CN116789928A - 柔性-可逆形状记忆性的储热调温相变材料及其制备方法和应用 - Google Patents
柔性-可逆形状记忆性的储热调温相变材料及其制备方法和应用 Download PDFInfo
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- CN116789928A CN116789928A CN202310510480.5A CN202310510480A CN116789928A CN 116789928 A CN116789928 A CN 116789928A CN 202310510480 A CN202310510480 A CN 202310510480A CN 116789928 A CN116789928 A CN 116789928A
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- change material
- phase change
- isocyanate
- flexible
- polyol
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- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 4
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- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 4
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- STFMTYFMMARGHA-UHFFFAOYSA-N hexane-1,6-diol;phthalic acid Chemical compound OCCCCCCO.OC(=O)C1=CC=CC=C1C(O)=O STFMTYFMMARGHA-UHFFFAOYSA-N 0.000 claims description 2
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- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 2
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Classifications
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- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/40—High-molecular-weight compounds
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- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/4269—Lactones
- C08G18/4277—Caprolactone and/or substituted caprolactone
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
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- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
- C08G18/6677—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203 having at least three hydroxy groups
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Combustion & Propulsion (AREA)
- Thermal Sciences (AREA)
- Materials Engineering (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
本发明涉及新型能源材料技术领域,具体为一种柔性‑可逆形状记忆性的储热调温相变材料及其制备方法和应用。该相变材料包括:聚醚型多元醇、聚酯型多元醇、异氰酸酯和小分子多元醇;其中,所述聚醚型多元醇与所述聚酯型多元醇的摩尔比为1:(1‑1000),所述聚醚型多元醇的分子量为10000‑900000,可通过接枝缩聚或预聚聚合的方法得到。该柔性‑可逆形状记忆性相变材料的储能密度高,在25‑65℃内相变温度可调,同时具备高焓值、良好的柔弹性及可逆形状记忆性,且制备方法简单,成本低廉,可广泛用于热管理、调温纺织品以及人工肌肉纤维等方面。
Description
技术领域
本发明涉及新型能源材料技术领域,尤其涉及一种柔性-可逆形状记忆性的储热调温相变材料及其制备方法和应用。
背景技术
能源是人类生存和发展的基础,是国民经济发展的重要物质根基,提高能源利用率,节能减排,推动绿色低碳循环是目前社会发展的当之要务。相变储热调温技术具有储能密度高,储放能恒温,可循环使用等优势,可广泛用于太阳能存储、智能建筑、电子设备热控制、电池热管理等领域。但有机相变材料存在易泄漏、低热导率、强度差等缺点,限制了其应用。因此,开发具有稳定形状的相变材料为相变储热调温领域的主要研究目标。
目前存在多孔介质封装、微胶囊技术等可以实现固-液相变材料的一维、二维、三维的封装,但在储能效率以及力学强度性能的提升方面仍具有较大挑战。聚氨酯相变材料相变热焓相对较大,相转变温度基本恒定,同时具有优异的力学性能、耐磨性能和热稳定性能,因此相变储能方面具有广泛的应用前景。
专利CN102690511A公开了一种高强度聚氨酯固―固相变储能材料及其制备方法,其配方包括聚酯多元醇:70%-96%、异氰酸酯:4%-20%、扩链剂:0%-10%、催化剂:0%-1%。利用分子结构高度对称的具有良好结晶性能的聚酯多元醇作为聚氨酯的软段,用以形成具有相变功能的结晶,同时赋于材料较高的力学性能。但其相变焓值明显较低。
专利CN101891877A公开了一种相变保温聚氨酯树脂的制备方法,采用聚乙二醇作软段,多异氰酸酯及含有四重氢键脲基嘧啶酮基元的扩链剂作硬段,合成了含有四重氢键作用的相变保温聚氨酯树脂。相变焓虽然高达150J/g,但断裂拉伸强度为8MPa,断裂延伸率仅为367%。
专利CN101787108A公开了一种相变保温聚氨酯树脂的制备方法,采用了在聚氨酯的合成中同时加入聚醚二醇和聚酯二醇作软段,通过本体聚合法合成相变保温聚氨酯树脂的方法。与单一聚乙二醇作软段的聚氨酯树脂相比,该相变保温聚氨酯树脂能同时满足相变保温性能良好和力学性能优异两个特点。但其相变焓值和断裂伸长率的提高程度仍有限。
因此,有必要开发一种兼具高相变焓值、一定力学强度、柔韧性和可逆形状记忆性的相变储能材料,以为柔性可穿戴设备的调温控温、电子器件的散热、医疗卫生、体育运动等方面提供更多选择。
发明内容
本发明的目的在于提供一种柔性-可逆形状记忆性的储热调温相变储能材料及其制备方法和应用,利用超长分子链的聚醚型多元醇合成柔弹性极好的聚氨酯固固相变材料,同时具备高焓值和可逆形状记忆性,可进行纺丝,或可用于热管理和人工肌肉纤维等方面。
为实现上述目的,第一方面,本发明提供一种柔弹性储热调温相变材料,包括:聚醚型多元醇、聚酯型多元醇、异氰酸酯和小分子多元醇;其中,所述聚醚型多元醇与所述聚酯型多元醇的摩尔比为1:(1-1000),所述聚醚型多元醇的分子量为10000-900000,通常指数均分子量。
本发明以聚酯型多元醇和具有超长分子链的聚醚型多元醇两种液固相变材料为聚氨酯软段,通过控制两者的相对含量,并依据糖醇以及小分子多元醇多氢键特性,利用接枝缩聚或预聚聚合方法制备柔弹性极好的聚氨酯,该材料在25-65℃内相变温度可调,具有形状稳定性,可避免材料使用过程中的泄漏问题,表现出可逆形状记忆性和柔韧性,能够实现循环自由形状变化和回复,且循环稳定性好。
进一步的,所述聚醚型多元醇的分子量为100000-700000;优选为300000-600000;例如为300000、400000、500000、600000。
和/或,所述聚酯型多元醇的分子量为500-3500;例如为800、1000、2000、3000、3500等,通常指重均分子量。
和/或,所述聚醚型多元醇与所述聚酯型多元醇的摩尔比为1:(100-1000),优选为1:(200-700),更优选为1:400。两种多元醇对聚氨酯的相变性能和力学性能有重要影响,本发明通过调控聚醚型多元醇和聚酯型多元醇的分子量以及各组分的相对含量,得到的聚氨酯固固相变材料的断裂伸长率可高达1728%,断裂强度达5-23MPa,且具有高焓值70-150J/g。
进一步的,所述小分子多元醇的添加量为所述聚醚型多元醇、聚酯型多元醇和异氰酸酯总质量的0.01%-0.3%,优选为0.16%;
和/或,所述小分子多元醇包括糖醇或普通小分子多元醇,例如为D-山梨糖醇、D-甘露糖醇、赤藓糖醇、木糖醇、D-阿拉伯糖醇、1,4-丁二醇中的一种或多种。当选择加入小分子二元醇时,可获得线性结构的聚氨酯相变材料,当选择加入糖醇或小分子三元或更多元醇时,可获得网状结构的聚氨酯相变材料。
进一步的,所述聚醚型多元醇包括聚乙二醇、聚丙二醇、聚四亚甲基二醇、聚氧化乙烯二元醇、聚氧化丙烯二元醇、聚1,4-氧四亚甲基二醇中的一种或多种;优选为聚乙二醇或聚氧化乙烯二元醇;
和/或,所述聚酯型多元醇包括聚己内酯二醇、聚己二酸二元醇、聚己二酸乙二醇酯二醇、聚己二酸丙二醇酯二醇、聚己二酸丁二醇酯二醇、聚己二酸己二醇丁二醇酯二醇、聚己二酸丁二醇己二醇酯二醇、聚碳酸酯二醇、聚邻苯二甲酸一缩二乙二醇酯二醇、聚邻苯二甲酸-1,6-己二醇酯二醇、聚邻苯二甲酸新戊二醇酯二醇中的一种或多种,优选为聚己内酯二醇。
进一步的,所述异氰酸酯的指数为0.95-1.05;
和/或,所述异氰酸酯包括甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、4’4-二环己基甲烷二异氰酸酯、1,5-萘二异氰酸酯、对苯二异氰酸酯、苯二亚甲基二异氰酸酯、1,4-环己烷二异氰酸酯、六亚甲基二异氰酸酯、异氟尔酮二异氰酸酯中的一种或多种。
第二方面,本发明提供一种柔弹性储热调温相变材料的制备方法,包括以下步骤:
S1、将聚酯型多元醇与异氰酸酯在催化剂作用下反应,得到端异氰酸酯预聚物一;
S2、将所述端异氰酸酯预聚物一与聚醚型多元醇反应,得到端异氰酸酯预聚物二;所述聚醚型多元醇的分子量为10000-900000;
S3、将所述端异氰酸酯预聚物二与小分子多元醇反应得到柔弹性储热调温相变材料。
进一步的,所述聚醚型多元醇与所述聚酯型多元醇的摩尔比为1:(1-1000),优选为1:(200-700),更优选为1:(250-450);
上述步骤为接枝缩聚和预聚聚合法,先通过分子量相对较小的聚酯型多元醇与异氰酸酯反应,得到端异氰酸酯预聚物一;接着加入聚醚型多元醇,由于聚醚型多元醇分子量较高,常温下通常为固态,因此需要配制成溶液或者加热熔融后再反应,其与端异氰酸酯预聚物一的端异氰酸根聚合,使得分子链进一步延长;最后再通过小分子多元醇进一步扩链,得到线性或网状结构的聚氨酯相变材料。
优选地,所述聚醚型多元醇和聚酯型多元醇在反应前,分别在120-130℃的温度下干燥除水。
进一步的,所述催化剂为二月桂酸二丁基锡、钛酸四丁酯、叔胺类(例如三亚乙基二胺)、非锡有机化合物、油酸、己二酸、氢氧化钾中的一种或多种。催化剂的添加量约为聚酯型多元醇和异氰酸酯总质量的0.01%。
具体地,柔弹性储热调温相变材料的制备方法包括以下步骤:
S1、将聚酯型多元醇干燥后,加入异氰酸酯,在氮气气氛的保护下,在65-75℃温度条件持续搅拌反应45-60min后,加入催化剂,持续反应60-120min,得到端异氰酸酯预聚物一;
所述异氰酸酯的指数为0.95-1.05;所述聚酯型多元醇的分子量为500-3500;
S2、将干燥后聚醚型多元醇加入到所述端异氰酸酯预聚物一中,在65-75℃中搅拌反应60-180min,得到端异氰酸酯预聚物二;
S3、将小分子多元醇加入到所述端异氰酸酯预聚物二中,在75-85℃下持续搅拌反应60-180min,在80℃的真空环境下干燥6-8h,得到柔弹性储热调温相变材料。
第三方面,本发明提供一种以上任一项所述的柔弹性储热调温相变材料或以上任一项所述的制备方法得到的柔弹性储热调温相变材料的应用,所述柔弹性储热调温相变材料用于人工肌肉纤维、储热调温纺织品以及热管理等领域。
实验表明,本发明制备的聚氨酯柔弹性储热调温相变储能材料可以利用静电纺丝技术获得微纳米相变纤维膜,这对于热管理领域的应用具有重要意义,而现有技术制备的固固相变材料鲜少见有能够单独成纤的,需要复合一定量的高分子聚合物才能纺丝成型。
本发明的有益效果如下:
1、本发明提供的柔弹性储热调温相变材料,以聚酯型多元醇和具有超长分子链的聚醚型多元醇为聚氨酯软段,与二异氰酸酯反应,通过调控各组分含量,可得到柔弹性极好的聚氨酯固固相变材料,可避免材料使用过程中的泄漏问题。该聚氨酯相变材料在25-65℃内相变温度可调,同时具备高焓值、良好的力学性能以及可逆形状记忆性,可实现多次循环并维持形状稳定性,且热循环耐久性好。
2、本发明制备方法简单,可通过多种方式实施,成本低廉,绿色环保,适于工业化应用。产品的蓄热调温范围广,物性稳定,柔性及可逆形状记忆性稳定,可用于热管理、调温纺织品以及人工肌肉纤维等领域。
附图说明
图1为实施例1所制备的柔性-可逆形状记忆性的储热调温相变材料在不同温度下的外观图(上图)以及受力拉伸和应力去除图(下图);
图2为实例1所制备的柔性-可逆形状记忆性的储热调温相变材料的热分析图;
图3为聚环氧乙烷、聚己内酯二醇以及D-山梨糖醇制得的聚氨酯相变材料的XRD谱图;
图4为实例1所制备的柔性-可逆形状记忆性的储热调温相变材料的不同温度下的XRD谱图;
图5为实例1所制备的柔性-可逆形状记忆性的储热调温相变材料的应力-应变曲线;
图6为实例1所制备的柔性-可逆形状记忆性的储热调温相变材料的DMA曲线;
图7为实例1所制备的柔性-可逆形状记忆性的储热调温相变材料形变与应力和温度的关系曲线。
具体实施方式
为使本发明的目的、技术方案和优点更加清楚,下面对本发明中的技术方案进行清楚、完整地描述,显然,所描述的实施例是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例,都属于本发明保护的范围。
实施例1
一种具有柔性-可逆形状记忆性的储热调温相变材料,通过以下步骤制备:
(1)称取4g聚己内酯二醇(Mw=1000)在120℃条件下干燥2h后,加入0.73g HDI(六亚甲基二异氰酸酯),在75℃的氮气气氛环境中持续反应60min后加入二月桂酸二丁基锡后,在75℃条件下持续反应120min获得端异氰酸酯预聚物;
(2)称取6g聚氧化乙烯(Mn=600000)置于120℃的环境下干燥2h后,均匀分散在N,N-二甲基甲酰胺溶剂中;经计算,聚氧化乙烯与聚己内酯二醇的摩尔比为1:400;
(3)将聚氧化乙烯(又名聚环氧乙烷,Mn=600000)溶液加入到步骤(1)获得的端异氰酸酯预聚物中,在75℃的条件下持续反应180min;
(4)称取0.02g的D-山梨糖醇加入到步骤(3)的产物中,将体系升温到80℃,持续反应180min后终止反应,得到超高分子量的聚氨酯溶液;
(5)将步骤(4)获得聚氨酯溶液置于80℃的真空环境下固化干燥后,即可得到柔性-可逆形状记忆性的聚氨酯相变材料薄膜产品。
本实施例制得的柔性-可逆形状记忆性的相变材料的形貌图以及形态变化如图1所示,可以看出其为柔软透明的固态,且具有良好的柔弹性,拉伸形变至300%,撤销应力后可恢复到原始形态。
从图2可以看出,本实施例制得的柔性-可逆形状记忆性相变材料具有较宽的调温范围和高焓值,表现出良好的蓄热调温性能。当外界温度逐渐升高时,聚氨酯发生相转变吸收外界热量,其相变温度为:62℃,相变焓值为:110J/g;相变温度为45℃,相变焓值为108J/g。
从图3可以看出本实施例制得的柔弹性相变材料具有良好的结晶性能;从图4可以看出,柔弹性相变材料的结晶性能能够随着温度变化发生结晶行为变化,低温下结晶性较好,随着温度升高,相变材料从有规排列逐渐转变为无序状态。
从图5可以看出,本实施例制得的柔弹性相变材料拉伸强度约为10.4MPa,断裂伸长率约为1728.0%,此时最大受力可达15.3N,说明柔弹性极好。可见本发明能够兼具高焓值和较优的力学性能。
从图6可以看出,本实施例制得的柔弹性相变材料能够随着负载力的加载和去除发生形态改变,并且这种变化具有循环稳定性。
聚氨酯相变材料是一种半结晶型的形状记忆性聚合物,主要依靠结晶半结晶分子链段的熔融-结晶的相变过程实现形状记忆性。从图7可以看出,聚氨酯在外力的作用下,分子链能够由原来的蜷曲状态变为伸展状态,当外力去除后,就会自发回复到初始的状态。曲线的变化表明这种聚氨酯相变材料能够在发生形变后,在热刺激下回复到原来的形状尺寸。
实施例2
一种具有柔性-可逆形状记忆性的储热调温相变材料,与实施例1相比,不同之处在于,聚氧化乙烯的分子量Mn=300000,其他与实施例1相同,在此不再赘述。
实施例3
一种具有柔性-可逆形状记忆性的储热调温相变材料,与实施例1相比,不同之处在于,聚酯多元醇的分子量Mn=3500,其他与实施例1相同,在此不再赘述。
实施例4
一种具有柔性-可逆形状记忆性的储热调温相变材料,与实施例1相比,不同之处在于,步骤(2)中聚氧化乙烯与聚己内酯二醇的摩尔比为1:200,其他与实施例1相同,在此不再赘述。
实施例5
一种具有柔性-可逆形状记忆性的储热调温相变材料,与实施例1相比,不同之处在于,步骤(2)中聚氧化乙烯与聚己内酯二醇的摩尔比为1:700,其他与实施例1相同,在此不再赘述。
实施例6
(1)称取3g聚己内酯二醇(Mw=1000)在120℃的条件下干燥2h后,加入0.56g HDI(六亚甲基二异氰酸酯),在75℃的氮气气氛环境中持续反应60min,加入钛酸四丁酯催化后,在75℃条件下持续反应120min获得端异氰酸酯预聚物;
(2)称取6g聚氧化乙烯(Mn=600000)置于120℃的环境下干燥2h后,均匀分散在N,N-二甲基乙酰胺溶剂中;
(3)将聚氧化乙烯(Mn=600000)溶液加入到步骤(1)中获得端异氰酸酯预聚物中,在75℃的条件下持续反应180min;
(4)称取0.02g的D-山梨糖醇加入到步骤(3)的产物中,将体系升温到80℃,持续反应180min后终止反应,得到超高分子量的聚氨酯溶液;
(5)将步骤(4)反应获得的聚氨酯溶液置于80℃的真空环境下固化干燥后即可得到柔性-可逆形状记忆性的聚氨酯相变材料薄膜产品。
实施例7
(1)称取2.5g聚己内酯二醇(Mn=1000)在120℃的条件下干燥2h,加入0.63g的MDI(二苯基甲烷二异氰酸酯),在75℃的氮气气氛环境中持续反应60min,加入二月桂酸二丁基锡后,在75℃的条件下持续反应120min后获得端异氰酸酯预聚物;
(2)称取3g聚乙二醇(Mn=600000)置于120℃的环境下干燥2h后,均匀分散在N,N-二甲基甲酰胺溶剂中;
(3)将聚乙二醇(Mn=600000)溶液加入到步骤(1)获得的端异氰酸酯预聚物中,在75℃的条件下持续反应180min;
(4)称取0.01g D-山梨糖醇加入到步骤(3)的产物中,将体系升温到80℃,持续反应180min后终止反应,得到超高分子量的聚氨酯溶液;
(5)将步骤(4)获得的聚氨酯溶液置于80℃的真空环境下固化干燥后即可得到柔性-可逆形状记忆性的聚氨酯相变材料薄膜产品。
实施例8
(1)称取16g聚酯多元醇(Mn=1000)在120℃的条件下干燥2h后,加入2.8g HDI(六亚甲基二异氰酸酯),在75℃的氮气气氛环境中持续反应60min,加入钛酸四丁酯催化后,在75℃的条件下持续反应120min后获得端异氰酸酯预聚物;
(2)称取24g聚氧化乙烯(Mn=600000)置于120℃的环境下干燥2h后,均匀分散在N,N-二甲基甲酰胺溶剂中;
(3)将聚氧化乙烯(Mn=600000)溶液加入到步骤(1)获得的端异氰酸酯预聚物中,在75℃的条件下持续反应180min;
(4)称取0.0728g赤藓糖醇加入到步骤(3)的产物中,将体系升温到80℃后,持续反应180min终止反应,得到超高分子量的聚氨酯溶液;
(5)将步骤(4)获得的聚氨酯溶液置于80℃的真空环境下固化干燥后即可得到柔性-可逆形状记忆性的聚氨酯相变材料薄膜产品。
表1实施例1-8的相变焓值及力学性能测试结果
实施例 | 相变焓值(J/g) | 断裂强度(MPa) | 断裂伸长率 |
实施例1 | 110.0 | 10.4 | 1702.9% |
实施例2 | 157.3 | 6.5 | 13.0% |
实施例3 | 94.1 | 13.7 | 145.4% |
实施例4 | 128.0 | 5.3 | 64.0% |
实施例5 | 75.0 | 8.2 | 893.0% |
实施例6 | 115.0 | 12.2 | 1635.0% |
实施例7 | 94.0 | 8.7 | 1215.0% |
实施例8 | 109.5 | 10.0 | 1700.0% |
从表1可以看出,本发明采用超高分子量的聚醚多元醇能够同时提高聚氨酯相变材料的柔弹性和相变焓值。聚醚型多元醇的分子量的提高有助于提高柔弹性相变材料的取向拉伸强度和伸展率;聚酯型多元醇的分子量的提高使得相变焓值有所降低,但材料模量增加刚性增强;此外,聚酯型多元醇的类型以及投入量的差异对于相变材料的焓值以及柔弹性有很大影响。氢键作用以及分子间作用力对相变材料结构的柔弹性有较大贡献。
综上所述,本发明提供的柔性-可逆形状记忆性的相变材料,制备方法简单,成本低廉,适用范围广泛。该制备方法制得的柔性-可逆形状记忆性的相变材料不但具有稳定的形状,良好的柔韧性和储热调温性,还可以在室温条件受到外力作用下发生形变,当温度升高至某一响应温度以上时,此相变材料的形变得以很快恢复到初始状态,使用安全,用途广泛。
最后应说明的是:以上实施例仅用以说明本发明的技术方案,而非对其限制;尽管参照前述实施例对本发明进行了详细的说明,本领域的普通技术人员应当理解:其依然可以对前述各实施例所记载的技术方案进行修改,或者对其中部分技术特征进行等同替换;而这些修改或者替换,并不使相应技术方案的本质脱离本发明各实施例技术方案的精神和范围。
Claims (10)
1.一种柔弹性储热调温相变材料,其特征在于,包括:聚醚型多元醇、聚酯型多元醇、异氰酸酯和小分子多元醇;其中,所述聚醚型多元醇与所述聚酯型多元醇的摩尔比为1:(1-1000),所述聚醚型多元醇的分子量为10000-900000。
2.根据权利要求1所述的柔弹性储热调温相变材料,其特征在于,所述聚醚型多元醇的分子量为100000-700000;优选为300000-600000;
所述聚酯型多元醇的分子量为500-3500;
和/或,所述聚醚型多元醇与所述聚酯型多元醇的摩尔比为1:(100-1000),优选为1:(200-700)。
3.根据权利要求1或2所述的柔弹性储热调温相变材料,其特征在于,所述小分子多元醇的添加量为所述聚醚型多元醇、聚酯型多元醇和异氰酸酯总质量的0.01%-0.3%;
和/或,所述小分子多元醇为D-山梨糖醇、D-甘露糖醇、赤藓糖醇、木糖醇、D-阿拉伯糖醇、1,4-丁二醇中的一种或多种。
4.根据权利要求1-3中任一项所述的柔弹性储热调温相变材料,其特征在于,所述聚醚型多元醇包括聚乙二醇、聚丙二醇、聚四亚甲基二醇、聚氧化乙烯二元醇、聚氧化丙烯二元醇、聚1,4-氧四亚甲基二醇中的一种或多种;
和/或,所述聚酯型多元醇包括聚己内酯二醇、聚己二酸二元醇、聚己二酸乙二醇酯二醇、聚己二酸丙二醇酯二醇、聚己二酸丁二醇酯二醇、聚己二酸己二醇丁二醇酯二醇、聚己二酸丁二醇己二醇酯二醇、聚碳酸酯二醇、聚邻苯二甲酸一缩二乙二醇酯二醇、聚邻苯二甲酸-1,6-己二醇酯二醇、聚邻苯二甲酸新戊二醇酯二醇中的一种或多种。
5.根据权利要求1-3中任一项所述的柔弹性储热调温相变材料,其特征在于,所述异氰酸酯的指数为0.95-1.05;
和/或,所述异氰酸酯包括甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、4’4-二环己基甲烷二异氰酸酯、1,5-萘二异氰酸酯、对苯二异氰酸酯、苯二亚甲基二异氰酸酯、1,4-环己烷二异氰酸酯、六亚甲基二异氰酸酯、异氟尔酮二异氰酸酯中的一种或多种。
6.一种柔弹性储热调温相变材料的制备方法,其特征在于,包括以下步骤:
S1、将聚酯型多元醇与异氰酸酯在催化剂作用下反应,得到端异氰酸酯预聚物一;
S2、将所述端异氰酸酯预聚物一与聚醚型多元醇反应,得到端异氰酸酯预聚物二;所述聚醚型多元醇的分子量为10000-900000;所述聚醚型多元醇与所述聚酯型多元醇的摩尔比为1:(1-1000);
S3、将所述端异氰酸酯预聚物二与小分子多元醇反应得到柔弹性储热调温相变材料。
7.根据权利要求6所述的柔弹性储热调温相变材料的制备方法,其特征在于,所述聚醚型多元醇与所述聚酯型多元醇的摩尔比为1:(1-1000),优选为1:(200-700);
和/或,所述聚醚型多元醇和聚酯型多元醇在反应前,分别在120-130℃的温度下干燥除水。
8.根据权利要求6所述的柔弹性储热调温相变材料的制备方法,其特征在于,所述催化剂为二月桂酸二丁基锡、钛酸四丁酯、叔胺类、非锡有机化合物、油酸、己二酸、氢氧化钾中的一种或多种。
9.根据权利要求6-8中任一项所述的柔弹性储热调温相变材料的制备方法,其特征在于,包括以下步骤:
S1、将聚酯型多元醇干燥后,加入异氰酸酯,在氮气气氛的保护下,在65-75℃温度条件持续搅拌反应45-60min后,加入催化剂,持续反应60-120min,得到端异氰酸酯预聚物一;
所述异氰酸酯的指数为0.95-1.05;所述聚酯型多元醇的分子量为500-3500;
S2、将干燥后聚醚型多元醇加入到所述端异氰酸酯预聚物一中,在65-75℃中搅拌反应60-180min,得到端异氰酸酯预聚物二;
S3、将小分子多元醇加入到所述端异氰酸酯预聚物二中,在75-85℃下持续搅拌反应60-180min,80℃真空干燥,可得到柔弹性储热调温相变材料。
10.一种权利要求1-5中任一项所述的柔弹性储热调温相变材料或权利要求6-9中任一项所述的制备方法得到的柔弹性储热调温相变材料的应用,其特征在于,所述柔弹性储热调温相变材料用于人工肌肉纤维、储热调温智能纺织品以及热管理领域。
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