CN104911747B - A kind of elastic energy storage phase change fiber and preparation method thereof - Google Patents
A kind of elastic energy storage phase change fiber and preparation method thereof Download PDFInfo
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- CN104911747B CN104911747B CN201510299183.6A CN201510299183A CN104911747B CN 104911747 B CN104911747 B CN 104911747B CN 201510299183 A CN201510299183 A CN 201510299183A CN 104911747 B CN104911747 B CN 104911747B
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Abstract
The invention provides a kind of elastic energy storage phase change fiber and preparation method thereof.Described elastic energy storage phase change fiber, it is characterized in that, including Part I and Part II, described Part II is inside Part I, described Part I is made up of the raw material comprising spinning-grade polymer, described spinning-grade polymer is polyurethane or polyolefin elastomer, described Part II is by comprising matrix polymer, phase change medium, foaming agent azodicarbonamide, activator and assistant crosslinking agent are made in interior raw material, described Part II has hole-closing structure, described phase change medium is distributed in hole-closing structure and hole-closing structure between.Elastic energy storage phase change fiber prepared by the present invention has imitation leather cored structure, and its sandwich layer has a uniform hole-closing structure, and phase transformation medium storing is in closed pore space or being embedded in the middle of hole wall.Closed pore in the structure both can seal air up for safekeeping again with grappling phase change medium, reach the effect of insulation cooperative effect.
Description
Technical field
The invention belongs to the preparation field of intelligent temperature adjusting fiber, more particularly to a kind of elastic energy storage phase change fiber and its preparation
Method.
Background technology
With the continuing to develop of social demand, the increasingly change of living environment, people are to taking and household textiles is proposed
The demand of multifunctional intelligent.In terms of the comfortableness of skin contact, human body warm is particularly important.Warming-type intelligent thermoregulating is fine
Dimension can utilize fiber itself to the storage of heat and discharge to reach the purpose of microenvironment between regulation human body and fabric, and have
The energy-saving and temperature-regulating fiber of spring function can be combined with conventional fibre, prepare the energy-storage thermal-insulating fabric with high-elastic characteristic.
The preparation method of current thermo-regulated fiber has microcapsules wet spinning process, doughnut completion method, fiber surface
Completion method etc..There is the drawbacks of preparation process pollution is big, and operation is numerous and diverse in microcapsules wet spinning process；Doughnut completion method,
Have the shortcomings that phase-change material is easily revealed；There is the defect of washability difference in fiber surface coating.Patent of invention CN
Doughnut is put into hopper by 103710964 A, carries out the filling of phase-change material, and the end-blocking of its fiber ends has problem.
The B of patent of invention CN 101906670 disclose spinning equipment and its preparation side of a kind of melt-spun type solid-liquid composite phase change fiber
Method, fibrous inside is directly stored in by liquid state phase change material in liquid form, and liquid state phase change material fusingization there is also shakiness
Fixed problem.
The content of the invention
The technical problems to be solved by the invention are to provide a kind of elastic energy storage phase change fiber and preparation method thereof, the method
The fibre section of preparation is rendered as imitation leather cored structure, and its sandwich layer has uniform hole-closing structure, and phase transformation medium storing is in closed pore space
It is interior or be embedded in the middle of hole wall.Elastic energy storage temperature-regulating fiber of the invention has low cost, pollute that small, enthalpy is high, energy-saving and temperature-regulating
The strong advantage of ability, can preferably apply in the functional modification field of elastomer, meet chemical fibre industry Production requirement.
In order to solve the above problems, the invention provides a kind of elastic energy storage phase change fiber, it is characterised in that including first
Part and Part II, inside Part I, described Part I is polymerized described Part II by comprising spinning-grade
Thing is made in interior raw material, and described spinning-grade polymer is polyurethane or polyolefin elastomer, and described Part II is by wrapping
Containing matrix polymer, phase change medium, foaming agent azodicarbonamide, activator and assistant crosslinking agent in interior raw material system
Into described Part II has hole-closing structure, and described phase change medium is distributed in hole-closing structure and hole-closing structure between.
Preferably, it is cortex that described Part I and Part II constitute Part I, and Part II is the skin of sandwich layer
Cored structure.
Preferably, described matrix polymer is polyurethane, polyolefin elastomer or polyethylene.
Preferably, melting temperature is 90~130 DEG C to described matrix polymer at one atm.
Preferably, described phase change medium is polyethylene glycol, paraffin, stearic acid, laurate, SA, polyethyleneglycol
In acrylate, stearyl chloride, lauroyl chloride and certain herbaceous plants with big flowers diacid chloride one or more.
Preferably, described assistant crosslinking agent is cumyl peroxide or di-tert-butyl peroxide.
Preferably, the weight ratio of described Part I and Part II is 1/3~9/1.
Preferably, the raw material of described Part II by, 20~60wt% of phase change medium, foaming agent azodicarbonamide
0.5~5%, the matrix polymer composition of activator 0.5~1%, assistant crosslinking agent 0.2~1% and surplus,
Preferably, the hole ratio of described uniform hole-closing structure is 20~50%, and aperture is 0.1~1 μm.
Present invention also offers the preparation method of above-mentioned elastic energy storage phase change fiber, it is characterised in that including：By first
Partial raw material and the raw material of Part II have two single screw rods using the composite spinning systems addition with two single screw rods
Composite spinning system in, carry out melt spinning using bi-component sheath-core filament spinning component, obtain elastic energy storage phase change fiber.
The method that the present invention utilizes imitation leather cored structure bicomponent fibre is right using uniform hole-closing structure in core structure
Phase transformation medium is sealed up for safekeeping, and partial phase change material can be directly embedded in the middle of hole wall.
Compared with prior art, the beneficial effects of the invention are as follows：
(1) elastic energy storage phase change fiber prepared by the present invention has imitation leather cored structure, and its sandwich layer has uniform hole-closing structure,
Phase transformation medium storing is in closed pore space or being embedded in the middle of hole wall.Closed pore in the structure both can with grappling phase change medium, and
Air can be sealed up for safekeeping, the effect of insulation cooperative effect is reached.
(2) elastic energy storage phase change fiber of the invention has low cost, pollutes that small, enthalpy is high, energy-saving and temperature-regulating ability is strong
Advantage, can preferably apply in the functional modification field of elastomer, meet chemical fibre industry Production requirement.
Brief description of the drawings
Fig. 1 a are the imitation leather cored structure schematic diagram of the elastic energy storage phase change fiber prepared by the present invention.
Fig. 1 b are the imitation leather cored structure sectional view of the elastic energy storage phase change fiber prepared by the present invention.
In figure, 1 is Part I, 2 is Part II, and 3 is phase change medium.
Specific embodiment
With reference to specific embodiment, the present invention is expanded on further.It should be understood that these embodiments are merely to illustrate the present invention
Rather than limitation the scope of the present invention.In addition, it is to be understood that after the content for having read instruction of the present invention, people in the art
Member can make various changes or modifications to the present invention, and these equivalent form of values equally fall within the application appended claims and limited
Scope.Polyethylene glycol monoacrylate described in various embodiments of the present invention is closed with reference to the B of national inventing patent CN 102516471
Into its number-average molecular weight is 1000~10000.Phase transformation enthalpy in various embodiments of the present invention is determined by DSC and obtained.
Embodiment 1
As seen in figure la and lb, it is a kind of elastic energy storage phase change fiber, is made up of Part I 1 and Part II 2, it is described
Part II 2 inside the Part I 1, described Part I 1 is made up of the raw material comprising spinning-grade polymer,
Described Part II 2 is by comprising matrix polymer, phase change medium, foaming agent azodicarbonamide, activator and helping
Crosslinking agent is made in interior raw material, and described Part II 2 has hole-closing structure, and described phase change medium 3 is distributed in described
In hole-closing structure and hole-closing structure between.
It is cortex that described Part I and Part II constitute Part I, and Part II is the skin-core structure of sandwich layer.
Described spinning-grade polymer is polyurethane, and melting temperature is 130 DEG C poly- at one atm for described matrix polymer
Olefin elastomer.Described phase change medium is polyethylene glycol monoacrylate.Described assistant crosslinking agent is cumyl peroxide.
The preparation method of above-mentioned elastic energy storage phase change fiber is：First, with two composite spinning systems of single screw rod
50 parts by weight of polyurethane are added to cut into slices in first single screw rod of system, with two second lists of the composite spinning system of single screw rod
The polyethylene glycol monoacrylate of 30 weight portions, the azodicarbonamide of 2.5 weight portions, 0.5 weight portion is added to receive in screw rod
Rice zinc oxide (50~200nm of particle diameter), the cumyl peroxide of 0.5 weight portion, the fusing point of 16.5 weight portions are 130 DEG C of polyenes
The pre-composition of olefin elastomer, wherein the head pressure of the second single screw rod 0.5~1MPa higher than the head pressure of the first single screw rod.So
Melt spinning is carried out using the bi-component sheath-core filament spinning component with two composite spinning systems of single screw rod afterwards, spinning temperature is
180~240 DEG C, spinning speed is 500~2000m/min, obtains elastic energy storage phase change fiber, and its center core layer hole ratio is for about
50% and aperture is about 1 μm of uniform hole-closing structure.Test discovery, prepares the phase transformation 10~25J/g of enthalpy of elastomer, elasticity
Response rate is 100%.
Embodiment 2
As seen in figure la and lb, it is a kind of elastic energy storage phase change fiber, is made up of Part I 1 and Part II 2, it is described
Part II 2 inside the Part I 1, described Part I 1 is made up of the raw material comprising spinning-grade polymer,
Described Part II 2 is by comprising matrix polymer, phase change medium, foaming agent azodicarbonamide, activator and helping
Crosslinking agent is made in interior raw material, and described Part II 2 has hole-closing structure, and described phase change medium 3 is distributed in described
In hole-closing structure and hole-closing structure between.
It is cortex that described Part I and Part II constitute Part I, and Part II is the skin-core structure of sandwich layer.
Described spinning-grade polymer is polyurethane, and melting temperature is 90 DEG C of poly- ammonia at one atm for described matrix polymer
Ester.Described phase change medium is polyethylene glycol (number-average molecular weight is 2000) and SA.Described assistant crosslinking agent is two tertiary fourths
Base peroxide.
The preparation method of above-mentioned elastic energy storage phase change fiber is：First, with two composite spinning systems of single screw rod
50 parts by weight of polyurethane are added to cut into slices in first single screw rod of system, with two second lists of the composite spinning system of single screw rod
Polyethylene glycol, the SA of 15 weight portions, the azodicarbonamide of 2.5 weight portions, 0.5 weight of 15 weight portions are added in screw rod
The nano zine oxide (50~200nm of particle diameter) of part, the di-tert-butyl peroxide of 0.5 weight portion, the fusing point of 16.5 weight portions are
90 DEG C of pre-compositions of polyurethane, wherein the head pressure of the second single screw rod 0.5~1MPa higher than the head pressure of the first single screw rod
Then melt spinning, spinning temperature are carried out using the bi-component sheath-core filament spinning component with two composite spinning systems of single screw rod
It is 180~240 DEG C, spinning speed is 500~2000m/min, obtains elastic energy storage phase change fiber, its center core layer hole ratio is
About 20% and aperture is about 0.1 μm of uniform hole-closing structure.Test discovery, prepares the 10~25J/ of phase transformation enthalpy of elastomer
G, elastic recovery rate is 100%.
Embodiment 3
As seen in figure la and lb, it is a kind of elastic energy storage phase change fiber, is made up of Part I 1 and Part II 2, it is described
Part II 2 inside the Part I 1, described Part I 1 is made up of the raw material comprising spinning-grade polymer,
Described Part II 2 is by comprising matrix polymer, phase change medium, foaming agent azodicarbonamide, activator and helping
Crosslinking agent is made in interior raw material, and described Part II 2 has hole-closing structure, and described phase change medium 3 is distributed in described
In hole-closing structure and hole-closing structure between.
It is cortex that described Part I and Part II constitute Part I, and Part II is the skin-core structure of sandwich layer.
Described spinning-grade polymer is polyurethane, and melting temperature is 100 DEG C poly- at one atm for described matrix polymer
Ethene.Described phase change medium is stearic acid.Described assistant crosslinking agent is cumyl peroxide.
The preparation method of above-mentioned elastic energy storage phase change fiber is：First, with two composite spinning systems of single screw rod
25 parts by weight of polyurethane are added to cut into slices in first single screw rod of system, with two second lists of the composite spinning system of single screw rod
Stearic acid, the azodicarbonamide of 2.25 weight portions, the nano zine oxide of 0.75 weight portion of 22.5 weight portions are added in screw rod
(50~200nm of particle diameter), the cumyl peroxide of 0.375 weight portion, the fusing point of 49.125 weight portions are 100 DEG C of polyethylene
Pre-composition, wherein the head pressure of the second single screw rod 0.5~1MPa higher than the head pressure of the first single screw rod.Then using having
The bi-component sheath-core filament spinning component of two composite spinning systems of single screw rod carries out melt spinning, and spinning temperature is 180~240
DEG C, spinning speed be 500~2000m/min, obtain elastic energy storage phase change fiber, its center core layer hole ratio be about 30% and
Aperture is about 0.5 μm of uniform hole-closing structure.Test discovery, prepares the phase transformation 8~20J/g of enthalpy of elastomer, elastic recovery rate
It is 100%.
Embodiment 4
As seen in figure la and lb, it is a kind of elastic energy storage phase change fiber, is made up of Part I 1 and Part II 2, it is described
Part II 2 inside the Part I 1, described Part I 1 is made up of the raw material comprising spinning-grade polymer,
Described Part II 2 is by comprising matrix polymer, phase change medium, foaming agent azodicarbonamide, activator and helping
Crosslinking agent is made in interior raw material, and described Part II 2 has hole-closing structure, and described phase change medium 3 is distributed in described
In hole-closing structure and hole-closing structure between.
It is cortex that described Part I and Part II constitute Part I, and Part II is the skin-core structure of sandwich layer.
Described spinning-grade polymer is polyolefin elastomer, and melting temperature is 90 DEG C to described matrix polymer at one atm
Polyurethane.Described phase change medium is stearyl chloride, lauroyl chloride.Described assistant crosslinking agent is cumyl peroxide.
The preparation method of above-mentioned elastic energy storage phase change fiber is：First, with two composite spinning systems of single screw rod
The 50 weight portion polyolefin elastomers are added to cut into slices in first single screw rod of system, with two composite spinning systems of single screw rod
Stearyl chloride, the lauroyl chloride of 10 weight portions, the formyl of azo two of 2.5 weight portions of 20 weight portions are added in second single screw rod
Amine, the nano zine oxide (50~200nm of particle diameter) of 0.5 weight portion, the cumyl peroxide of 0.5 weight portion, 16.5 weight portions
Fusing point be 90 DEG C polyurethane pre-composition, wherein the head pressure of the second single screw rod is higher than the head pressure of the first single screw rod
0.5~1MPa.Then melting spinning is carried out using the bi-component sheath-core filament spinning component with two composite spinning systems of single screw rod
Silk, spinning temperature is 150~180 DEG C, and spinning speed is 500~2000m/min, obtains elastic energy storage phase change fiber, its SMIS
Layer hole ratio is about 40% and aperture is about 0.8 μm of uniform hole-closing structure.Test discovery, prepares the enthalpy of phase change of elastomer
8~20J/g of value, elastic recovery rate is 100%.
Embodiment 5
As seen in figure la and lb, it is a kind of elastic energy storage phase change fiber, is made up of Part I 1 and Part II 2, it is described
Part II 2 inside the Part I 1, described Part I 1 is made up of the raw material comprising spinning-grade polymer,
Described Part II 2 is by comprising matrix polymer, phase change medium, foaming agent azodicarbonamide, activator and helping
Crosslinking agent is made in interior raw material, and described Part II 2 has hole-closing structure, and described phase change medium 3 is distributed in described
In hole-closing structure and hole-closing structure between.
It is cortex that described Part I and Part II constitute Part I, and Part II is the skin-core structure of sandwich layer.
Described spinning-grade polymer is polyurethane, and melting temperature is 95 DEG C of poly- ammonia to described matrix polymer at one atm
Ester.Described phase change medium is certain herbaceous plants with big flowers diacid chloride.Described assistant crosslinking agent is cumyl peroxide.
The preparation method of above-mentioned elastic energy storage phase change fiber is：First, with two composite spinning systems of single screw rod
50 parts by weight of polyurethane are added to cut into slices in first single screw rod of system, with two second lists of the composite spinning system of single screw rod
Certain herbaceous plants with big flowers diacid chloride, the azodicarbonamide of 2.5 weight portions, the nano zine oxide (grain of 0.5 weight portion of 30 weight portions are added in screw rod
50~200nm of footpath), the cumyl peroxide of 0.5 weight portion, the fusing point of 16.5 weight portions be 95 DEG C of pre-compositions of polyurethane,
The wherein head pressure of the second single screw rod 0.5~1MPa higher than the head pressure of the first single screw rod.Then using with two lists
The bi-component sheath-core filament spinning component of the composite spinning system of screw rod carries out melt spinning, and spinning temperature is 180~240 DEG C, spinning
Speed is 500~2000m/min, obtains elastic energy storage phase change fiber, and its center core layer hole ratio is that about 45% and aperture are about
1 μm of uniform hole-closing structure.Test finds that prepare the phase transformation 12~25J/g of enthalpy of elastomer, elastic recovery rate is 100%.
Claims (6)
1. a kind of elastic energy storage phase change fiber, it is characterised in that including Part I and Part II, described Part II
Inside Part I, described Part I is made up of the raw material comprising spinning-grade polymer, described spinning-grade
Polymer is polyurethane or polyolefin elastomer, and described Part II is by 20~60wt% of phase change medium, foaming agent azo two
The matrix polymer of formamide 0.5~5%, activator 0.5~1%, assistant crosslinking agent 0.2~1% and surplus is made,
Described Part II has hole-closing structure, and described phase change medium is distributed in hole-closing structure and hole-closing structure between；It is described
Matrix polymer be polyurethane, polyolefin elastomer or polyethylene；Described phase change medium is polyethylene glycol, paraffin, tristearin
In acid, laurate, SA, polyethylene glycol monoacrylate, stearyl chloride, lauroyl chloride and certain herbaceous plants with big flowers diacid chloride one or more；
The hole ratio of uniform hole-closing structure is 20~50%, and aperture is 0.1~1 μm；The preparation method of the elastic energy storage phase change fiber
For：During the raw material of the raw material of Part I and Part II is added with two composite spinning systems of single screw rod, wherein the
The head pressure of two single screw rods 0.5~1MPa higher than the head pressure of the first single screw rod, then using having two single screw rods
The bi-component sheath-core filament spinning component of composite spinning system carries out melt spinning, and spinning temperature is 180~240 DEG C, and spinning speed is
500~2000m/min, obtains elastic energy storage phase change fiber.
2. elastic energy storage phase change fiber as claimed in claim 1, it is characterised in that described Part I and Part II structure
It is cortex into Part I, Part II is the skin-core structure of sandwich layer.
3. elastic energy storage phase change fiber as claimed in claim 1, it is characterised in that described matrix polymer is in an air
Pressure melting temperature is 90~130 DEG C.
4. elastic energy storage phase change fiber as claimed in claim 1, it is characterised in that described assistant crosslinking agent is that peroxidating two is different
Propyl benzene or di-tert-butyl peroxide.
5. elastic energy storage phase change fiber as claimed in claim 1, it is characterised in that described Part I and Part II
Weight ratio is 1/3~9/1.
6. the preparation method of the elastic energy storage phase change fiber any one of claim 1-5, it is characterised in that including：Will
During the raw material of Part I and the raw material of Part II are added with two composite spinning systems of single screw rod, wherein second single spiral shell
The head pressure of bar 0.5~1MPa higher than the head pressure of the first single screw rod, then using with two Compound spinnings of single screw rod
The bi-component sheath-core filament spinning component of silk system carries out melt spinning, and spinning temperature is 180~240 DEG C, and spinning speed is 500~
2000m/min, obtains elastic energy storage phase change fiber.
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| WO2021003236A1 (en) * | 2019-07-03 | 2021-01-07 | Lubrizol Advanced Materials, Inc. | Bicomponent thermoplastic polyurethane fibers and fabrics made therfrom |
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| CN110067041B (en) * | 2019-01-28 | 2021-09-17 | 上海益弹新材料有限公司 | Wear-resistant elastic fiber and preparation method thereof |
| CN115074862B (en) * | 2022-06-22 | 2024-03-29 | 五邑大学 | Flexible phase-change energy storage sensing material with core-shell structure and preparation method and application thereof |
| CN115991944A (en) * | 2022-12-02 | 2023-04-21 | 苏州时分秒家纺整理有限公司 | Water-based phase change ink particles and preparation method and application thereof |
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| JP2000160450A (en) * | 1998-11-27 | 2000-06-13 | Unitika Ltd | Woven/knitted fabric with high moisture absorbability/ releasability and thermal insulation |
| US7160612B2 (en) * | 2000-09-21 | 2007-01-09 | Outlast Technologies, Inc. | Multi-component fibers having enhanced reversible thermal properties and methods of manufacturing thereof |
| EP1715089B1 (en) * | 2000-09-21 | 2014-03-05 | Outlast Technologies LLC | Multi-component fibers having reversible thermal properties |
| KR100696914B1 (en) * | 2000-10-19 | 2007-03-20 | 아웃래스트 테크날러지스 인코포레이티드 | Temperature adaptable textile fibers and method of preparing same |
| US8349920B2 (en) * | 2006-10-25 | 2013-01-08 | Dow Global Technologies Llc | Polyolefin dispersions, froths, and foams |
| CN201634800U (en) * | 2010-01-22 | 2010-11-17 | 东华大学 | Sheath-core composite fiber containing phase-change material for hair products |
| CN101906670B (en) * | 2010-08-26 | 2011-12-14 | 东华大学 | Melt spinning solid-liquid composite phase change fiber spinning equipment and preparation method thereof |
| CN103772963B (en) * | 2012-10-24 | 2016-01-20 | 中国石油化工股份有限公司 | A kind of phase-change accumulation energy polyurethane foam and preparation method thereof |
| CN103102552A (en) * | 2013-03-12 | 2013-05-15 | 泰山体育产业集团有限公司 | Phase-changed heat insulation polyolefin foam material and preparation method thereof |
| CN104195674B (en) * | 2014-09-02 | 2016-01-13 | 浙江华峰氨纶股份有限公司 | A kind of energy storage spandex fibre and preparation method thereof |
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