CN104911724B - A kind of environment protection type energy storage temperature-regulating fiber and preparation method thereof - Google Patents
A kind of environment protection type energy storage temperature-regulating fiber and preparation method thereof Download PDFInfo
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- CN104911724B CN104911724B CN201510299133.8A CN201510299133A CN104911724B CN 104911724 B CN104911724 B CN 104911724B CN 201510299133 A CN201510299133 A CN 201510299133A CN 104911724 B CN104911724 B CN 104911724B
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Abstract
The invention provides a kind of environment protection type energy storage temperature-regulating fiber and preparation method thereof.Described environment protection type energy storage temperature-regulating fiber, it is characterized in that, including Part I and Part II, described Part II is inside Part I, described Part I comprising the raw material including spinning-grade polymer by being made, described Part II comprising the raw material including matrix polymer, phase change medium, foaming agent azodicarbonamide, activator and assistant crosslinking agent by being made, described Part II has hole-closing structure, and phase change medium is stored in hole-closing structure between hole-closing structure.Environment protection type energy storage temperature-regulating fiber prepared by the present invention has imitation leather cored structure or a double structure separation structures, and its sandwich layer or fibril have a uniform hole-closing structure, and phase transformation medium storing is in closed pore space or being embedded among 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 environment protection type energy storage temperature-regulating fiber and its system
Preparation Method.
Background technology
With the continuous development of social demand, the increasingly change of living environment, people to take and household textiles propose
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 reach the purpose of microenvironment between regulation human body and fabric using storage of the fiber itself to heat and release.
The preparation method of thermo-regulated fiber has microcapsules wet spinning process, doughnut completion method, fiber surface at present
Completion method etc..The drawbacks of preparation process pollution is big, and process is numerous and diverse be present in microcapsules wet spinning process；Doughnut completion method,
The shortcomings that phase-change material is easily revealed be present；The defects of washability difference be present 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, liquid state phase change material is directly stored in fibrous inside in liquid form, there is also shakiness for liquid state phase change material fusingization
The problem of determining.
The content of the invention
The technical problems to be solved by the invention are to provide a kind of environment protection type energy storage temperature-regulating fiber and preparation method thereof, the party
Fibre section prepared by method is rendered as imitation leather cored structure or double structure separation structures, and its sandwich layer or fibril have uniform hole-closing structure, phase
Become medium storing in closed pore space or being embedded among hole wall.The present invention Intelligent energy storage temperature-regulating fiber have cost it is low,
The advantages of small, enthalpy is high, energy-saving and temperature-regulating ability is strong is polluted, can preferably apply the functional modification neck in environment-friendly function fiber
Domain, meet chemical fibre industry production requirement.
In order to solve the above-mentioned technical problem, the invention provides a kind of environment protection type energy storage temperature-regulating fiber, it is characterised in that bag
Part I and Part II are included, described Part II is inside Part I, and described Part I is by including spinning
Raw material including level polymer is made, and described Part II is by including matrix polymer, phase change medium, foaming agent azo diformazan
Raw material including acid amides, activator and assistant crosslinking agent is made, and described Part II has hole-closing structure, phase change medium
It is stored in hole-closing structure between hole-closing structure.
Preferably, it is cortex that described Part I and Part II, which form Part I, and Part II is the skin of sandwich layer
Cored structure forms double structure separation structures that Part II is dispersed in inside Part I.
Preferably, described spinning-grade polymer is makrolon, PLA, polyhydroxyalkanoate and poly-succinic fourth
One kind in diol ester.
Preferably, described matrix polymer is the polymer that melting temperature is 90~130 DEG C at one atm.
Preferably, described matrix polymer is makrolon, PLA, polyhydroxyalkanoate or poly-succinic fourth two
Alcohol ester.
Preferably, described phase change medium is polyethylene glycol, paraffin, stearic acid, laurate, SA, polyethyleneglycol
It is one or more of in acrylate, stearyl chloride, lauroyl chloride and certain herbaceous plants with big flowers diacid chloride.
Preferably, described assistant crosslinking agent is cumyl peroxide or di-tert-butyl peroxide.
Preferably, the mass ratio of described Part I and Part II is 1/3~9/1.
Preferably, the raw material of described Part II is by 20~60wt% of phase change medium, foaming agent azodicarbonamide 0.5
~5wt%, 0.5~1wt% of activator, the matrix polymer composition of 0.2~1wt% of assistant crosslinking agent and surplus.
Preferably, the hole ratio of the hole-closing structure of described Part II is 20~50%, and aperture is 0.1~1 μm.
Present invention also offers the preparation method of above-mentioned environment protection type energy storage temperature-regulating fiber, it is characterised in that specific steps
Including：The raw material of the raw material of Part I and Part II is added in the composite spinning system with two single screw rods, used
Bicomponent fibre component or double structures divide fiber sprinning assembly to carry out melt spinning.
The present invention divides the method for fiber using imitation leather cored structure bicomponent fibre or double structures, utilizes sandwich layer or fibrillar structure
In uniform hole-closing structure, phase transformation medium is sealed up for safekeeping, and partial phase change material can be directly embedded among hole wall.
Compared with prior art, the beneficial effects of the invention are as follows：
(1) the environment protection type energy storage temperature-regulating fiber for preparing of the present invention has imitation leather cored structure or a double structure separation structures, its sandwich layer or
Fibril has a uniform hole-closing structure, and phase transformation medium storing is in closed pore space or being embedded among hole wall.Closed pore in the structure
Both air can be sealed up for safekeeping with grappling phase change medium again, and reached the effect of insulation cooperative effect.
(2) environment protection type energy storage temperature-regulating fiber of the invention has that cost is low, pollution is small, enthalpy is high, energy-saving and temperature-regulating ability is strong
The advantages of, it can preferably apply in the functional modification field of general fiber, meet chemical fibre industry production requirement.
Brief description of the drawings
Fig. 1 a are the skin-core structure schematic diagram of the environment protection type energy storage temperature-regulating fiber prepared by the present invention.
Fig. 1 b are the skin-core structure sectional view of the environment protection type energy storage temperature-regulating fiber prepared by the present invention.
Fig. 2 a are double structure separation structure schematic diagrames of the environment protection type energy storage temperature-regulating fiber prepared by the present invention.
Fig. 2 b are double structure separation structure sectional views of the environment protection type energy storage temperature-regulating fiber prepared by the present invention.
In figure, 1 it is Part I, 2 is Part II, 3 be phase change medium.
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 of the invention lectured has been read, 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 closes with reference to national inventing patent CN102516471B
Into its number-average molecular weight is 1000~10000.Phase transformation enthalpy in various embodiments of the present invention determines to obtain by DSC.
Embodiment 1
A kind of environment protection type energy storage temperature-regulating fiber, is made up of Part I and Part II, and described Part II is located at the
A part of internal, described Part I is made up of spinning-grade polymer, and described Part II is situated between by matrix polymer, phase transformation
Matter, foaming agent azodicarbonamide, activator and assistant crosslinking agent are made, and described Part II has hole-closing structure,
Phase change medium is stored in hole-closing structure between hole-closing structure.
It is cortex that described Part I and Part II, which form Part I, and Part II is the skin-core structure of sandwich layer.
Described spinning-grade polymer is makrolon.Described matrix polymer is 130 DEG C for melting temperature at one atm
Makrolon.Described phase change medium is polyethylene glycol monoacrylate.Described assistant crosslinking agent is cumyl peroxide.
The preparation method of above-mentioned environment protection type energy storage temperature-regulating fiber is：First, in the composite spinning system for having two single screw rods
The section of 50 weight part polycarbonates is added in first single screw rod of system, second in the composite spinning system for there are two single screw rods is single
The polyethylene glycol monoacrylates of 30 parts by weight, the azodicarbonamide of 2.5 parts by weight, 0.5 parts by weight are added in screw rod to receive
Rice zinc oxide (50~200nm of particle diameter), the cumyl peroxide of 0.5 parts by weight, the fusing point of 16.5 parts by weight are 130 DEG C of poly- carbon
The pre-composition of acid esters, wherein the head pressure of the second single screw rod is higher 0.5~1MPa than the head pressure of the first single screw rod.Using having
The bi-component sheath-core filament spinning component of the composite spinning system of two single screw rods carries out melt spinning and obtains environment protection type energy storage temperature adjustment fibre
Dimension, spinning temperature are 300~315 DEG C, and spinning speed is 500~3000m/min, as seen in figure la and lb, wherein Part II 2
Hole ratio for about 50% and aperture be about 1 μm of uniform hole-closing structure.Experiment finds that the phase transformation enthalpy for preparing fiber reaches
15~25J/g.
Embodiment 2
A kind of environment protection type energy storage temperature-regulating fiber, is made up of Part I and Part II, and described Part II is located at the
A part of internal, described Part I is made up of spinning-grade polymer, and described Part II is situated between by matrix polymer, phase transformation
Matter, foaming agent azodicarbonamide, activator and assistant crosslinking agent are made, and described Part II has hole-closing structure,
Phase change medium is stored in hole-closing structure between hole-closing structure.
It is cortex that described Part I and Part II, which form Part I, and Part II is the skin-core structure of sandwich layer.
Described spinning-grade polymer is PLA.Described matrix polymer is 90 DEG C of poly- carbon for melting temperature at one atm
Acid esters.Described phase change medium is polyethylene glycol (number-average molecular weight (2000~6000)) and SA.Described assistant crosslinking agent
For di-tert-butyl peroxide.
The preparation method of above-mentioned environment protection type energy storage temperature-regulating fiber is：First, in the composite spinning system for having two single screw rods
50 parts by weight polylactic acid slices are added in first single screw rod of system, in second single spiral shell of the composite spinning system for there are two single screw rods
The polyethylene glycol of 15 parts by weight, the SA of 15 parts by weight, the azodicarbonamide of 2.5 parts by weight, 0.5 parts by weight are added in bar
Nano zine oxide (50~200nm of particle diameter), the di-tert-butyl peroxide of 0.5 parts by weight, 16.5 parts by weight fusing point be 90
The pre-composition of DEG C makrolon, wherein the head pressure of the second single screw rod is higher 0.5~1MPa than the head pressure of the first single screw rod.
Melt spinning, which is carried out, using the bi-component sheath-core filament spinning component for the composite spinning system for there are two single screw rods obtains environment protection type energy storage
Temperature-regulating fiber, spinning temperature are 200~240 DEG C, and spinning speed is 500~3000m/min, as seen in figure la and lb, wherein the
The hole ratio of two parts 2 is about 20% and aperture is about 0.1 μm of uniform hole-closing structure.Experiment is found, prepares the phase transformation of fiber
Enthalpy reaches 6~15J/g.
Embodiment 3
A kind of environment protection type energy storage temperature-regulating fiber, is made up of Part I and Part II, and described Part II is located at the
A part of internal, described Part I is made up of spinning-grade polymer, and described Part II is situated between by matrix polymer, phase transformation
Matter, foaming agent azodicarbonamide, activator and assistant crosslinking agent are made, and described Part II has hole-closing structure,
Phase change medium is stored in hole-closing structure between hole-closing structure.
Described Part I and Part II form double structure separation structures that Part II is dispersed in inside Part I.Institute
The spinning-grade polymer stated is PLA.Described matrix polymer is 130 DEG C of poly- breasts for melting temperature at one atm
Acid.Described phase change medium is paraffin.Described assistant crosslinking agent is cumyl peroxide.
The preparation method of above-mentioned environment protection type energy storage temperature-regulating fiber is：First, in the composite spinning system for having two single screw rods
90 parts by weight polylactic acid slices are added in first single screw rod of system, in second single spiral shell of the composite spinning system for there are two single screw rods
The paraffin of 2 parts by weight, the azodicarbonamide of 0.05 parts by weight, the nano zine oxide (particle diameter 50 of 0.05 parts by weight are added in bar
~200nm), the cumyl peroxide of 0.02 parts by weight, 7.88 parts by weight fusing point for 130 DEG C of polylactic acid slices premix
Thing, wherein the head pressure of the second single screw rod is higher 0.5~1MPa than the head pressure of the first single screw rod.Using there is two single screw rods
Double structures of composite spinning system divide filament spinning component to carry out melt spinning to obtain environment protection type energy storage temperature-regulating fiber, spinning temperature is
200~240 DEG C, spinning speed is 500~3000m/min, as shown in figures 2 a and 2b, the wherein class fibrillar structure of Part II 2
Hole ratio is about 50% and aperture is about 1 μm of uniform hole-closing structure.Experiment finds, the phase transformation enthalpy for preparing fiber reaches 3~
10J/g。
Embodiment 4
A kind of environment protection type energy storage temperature-regulating fiber, is made up of Part I and Part II, and described Part II is located at the
A part of internal, described Part I is made up of spinning-grade polymer, and described Part II is situated between by matrix polymer, phase transformation
Matter, foaming agent azodicarbonamide, activator and assistant crosslinking agent are made, and described Part II has hole-closing structure,
Phase change medium is stored in hole-closing structure between hole-closing structure.
It is cortex that described Part I and Part II, which form Part I, and Part II is the skin-core structure of sandwich layer.
Described spinning-grade polymer is polyhydroxyalkanoate.Described matrix polymer is that melting temperature is at one atm
100 DEG C of polyhydroxyalkanoates.Described phase change medium is stearic acid.Described assistant crosslinking agent is cumyl peroxide.
The preparation method of above-mentioned environment protection type energy storage temperature-regulating fiber is：First, in the composite spinning system for having two single screw rods
The section of 25 parts by weight polyhydroxyalkanoates is added in first single screw rod of system, in the composite spinning system for there are two single screw rods
The middle stearic acid of 22.5 parts by weight, the azodicarbonamide of 2.25 parts by weight, 0.75 parts by weight of adding are received in second single screw rod
Rice zinc oxide (50~200nm of particle diameter), the cumyl peroxide of 0.375 parts by weight, the fusing point of 49.125 parts by weight are 100 DEG C
The pre-composition of polyhydroxyalkanoate, wherein the head pressure of the second single screw rod it is higher than the head pressure of the first single screw rod by 0.5~
1MPa.Melt spinning, which is carried out, using the bi-component sheath-core filament spinning component for the composite spinning system for there are two single screw rods obtains environment-friendly type
Energy-saving and temperature-regulating fiber, spinning temperature are 180~210 DEG C, and spinning speed is 500~3000m/min, as seen in figure la and lb, its
The hole ratio of middle Part II 2 is about 30% and aperture is about 0.5 μm of uniform hole-closing structure.Experiment is found, prepares fiber
Phase transformation enthalpy reaches 8~18J/g.
Embodiment 5
A kind of environment protection type energy storage temperature-regulating fiber, is made up of Part I and Part II, and described Part II is located at the
A part of internal, described Part I is made up of spinning-grade polymer, and described Part II is situated between by matrix polymer, phase transformation
Matter, foaming agent azodicarbonamide, activator and assistant crosslinking agent are made, and described Part II has hole-closing structure,
Phase change medium is stored in hole-closing structure between hole-closing structure.
It is cortex that described Part I and Part II, which form Part I, and Part II is the skin-core structure of sandwich layer.
Described spinning-grade polymer is polyhydroxyalkanoate.Described matrix polymer is that melting temperature is at one atm
90 DEG C of polyhydroxyalkanoate.Described phase change medium is stearyl chloride and lauroyl chloride.Described assistant crosslinking agent is peroxide
Change diisopropylbenzene (DIPB).
The preparation method of above-mentioned environment protection type energy storage temperature-regulating fiber is：First, in the composite spinning system for having two single screw rods
50 parts by weight polyhydroxyalkanoates of middle addition section in first single screw rod of system, in the composite spinning system for having two single screw rods
The second single screw rod in add the stearyl chloride of 20 parts by weight, the lauroyl chloride of 10 parts by weight, the formyl of azo two of 2.5 parts by weight
Amine, the nano zine oxide (50~200nm of particle diameter) of 0.5 parts by weight, the cumyl peroxide of 0.5 parts by weight, 16.5 parts by weight
Fusing point be 90 DEG C polyhydroxyalkanoate pre-composition, wherein machine of the head pressure of the second single screw rod than the first single screw rod
High 0.5~the 1MPa of head pressure.Melted using the bi-component sheath-core filament spinning component for the composite spinning system for there are two single screw rods
Spinning obtains environment protection type energy storage temperature-regulating fiber, and spinning temperature is 180~210 DEG C, and spinning speed is 500~3000m/min, is such as schemed
Shown in 1a and 1b, wherein the hole ratio of Part II 2 is about 40% and aperture is about 0.8 μm of uniform hole-closing structure.Experiment hair
Existing, the phase transformation enthalpy for preparing fiber reaches 15~25J/g.
Embodiment 6
A kind of environment protection type energy storage temperature-regulating fiber, is made up of Part I and Part II, and described Part II is located at the
A part of internal, described Part I is made up of spinning-grade polymer, and described Part II is situated between by matrix polymer, phase transformation
Matter, foaming agent azodicarbonamide, activator and assistant crosslinking agent are made, and described Part II has hole-closing structure,
Phase change medium is stored in hole-closing structure between hole-closing structure.
It is cortex that described Part I and Part II, which form Part I, and Part II is the skin-core structure of sandwich layer.
Described spinning-grade polymer is poly butylene succinate.Described matrix polymer is melting temperature at one atm
For 95 DEG C of poly butylene succinate.Described phase change medium is certain herbaceous plants with big flowers diacid chloride.Described assistant crosslinking agent is that peroxidating two is different
Propyl benzene.
The preparation method of above-mentioned environment protection type energy storage temperature-regulating fiber is：First, in the composite spinning system for having two single screw rods
The section of 50 parts by weight poly butylene succinates is added in first single screw rod of system, in the composite spinning system for there are two single screw rods
The second single screw rod in add the certain herbaceous plants with big flowers diacid chloride of 30 parts by weight, the azodicarbonamide of 2.5 parts by weight, the nanometer of 0.5 parts by weight
Zinc oxide (50~200nm of particle diameter), the cumyl peroxide of 0.5 parts by weight, the fusing point of 16.5 parts by weight are 95 DEG C of polybutadienes
The pre-composition of sour butanediol ester, wherein the head pressure of the second single screw rod is higher 0.5~1MPa than the head pressure of the first single screw rod.
Melt spinning, which is carried out, using the bi-component sheath-core filament spinning component for the composite spinning system for there are two single screw rods obtains environment protection type energy storage
Temperature-regulating fiber, spinning temperature are 250~290 DEG C, and spinning speed is 500~3000m/min, as seen in figure la and lb, wherein the
The hole ratio of two parts 2 is about 45% and aperture is about 1 μm of uniform hole-closing structure.Experiment is found, prepares the enthalpy of phase change of fiber
Value reaches 15~25J/g.
Claims (7)
- A kind of 1. environment protection type energy storage temperature-regulating fiber, it is characterised in that including Part I and Part II, described second It is divided into inside Part I, described Part I comprising the raw material including spinning-grade polymer by being made, and described second Partial raw material by 20~60wt% of phase change medium, 0.5~5wt% of foaming agent azodicarbonamide, activator 0.5~ 1wt%, 0.2~1wt% of assistant crosslinking agent and surplus matrix polymer composition, described Part II have hole-closing structure, phase Become medium to be stored in hole-closing structure between hole-closing structure；Closed pore can both be sealed up for safekeeping air, be made again with grappling phase change medium It reaches the effect of insulation cooperative effect；The hole ratio of the hole-closing structure of described Part II is 20 ~ 50%, and aperture is 0.1 ~ 1 μm；Described phase change medium is polyethylene glycol, paraffin, stearic acid, laurate, SA, polyethylene glycol monoacrylate, tristearin It is one or more of in acyl chlorides, lauroyl chloride and certain herbaceous plants with big flowers diacid chloride；The preparation method of the environment protection type energy storage temperature-regulating fiber includes：By The raw material of a part and the raw material of Part II are added in the composite spinning system with two single screw rods, wherein the second single screw rod Head pressure it is higher 0.5~1MPa than the head pressure of the first single screw rod, then utilize the composite spinning with two single screw rods The bi-component sheath-core filament spinning component of system carries out melt spinning, and spinning speed is 500~3000m/min, obtains environment protection type energy storage Temperature-regulating fiber.
- 2. environment protection type energy storage temperature-regulating fiber as claimed in claim 1, it is characterised in that described spinning-grade polymer is poly- carbon One kind in acid esters, PLA, polyhydroxyalkanoate and poly butylene succinate.
- 3. environment protection type energy storage temperature-regulating fiber as claimed in claim 1, it is characterised in that described matrix polymer is at one Melting temperature is 90 ~ 130 under atmospheric pressureoC polymer.
- 4. environment protection type energy storage temperature-regulating fiber as claimed in claim 1, it is characterised in that described matrix polymer is poly- carbonic acid Ester, PLA, polyhydroxyalkanoate or poly butylene succinate.
- 5. environment protection type energy storage temperature-regulating fiber as claimed in claim 1, it is characterised in that described assistant crosslinking agent is peroxidating two Isopropylbenzene or di-tert-butyl peroxide.
- 6. environment protection type energy storage temperature-regulating fiber as claimed in claim 1, it is characterised in that described Part I and Part II Mass ratio be 1/3 ~ 9/1.
- 7. the preparation method of the environment protection type energy storage temperature-regulating fiber any one of claim 1-6, it is characterised in that specific step Suddenly include：The raw material of the raw material of Part I and Part II is added in the composite spinning system with two single screw rods, adopted Melt spinning is carried out with bicomponent fibre spinning component.
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| CN108018616A (en) * | 2017-10-25 | 2018-05-11 | 衢州福创工业设计有限公司 | A kind of antibacterial composite high-molecular fiber and preparation method |
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| CN201634800U (en) * | 2010-01-22 | 2010-11-17 | 东华大学 | Sheath-core composite fiber containing phase-change material for hair products |
| CN102199231A (en) * | 2011-04-13 | 2011-09-28 | 天津工业大学 | Preparation method of comb-type polymer phase change energy storage material |
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Application publication date: 20150916 Assignee: Zhejiang Wanzhou Holding Group Co., Ltd. Assignor: Donghua University Contract record no.: X2019980000234 Denomination of invention: Environment-friendly energy storage and temperature regulation fiber and preparation method thereof Granted publication date: 20171226 License type: Exclusive License Record date: 20191008 |
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