CN105670646B - 高导热主链尾接型液晶高分子膜材料及其制备方法 - Google Patents
高导热主链尾接型液晶高分子膜材料及其制备方法 Download PDFInfo
- Publication number
- CN105670646B CN105670646B CN201511010591.1A CN201511010591A CN105670646B CN 105670646 B CN105670646 B CN 105670646B CN 201511010591 A CN201511010591 A CN 201511010591A CN 105670646 B CN105670646 B CN 105670646B
- Authority
- CN
- China
- Prior art keywords
- liquid crystal
- main chain
- type liquid
- direct type
- crystal polymer
- 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.)
- Active
Links
- 229920000106 Liquid crystal polymer Polymers 0.000 title claims abstract description 47
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 title claims abstract description 47
- 239000000463 material Substances 0.000 title claims abstract description 40
- 239000012528 membrane Substances 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title abstract description 17
- 239000004973 liquid crystal related substance Substances 0.000 claims abstract description 47
- 239000011521 glass Substances 0.000 claims abstract description 26
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 19
- 239000000178 monomer Substances 0.000 claims abstract description 19
- 210000002858 crystal cell Anatomy 0.000 claims abstract description 15
- 239000003999 initiator Substances 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 12
- 238000004132 cross linking Methods 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 33
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 16
- 239000000758 substrate Substances 0.000 claims description 10
- 238000005530 etching Methods 0.000 claims description 9
- 238000001704 evaporation Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- MRNHPUHPBOKKQT-UHFFFAOYSA-N indium;tin;hydrate Chemical compound O.[In].[Sn] MRNHPUHPBOKKQT-UHFFFAOYSA-N 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 239000005864 Sulphur Substances 0.000 abstract description 18
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 abstract description 10
- 239000002131 composite material Substances 0.000 abstract description 4
- 238000006116 polymerization reaction Methods 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 230000005669 field effect Effects 0.000 abstract 1
- 230000000977 initiatory effect Effects 0.000 abstract 1
- 238000007711 solidification Methods 0.000 abstract 1
- 230000008023 solidification Effects 0.000 abstract 1
- 239000010408 film Substances 0.000 description 52
- 238000012360 testing method Methods 0.000 description 13
- -1 sulphur alkene Chemical class 0.000 description 9
- 239000004971 Cross linker Substances 0.000 description 8
- 150000001336 alkenes Chemical class 0.000 description 8
- 150000003573 thiols Chemical class 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000007788 liquid Substances 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 238000011160 research Methods 0.000 description 6
- 239000000945 filler Substances 0.000 description 5
- 150000003384 small molecules Chemical class 0.000 description 5
- 238000009792 diffusion process Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000005684 electric field Effects 0.000 description 4
- 230000005484 gravity Effects 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000002861 polymer material Substances 0.000 description 4
- 239000004642 Polyimide Substances 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 125000003963 dichloro group Chemical group Cl* 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229920002521 macromolecule Polymers 0.000 description 3
- 229920001721 polyimide Polymers 0.000 description 3
- 229910052594 sapphire Inorganic materials 0.000 description 3
- 239000010980 sapphire Substances 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- 0 CCC=CC(C(C(*)(*)c1ccccc1)=O)=CC=C Chemical compound CCC=CC(C(C(*)(*)c1ccccc1)=O)=CC=C 0.000 description 2
- 239000004990 Smectic liquid crystal Substances 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 238000001739 density measurement Methods 0.000 description 2
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000012774 insulation material Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 230000002269 spontaneous effect Effects 0.000 description 2
- RVPXTMQYCOZVHH-UHFFFAOYSA-N CCC(OCCOC(CCN=C)=O)=O Chemical compound CCC(OCCOC(CCN=C)=O)=O RVPXTMQYCOZVHH-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 239000000615 nonconductor Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/38—Polymers
- C09K19/3804—Polymers with mesogenic groups in the main chain
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
- C08F216/12—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
- C08F216/125—Monomers containing two or more unsaturated aliphatic radicals, e.g. trimethylolpropane triallyl ether or pentaerythritol triallyl ether
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
- C08F216/12—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
- C08F216/14—Monomers containing only one unsaturated aliphatic radical
- C08F216/1466—Monomers containing sulfur
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
- C08F216/12—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
- C08F216/14—Monomers containing only one unsaturated aliphatic radical
- C08F216/1466—Monomers containing sulfur
- C08F216/1475—Monomers containing sulfur and oxygen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2329/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2329/10—Homopolymers or copolymers of unsaturated ethers
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
本发明公开了一种高导热主链尾接型液晶高分子膜材料及其制备方法,该材料是液晶高分子构成的主链沿薄膜法线方向有序排列,从而大幅度提高法向热导率,帮助电子元器件和电子设备将产生的热量快速有效地传输释放。制备方法通过对硫烯类主链型液晶单体垂直配向,获得较为理想的单畴取向,然后光引发聚合/交联,获得液晶高分子导热薄膜。该复合膜是由主链尾接型液晶单体,交联剂和光致自由基引发剂混合后,填充入涂有氧化铟锡导电玻璃的液晶盒中,在交流电场作用下实现液晶分子垂直取向后,在紫外光照固化下制备形成的。本发明材料可用于帮助电子元器件和电子设备将产生的热量快速有效地传输释放,可以有效的缓解电子器件散热的问题。
Description
技术领域
本发明涉及一种高导热液晶高分子薄膜材料,特别涉及一类垂直取向的主链尾接型液晶高分子构成的聚合物膜及其制备方法。
背景技术
随着微电子集成技术和封装技术的快速发展,及时散热能力已成为影响器件使用寿命的重要制约因素,研制高导热性能的绝缘材料是电子信息产业的迫切需求,具有重要的科学意义。传统的高导热绝缘材料采用的是高分子复合材料。由于高分子聚合物本身是热的不良导体,热导率数值大多在0.2-0.3W·K-1·m-1,目前的高导热绝缘高分子材料主要采用向聚合物中填充导热组分的方法来制备,材料的制备工艺较为复杂,成本较高,而且机械性能普遍很差,限制了其的广泛应用。现在普遍研究以液晶弹性体为代表的具有高热导率、无需填充导热组分的新型聚合物材料来尝试替代传统的高分子复合材料,大多数是采用配向处理的方法,如机械摩擦、电场、磁场等,使液晶高分子链实现宏观的单畴有序性,从而使沿配向方向上的热导率大幅度提高。目前的研究工作大多采取面平行配向,使得面向热导率大幅提升,而针对垂直取向液晶高分子材料的研究工作非常少。
文献Microscale Thermophys.Eng.2003,7,87报道了一种带电荷的溶致液晶聚合物,其特征在于利用1V/μm电场实现面平行配向。研究表明利用此液晶聚合物制得的膜在不同方向上的热导率差异化比较明显,沿面平行方向的热导率是面垂直方向的5~20倍。
文献Adv.Mater.1993,5,107报道了一种面平行取向的液晶高分子薄膜,其特征在于采用机械摩擦聚酰亚胺表面的方法,研究了双丙烯酸酯封端液晶小分子单体在旋涂并交联后,得到的面平行配向的液晶高分子薄膜的热导率,研究表明热导率在面平行方向得到了一个明显的提升,达到5.2±0.9W·K-1·m-1。缺点在于然在薄膜法线方向上仅为0.33±0.03W·K-1·m-1。
文献Macromolecules 2013,46,747报道了一种近晶相结构聚酰亚胺类液晶聚合物,其特征在于利用自支撑膜实现自发垂直取向,并通过热固化交联成膜。缺点是此研究是直接对高粘度的液晶聚合物进行垂直配向,导致实际配向效果并不理想,热导率提升不明显。
US8465670-B2公开了一种带有导热填充物的液晶聚酯聚合物材料。这种材料包含了50~90%体积分数的导热填充物,可以在电子器件上很高效地形成具有优良导热性能的绝缘层。
发明内容
技术问题:为解决传统高导热绝缘材料中填充材料过多,机械性能差,法向导热性能较差等缺点,本发明提供一种不添加填充物的,具有较高热导率的,基于垂直取向的高导热主链尾接型液晶高分子膜材料。
技术方案:本发明的高导热主链尾接型液晶高分子膜材料,由分子主链沿膜法向方向有序排列而成,所述分子主链之间由交联剂连接,每个分子主链由主链尾接型液晶分子首尾连接而成,所述液晶分子构成的分子主链组成单元为以下任意一种:
其中m=1~8,n=2~10,i>2。
本发明的制备上述高导热主链尾接型液晶高分子膜材料的方法,包括以下步骤:
1)以物质的量计,将7~9份主链尾接型液晶单体,1~3份交联剂和0.01份紫外光引发剂按比例溶于二氯甲烷中,室温下搅拌20分钟以上,蒸发掉二氯甲烷后,真空干燥12~24小时;所述液晶单体和交联剂的份数之和为10,所述液晶单体为以下任意一种:
其中m=1~8,n=2~10;
2)取所述步骤1)的混合物,100~130℃下填充入20~200μm带氧化铟锡透明导电玻璃的液晶盒中间,降温至60~80℃后,利用信号发生器施加1~100kHz,100~1500V的交流电,365nm紫外光照交联2~10分钟后,撤去交流电场,冷却至室温;
3)取所述步骤2)的液晶盒放置于氢氟酸中浸泡2~3天,腐蚀玻璃基板后,取出薄膜,即获得主链尾接型液晶高分子薄膜材料。
进一步的,本发明方法中,交联剂为以下两种分子的混合:
所述光致自由基引发剂的分子结构为以下任意一种:
本发明还包括上述主链尾接型液晶高分子薄膜材料在增加电子器件散热性能中的应用。
有益效果:本发明与现有技术相比,具有以下优点:
本发明提供了一种高导热主链尾接型液晶高分子聚合物膜材料。目前,现有的液晶高分子复合导热材料将液晶高分子同无机高导热材料互混(含量达50-80%),导致材料的制备工艺较为复杂,成本较高,机械性能普遍很差,例如专利US8465670-B2公开了一种带有导热填充物的液晶聚酯聚合物材料,这种材料包含了50~90%体积分数的导热填充物,而利用液晶高分子制备无填充的高导热聚合物材料的研究大体是利用机械摩擦、电场、磁场等配向处理的方法,使液晶高分子链实现宏观的单畴有序性,从而使沿配向方向上的热导率大幅度提高,目前存在的主要问题表现为:①绝大多数的材料局限于面平行配向,使得面垂直方向的热导率较低,如文献Adv.Mater.1993,5,107报道了一种采用机械摩擦制备平行取向的液晶高分子薄膜的方法,得到的面平行配向的液晶高分子薄膜,热导率在面平行方向达到5.2±0.9W·K-1·m-1,然而在面垂直方法上仅为0.33±0.03W·K-1·m-1;②少数垂直配向的材料普遍取向效果差,导致垂直方向的热导率较低,如文献Macromolecules2013,46,747报道了一种垂直配向的近晶相结构聚酰亚胺类液晶聚合物材料,它利用自支撑膜实现自发垂直取向,由于是直接对高粘度的液晶聚合物进行垂直配向,导致垂直效果较差,热导率明显偏低。本发明与现有技术相比,具有以下优点:①本发明设计发明了一类主链尾接型液晶小分子,直接通过电场对液晶小分子垂直配向,使得液晶小分子在面垂直方向上实现了很好的有序性;②利用硫烯点击的方法制备垂直取向液晶高分子薄膜,形成的主链尾接型液晶高分子主链为液晶小分子收尾相接而成,在面垂直方向上有很好的取向效果,而液晶高分子主链的高度有序性,使得整个材料沿着膜垂直方向具有较高的热导率;③本发明中的膜材料不添加任何导热填料,机械性能良好,制备成本低,从制备工艺而言,整个材料通过紫外光照固化成膜的方法制备,简单易行,便于工业化生产。
具体实施方式
下面通过实施例对本发明做进一步具体说明。
I主链尾接型液晶高分子聚合物膜材料的制备
将主链尾接型液晶单体,交联剂和紫外光引发剂按照(7~9):(1~3):0.01的摩尔当量比溶于二氯甲烷中,室温下搅拌20分钟以上,蒸发掉二氯甲烷后,真空干燥12~24小时,取混合物在100~130℃下填充入20~200μm带氧化铟锡透明导电玻璃的液晶盒中间,降温至60~80℃后,利用信号发生器施加1~100kHz,100~1500V的交流电,365nm紫外光照交联2~10分钟后,撤去交流电场,冷却至室温,将液晶盒放置于氢氟酸中浸泡2~3天,腐蚀玻璃基板后,取出薄膜,即获得主链尾接型液晶高分子薄膜材料。
所述液晶单体为以下任意一种:
其中m=1~8,n=2~10。
所述交联剂为以下两种的混合:
所述光致自由基引发剂的分子结构为以下任意一种:
II主链尾接型液晶高分子聚合物膜材料的比热容测试,密度测试,热扩散系数测试和热导率计算:
(1)比热容测试:利用耐驰公司的差示热扫描仪中的蓝宝石方法,通过三次测试:空白测试、蓝宝石测试、样品测试检测出薄膜热导率。将8mg剪碎的薄膜放入坩埚内放入仪器中,经过等温-升温-等温的温度程序得到DSC曲线,在扣除空白曲线后和蓝宝石标准样品的DSC曲线进行比较,得到薄膜样品的比热容参数。
(2)密度测试:将干净的比重瓶注满蒸馏水,用带有毛细管的磨石玻璃塞子缓慢地将瓶口塞住,多余的液体从毛细管溢出,设比重瓶盛满蒸馏水后的质量为m水。将质量为m物的待测薄膜样品投入盛满蒸馏水的比重瓶中,溢出水的体积就等于固体的体积,此时比重瓶及瓶内剩余的水和待测固体总质量为m总。利用分析天平测出m水、m物、m总,利用公式ρ物=(m物×ρ水)/(m水+m物-m总)得出薄膜样品的密度数据。
(3)热扩散系数测试:采用激光闪光法测试薄膜的法向热导率和面向热导率。薄膜样品裁剪成25.4毫米直径的圆柱形状,整个表面涂上一层碳作为挡光层,作为加热源的氙灯发射一束激光脉冲,打在样品的下表面,由红外探测器测量样品上表面的相应温升,并由软件计算出样品的热扩散系数。
(4)热导率计算:热导率数据通过以下公式计算得到:热导率=比热容×密度×热扩散系数。
实施例1:硫烯类主链尾接型液晶高分子薄膜,其制备步骤及导热性能测试为:
将3.73克(9mmol)含双键的硫烯类主链型液晶单体0.25克(0.5mmol)的巯基交联剂0.13克(0.5mmol)的烯烃交联剂和0.026克(0.01mmol)的光致自由基引发剂在室温下加入2毫升二氯甲烷帮助溶解,搅拌混合旋干,然后将混合物在130℃下填充入20μm带氧化铟锡导电玻璃的液晶盒中间,降温至60℃后,利用信号发生器施加1kHz,100V的交流电场,使用365nm的紫外光照交联2分钟后,撤去交流电场,冷却至室温后放置于氢氟酸中浸泡2天,腐蚀玻璃基板后,取出薄膜,即获得主链尾接型液晶高分子薄膜材料,薄膜法向热导率为2.439W·m-1·K-1,面向热导率为0.219W·m-1·K-1,比值为11.1。
实施例2:硫烯类主链尾接型液晶高分子薄膜,其制备步骤及导热性能测试为:
将3.51克(9mmol)含双键的硫烯类主链型液晶单体0.25克(0..5mmol)的巯基交联剂0.13克(0.5mmol)的烯烃交联剂和0.026克(0.01mmol)的光致自由基引发剂在室温下加入2毫升二氯甲烷帮助溶解,搅拌混合旋干,然后将混合物在100℃下填充入200μm带氧化铟锡导电玻璃的液晶盒中间,降温至60℃后,利用信号发生器施加100kHz,1500V的交流电场,使用365nm的紫外光照交联10分钟后,撤去交流电场,冷却至室温后放置于氢氟酸中浸泡2天,腐蚀玻璃基板后,取出薄膜,即获得主链尾接型液晶高分子薄膜材料,薄膜法向热导率为2.210W·m-1·K-1,面向热导率为0.256W·m-1·K-1,比值为8.6。
实施例3:硫烯类主链尾接型液晶高分子薄膜,其制备步骤及导热性能测试为:
将3.30克(8mmol)含双键的硫烯类主链型液晶单体0.49克(1mmol)的巯基交联剂0.26克(1mmol)的烯烃交联剂和0.026克(0.01mmol)的光致自由基引发剂在室温下加入2毫升二氯甲烷帮助溶解,搅拌混合旋干,然后将混合物在120℃下填充入100μm带氧化铟锡导电玻璃的液晶盒中间,降温至80℃后,利用信号发生器施加10kHz,300V的交流电场,使用365nm的紫外光照交联3分钟后,撤去交流电场,冷却至室温后放置于氢氟酸中浸泡2天,腐蚀玻璃基板后,取出薄膜,即获得主链尾接型液晶高分子薄膜材料,薄膜法向热导率为1.926W·m-1·K-1,面向热导率为0.192W·m-1·K-1,比值为10。
实施例4:硫烯类主链尾接型液晶高分子薄膜,其制备步骤及导热性能测试为:
将3.30克(8mmol)含双键的硫烯类主链型液晶单体0.25克(0.5mmol)的巯基交联剂0.39克(1.5mmol)的烯烃交联剂和0.026克(0.01mmol)的光致自由基引发剂在室温下加入2毫升二氯甲烷帮助溶解,搅拌混合旋干,然后将混合物在110℃下填充入150μm带氧化铟锡导电玻璃的液晶盒中间,降温至75℃后,利用信号发生器施加50kHz,700V的交流电场,使用365nm的紫外光照交联6分钟后,撤去交流电场,冷却至室温后放置于氢氟酸中浸泡2天,腐蚀玻璃基板后,取出薄膜,即获得主链尾接型液晶高分子薄膜材料,薄膜法向热导率为1.932W·m-1·K-1,面向热导率为0.201W·m-1·K-1,比值为9.6。
实施例5:硫烯类主链尾接型液晶高分子薄膜,其制备步骤及导热性能测试为:
将3.12克(8mmol)含双键的硫烯类主链型液晶单体0.49克(1mmol)的巯基交联剂0.26克(1mmol)的烯烃交联剂和0.026克(0.01mmol)的光致自由基引发剂在室温下加入2毫升二氯甲烷帮助溶解,搅拌混合旋干,然后将混合物在105℃下填充入120μm带氧化铟锡导电玻璃的液晶盒中间,降温至65℃后,利用信号发生器施加50kHz,900V的交流电场,使用365nm的紫外光照交联6分钟后,撤去交流电场,冷却至室温后放置于氢氟酸中浸泡3天,腐蚀玻璃基板后,取出薄膜,即获得主链尾接型液晶高分子薄膜材料,薄膜法向热导率为2.130W·m-1·K-1,面向热导率为0.226W·m-1·K-1,比值为9.4。
实施例6:硫烯类主链尾接型液晶高分子薄膜,其制备步骤及导热性能测试为:将2.89克(7mmol)含双键的硫烯类主链型液晶单体0.74克(1.5mmol)的巯基交联剂0.39克(1.5mmol)的烯烃交联剂和0.026克(0.01mmol)的光致自由基引发剂在室温下加入2毫升二氯甲烷帮助溶解,搅拌混合旋干,然后将混合物在125℃下填充入180μm带氧化铟锡导电玻璃的液晶盒中间,降温至68℃后,利用信号发生器施加40kHz,800V的交流电场,使用365nm的紫外光照交联5分钟后,撤去交流电场,冷却至室温后放置于氢氟酸中浸泡2天,腐蚀玻璃基板后,取出薄膜,即获得主链尾接型液晶高分子薄膜材料,薄膜法向热导率为1.739W·m-1·K-1,面向热导率为0.181W·m-1·K-1,比值为9.6。
实施例7:硫烯类主链尾接型液晶高分子薄膜,其制备步骤及导热性能测试为:
将2.89克(7mmol)含双键的硫烯类主链型液晶单体0.49克(1mmol)的巯基交联剂0.51克(2mmol)的烯烃交联剂和0.026克(0.01mmol)的光致自由基引发剂在室温下加入2毫升二氯甲烷帮助溶解,搅拌混合旋干,然后将混合物在115℃下填充入70μm带氧化铟锡导电玻璃的液晶盒中间,降温至70℃后,利用信号发生器施加4kHz,500V的交流电场,使用365nm的紫外光照交联6分钟后,撤去交流电场,冷却至室温后放置于氢氟酸中浸泡3天,腐蚀玻璃基板后,取出薄膜,即获得主链尾接型液晶高分子薄膜材料,薄膜法向热导率为1.713W·m-1·K-1,面向热导率为0.193W·m-1·K-1,比值为8.8。
实施例8:硫烯类主链尾接型液晶高分子薄膜,其制备步骤及导热性能测试为:
将2.73克(7mmol)含双键的硫烯类主链型液晶单体0.98克(2mmol)的巯基交联剂0.26克(1mmol)的烯烃交联剂和0.026克(0.01mmol)的光致自由基引发剂在室温下加入2毫升二氯甲烷帮助溶解,搅拌混合旋干,然后将混合物在105℃下填充入70μm带氧化铟锡导电玻璃的液晶盒中间,降温至60℃后,利用信号发生器施加60kHz,1100V的交流电场,使用365nm的紫外光照交联8分钟后,撤去交流电场,冷却至室温后放置于氢氟酸中浸泡3天,腐蚀玻璃基板后,取出薄膜,即获得主链尾接型液晶高分子薄膜材料,薄膜法向热导率为1.751W·m-1·K-1,面向热导率为0.190W·m-1·K-1,比值为9.2。
上述实施例仅是本发明的优选实施方式,应当指出:对于本技术领域的普通技术人员来说,在不脱离本发明原理的前提下,还可以做出若干改进和等同替换,这些对本发明权利要求进行改进和等同替换后的技术方案,均落入本发明的保护范围。
Claims (3)
1.一种高导热主链尾接型液晶高分子膜材料,其特征在于,该材料由分子主链沿膜法向方向有序排列而成,所述分子主链之间由交联剂连接,每个分子主链由主链尾接型液晶分子首尾连接而成,所述液晶分子构成的分子主链组成单元为以下任意一种:
其中m=1~8,n=2~10,i>2。
2.一种制备权利要求1所述的高导热主链尾接型液晶高分子膜材料的方法,其特征在于,该方法包括以下步骤:
1)以物质的量计,将7~9份主链尾接型液晶单体,1~3份交联剂和0.01份紫外光引发剂按比例溶于二氯甲烷中,室温下搅拌20分钟以上,蒸发掉二氯甲烷后,真空干燥12~24小时;所述液晶单体和交联剂的份数之和为10,所述液晶单体为以下任意一种:
其中m=1~8,n=2~10;
2)取所述步骤1)的混合物,100~130℃下填充入20~200μm带氧化铟锡透明导电玻璃的液晶盒中间,降温至60~80℃后,利用信号发生器施加1~100kHz,100~1500V的交流电,365nm紫外光照交联2~10分钟后,撤去交流电场,冷却至室温;
3)取所述步骤2)的液晶盒放置于氢氟酸中浸泡2~3天,腐蚀玻璃基板后,取出薄膜,即获得主链尾接型液晶高分子薄膜材料。
3.根据权利要求2所述的方法,其特征在于,所述交联剂为以下两种分子的混合:
所述光致自由基引发剂的分子结构为以下任意一种:
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201511010591.1A CN105670646B (zh) | 2015-12-29 | 2015-12-29 | 高导热主链尾接型液晶高分子膜材料及其制备方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201511010591.1A CN105670646B (zh) | 2015-12-29 | 2015-12-29 | 高导热主链尾接型液晶高分子膜材料及其制备方法 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN105670646A CN105670646A (zh) | 2016-06-15 |
CN105670646B true CN105670646B (zh) | 2018-07-17 |
Family
ID=56297881
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201511010591.1A Active CN105670646B (zh) | 2015-12-29 | 2015-12-29 | 高导热主链尾接型液晶高分子膜材料及其制备方法 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN105670646B (zh) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107365401B (zh) * | 2017-06-15 | 2019-09-10 | 东南大学 | 一种近红外响应主链型液晶弹性体及其制备方法 |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102498149A (zh) * | 2009-09-16 | 2012-06-13 | 株式会社钟化 | 有机导热性添加剂、树脂组合物及硬化物 |
-
2015
- 2015-12-29 CN CN201511010591.1A patent/CN105670646B/zh active Active
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102498149A (zh) * | 2009-09-16 | 2012-06-13 | 株式会社钟化 | 有机导热性添加剂、树脂组合物及硬化物 |
Non-Patent Citations (7)
Title |
---|
Facile Fabrication of Color Tunable Film and Fiber Nanocomposites via Thiol Click Chemistry;Darryl A. Boyd et al.;《Macromolecules》;20140107;695-704 * |
Microactuators from a main-chain liquid crystalline elastomer via thiol–ene "click" chemistry;Eva-Kristina Fleischmann et al.;《J. Mater. Chem. C》;20130813;5885–5891 * |
Photo-Induced Anomalous Deformation of Poly( N -Isopropylacrylamide) Gel Hybridized with an Inorganic Nanosheet Liquid Crystal Aligned by Electric Field;Takumi Inadomi et al.;《Macromolecular Rapid Communications》;20141231;1741-1746 * |
Photoinitiated Bulk Polymerization of Liquid Crystalline Thiolene Monomers;Hans T. A. Wilderbeek et al.;《Macromolecules》;20021026;8962-8968 * |
Photo-Initiated Polymerization of Liquid Crystalline Thiol-Ene Monomers in Isotropic and Anisotropic Solvents;Hans T. A. Wilderbeek et al.;《J. Phys. Chem. B》;20021123;12874-12883 * |
Poly(vinyl benzoate)-backbone mesogen-jacketed liquid crystalline polymers;Hong Yang et al.;《Polymer Chemistry》;20150807;6709–6719 * |
基于硫一烯点击化学的新型聚硅氧烷液晶高分子;杨洪等;《两岸三地高分子液晶态与超分子有序结构学术研讨会》;20120831;77-80 * |
Also Published As
Publication number | Publication date |
---|---|
CN105670646A (zh) | 2016-06-15 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Park et al. | Autonomous surface reconciliation of a liquid‐metal conductor micropatterned on a deformable hydrogel | |
WO2008026356A1 (en) | Conductive adhesive film and solar cell module | |
CN103531693B (zh) | 一种大发光角度的cob面光源的制备方法 | |
CN103013122B (zh) | 微纳米混合填料/液体硅橡胶导热复合材料的制备方法 | |
US20170306207A1 (en) | Composition for heat-dissipation members, heat-dissipation member, electronic device, and heat-dissipation-member production method | |
Yang et al. | Phase change mediated graphene hydrogel-based thermal interface material with low thermal contact resistance for thermal management | |
JP5562574B2 (ja) | 熱伝導性接着剤 | |
TW201000561A (en) | Curable organopolysiloxane composition and semiconductor device | |
MX2010011159A (es) | Materiales conductores termicos para componentes de panel solar. | |
CN105670647A (zh) | 侧链腰接型液晶高分子导热膜材料及其制备方法 | |
CN107849351A (zh) | 导热性树脂组合物、导热片和半导体装置 | |
US10930827B2 (en) | Fluororesin interfacial agent for LED packaging, and methods for preparing and using same | |
TW201840722A (zh) | 螢光體片、使用其的led晶片及led封裝、led封裝的製造方法、以及含有led封裝的發光裝置、背光單元及顯示器 | |
CN105670646B (zh) | 高导热主链尾接型液晶高分子膜材料及其制备方法 | |
JP2019024097A (ja) | 導電性接着フィルム及び太陽電池モジュール | |
JP6902192B2 (ja) | 放熱部材用組成物、放熱部材、電子機器、放熱部材用組成物の製造方法、放熱部材の製造方法 | |
CN104882529B (zh) | 一种cob型led芯片的快速封装方法 | |
Li et al. | An improvement of thermal conductivity of underfill materials for flip-chip packages | |
Yang et al. | Grafted alkene chains: triggers for defeating contact thermal resistance in composite elastomers | |
Tuersun et al. | Enhanced thermal performance from liquid metal in copper/graphite filled elastomer | |
CN111087819A (zh) | 一种液体硅材料复合物及其制备方法和应用 | |
Bao et al. | Polyester–polysiloxane hyperbranched block polymers for transparent flexible materials | |
CN104637898B (zh) | 集成电路器件的导热复合材料层及电子器件导热结构封装方法 | |
JP4730501B2 (ja) | 液状エポキシ樹脂組成物及びこれを用いた半導体装置 | |
Liu et al. | Barrier and thermal properties of polyimide derived from a diamine monomer containing a rigid planar moiety |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |