CN105019053A - Weaving phase-change energy-storage polyester fiber - Google Patents
Weaving phase-change energy-storage polyester fiber Download PDFInfo
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- CN105019053A CN105019053A CN201510384071.0A CN201510384071A CN105019053A CN 105019053 A CN105019053 A CN 105019053A CN 201510384071 A CN201510384071 A CN 201510384071A CN 105019053 A CN105019053 A CN 105019053A
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Abstract
The invention discloses a weaving phase-change energy-storage polyester fiber, which takes terylene as a carrier and polyethyleneglycol polyurethane as a phase-change energy-storage material, the phase-change energy-storage material and terylene are performed with melt blending, and then fiber can be prepared by a melt blending method. Total weight of terylene carrier accounts for 50-95% of that of fiber, total mass of the phase-change energy-storage material accounts for 5-50% of that of fiber; fiber intensity of the phase-change energy-storage polyester fiber is 2-10 cN/dtex, phase transition temperature is -10-100 DEG C, and enthalpy of phase change is 10-100Kj/kg. The phase-change energy-storage polyester fiber of the present invention has the advantages of good thermostability, higher intensity than that of other phase-change energy-storage material, and has high intensity and taking performance.
Description
Technical field
The present invention relates to a kind of functional fiber material, particularly relate to a kind of fibrous material with phase change energy storage function.Phase-change energy-storage fibre material of the present invention has excellent energy-storage property, higher intensity and good wearability simultaneously.
Background technology
Terylene is the trade name of China's polyester fiber, is the important kind of synthetic fiber.Terylene be with p-phthalic acid (PTA) or dimethyl terephthalate (DMT) (DMT) with ethylene glycol (EG) for raw material, fiber-forming polymer is obtained by esterification or ester exchange and polycondensation reaction---polyethylene terephthalate (PET), the fiber made after spinning and post processing, has extremely excellent setting performance.Spun polyester thread or fabric generate after setting flat very, fluffy form or rivel etc., in use still can be prolonged constant through repeatedly washing.Terylene is the one that in three large synthetic fiber, technique is the simplest, price is relatively the most cheap, because it is durable, good springiness, not yielding, corrosion-resistant, insulation, the feature such as well-pressed, quick-drying washable, be loved by the people.
Phase-change material (phase change material, PCM) in a narrow temperature range, can absorb or discharge a large amount of latent heat (Δ H) by phase in version (as solid-to-solid transition or solid-liquid phase change).This process can be stopped by absorbing or release along with the latent heat of PCM.Because PCM has high storage density and melting heat, a compact energy storage system can be formed under the condition of almost isothermal.PCM first by among a small circle be applied to space craft, be then applied in larger scope in 20 century 70 later stages, as in building and solar energy system, to tackle global energy crisis.
According to the requirement of different application type, organic PCM that phase transition temperature is different can be selected.Such as, when the phase transition temperature of organic PCM is lower than 15 DEG C, this material can be applied to cooling, and the phase transition temperature of organic PCM more than 90 DEG C time, then may be used for absorption refrigeration.The phase transition temperature of organic PCM and composition thereof is about 18 ~ 65 DEG C, and its thermal comfort is applicable to textile industry and building industry.Polyethylene glycol (Polyethylene Glycol, PEG), belongs to polyethylene glycol oxide class, is made up of, molecular formula HO-CH dimethylether chain and terminal hydroxy group
2-(CH
2-O-CH
2)
n-CH
2-OH, water-soluble and organic solvent.PEG has high ablation heat, stable phase transition temperature and narrow transition temperature range, and melting steam forces down, and chemical property and hot property are stablized, nonflammable, biodegradable, nontoxic, and non-corrosiveness is cheap.As phase-changing energy storage material, PEG has many premium properties, obtains application in a lot of field such as building trade and fabric, fiber, foamed material.
In recent ten years, about the research of phase-changing energy storage material be the problem of a common concern in the world.Phase-changing energy storage material can be used for the contradiction solving heat energy Supply and Demand; be the important materials improving efficiency of energy utilization and environmental protection, it has in fields such as Solar use, energy recovery, phase change energy-storage type air-conditioning, warmth-retaining clothing, energy storage cooker, building energy conservation, Aero-Space and agriculturals applies very widely.At present to the research of phase-changing energy storage material, oneself obtains larger progress, but more or less to there is chemical stability poor for these materials, the shortcomings such as Long-Time Service easily leaks, and enthalpy of phase change is on the low side, and heat accumulation effect is bad.So develop a kind of polymer solid-solid phase transition energy storage material of good performance, will have great application prospect and practical value.Polyurethanes phase-changing energy storage material is the material that a class is also being developed, and it utilizes the fuel factor in material phase transition process to realize storage and the release of energy, and phase transition process is a kind of transformation from solid to solid.Large except having common phase-change material energy storage density, heat accumulation, exothermic process are similar to isothermal, outside the advantages such as process is easy to control, it also has processing characteristics that macromolecular material is good and polyurethane material high mechanical properties, the excellent properties such as corrosion-resistant, is therefore expected to become a kind of phase-changing energy storage material having value.
At present, the common method preparing phase-change energy-storage fibre prepares phase-change accumulation energy nonwoven fabric by method of electrostatic spinning, although have good phase-change accumulation energy performance, it does not have spinnability.Another kind of common method prepares phase-change accumulation energy viscose with microcapsule method, but its mechanical property is poor, and the fabric therefore made easily extends, poor dimensional stability, and wearability is not strong.
Summary of the invention
The object of the invention is the shortcoming overcoming existing phase-change energy-storage fibre, provide a kind of phase-change accumulation energy effective, also there is the phase-change accumulation energy the weaved polyster fibre of higher mechanical strength and good wearability simultaneously.
Another object of the present invention is 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 take terylene as carrier, polyethylene glycol based polyurethanes is phase-changing energy storage material, by described phase-changing energy storage material and terylene melt blending, and be prepared from melt spinning method, the phase-change accumulation energy polyster fibre that terylene carrier accounts for total fiber mass 50 ~ 95%, phase-changing energy storage material accounts for total fiber mass 5 ~ 50%.
The present invention passes through blend melt spinning, described phase-changing energy storage material is coated on the inside of terylene carrier, preparing can woven phase-change accumulation energy polyster fibre, the fibre strength 2 ~ 10cN/dtex of described phase-change accumulation energy polyster fibre, phase transition temperature-10 ~ 100 DEG C, enthalpy of phase change 10 ~ 100kJ/kg.
Polyethylene glycol based polyurethanes phase-changing energy storage material of the present invention is soft section with the good polyethylene glycol of crystal property, with isocyanates, 1,4-butanediol is the polymer solid-solid phase transition energy storage material with polyurethane structural of hard section synthesis, wherein, polyethylene glycol, isocyanates are 1: 0.01 ~ 2: 0.01 ~ 2 with the material quality ratio of BDO.Phase-changing energy storage material of the present invention utilizes the crystallization of soft section-melting change to realize storage and the release of energy, finally obtains the phase-changing energy storage material that a kind of decomposition temperature is greater than PET spinning temperature.
Further, in phase-changing energy storage material of the present invention, the number-average molecular weight of described polyethylene glycol is 200 ~ 20000; Described isocyanates is toluene di-isocyanate(TDI) (TDI), methyl diphenylene diisocyanate (MDI), non-yellow stain type 1, the one in the isocyanates such as hexamethylene-diisocyanate (HDI).
Phase-changing energy storage material of the present invention can adopt following methods to prepare: polyethylene glycol and isocyanates are dissolved in organic solvent; under inert gas shielding, 40 ~ 80 DEG C are reacted 0.5 ~ 5 hour; add 1 again; 4-chain expansion of succinic acid reaction 0.5 ~ 4 hour, evaporation is reclaimed organic solvent and is obtained solid polyurethane type phase-changing energy storage material.
Wherein preferably, described organic solvent is the one in acetone, butanone, ethyl acetate, chloroform, glycerin ether, dioxane, glyceride or aromatic hydrocarbon etc.
The present invention by terylene carrier master batch and phase-changing energy storage material blended with described mass percentage after, add in double screw extruder, prepare co-blended spinning master batch, and then co-blended spinning master batch joined in melt spinning machine form melt, melt extrudes formation melt stream by spinneret orifice, after Air flow solidification, form as-spun fibre, as-spun fibre is again through oiling, reeling, after the post processing such as drawing-off, make and of the present inventionly weave phase-change accumulation energy polyster fibre.
The present invention can also adopt following methods to carry out post processing to the phase-change accumulation energy polyster fibre prepared: the modified amido organosilicon aqueous solution of preparation 0.5 ~ 15wt%, adjust ph to 6 is made and is arranged bath, by phase-change accumulation energy polyster fibre according to 1: 10 bath raio add described arrangement bath in process 5 ~ 45min, after taking out dehydration, 65 ~ 100 DEG C of constant temperature dryings.
The phase transition temperature of the phase-change accumulation energy weaved polyster fibre prepared by the present invention-10 ~ 100 DEG C, enthalpy of phase change 10 ~ 100kJ/kg, and do not change fiber trait before and after phase transformation, there is not Small molecular to reveal, phase transition temperature and enthalpy of phase change can be changed by the change molecular weight of polyethylene glycol and the kind of isocyanates.Meanwhile, the phase-changing energy storage material adopted due to the present invention is polyurethanes, has good compatibility with polyester fiber (terylene).
The phase-change accumulation energy weaved polyster fibre prepared by the present invention compared with prior art, has the following advantages and effect.
1) the present invention can weave the thermally-stabilised good of phase-change accumulation energy polyster fibre, and large molecule phase-changing energy storage material is dispersed in terylene matrix uniformly, there is not the leakage problem of Small molecular phase-change material, and appearance stablity, good mechanical property.
2) the present invention can weave the characteristic that phase-change accumulation energy polyster fibre has polyster fibre and phase-change accumulation energy simultaneously, not only can be applied to each field as functional material, can also weave, using as taking material.
3) phase-change accumulation energy the weaved polyster fibre fiber number 1 ~ 10dtex prepared by the present invention, single fiber brute force higher (2 ~ 10CN/dtex), feel is smooth, easily paints, and is the fibre in differentiation that a kind of wearability is excellent.
4) preparation technology of the present invention is simple, workable.
Accompanying drawing explanation
Fig. 1 is the DSC figure 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.
Detailed description of the invention
Summary of the invention of the present invention is set forth further below in conjunction with specific embodiment.Described embodiment only for technical conceive of the present invention and feature are described, can not limit the scope of the invention with this.All equivalences on basis of the present invention change or modify, and all should be encompassed within protection scope of the present invention.
Embodiment 1
Get 100g Macrogol 2000,15g methyl diphenylene diisocyanate (MDI) is dissolved in 500ml ethyl acetate, N
2be warming up to 40 DEG C of stirring reactions 3 hours under protection, then add 5g BDO, carry out chain extending reaction 2 hours, ethyl acetate is reclaimed in evaporation, obtains solid polyurethane type phase-changing energy storage material polyethylene glycol based polyurethanes.
Get 400g dacron master grain, add together with 100g phase-changing energy storage material in double screw extruder, preparation spinning master batch, then co-blended spinning master batch is joined in melt spinning machine, melt extrudes formation melt stream by spinneret orifice, final melt stream cooling curing forms as-spun fibre, and as-spun fibre oils, reel, namely obtainedly after drawing-off can weave phase-change accumulation energy polyster fibre.Phase-change material, by melt blending, is covered by the inside of terylene matrix.
Can weave phase-change accumulation energy polyster fibre with 1: 10 bath raio pass in the Final finishing liquid of 35 DEG C, take out after post processing 30min, dehydration, 70 DEG C of constant temperature dryings, obtain the soft phase-change accumulation energy weaved polyster fibre.Described Final finishing liquid contains 4% modified amido silicone softening agent, and is adjusted to pH=6 with glacial acetic acid.
Phase-change accumulation energy polyster fibre single fiber intensity 5.2CN/dtex prepared by the present embodiment, elongation at break 17%.
Fig. 1 is intensification and the cooling DSC curve of the phase-change accumulation energy the weaved polyster fibre that the present embodiment prepares.This curve shows, the phase transition performance can weaving phase-change accumulation energy polyster fibre is reversible, and about 18 DEG C start heat absorption, occur endothermic peak, start heat release when temperature drops to about 12 DEG C, about-5 DEG C time, occur exothermic peak at about 28 DEG C.Transition temperature range-10 ~ 32 DEG C, enthalpy of phase change is about 28.76kJ/kg.
Embodiment 2
Get 300g Macrogol 6000,15g methyl diphenylene diisocyanate (MDI) is dissolved in 1000ml toluene, N
2be warming up to 50 DEG C of stirring reactions 3 hours under protection, then add 5g BDO, carry out chain extending reaction 2 hours, toluene is reclaimed in evaporation, obtains solid polyurethane type phase-changing energy storage material polyethylene glycol based polyurethanes.
Get 350g dacron master grain, add together with 150g phase-changing energy storage material in double screw extruder, preparation spinning master batch (fiber-forming polymer is cut into slices melting or obtain melt by continuous polymerization), then co-blended spinning master batch is joined in melt spinning machine, melt extrudes formation melt stream by spinneret orifice, final melt stream cooling curing forms as-spun fibre, and as-spun fibre oils, reel, namely obtainedly after drawing-off can weave phase-change accumulation energy polyster fibre.
Can weave phase-change accumulation energy polyster fibre with 1: 10 bath raio pass in the Final finishing liquid of 35 DEG C, take out after post processing 30min, dehydration, 70 DEG C of constant temperature dryings, obtain the soft phase-change accumulation energy weaved polyster fibre.Described Final finishing liquid contains 4% modified amido silicone softening agent, and is adjusted to pH=6 with glacial acetic acid.
Phase-change accumulation energy polyster fibre single fiber intensity 4.5CN/dtex prepared by the present embodiment, elongation at break 19%.Transition temperature range 0 ~ 35 DEG C, enthalpy of phase change is about 46.8kJ/kg.
Embodiment 3
Get 400g PEG 8000,15g toluene di-isocyanate(TDI) (TDI) is dissolved in 1000ml acetone, N
2be warming up to 60 DEG C of stirring reactions 1 hour under protection, then add 5g BDO, carry out chain extending reaction 1 hour, acetone is reclaimed in evaporation, obtains solid polyurethane type phase-changing energy storage material polyethylene glycol based polyurethanes.
Get 300g dacron master grain, add together with 100g phase-changing energy storage material in double screw extruder, preparation spinning master batch, then co-blended spinning master batch is joined in melt spinning machine, melt extrudes formation melt stream by spinneret orifice, final melt stream cooling curing forms as-spun fibre, and as-spun fibre oils, reel, namely obtainedly after drawing-off can weave phase-change accumulation energy polyster fibre.
Can weave phase-change accumulation energy polyster fibre with 1: 10 bath raio pass in the Final finishing liquid of 35 DEG C, take out after post processing 30min, dehydration, 70 DEG C of constant temperature dryings, obtain the soft phase-change accumulation energy weaved polyster fibre.Described Final finishing liquid contains 4% modified amido silicone softening agent, and is adjusted to pH=6 with glacial acetic acid.
Phase-change accumulation energy polyster fibre single fiber intensity 3.6CN/dtex prepared by the present embodiment, elongation at break 22%.Transition temperature range 10 ~ 40 DEG C, enthalpy of phase change is about 72.8kJ/kg.
Claims (8)
1. can weave phase-change accumulation energy polyster fibre for one kind, take terylene as carrier, polyethylene glycol based polyurethanes is phase-changing energy storage material, by described phase-changing energy storage material and terylene melt blending, and with the fiber that melt spinning method is prepared from, wherein said terylene carrier accounts for 50 ~ 95% of total fiber mass, and phase-changing energy storage material accounts for 5 ~ 50% of total fiber mass; Fibre strength 2 ~ the 10cN/dtex of described phase-change accumulation energy polyster fibre, phase transition temperature-10 ~ 100 DEG C, enthalpy of phase change 10 ~ 100kJ/kg.
2. according to claim 1ly weave phase-change accumulation energy polyster fibre, wherein said polyethylene glycol based polyurethanes phase-changing energy storage material is soft section with polyethylene glycol, with isocyanates, 1,4-butanediol is hard section, according to polyethylene glycol, isocyanates and the material quality ratio of BDO be 1: 0.01 ~ 2: 0.01 ~ 2-in-1 become the polymer solid-solid phase transition energy storage material with polyurethane structural.
3. according to claim 2ly weave phase-change accumulation energy polyster fibre, it is characterized in that the number-average molecular weight of described polyethylene glycol is 200 ~ 20000.
4. according to claim 2ly weave phase-change accumulation energy polyster fibre, it is characterized in that described isocyanates is toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, non-yellow stain type 1, the one in hexamethylene-diisocyanate.
5. according to claim 2ly weave phase-change accumulation energy polyster fibre; it is characterized in that described phase-changing energy storage material adopts following methods to prepare: polyethylene glycol and isocyanates are dissolved in organic solvent; under inert gas shielding, 40 ~ 80 DEG C are reacted 0.5 ~ 5 hour; add 1 again; 4-chain expansion of succinic acid reaction 0.5 ~ 4 hour, evaporation is reclaimed organic solvent and is obtained solid polyurethane type phase-changing energy storage material.
6. according to claim 5ly weave phase-change accumulation energy polyster fibre, it is characterized in that described organic solvent is the one in acetone, butanone, ethyl acetate, chloroform, glycerin ether, dioxane, glyceride or aromatic hydrocarbon.
7. the preparation method of the phase-change accumulation energy the weaved polyster fibre described in any one of claim 1 ~ 6, be by terylene carrier master batch and phase-changing energy storage material blended with described mass percentage after add in double screw extruder and prepare co-blended spinning master batch, again co-blended spinning master batch is formed melt in melt spinning machine, formation melt stream is extruded by spinneret orifice, as-spun fibre is solidify to form through Air flow, again through oiling, reel, drawing-off, make and can weave phase-change accumulation energy polyster fibre.
8. the preparation method of phase-change accumulation energy polyster fibre according to claim 7, it is characterized in that also comprising following postprocessing working procedures: the modified amido organosilicon aqueous solution of preparation 0.5 ~ 15wt%, adjust ph to 6 is made and is arranged bath, by phase-change accumulation energy polyster fibre according to 1: 10 bath raio add described arrangement bath in process 5 ~ 45min, after taking out dehydration, 65 ~ 100 DEG C of constant temperature dryings.
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| 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 |
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| 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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| 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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