherein polyethylene glycol 75-85%, catalyst 0.01-0.5%, the chain termination
Agent accounts for the 0.5-3.5% of polyethylene glycol quality, hydroxyl summation and institute in the hydroxyl and alcohols chain extender in the polyethylene glycol
Stating the isocyanate groups molar ratio in diisocyanate is 0.93-0.99.
9. a kind of application of the polyurethane phase-change material in apparel textile field as described in claim any one of 1-6.
10. a kind of apparel textile, which is characterized in that be made of polyurethane phase-change material described in any one of claims 1-6.
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| CN111286285A (en) * | 2020-04-20 | 2020-06-16 | 昆山博益鑫成高分子材料有限公司 | Aluminum-shell battery heat-preservation protective film |
| CN112521570A (en) * | 2020-10-30 | 2021-03-19 | 西安工程大学 | Preparation method of novel solid-solid phase change energy storage material |
| CN113999385A (en) * | 2021-12-06 | 2022-02-01 | 四川朗迪新材料有限公司 | Recyclable and reprocessable solid-solid phase change material based on dynamic urethane bond and preparation method thereof |
| CN114606597A (en) * | 2022-03-28 | 2022-06-10 | 浙江理工大学 | Preparation method of phase-change polyurethane fiber |
| CN116375970A (en) * | 2023-03-01 | 2023-07-04 | 中山博锐斯新材料股份有限公司 | Ultra-high water absorption TPU material and preparation method thereof |
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| CN116375970A (en) * | 2023-03-01 | 2023-07-04 | 中山博锐斯新材料股份有限公司 | Ultra-high water absorption TPU material and preparation method thereof |
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Application publication date: 20190618 |