CN105019053B - One kind can weave phase-change accumulation energy polyster fibre - Google Patents
One kind can weave phase-change accumulation energy polyster fibre Download PDFInfo
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- CN105019053B CN105019053B CN201510384071.0A CN201510384071A CN105019053B CN 105019053 B CN105019053 B CN 105019053B CN 201510384071 A CN201510384071 A CN 201510384071A CN 105019053 B CN105019053 B CN 105019053B
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Abstract
Phase-change accumulation energy polyster fibre can be weaved the invention discloses one kind, it is with terylene as carrier, polyethylene glycol based polyurethanes are phase-changing energy storage material, by phase-changing energy storage material and terylene melt blending, and the fiber being prepared from melt spinning method, wherein terylene carrier accounts for the 50~95% of total fiber mass, and phase-changing energy storage material accounts for the 5~50% of total fiber mass；2~the 10cN/dtex of fibre strength of phase-change accumulation energy polyster fibre, 10~100 DEG C of phase transition temperature, 10~100kJ/kg of enthalpy of phase change.Phase-change accumulation energy polyster fibre heat endurance of the invention is good, and intensity is high compared with other phase-change energy-storage fibres, while having intensity and wearability higher.
Description
Technical field
The present invention relates to a kind of functional fiber material, more particularly to a kind of undulation degree with phase change energy storage function
Material.Phase-change energy-storage fibre material of the invention has excellent energy-storage property, intensity higher and good taking simultaneously
Energy.
Background technology
Terylene is the trade name of China's polyester fiber, is the important kind of synthetic fibers.Terylene is with smart terephthaldehyde
Acid（PTA）Or dimethyl terephthalate (DMT)（DMT）With ethylene glycol（EG）It is raw material, by esterification or ester exchange and polycondensation reaction system
Obtain fiber-forming polymer --- polyethylene terephthalate（PET）, the fiber being made after spinning and post processing, with extremely excellent
Good setting performance.After spun polyester thread or fabric are shaped generation it is flat very, fluffy form or rivel etc., in use through multiple
Washing remains to prolonged constant.Terylene is technique most relatively generally the least expensive one kind of simple, price in three big synthetic fibers, due to its knot
It is real it is durable, elasticity is good, be unlikely to deform, corrosion-resistant, insulation, it is well-pressed, quick-drying washable the features such as, be loved by people.
Phase-change material（Phase change material, PCM）Can be turned by phase within the scope of a narrow temperature
Become（Such as solid-to-solid transition or solid-liquid phase in version）Absorb or discharge substantial amounts of latent heat（ΔH）.This process can diving with PCM
Heat has been absorbed or released and has terminated.Because PCM has storage density and heat of fusion high, can be in almost isothermal
Under the conditions of formed a compact energy storage system.PCM first by the space craft that is applied to of small range, then in 20 generation
The discipline later stage seventies is applied in bigger scope, such as in building and solar energy system, to tackle the energy crisis in the whole world.
Can be according to the requirement of different application type, the organic PCM for selecting phase transition temperature different.For example, the phase of organic PCM
When temperature is less than 15 DEG C, the material can apply to cooling, and the phase transition temperature of organic PCM more than 90 DEG C when, then can be with
For absorption refrigeration.The phase transition temperature of organic PCM and its mixture is about 18~65 DEG C, and its thermal comfort is applied to textile industry
And construction industry.Polyethylene glycol（Polyethylene Glycol, PEG）, belong to polyoxyethylene alkenes, by dimethylether chain and
Terminal hydroxy group is constituted, molecular formula HO-CH2-(CH2-O-CH2)n-CH2- OH, is dissolved in water and organic solvent.PEG has ablation heat high, steady
Fixed phase transition temperature and narrow transition temperature range, melting steam are forced down, and chemical property and hot property are stable, nonflammable, can give birth to
Thing is degraded, and nontoxic, non-corrosiveness is cheap.Used as phase-changing energy storage material, PEG has many premium properties, in building trade
And many fields such as fabric, fiber, foamed material are applied.
In recent ten years, the research on phase-changing energy storage material is a problem for common concern in the world.Phase-change accumulation energy
Material can be used to solve the contradiction of heat energy Supply and Demand, be the important materials for improving efficiency of energy utilization and environmental protection, it
In Solar use, energy recovery, phase change energy-storage type air-conditioning, warmth-retaining clothing, energy storage cooker, building energy conservation, Aero-Space and agriculture
The fields such as industry have and are widely applied very much.Progress larger to the own acquirement of research of phase-changing energy storage material at present, but these materials
Material more or less has the shortcomings of chemical stability is poor, and long-term use is easily leaked, and enthalpy of phase change is relatively low, heat accumulation effect is bad.
So developing a kind of polymer solid-solid phase transition energy storage material of good performance, will have great application prospect and practical valency
Value.Polyurethanes phase-changing energy storage material be a class also in the material of exploitation, it is realized using the fuel factor in material phase transition process
The storage and release of energy, and phase transition process is a kind of transformation from solid to solid.Except with common phase-change material energy storage
Density is big, the approximate isothermal of heat accumulation, exothermic process, the advantages of process is easy to control outside, it also has the good processing of macromolecular material
Performance and the excellent properties such as polyurethane material high mechanical properties, corrosion-resistant, therefore be expected to turn into a kind of phase of great value
Change energy-storage material.
At present, the common method for preparing phase-change energy-storage fibre is to prepare phase-change accumulation energy non-woven fabrics by method of electrostatic spinning, though
So there is good phase-change accumulation energy performance, but it does not have spinnability.Another common method is to prepare phase with microcapsule method
Become energy storage viscose rayon, but its mechanical property is poor, therefore the fabric being made easily extends, poor dimensional stability, wearability
It is not strong.
The content of the invention
The purpose of the present invention is the shortcoming for overcoming existing phase-change energy-storage fibre, there is provided a kind of phase-change accumulation energy effect is good, while
Also there is the phase-change accumulation energy the weaved polyster fibre of mechanical strength and good wearability higher.
It is a further object of the present invention to provide the preparation method of above-mentioned phase-change accumulation energy polyster fibre.
Phase-change accumulation energy polyster fibre of weaving provided by the present invention is that, with terylene as carrier, polyethylene glycol based polyurethanes are
Phase-changing energy storage material, by the phase-changing energy storage material and terylene melt blending, and be prepared from melt spinning method, terylene is carried
Body accounts for the phase-change accumulation energy polyster fibre that total fiber mass 50~95%, phase-changing energy storage material accounts for total fiber mass 5~50%.
The phase-changing energy storage material is coated on the inside of terylene carrier by blend melt spinning for the present invention, is prepared into
Having arrived can woven phase-change accumulation energy polyster fibre, the 2~10cN/dtex of fibre strength of the phase-change accumulation energy polyster fibre, phase transformation
Temperature -10~100 DEG C, 10~100kJ/kg of enthalpy of phase change.
Polyethylene glycol based polyurethanes phase-changing energy storage material of the present invention is to be with the preferable polyethylene glycol of crystal property
Soft section, with the macromolecule solid-solid phase-change energy storage material with polyurethane structural that isocyanates, BDO synthesize as hard section
Material, wherein, the material quality ratio of polyethylene glycol, isocyanates and BDO is 1: 0.01~2: 0.01~2.It is of the invention
Phase-changing energy storage material realizes the storage and release of energy using the crystallization-melting change of soft section, has finally given a kind of decomposition
Phase-changing energy storage material of the temperature more than PET spinning temperatures.
Further, in phase-changing energy storage material of the invention, the number-average molecular weight of the polyethylene glycol is 200~20000；
Described isocyanates is toluene di-isocyanate(TDI)（TDI）, methyl diphenylene diisocyanate（MDI）, non-yellow stain type 1,6- oneself
Diisocyanate（HDI）Deng the one kind in isocyanates.
Phase-changing energy storage material of the present invention can be prepared using following methods：Polyethylene glycol and isocyanates is molten
In organic solvent, 40~80 DEG C are reacted 0.5~5 hour solution under inert gas shielding, add BDO chain extending reaction
0.5~4 hour, evaporation was reclaimed organic solvent and obtains solid polyurethane type phase-changing energy storage material.
Wherein preferably, the organic solvent is acetone, butanone, ethyl acetate, chloroform, glycerin ether, dioxane, glycerine
One kind in ester or aromatic hydrocarbon etc..
After terylene carrier master batch and phase-changing energy storage material are blended the present invention with the weight/mass percentage composition, twin-screw is added
In extruder, co-blended spinning master batch is prepared, co-blended spinning master batch is added to again then melt, melt are formed in melt spinning machine
Melt stream is extruded into by spinneret orifice, as-spun fibre is formed after being cooled and solidified through air, as-spun fibre is again by oiling, rolling up
After the post processing such as, drawing-off, it has been made and of the invention has weaved phase-change accumulation energy polyster fibre.
The present invention can also be post-processed using following methods to the phase-change accumulation energy polyster fibre for preparing：Prepare
The modified amido organosilicon aqueous solution of 0.5~15wt%, regulation pH value is made penetrant arranging bath to 6, by phase-change accumulation energy polyster fibre according to
1: 10 bath raio processes 5~45min in adding the penetrant arranging bath, after taking out dehydration, 65~100 DEG C of constant temperature dryings.
Phase transition temperature -10~100 DEG C of the phase-change accumulation energy weaved polyster fibre prepared by the present invention, enthalpy of phase change 10~
Do not change fiber trait before and after 100kJ/kg, and phase transformation, small molecule leakage does not occur, can be by changing the molecule of polyethylene glycol
The species of amount and isocyanates changes phase transition temperature and enthalpy of phase change.Simultaneously as the phase-changing energy storage material that uses of the present invention for
Polyurethanes, with polyester fiber（Terylene）There is preferable compatibility.
The present invention prepare the phase-change accumulation energy weaved polyster fibre compared with prior art, with advantages below and effect.
1）The present invention can weave the thermally-stabilised good of phase-change accumulation energy polyster fibre, and macromolecular phase-changing energy storage material is uniformly divided
It is dispersed in terylene matrix, in the absence of the leakage problem of small molecule phase-change material, and appearance stablity, good mechanical property.
2）The present invention can weave phase-change accumulation energy polyster fibre while having the characteristic of polyster fibre and phase-change accumulation energy, not only may be used
Each field is applied to as functional material, can also be weaved, as taking material.
3）The phase-change accumulation energy weaved polyster fibre 1~10dtex of fiber number prepared by the present invention, single fiber strength is higher（2~
10CN/dtex）, feel is smooth, and easily colouring, is a kind of excellent fibre in differentiation of wearability.
4）Preparation process is simple of the present invention, it is workable.
Brief description of the drawings
Fig. 1 is the DSC figures of the phase-change accumulation energy weaved polyster fibre prepared by the embodiment of the present invention 1.
In figure, a is the heating curve of phase-change accumulation energy polyster fibre, and b is the temperature lowering curve of phase-change accumulation energy polyster fibre.
Specific embodiment
The content of the invention of the invention is expanded on further with reference to specific embodiment.The embodiment is to illustrate the invention
Technology design and feature, it is impossible to limited the scope of the invention with this.All equivalence changes on the basis of the present invention are repaiied
Decorations, should all be included within the scope of the present invention.
Embodiment 1
Take 100g polyethylene glycol 2000s, 15g methyl diphenylene diisocyanates（MDI）It is dissolved in 500ml ethyl acetate,
N240 DEG C of stirring reactions are warming up under protection 3 hours, add 5g BDOs, carry out chain extending reaction 2 hours, evaporated back
Ethyl acetate is received, solid polyurethane type phase-changing energy storage material polyethylene glycol based polyurethanes are obtained.
400g dacron master grains are taken, in adding double screw extruder together with 100g phase-changing energy storage materials, spinning master batch is prepared,
Then co-blended spinning master batch is added in melt spinning machine, melt is extruded into melt stream, final melt by spinneret orifice
Thread cools and solidifies to form as-spun fibre, and as-spun fibre oils, winds, be obtained that can to weave phase-change accumulation energy terylene fine after drawing-off
Dimension.Phase-change material is covered by the inside of terylene matrix by melt blending.
Phase-change accumulation energy polyster fibre can be weaved to be passed through in 35 DEG C of post-finishing liquid with 1: 10 bath raio, 30min is post-processed
After take out, be dehydrated, 70 DEG C of constant temperature dryings obtain the soft phase-change accumulation energy weaved polyster fibre.The post-finishing liquid contains
There is 4% modified amido silicone softening agent, and adjusted to pH=6 with glacial acetic acid.
Phase-change accumulation energy polyster fibre single fiber intensity 5.2CN/dtex manufactured in the present embodiment, elongation at break 17%.
Fig. 1 is that the liter of the phase-change accumulation energy the weaved polyster fibre that the present embodiment is prepared gently is lowered the temperature DSC curve.The song
Line shows that the phase transition performance that can weave phase-change accumulation energy polyster fibre is reversible, and 18 DEG C or so start heat absorption, go out at 28 DEG C or so
Existing endothermic peak, heat release is started when temperature drop is to 12 DEG C or so, exothermic peak occurs at -5 DEG C or so.Transition temperature range-
10~32 DEG C, enthalpy of phase change is about 28.76kJ/kg.
Embodiment 2
Take 300g Macrogol 6000s, 15g methyl diphenylene diisocyanates（MDI）It is dissolved in 1000ml toluene, N2
50 DEG C of stirring reactions are warming up under protection 3 hours, add 5g BDOs, carry out chain extending reaction 2 hours, evaporation is reclaimed
Toluene, obtains solid polyurethane type phase-changing energy storage material polyethylene glycol based polyurethanes.
350g dacron master grains are taken, in adding double screw extruder together with 150g phase-changing energy storage materials, spinning master batch is prepared
（Fiber-forming polymer is cut into slices and is melted or melt is obtained by continuous polymerization）, co-blended spinning master batch is then added to melt spinning machine
In, melt is extruded into melt stream by spinneret orifice, and final melt stream cools and solidifies to form as-spun fibre, on as-spun fibre
Being obtained after oil, winding, drawing-off can weave phase-change accumulation energy polyster fibre.
Phase-change accumulation energy polyster fibre can be weaved to be passed through in 35 DEG C of post-finishing liquid with 1: 10 bath raio, 30min is post-processed
After take out, be dehydrated, 70 DEG C of constant temperature dryings obtain the soft phase-change accumulation energy weaved polyster fibre.The post-finishing liquid contains
There is 4% modified amido silicone softening agent, and adjusted to pH=6 with glacial acetic acid.
Phase-change accumulation energy polyster fibre single fiber intensity 4.5CN/dtex manufactured in the present embodiment, elongation at break 19%.Phase alternating temperature
0~35 DEG C of scope of degree, enthalpy of phase change is about 46.8kJ/kg.
Embodiment 3
Take 400g PEG 8000s, 15g toluene di-isocyanate(TDI)s（TDI）It is dissolved in 1000ml acetone, N2Under protection
It is warming up to 60 DEG C of stirring reactions 1 hour, adds 5g BDOs, carry out chain extending reaction 1 hour, acetone is reclaimed in evaporation, is obtained
To solid polyurethane type phase-changing energy storage material polyethylene glycol based polyurethanes.
300g dacron master grains are taken, in adding double screw extruder together with 100g phase-changing energy storage materials, spinning master batch is prepared,
Then co-blended spinning master batch is added in melt spinning machine, melt is extruded into melt stream, final melt by spinneret orifice
Thread cools and solidifies to form as-spun fibre, and as-spun fibre oils, winds, be obtained that can to weave phase-change accumulation energy terylene fine after drawing-off
Dimension.
Phase-change accumulation energy polyster fibre can be weaved to be passed through in 35 DEG C of post-finishing liquid with 1: 10 bath raio, 30min is post-processed
After take out, be dehydrated, 70 DEG C of constant temperature dryings obtain the soft phase-change accumulation energy weaved polyster fibre.The post-finishing liquid contains
There is 4% modified amido silicone softening agent, and adjusted to pH=6 with glacial acetic acid.
Phase-change accumulation energy polyster fibre single fiber intensity 3.6CN/dtex manufactured in the present embodiment, elongation at break 22%.Phase alternating temperature
10~40 DEG C of scope of degree, enthalpy of phase change is about 72.8kJ/kg.
Claims (5)
1. one kind can weave phase-change accumulation energy polyster fibre, be that, with terylene as carrier, polyethylene glycol based polyurethanes are phase-change accumulation energy material
Material, by the phase-changing energy storage material and terylene melt blending, and the terylene carrier being prepared from melt spinning method to account for fiber total
Quality 50~95%, phase-changing energy storage material accounts for the fiber of total fiber mass 5~50%；
Wherein, described polyethylene glycol based polyurethanes phase-changing energy storage material be with polyethylene glycol as soft section, with isocyanates, Isosorbide-5-Nitrae-
Butanediol is hard section, according to the material quality ratio of polyethylene glycol, isocyanates and BDO for 1: 0.01~2: 0.01~
2, the polymer solid-solid phase transition energy storage material with polyurethane structural prepared using following methods：By polyethylene glycol and
Isocyanates is dissolved in organic solvent, and 40~80 DEG C are reacted 0.5~5 hour under inert gas shielding, add Isosorbide-5-Nitrae-fourth two
Alcohol chain extending reaction 0.5~4 hour, evaporation is reclaimed organic solvent and obtains solid polyurethane type phase-changing energy storage material；Described is organic
Solvent is the one kind in acetone, butanone, ethyl acetate, chloroform, glycerin ether, dioxane, glyceride or aromatic hydrocarbon；
2~the 10cN/dtex of fibre strength of the phase-change accumulation energy polyster fibre, phase transition temperature -10~100 DEG C, enthalpy of phase change 10~
100kJ/kg。
2. it is according to claim 1 to weave phase-change accumulation energy polyster fibre, it is characterized in that the number of the polyethylene glycol is divided equally
Son amount is 200~20000.
3. it is according to claim 1 to weave phase-change accumulation energy polyster fibre, it is characterized in that described isocyanates is toluene
One kind in diisocyanate, methyl diphenylene diisocyanate, non-yellow stain type hexamethylene diisocyanate.
4. the preparation method of the phase-change accumulation energy the weaved polyster fibre described in any one of claims 1 to 3, is that terylene carrier is female
Grain prepares co-blended spinning master batch during double screw extruder is added after being blended with the weight/mass percentage composition with phase-changing energy storage material, then
Co-blended spinning master batch is formed into melt in melt spinning machine, melt stream is extruded into by spinneret orifice, it is solid through air cooling
Change forms as-spun fibre, then by oiling, winding, drawing-off, being made can weave phase-change accumulation energy polyster fibre.
5. the preparation method of phase-change accumulation energy polyster fibre according to claim 4, it is characterized in that also including following post processing
Operation：The modified amido organosilicon aqueous solution of 0.5~15wt% is prepared, regulation pH value to 6 is made penetrant arranging bath, phase-change accumulation energy is washed
Synthetic fibre fiber processes 5~45min in adding the penetrant arranging bath according to 1: 10 bath raio, and after taking out dehydration, 65~100 DEG C of constant temperature dry
It is dry.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106120010A (en) * | 2016-06-21 | 2016-11-16 | 深圳市乐乐趣文化科技有限公司 | A kind of clothes of temp. controllable insulation |
| CN107447294A (en) * | 2017-09-01 | 2017-12-08 | 青岛大学 | A kind of method that PEG/PET solid-solid phase change materials are prepared using electrostatic spinning technique |
| CN107447319B (en) * | 2017-09-21 | 2019-04-23 | 广东万合科技有限公司 | A kind of phase-change temperature control textile fabric that dissaving polymer is stable and preparation method |
| CN109762133A (en) * | 2017-11-09 | 2019-05-17 | 江苏梦溪智能环境科技有限公司 | A kind of novel high polymer sizing phase-change heat-storage material and preparation method thereof |
| CN114574998A (en) * | 2022-03-28 | 2022-06-03 | 浙江理工大学 | Preparation method of temperature-adjustable polyurethane composite phase-change fiber |
| CN114606597A (en) * | 2022-03-28 | 2022-06-10 | 浙江理工大学 | Preparation method of phase-change polyurethane fiber |
| CN115142162A (en) * | 2022-07-05 | 2022-10-04 | 诸暨鼎丰化纤有限公司 | Regenerated polyester composite antibacterial polyester filament yarn and production process thereof |
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| CN1916248A (en) * | 2006-08-23 | 2007-02-21 | 中国科学院广州化学研究所 | Super fine composite terylene fibers storing energy through phase change, and preparation method |
| CN101781394A (en) * | 2009-01-21 | 2010-07-21 | 南通芯迎设计服务有限公司 | Synthesis of polyurethane macromolecular solid-solid phase change energy storage material |
| CN103243406A (en) * | 2013-05-22 | 2013-08-14 | 东华大学 | Method for preparing intelligent temperature regulation fiber by melt spinning process |
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| CN102718905B (en) * | 2012-07-03 | 2014-01-08 | 天津工业大学 | Preparation method of polymer type phase change materials |
| CN102704037B (en) * | 2012-07-03 | 2014-01-22 | 天津工业大学 | Heat accumulating temperature regulating fiber and method for preparing same |
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| CN1916248A (en) * | 2006-08-23 | 2007-02-21 | 中国科学院广州化学研究所 | Super fine composite terylene fibers storing energy through phase change, and preparation method |
| CN101781394A (en) * | 2009-01-21 | 2010-07-21 | 南通芯迎设计服务有限公司 | Synthesis of polyurethane macromolecular solid-solid phase change energy storage material |
| CN103243406A (en) * | 2013-05-22 | 2013-08-14 | 东华大学 | Method for preparing intelligent temperature regulation fiber by melt spinning process |
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Effective date of registration: 20190415 Address after: 030600 extension of Yingbin West Street, Yuci District, Jinzhong City, Shanxi Province Co-patentee after: Taiyuan University of Technology Patentee after: SHANXI RUISAIGE TEXTILE TECHNOLOGY CO., LTD. Address before: 030600 extension of Yingbin West Street, Yuci District, Jinzhong City, Shanxi Province Patentee before: SHANXI RUISAIGE TEXTILE TECHNOLOGY CO., LTD. |