CN104894684A - Woven phase change energy storage polypropylene fiber - Google Patents
Woven phase change energy storage polypropylene fiber Download PDFInfo
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- CN104894684A CN104894684A CN201510384072.5A CN201510384072A CN104894684A CN 104894684 A CN104894684 A CN 104894684A CN 201510384072 A CN201510384072 A CN 201510384072A CN 104894684 A CN104894684 A CN 104894684A
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Abstract
The invention discloses a woven phase change energy storage polypropylene fiber. A polypropylene fiber serves as a carrier, polyethylene glycol polyurethane serves as a phase change energy storage material, the phase change energy storage material is coated by the polypropylene fiber through melt blending, and then the woven fiber is prepared through a melt spinning method. The polypropylene fiber carrier accounts for 50-95 percent of the total mass of the fiber, the phase change energy storage material accounts for 5-50 percent of the total mass of the fiber, the fiber strength of a phase change energy storage polyester fiber is 1-10cN/dtex, the phase change temperature is minus 10 to 100 DEG C, and the phase change enthalpy is 5-100kJ/kg. The thermal stability of the phase change energy storage polypropylene fiber is high, the strength of the phase change energy storage polypropylene fiber is higher than that of other phase change energy storage fibers, and the phase change energy storage polypropylene fiber is higher in strength and higher in wearability.
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
Polypropylene fibre is the synthetic fiber that raw material spinning is made with isotactic polypropylene, is kind the lightest in chemical synthetic fiber, intensity 35 ~ 62cN/dtex, ABRASION RESISTANCE is only second to polyamide fiber, and corrosion resistance is good, especially fine to the stability of inorganic acid, alkali, not mouldy, without putrefaction, is not afraid of and damages by worms.
Polypropylene fibre product is mainly used in decorating cloth and industrial circle, such as various UPHOLSTERY FABRIC, bunting, carpet, building reinforcing material, geotextiles, asphalt felt, conveyer belt rope, fishery apparatus, packaging material and filter cloth etc., also can be used for manufacturing various coat, underwear, swimsuit, sweater, socks and cotton for wadding etc.
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, what also have higher mechanical strength and a good wearability can woven phase-change accumulation energy polypropylene fibre simultaneously.
Another object of the present invention is to provide the preparation method of above-mentioned phase-change accumulation energy polypropylene fibre.
Provided by the present invention can woven phase-change accumulation energy polypropylene fibre be take polypropylene fibre as carrier, polyethylene glycol based polyurethanes is phase-changing energy storage material, described phase-changing energy storage material is coated on carrier inside by melt blending, with the fiber that melt spinning method is prepared into, the phase-change accumulation energy polyster fibre that wherein polypropylene fibre 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 polypropylene fibre carrier, preparing can woven phase-change accumulation energy polypropylene fibre, the fibre strength 1 ~ 10cN/dtex of described phase-change accumulation energy polypropylene fibre, phase transition temperature-10 ~ 100 DEG C, enthalpy of phase change 5 ~ 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: 0.1 ~ 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 polypropylene fibre 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 polypropylene fibre carrier master batch and phase-changing energy storage material blended with described mass percentage after, add in high temperature double-screw rod 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 again through oiling, reeling, after the post processing such as drawing-off, make of the present invention can woven phase-change accumulation energy polypropylene fibre.
The present invention can also adopt following methods to carry out post processing to the phase-change accumulation energy polypropylene 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 polypropylene 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.
Prepared by the present invention can the phase transition temperature-10 ~ 100 DEG C of woven phase-change accumulation energy polypropylene fibre, enthalpy of phase change 5 ~ 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 polypropylene fiber.
The present invention prepare can woven phase-change accumulation energy polypropylene fibre compared with prior art, have the following advantages and effect.
1) the present invention can woven phase-change accumulation energy polypropylene fibre thermally-stabilised good, large molecule phase-changing energy storage material is dispersed in polypropylene fibre 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 have the characteristic of polypropylene fiber and phase-change accumulation energy by woven phase-change accumulation energy polypropylene fibre simultaneously, not only can be applied to each field as functional material, can also weave, using as taking material.
3) prepared by the present invention can woven phase-change accumulation energy polypropylene fiber fiber number 1 ~ 10dtex, single fiber brute force higher (1 ~ 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 be the embodiment of the present invention 1 prepare can woven phase-change accumulation energy polypropylene fibre DSC figure.
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 polypropylene fibre master batch, 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, as-spun fibre oils, reel, namely obtained after drawing-off can woven phase-change accumulation energy polypropylene fibre.Phase-change material, by melt blending, is covered by the inside of polypropylene fibre matrix.
Can woven phase-change accumulation energy polypropylene 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 soft can woven phase-change accumulation energy polypropylene 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 polypropylene fibre single fiber intensity 6.4CN/dtex prepared by the present embodiment, elongation at break 25%.
Fig. 1 be the present embodiment prepare can the intensification of woven phase-change accumulation energy polypropylene fibre and cooling DSC curve.This curve shows, can the phase transition performance of woven phase-change accumulation energy polypropylene fibre be reversible, and about 32.5 DEG C start heat absorption, occur endothermic peak, start heat release when temperature drops to about 32 DEG C, about 27 DEG C time, occur exothermic peak at about 40.5 DEG C.Transition temperature range 18 ~ 45 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 500ml acetone, N
2be warming up to 50 DEG C of stirring reactions 2 hours under protection, then add 5g BDO, carry out chain extending reaction 2 hours, acetone is reclaimed in evaporation, obtains solid polyurethane type phase-changing energy storage material polyethylene glycol based polyurethanes.
Get 700g polypropylene fibre master batch, add together with 300g 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, as-spun fibre oils, reel, namely obtained after drawing-off can woven phase-change accumulation energy polypropylene fibre.
Can woven phase-change accumulation energy polypropylene 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 soft can woven phase-change accumulation energy polypropylene 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 polypropylene fibre single fiber intensity 4.5CN/dtex prepared by the present embodiment, elongation at break 20%.Transition temperature range 13 ~ 40 DEG C, enthalpy of phase change is about 48.2kJ/kg.
Embodiment 3
Get 400g PEG 8000,15g toluene di-isocyanate(TDI) (TDI) is dissolved in 1000ml toluene, N
2be warming up to 60 DEG C of stirring reactions 1 hour under protection, then add 10g BDO, carry out chain extending reaction 1 hour, toluene is reclaimed in evaporation, obtains solid polyurethane type phase-changing energy storage material polyethylene glycol based polyurethanes.
Get 600g polypropylene fibre master batch, add together with 400g 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, as-spun fibre oils, reel, namely obtained after drawing-off can woven phase-change accumulation energy polypropylene fibre.
Can weave phase-change accumulation energy polypropylene 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 soft can woven phase-change accumulation energy polypropylene 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 polypropylene fibre single fiber intensity 3.6CN/dtex prepared by the present embodiment, elongation at break 29%.Transition temperature range 8 ~ 37 DEG C, enthalpy of phase change is about 83.2kJ/kg.
Claims (8)
1. one kind can woven phase-change accumulation energy polypropylene fibre, take polypropylene fibre as carrier, polyethylene glycol based polyurethanes is phase-changing energy storage material, described phase-changing energy storage material is coated on carrier inside by melt blending, with the polypropylene fiber that melt spinning method is prepared into, wherein said polypropylene fibre carrier accounts for 50 ~ 95% of total fiber mass, and phase-changing energy storage material accounts for 5 ~ 50% of total fiber mass; The single fiber intensity 1 ~ 10cN/dtex of described phase-change accumulation energy polypropylene fibre, phase transition temperature-10 ~ 100 DEG C, enthalpy of phase change 5 ~ 100kJ/kg.
2. according to claim 1 can woven phase-change accumulation energy polypropylene 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 1, the material quality ratio of 4-butanediol is 1: 0.01 ~ 2: 0.1 ~ 2-in-1 one-tenth, has the polymer solid-solid phase transition energy storage material of polyurethane structural.
3. according to claim 2 can woven phase-change accumulation energy polypropylene fibre, it is characterized in that the number-average molecular weight of described polyethylene glycol is 200 ~ 20000.
4. according to claim 2 can woven phase-change accumulation energy polypropylene 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 2 can woven phase-change accumulation energy polypropylene 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 5 can woven phase-change accumulation energy polypropylene 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. described in any one of claim 1 ~ 6 can the preparation method of woven phase-change accumulation energy polypropylene fibre, be by polypropylene fibre carrier master batch and phase-changing energy storage material blended with described mass percentage after add in high temperature double-screw rod 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, making can woven phase-change accumulation energy polypropylene fibre.
8. according to claim 7 can the preparation method of woven phase-change accumulation energy polypropylene fibre, 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 polypropylene 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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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106273710A (en) * | 2016-08-11 | 2017-01-04 | 浙江金三发非织造布有限公司 | A kind of homoiothermic non-weaving cloth |
| CN106520077A (en) * | 2016-09-10 | 2017-03-22 | 北京工业大学 | Phase change energy storage fiber/SiO2 aerogel composite felt and preparation method thereof |
| CN107447319A (en) * | 2017-09-21 | 2017-12-08 | 成都新柯力化工科技有限公司 | A kind of stable phase-change temperature control textile fabric of dissaving polymer and preparation method |
| CN110004513A (en) * | 2019-04-12 | 2019-07-12 | 太原理工大学 | A kind of intelligent deformation polypropylene fiber and preparation method thereof |
| CN114262949A (en) * | 2021-12-28 | 2022-04-01 | 南通新帝克单丝科技股份有限公司 | Preparation method of heat-storage temperature-regulating polypropylene monofilament |
| CN114606597A (en) * | 2022-03-28 | 2022-06-10 | 浙江理工大学 | Preparation method of phase-change polyurethane fiber |
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2015
- 2015-07-03 CN CN201510384072.5A patent/CN104894684A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106273710A (en) * | 2016-08-11 | 2017-01-04 | 浙江金三发非织造布有限公司 | A kind of homoiothermic non-weaving cloth |
| CN106273710B (en) * | 2016-08-11 | 2019-10-29 | 浙江金三发卫生材料科技有限公司 | A kind of temperature adjustment non-woven cloth |
| CN106520077A (en) * | 2016-09-10 | 2017-03-22 | 北京工业大学 | Phase change energy storage fiber/SiO2 aerogel composite felt and preparation method thereof |
| CN107447319A (en) * | 2017-09-21 | 2017-12-08 | 成都新柯力化工科技有限公司 | A kind of stable phase-change temperature control textile fabric of dissaving polymer and preparation method |
| 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 |
| CN110004513A (en) * | 2019-04-12 | 2019-07-12 | 太原理工大学 | A kind of intelligent deformation polypropylene fiber and preparation method thereof |
| CN110004513B (en) * | 2019-04-12 | 2021-05-07 | 太原理工大学 | Intelligent deformation polypropylene fiber and preparation method thereof |
| CN114262949A (en) * | 2021-12-28 | 2022-04-01 | 南通新帝克单丝科技股份有限公司 | Preparation method of heat-storage temperature-regulating polypropylene monofilament |
| CN114606597A (en) * | 2022-03-28 | 2022-06-10 | 浙江理工大学 | Preparation method of phase-change polyurethane fiber |
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