CN114834115A - 一种相变储能柔性膜材料及其制备方法 - Google Patents

一种相变储能柔性膜材料及其制备方法 Download PDF

Info

Publication number
CN114834115A
CN114834115A CN202210199213.6A CN202210199213A CN114834115A CN 114834115 A CN114834115 A CN 114834115A CN 202210199213 A CN202210199213 A CN 202210199213A CN 114834115 A CN114834115 A CN 114834115A
Authority
CN
China
Prior art keywords
phase
membrane
polyethylene glycol
phase change
change
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202210199213.6A
Other languages
English (en)
Other versions
CN114834115B (zh
Inventor
路小荷
唐炳涛
张宇昂
张淑芬
吕荣文
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dalian University of Technology
Original Assignee
Dalian University of Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dalian University of Technology filed Critical Dalian University of Technology
Priority to CN202210199213.6A priority Critical patent/CN114834115B/zh
Publication of CN114834115A publication Critical patent/CN114834115A/zh
Application granted granted Critical
Publication of CN114834115B publication Critical patent/CN114834115B/zh
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/18—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer of foamed material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
    • B32B5/245—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it being a foam layer
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/02—Materials undergoing a change of physical state when used
    • C09K5/06—Materials undergoing a change of physical state when used the change of state being from liquid to solid or vice versa
    • C09K5/063—Materials absorbing or liberating heat during crystallisation; Heat storage materials
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/0007—Electro-spinning
    • D01D5/0015—Electro-spinning characterised by the initial state of the material
    • D01D5/003—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/04—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyolefins
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/04—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyolefins
    • D01F6/06—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyolefins from polypropylene
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/18—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polymers of unsaturated nitriles, e.g. polyacrylonitrile, polyvinylidene cyanide
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
    • D01F6/62—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyesters
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4382—Stretched reticular film fibres; Composite fibres; Mixed fibres; Ultrafine fibres; Fibres for artificial leather
    • D04H1/43825—Composite fibres
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
    • D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
    • D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/02—Synthetic macromolecular fibres
    • B32B2262/0253—Polyolefin fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/02—Synthetic macromolecular fibres
    • B32B2262/0276—Polyester fibres
    • B32B2262/0284—Polyethylene terephthalate [PET] or polybutylene terephthalate [PBT]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2266/00—Composition of foam
    • B32B2266/02—Organic
    • B32B2266/0214—Materials belonging to B32B27/00
    • B32B2266/0242—Acrylic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2266/00—Composition of foam
    • B32B2266/12—Gel
    • B32B2266/124—Organogel, i.e. a gel containing an organic composition
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/558—Impact strength, toughness
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/14—Thermal energy storage

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Combustion & Propulsion (AREA)
  • Fluid Mechanics (AREA)
  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Thermal Sciences (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)

Abstract

本发明涉及一种相变储能柔性膜材料及其制备方法，其属于新材料技术领域。一种相变储能柔性膜材料，所述膜材料是将相变组分置于两片高分子限域膜中热压所得，其中，所述相变组分为甲氧基聚乙二醇甲基丙烯酸酯的聚合物与聚乙二醇复合形成的定形相变材料；所述高分子限域膜为聚丙烯腈膜、聚丙烯膜、聚乙烯膜、聚对苯二甲酸乙二醇酯膜。本发明合成工艺简单、过程绿色环保，所得材料应用方便，相变焓值较高、相变温度可调，具有柔韧性好、无毒副作用等优势；该材料可在各种场景反复使用；且其热塑性能提高了其与物体的贴合度，可有效提高能量转换效率，在热能管理方面有广泛实际应用前景。

Description

一种相变储能柔性膜材料及其制备方法
技术领域
本发明涉及一种相变储能柔性膜材料及其制备方法，其属于新材料技 术领域。
背景技术
人类生产生活与热能息息相关、密不可分，但热能的时空不匹配是亟 待解决的重要问题。相变材料以潜热方式进行热能的储存和释放，利用自 身相变过程温度恒定的特性对周围环境温度进行调节，是解决热能时空不 匹配的有效途径。其中，有机相变材料具有化学性质稳定、无相分离、储 热密度大、相变温度可调、生物相容性好等诸多优点，在节能建筑、余热 回用、电子元件温度控制、智能调温纤维与服装等领域应用广泛。
相变材料在智能热管理、调温纺织品等领域应用的核心是赋予其柔 性，以利于与基质有效贴合，提高能量管理性能。通常采用共混纺丝、微 胶囊掺杂等方法将相变材料掺入纤维中，制备柔性相变材料，但往往存在 相变焓值低、易漏液、纤维韧性差等问题。因此，具有形状稳定、相变焓 值高、柔性好、韧性强的柔性相变储能材料是一类急需的重要新材料。
发明内容
为解决现有技术中存在的问题，本发明提供一类新的相变储能柔性材 料及其制备方法。本发明制备的相变储能柔性膜材料，其最大特征在于定 形相变储能材料被限域封装于限域膜材料中，形成限域膜-限域膜/相变融 合-定形相变材料-限域膜/相变融合-限域膜的层结构(如图1)。其相变组分 由高相变焓值的聚乙二醇及同样具有相变焓值的甲氧基聚乙二醇甲基丙 烯酸酯的聚合物复合而成，具有梳齿骨架结构的甲氧基聚乙二醇甲基丙烯 酸酯聚合物在赋予其自身定形相变的同时，使聚乙二醇在其长分子链中限 域，所得复合材料相变前后不流动，起到了定形和提高焓值的双重作用； 同时，高分子纤维膜的融合与包覆，不仅使材料具备良好的耐磨性，大大 提高了膜材料的使用寿命，更起到赋予材料柔性的作用，使其在远低于相 变温度的条件下仍具有较好的柔性，适用于绝大多数场景的应用。
本发明提供的相变储能柔性材料具有相对较高的相变焓值、可调的相 变温度、较好的柔韧性，其储能效果良好、应用范围广、可重复利用，且 优秀的热塑性更利于其贴合物体，提高能量转化率。此类材料制备工艺简 单，可用于实际应用，具有广阔的应用前景。
本发明的技术方案如下：
一种相变储能柔性膜材料，所述膜材料是将相变组分置于两片高分子 限域膜中热压所得，其中，
所述相变组分为甲氧基聚乙二醇甲基丙烯酸酯的聚合物与聚乙二醇 复合形成的定形相变材料；
所述高分子限域膜为聚丙烯腈膜、聚丙烯膜、聚乙烯膜、聚对苯二甲 酸乙二醇酯膜。
上述技术方案中，所述相变组分被部分压入高分子限域膜纤维交织所 形成的缝隙中。
上述技术方案中，所述柔性膜材料形成五层结构，两侧最外层为高分 子限域膜，中间层为相变组分，在最外层和中间层之间为混合层，混合层 由相变组分压入高分子限域膜形成。
本发明所述相变储能柔性膜材料中，所述高分子限域膜为静电纺丝所 得的高分子纤维膜，所述静电纺丝工艺的纺丝液由丙烯腈、聚丙烯、聚乙 烯、聚对苯二甲酸乙二醇酯溶于N，N-二甲基甲酰胺获得。
进一步地，高分子限域材料于纺丝液中的质量浓度为3～15w.t.％。
本发明所述相变储能柔性膜材料中，所述相变组分按下述方法制得： 将聚乙二醇与甲氧基聚乙二醇甲基丙烯酸酯水溶液在氮气保护下于80℃ 恒温水浴中加热搅拌，形成均匀溶液，其中，聚乙二醇在溶质中的质量分 数为10～70％；向所得溶液中加入引发剂，机械搅拌5～30min后得凝胶状 产物，经干燥处理得复合相变组分。
本发明所述相变储能柔性膜材料中，所述相变组分与高分子限域膜的 质量比为0.5～3:1。
本发明所述相变储能柔性膜材料中，所述甲氧基聚乙二醇甲基丙烯酸 酯的分子量为800～5000，聚乙二醇分子量为800～10000。
本发明的另一目的是提供上述相变储能柔性膜材料的制备方法。
一种相变储能柔性膜材料的制备方法，包括以下步骤：
(1)将聚乙二醇与甲氧基聚乙二醇甲基丙烯酸酯水溶液在氮气保护 下于80℃恒温水浴中加热搅拌，形成均匀溶液，其中，聚乙二醇在溶质 中的质量分数为10～70％；
(2)向步骤(1)得到的溶液中加入引发剂，机械搅拌5～30min后得 凝胶状产物，经干燥处理得复合相变组分；
(3)将高分子限域材料溶解在N，N-二甲基甲酰胺中，得纺丝液， 其中，所述高分子限域材料为丙烯腈、聚丙烯、聚乙烯、聚对苯二甲酸乙 二醇酯；
(4)利用静电纺丝设备对纺丝液进行纺丝，得到高分子限域膜；
(5)对步骤(2)所得的相变组分进行加热软化，将其置于两片步骤 (4)所得的高分子限域膜之间，进行热压，最终得到柔性膜材料。
优选地，所述引发剂为过硫酸钾(KPS)，所述引发剂的质量为甲氧基 聚乙二醇甲基丙烯酸酯的0.1～2％。
优选地，步骤(3)中，所述纺丝液中高分子限域材料质量浓度为3～15 w.t.％。
优选地，步骤(4)中，纺丝电压为9～20kV，进液速率为0.5～1.2mL/h， 针头距离接受器距离为15cm。
优选地，步骤(5)中，热压温度为80～160℃，压力为5～13kN。
本发明的有益效果：本发明提供了一种柔性的相变储热膜材料，该材 料复合相变组分焓值可达160J/g。膜材料整体焓值可在60～120J/g之间调 控，相变温度可在在40～60℃之间调节，具有较为优秀的储热效果。其柔 韧性较好且具有热塑性能，可反复弯折长久使用，无毒害作用，可与皮肤 直接接触。该材料合成工艺简单，应用方便，在个体热能管理方面具有广 阔的应用前景。
附图说明
图1为相变储能柔性膜材料结构示意图，其中1部分为聚丙烯腈纤维， 3为相变材料部分，2为相变材料压入聚丙烯腈纤维部分。
图2为实施例1中材料的XRD图谱，其中：a、复合相变材料及原料XRD 图谱；b、复合相变材料及膜材料XRD图谱。
图3为实施例1中相变材料原料与材料的红外图谱，分别为甲氧基聚 乙二醇甲基丙烯酸酯聚合前(mPEGMA)后(PPEGMA)。
图4为不同材料的DSC曲线，其中：a、实施例1中所用复合相变材料 及膜材料，b、实施例2-5中复合相变材料，c、实施例6中复合相变材料及 复合膜材料。
图5为实施例1所述样品SEM图像，其中：a、柔性膜截面示意图，b、 柔性膜截面电镜图像，c、无相变组分纤维膜热压后截面结构，d、柔性膜 表面电镜图像。
图6为实施例1所述膜材料及空白对照的时间温度曲线。
图7为实施例1所制膜材料数码照片。其中：a、室温状态，b、室温下 柔性弯折状态，c、加热塑形后状态。
图8为实施例1所制膜材料数码照片。其中：a、室温状态，b、加热塑 性后状态，c、施加外力使膜展开状态，d、卸除外力膜回弹状态。
具体实施方式
下述非限制性实施例可以使本领域的普通技术人员更全面地理解本 发明，但不以任何方式限制本发明。
下述实施例中所述试验方法，如无特殊说明，均为常规方法；所述试 剂和材料，如无特殊说明，均可从商业途径获得。
实施例1
(1)取质量比6:7的甲氧基聚乙二醇甲基丙烯酸酯水溶液(mPEGMA， 50w.t.％水溶液)与聚乙二醇(PEG，Mn＝6000)在80℃恒温水浴中加热， 机械搅拌30min形成均匀混合液；
(2)于流速为120mL/min的氮气流中，在上述配置好溶液中加入引 发剂KPS水溶液，其中KPS的质量为mPEGMA质量的0.9％，在300rpm转速 下机械搅拌3min，得凝胶状产物，将产物100摄氏度真空干燥12小时得相 变组分；
(3)将聚丙烯腈(PAN)溶于N，N-二甲基甲酰胺(DMF)中，质量 分数为10w.t.％.
(4)对质量分数为10w.t.％的聚丙烯腈溶液进行静电纺丝，电压为 17kV，进液速率为0.8mL/h，得PAN纤维膜.
(5)取两片大小相同的PAN纤维膜，取与其质量比为1:1的相变材料；
(6)将加热软化的相变材料置于两片PAN纤维膜间进行热压，热压温 度为100℃，压力为10kN，时间为10min.制备得到具有柔性的相变膜材料。
实施例1中所得材料相变温度为57.6℃，其XRD谱图如图2所示，其中 图2a为起支撑定形作用的PPEGMA及其原料mPEGMA的XRD谱图，其几 乎完全一致的出峰位置表明复合材料制备过程中的熔融共聚反应不影响 彼此结晶性能，从而确保复合相变材料的焓值；图2b为复合相变材料及热 压后复合膜材料的的XRD谱图，表明聚丙烯腈膜不影响复合相变材料的结 晶性能。图3红外光谱中，PPEGMA曲线中的碳碳双键峰在1636cm-1中明 显减弱，说明双键消失，聚合反应较为彻底。相变组分及复合膜材料的DSC 曲线如图4，相变组分焓值为153.4J/g，复合膜材料焓值为83.99J/g.复合 膜材料截面及表面电镜图像如图5所示，其截面可明显看到PAN/PCM/PAN 的层夹层结构；将其包覆探头至于80℃烘箱中，记录其与空白对照组的温 度变化结果如图6所示，可见包覆了相变材料的实验组温度上升明显减缓。
实施例2-5
将聚乙二醇的分子量改为2000、4000、8000、10000，得到相应的相 变柔性膜材料，其他条件与实施例1一致。DSC曲线显示，其相变温度分别 为：52℃、55℃、58℃、60℃，可以此为依据对相变材料应用温度进行调 整。
实施例6
将甲氧基聚乙二醇甲基丙烯酸酯的分子量改为950，得到相应的相变 柔性膜材料，其他条件与实施例1一致。
实施例7-10
将聚乙二醇与甲氧基聚乙二醇甲基丙烯酸酯质量比改为6:8、5:10、 4:12、3:14，得到相应的相变柔性膜材料，其他条件与实施例1一致。DSC 曲线如图4c所示，所得相变材料及复合膜相变焓值介于110J/g～160J/g， 可基于此实现对相变材料焓值的调控。
实施例11-12
将引发剂过硫酸钾质量分数分别改为0.1％和2％，得到相应的相变柔性 膜材料，其他条件与实施例1一致。
实施例13
将干燥方式改为冷冻干燥，得到相应的相变柔性膜材料，其他条件与 实施例1一致。
实施例14-16
将聚丙烯腈溶液质量分数改为5w.t.％、7w.t.％及15w.t.％，得到相应 的相变柔性膜材料，其他条件与实施例1一致。
实施例17-19
将静电纺丝电压改为11kV、13kV和15kV，得到相应的相变柔性膜材 料，其他条件与实施例1一致。
实施例20-22
将静电纺丝进液速率改为0.5mL/h、1.0mL/h和1.2mL/h，得到相 应的相变柔性膜材料，其他条件与实施例1一致。
实施例23-24
将热压温度改为80℃、120℃，得到相应的相变柔性膜材料，其他条 件与实施例1一致。
实施例25-26
将热压压力改为5KN、13kN，得到相应的相变柔性膜材料，其他条件 与实施例1一致。
实施例27-29
将热压时间改为5min、20min和30min，得到相应的相变柔性膜材料， 其他条件与实施例1一致。
实施例30-32
将相变组分与聚丙烯腈膜质量比改为1:2、2:1、2:3，得到相应的相变 柔性膜材料，其他条件与实施例1一致。
实施例33-35
将聚丙烯、聚乙烯、聚对苯二甲酸乙二醇酯代替聚丙烯腈，得到相应 的相变柔性膜材料，其他条件与实施例1一致。

Claims (10)

1.一种相变储能柔性膜材料，其特征在于：所述膜材料是将相变组分置于两片高分子限域膜中热压所得，其中，
所述相变组分为甲氧基聚乙二醇甲基丙烯酸酯的聚合物与聚乙二醇复合形成的定形相变材料；
所述高分子限域膜为聚丙烯腈膜、聚丙烯膜、聚乙烯膜、聚对苯二甲酸乙二醇酯膜。
2.根据权利要求1所述的材料，其特征在于：所述高分子限域膜为静电纺丝所得的高分子纤维膜，所述静电纺丝工艺的纺丝液由丙烯腈、聚丙烯、聚乙烯、聚对苯二甲酸乙二醇酯溶于N，N-二甲基甲酰胺获得。
3.根据权利要求1所述的材料，其特征在于：所述相变组分按下述方法制得：将聚乙二醇与甲氧基聚乙二醇甲基丙烯酸酯水溶液在氮气保护下于80℃恒温水浴中加热搅拌，形成均匀溶液，其中，聚乙二醇在溶质中的质量分数为10～70％；向所得溶液中加入引发剂，机械搅拌5～30min后得凝胶状产物，经干燥处理得复合相变组分。
4.根据权利要求1所述的材料，其特征在于：所述相变组分与高分子限域膜的质量比为0.5～3:1。
5.根据权利要求1所述的材料，其特征在于：所述甲氧基聚乙二醇甲基丙烯酸酯的分子量为800～5000，聚乙二醇分子量为800～10000。
6.权利要求1所述相变储能柔性膜材料的制备方法，其特征在于，包括以下步骤：
(1)将聚乙二醇与甲氧基聚乙二醇甲基丙烯酸酯水溶液在氮气保护下于80℃恒温水浴中加热搅拌，形成均匀溶液，其中，聚乙二醇在溶质中的质量分数为10～70％；
(2)向步骤(1)得到的溶液中加入引发剂，机械搅拌5～30min后得凝胶状产物，经干燥处理得复合相变组分；
(3)将高分子限域材料溶解在N，N-二甲基甲酰胺中，得纺丝液，其中，所述高分子限域材料为丙烯腈、聚丙烯、聚乙烯、聚对苯二甲酸乙二醇酯；
(4)利用静电纺丝设备对纺丝液进行纺丝，得到高分子限域膜；
(5)对步骤(2)所得的相变组分进行加热软化，将其置于两片步骤(4)所得的高分子限域膜之间，进行热压，最终得到柔性膜材料。
7.根据权利要求6所述的方法，其特征在于：所述引发剂为过硫酸钾，所述引发剂的质量为甲氧基聚乙二醇甲基丙烯酸酯的0.1～2％。
8.根据权利要求6所述的方法，其特征在于：步骤(3)中，所述纺丝液中高分子限域材料质量浓度为3～15w.t.％。
9.根据权利要求6所述的方法，其特征在于：步骤(4)中，纺丝电压为9～20kV，进液速率为0.5～1.2mL/h，针头距离接受器距离为15cm。
10.根据权利要求6所述的方法，其特征在于：步骤(5)中，热压温度为80～160℃，压力为5～13kN。
CN202210199213.6A 2022-03-02 2022-03-02 一种相变储能柔性膜材料及其制备方法 Active CN114834115B (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210199213.6A CN114834115B (zh) 2022-03-02 2022-03-02 一种相变储能柔性膜材料及其制备方法

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210199213.6A CN114834115B (zh) 2022-03-02 2022-03-02 一种相变储能柔性膜材料及其制备方法

Publications (2)

Publication Number Publication Date
CN114834115A true CN114834115A (zh) 2022-08-02
CN114834115B CN114834115B (zh) 2023-07-21

Family

ID=82562974

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210199213.6A Active CN114834115B (zh) 2022-03-02 2022-03-02 一种相变储能柔性膜材料及其制备方法

Country Status (1)

Country Link
CN (1) CN114834115B (zh)

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004300424A (ja) * 2003-03-14 2004-10-28 Dainichiseika Color & Chem Mfg Co Ltd 蓄熱材、その製造方法、加温あるいは冷却システムおよび蓄熱性物品、および共重合体
CN102471673A (zh) * 2010-02-09 2012-05-23 纺织和塑料研究协会图林根研究院 储热模制体
CN107794004A (zh) * 2017-10-26 2018-03-13 大连理工大学 一种相变蓄冷凝胶材料及其制备方法
CN108779203A (zh) * 2016-03-24 2018-11-09 Sika技术股份公司 用于制备水凝胶的单组分或多组分组合物
CN109504351A (zh) * 2018-12-20 2019-03-22 大连理工大学 一种聚醚基复合相变储能材料及其制备方法
CN111231461A (zh) * 2020-03-28 2020-06-05 广东卫国者高新科技有限公司 一种防爆防护复合材料及其制备方法和防爆防护服
CN112194809A (zh) * 2020-10-09 2021-01-08 天津工业大学 一种具有三明治夹层结构的相变储能复合膜及其制备方法
CN113500833A (zh) * 2021-05-19 2021-10-15 深圳市华科创智技术有限公司 一种用于智能穿戴的柔性相变自动控温器件及其制备方法

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004300424A (ja) * 2003-03-14 2004-10-28 Dainichiseika Color & Chem Mfg Co Ltd 蓄熱材、その製造方法、加温あるいは冷却システムおよび蓄熱性物品、および共重合体
CN102471673A (zh) * 2010-02-09 2012-05-23 纺织和塑料研究协会图林根研究院 储热模制体
CN108779203A (zh) * 2016-03-24 2018-11-09 Sika技术股份公司 用于制备水凝胶的单组分或多组分组合物
CN107794004A (zh) * 2017-10-26 2018-03-13 大连理工大学 一种相变蓄冷凝胶材料及其制备方法
CN109504351A (zh) * 2018-12-20 2019-03-22 大连理工大学 一种聚醚基复合相变储能材料及其制备方法
CN111231461A (zh) * 2020-03-28 2020-06-05 广东卫国者高新科技有限公司 一种防爆防护复合材料及其制备方法和防爆防护服
CN112194809A (zh) * 2020-10-09 2021-01-08 天津工业大学 一种具有三明治夹层结构的相变储能复合膜及其制备方法
CN113500833A (zh) * 2021-05-19 2021-10-15 深圳市华科创智技术有限公司 一种用于智能穿戴的柔性相变自动控温器件及其制备方法

Also Published As

Publication number Publication date
CN114834115B (zh) 2023-07-21

Similar Documents

Publication Publication Date Title
CN104993089B (zh) 一种芳纶涂覆的锂离子电池隔膜及其制备方法
CN102218871B (zh) 锂离子二次电池用改性隔膜的制备方法及其产品、制备装置
CN112531285B (zh) 一种耐高温对位芳纶涂覆锂离子电池隔膜及其制备方法
CN104766937B (zh) 一种环保型锂离子电池隔膜及其制备方法
KR102331373B1 (ko) 리튬 이온 배터리용 양방향 인장 코팅의 미세공 분리막 및 그 제조방법
CN108794942A (zh) 一种聚合物与三维多孔石墨烯复合的超材料的制备方法
CN105040276A (zh) 一种具有交联形貌的聚酰亚胺纤维膜及其制备方法
CN108774808B (zh) 一种具有交联形貌的表面包覆二氧化锆的聚酰亚胺纳米纤维膜及其制备方法
CN113506949B (zh) 一种具有微纳米多孔结构的芳纶纳米纤维基电池隔膜的制备方法
CN104213333A (zh) 一种具有交联结构的聚酰亚胺/聚烯烃复合纤维膜及制备方法
CN107275546A (zh) 一种电池隔膜及其制备方法
CN102443879B (zh) 一种智能调温纤维及其制备方法
CN111192994A (zh) 一种耐热收缩的聚乙烯锂电池隔膜及制备方法
CN103556465B (zh) 一种聚合物长丝表面复合天然蛋白质纤维粉体的方法
CN110327789B (zh) 一种碳纳米管/纳米纤维导电复合膜及其制备方法
CN109605868B (zh) 一种具有光热转换效果的混凝土高效保温保湿复合养护膜
CN114834115A (zh) 一种相变储能柔性膜材料及其制备方法
CN112038542B (zh) 一种纤维布基锂离子电池隔膜及其制备方法和应用
CN110828755B (zh) 一种复合隔膜、其制备方法及二次电池
CN109950453A (zh) 被聚多巴胺包覆的细菌纤维素膜及其制备方法
CN106823838B (zh) 海水淡化用反渗透膜支撑体及制备方法
CN113718367A (zh) 基于湿法纺丝的高弹性相变控温纤维及其制备方法
CN107916580A (zh) 一种耐候性高强度防水布料的制备方法
CN116231227B (zh) 一种四重氢键交联型聚酰亚胺锂电子电池隔膜的制备方法
CN106531929A (zh) 一种陶瓷包覆细菌纤维素多孔薄膜的干燥工艺

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant