CN104449337B - 一种高导热光固化功能涂料的制备方法 - Google Patents

一种高导热光固化功能涂料的制备方法 Download PDF

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CN104449337B
CN104449337B CN201410799746.3A CN201410799746A CN104449337B CN 104449337 B CN104449337 B CN 104449337B CN 201410799746 A CN201410799746 A CN 201410799746A CN 104449337 B CN104449337 B CN 104449337B
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姚伯龙
高旭瑞
姜峻
邓丽朵
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Jiangnan University
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Abstract

本发明涉及一种高导热光固化功能涂料的制备。通过将金属氧化物沉积到石墨烯的表面上，使得在石墨烯添加量很少的情况下，树脂具有高导热性能同时具有可以光固化的可能。通过以上反应，合成得到具有高导热性能的光固化树脂。该树脂可用于电子器件的内部导热材料上，由于，在具有高导热的性能基础上，该涂层采用光固化方式具有环保方面的优势，树脂中采用有机硅来改性，使得该树脂的应用范围进一步扩大。

Description

一种高导热光固化功能涂料的制备方法
技术领域
本发明属于具有高导热、可紫外光固化功能涂料的制备领域，具体涉及一种具有高导热光固化功能涂料的制备方法。
背景介绍
导热涂料广泛应用于国防和国民经济的各个领域，尤其在导热绝缘、导热防腐、元器件散热等领域有重要应用。近年来，随着科学技术的迅猛发展，电子电器产品性能的不断提高和改善，电子元器件体积加倍缩小，芯片高密度组装，电子设备在高频率的工作下会富集大量的热量。为了保证设备在使用环境温度下仍能高可靠性地正常运行并延长使用寿命，其在良好密封的同时产生的热量必须及时排出，由此对导热材料提出了更高的要求。传统的导热材料多为金属、金属氧化物以及非金属材料，其自身耐化学腐蚀性和电绝缘性差、加工成型成本高、力学性能不能满足实际需要等使其应用受到了限制。20世纪90年代发展起来的高分子材料，由于具有优良的电绝缘性及良好的力学性能、耐化学腐蚀性和可靠的加工性能等，因而人们希望以高分子材料为基材制备新型导热材料。但高分子材料普遍存在导热性能差的缺陷，因此采取有效的方法提高高分子基材的导热性能，成为研究新型导热高分子材料最重要的目标。
高分子材料本身的热传导系数比较小，所以填充型高分子复合材料导热性能主要依赖于填充物的导热系数、填充物在基体中的分布以及与基体的相互作用。填料用量较小时，填料虽均匀分散于树脂中，但彼此间未能形成相互接触和相互作用，导热性提高不大；填料用量提高到某～临界值时，填料间形成接触和相互作用，体系内形成了类似网状或链状结构形态，即形成导热网链。当导热网链的取向与热流方向～致时，材料导热性能提高很快，体系中在热流方向上未形成导热网链时，会造成热流方向上热阻很大，导致材料导热性能很差。
石墨烯是一种有效的强化传热填料，Yu利用石墨烯纳米片制备了环氧树脂基的热界面材料，当填充体积分数为25％的石墨烯纳米片时，体系热导率达到6.44W/(m·K)，此热导率值超过了传统填料在高填充量下的热导率值。
中国专利201110220802.x提供了～种高导热绝缘环氧树脂胶及其在LED用挠性铝基覆铜板上的应用该导热绝缘环氧树脂胶的制备，采用微电子用高纯环氧树脂和离子捕捉剂，减少环氧树脂胶中游离离子的存在和限制游离离子的活动，提高胶的绝缘性能，同时添加高导热无机填料，配制成高导热绝缘环氧树脂胶。用该种环氧树脂胶直接粘接铜箔和铝箔，再通过连续热压成型、高温后固化处理，制备成一种可以用作LED散热基板的高导热挠性铝基覆铜板。
发明内容
本发明的导热填料沉积在石墨烯上，使其在高填充量的时候仍然具有可光固化的性能。本发明的目的在于提供一种制备具有光固化高导热性能的涂料。
本发明的技术方案是：一种高导热光固化功能涂料的制备方法，包括如下步骤：
(1)可光固化树脂的制备:在氮气氛围下将聚酯二元醇及催化剂加入到三口烧瓶中,在60～80℃温度范围内搅拌滴加二异氰酸酯三聚体反应3～5h,得到溶液A；在氮气氛围下将二异氰酸酯、多羟基羧酸、硅油和催化剂加入到三口烧瓶中,在30～50℃温度范围内搅拌反应2～4h,得到溶液B；在氮气氛围下将二异氰酸酯、一端含羟基,一端含紫外光敏基团的化合物、催化剂加入到三口烧瓶中,在30～50℃温度范围内搅拌反应2～4h,得到溶液C；将得到的A溶液温度升高至60一80℃,然后将溶液C慢慢滴加到A内,反应4～6h,采用丙酮调节体系的粘度,得到溶液D。将得到的溶液B缓慢滴加到溶液D中,得到溶液E,在溶液E中加入一点阻聚剂,然后将一端含羟基,一端含紫外光敏基团的化合物滴加到溶液E中,保持温度不变,反应时间2～4h；将得到的溶液E降低温度至40～60℃,加入胺中和,加入去离子水,搅拌1～1.5h,制得有机硅改性的水性光固化聚氨酯；
(2)导热填料的制备:将一定量的石墨烯和NaNO3放到烧杯中,加入一定量的浓硫酸。将混合物室温搅拌1～3h,转移至80～100℃水浴锅,放置1～2h。接着将混合物放置于冰浴中,用1～3h将一定量的强氧化剂缓慢加入到混合物中,在冰浴中继续搅拌2～4h,再将混合物放在50～80℃水浴中搅拌数小时,混合物的颜色变化为黑一绿一深棕一砖棕,往混合物中倒入去离子水,并将其温度控制在80～95℃保持30～60min,当混合物的温度降至60～80℃时,加入一定量的氧化剂,溶液颜色迅速变为亮黄色,将混合物用酸洗通过搅拌、离心洗涤3～5次,用去离子水重复此过程3～5次,直到离心的上层清夜。将所得沉淀转移至60～80℃干燥箱干燥24～48h,所得产物即为氧化石墨,将所制备的氧化石墨样品,放置于超声机中数小时,得到棕色均一液体,转移至干燥箱中,条件也为60～80℃反应24～48h,所得产物即为氧化石墨烯,获得的氧化石墨烯粉末加入到金属氧化物或氮化物溶液中。强力搅拌2～4h,超声30～60min,快速加热到一定温度,获得石墨烯和金属氧化物或氮化物的复合样品；
(3)高导热光固化涂料的制备:称取一定量的树脂,加入一定量的导热填料,强烈搅拌2～4h,超声30～60min,加入一定量的流平助剂、成膜助剂、分散剂、消泡剂紫外灯下固化成膜。
步骤(1)中所述的A溶液中二异氰酸酯三聚体为己二异氰酸酯(HDI)三聚体、二异氰酸酯为甲苯二异氰酸酯(TDI)三聚体、异佛尔酮二异氰酸酯(IPDI)三聚体中的至少一种,聚酯二元醇为聚碳酸酯二元醇、聚己内酯二元醇、己二酸聚酯二元醇中的一种或几种的混合物,聚酯二元醇与二异氰酸酯三聚体的摩尔比为:n(二异氰酸酯三聚体)/n(聚酯二元醇)＝1:(1.5-3)；B溶液中的端羟基硅油为端羟甲基硅油、端羟乙基硅油、端羟丙基硅油、端羟丁基硅油中的一种或几种的混合物,端羟基硅油的分子量在500～2000,二异氰酸酯为甲苯二异氰酸酯(TDI)、异佛尔酮二异氰酸酯(IPDI)、己二异氰酸酯(HDI)、4,4'-二苯基甲烷二异氰酸酯中的一种或几种的混合物；多羟基羧酸为2,2'一二羟甲基丙酸(DMPA)、2,2'一二羟甲基丁酸(DMBA)中的一种或几种的混合物,二异氰酸酯与多羟基羧酸的物质的量比:n(二异氰酸酯)/n(多羟基羧酸)＝(4～6):1；羟基硅油与二异氰酸酯的物质的量的比:n(羟基硅油)/n(二异氰酸酯)＝1:(2～4),催化剂为二月桂酸二丁基锡(DBTDL),催化剂的质量百分含量为0.1～0.3％；C溶液中的一端含羟基,一端含紫外光敏基团的化合物为羟基丙烯酸酯为季戊四醇三丙烯酸酯(PETA)或甲基丙烯酸羟乙酯(HEMA)或丙烯酸羟乙酯(HEA)一种或几种的混合物,阻聚剂为对苯二酚或对甲氧基酚中的一种或几种的混合物,羟基丙烯酸酯与二异氰酸酯比为:n(羟基丙烯酸):n(二异氰酸酯)＝1:(10～3)；溶液E中的阻聚剂为对苯二酚、对甲氧基苯酚、对羟基苯甲醚中的一种或几种混合物,胺为三乙胺或二甲氨基乙醇中的一种或几种的混合物,三乙胺的物质的量与羧基的摩尔比:n(三乙胺)/n(羧基含量)＝(0.6～1.1):1；去离子水的加入的质量分数为树脂的30～60％。
步骤(2)中所述的强氧化剂为高锰酸钾,氧化剂为高锰酸钾H2O2中的一种或几种的混合物,酸为盐酸、硫酸、酯酸、硝酸中的一种或几种的混合物,金属氧化物为氧化铁、氧化锌、氧化铜、氧化铝、碳化硅、氮化硼、氮化铝、氮化硼中的一种或几种的混合物；
步骤(3)树脂的质量与填料的质量比为:100:(1～40)；
本发明的有益效果是:通过以上反应,合成得到具有高导热性能的光固化树脂。该树脂可用于电子器件的内部导热材料上,由于,在具有高导热的性能基础上,该涂层采用光固化方式具有环保方面的优势,树脂中采用有机硅来改性,使得该树脂的应用范围进一步扩大。
具体实施方式
下面结合实施例对本发明作进一步的说明,但是实施例并不构成对本发明要求保护范围的限制:
实施例1
(1)可光固化树脂的制备:在氮气氛围下将27.69g聚碳酸酯二元醇及0.2g二月桂酸二丁基锡加入到三口烧瓶中,在60℃温度范围内搅拌滴加10.35g HDI三聚体反应3h,得到溶液A；在氮气氛围下将16.56g异氟尔酮二异氰酸酯、5.3g 2,2'-二羟甲基丙酸(DMPA)、15.31g硅油和0.2g二月桂酸二丁基锡加入到三口烧瓶中,在50℃搅拌反应4h,得到溶液B；在氮气氛围下将13.46g异氟尔酮二异氰酸酯、8.54g甲基丙烯酸羟乙酯、0.2g二月桂酸二丁基锡加入到三口烧瓶中,在30℃温度范围内搅拌反应4h,得到溶液C；将得到的A溶液温度升高至80℃,然后将溶液C慢慢滴加到A内,反应4h,采用丙酮调节体系的粘度,得到溶液D。将得到的溶液B缓慢滴加到溶液D中,得到溶液E,在溶液E中加入0.1g对甲氧基苯酚,然后将5.25g甲基丙烯酸羟乙酯滴加到溶液E中,保持温度不变,反应时间2h；将得到的溶液E降低温度至40℃,加入5.47g三乙胺中和,加入去离子水,搅拌1.5h,制得有机硅改性的水性光固化聚氨酯。
(2)导热填料的制备:将一定量的石墨烯和NaNO3放到烧杯中,加入100mL浓硫酸。将混合物室温搅拌1h,转移至80℃水浴锅,放置1h。接着将混合物放置于冰浴中,用1h将10g高锰酸钾缓慢加入到混合物中,在冰浴中继续搅拌2h,再将混合物放在50℃水浴中搅拌5小时,混合物的颜色变化为黑一绿一深棕一砖棕。往混合物中倒入500mL去离子水,并将其温度控制在80℃保持30min。当混合物的温度降至60℃时,加入10mL的H2O2,溶液颜色迅速变为亮黄色。将混合物用酸洗通过搅拌、离心洗涤3次,用去离子水重复此过程3次,直到离心的上层清夜。将所得沉淀转移至60℃干燥箱干燥48h,所得产物即为氧化石墨。将所制备的氧化石墨样品,放置于超声机中6小时,得到棕色均一液体,转移至干燥箱中,条件也为80℃反应48h,所得产物即为氧化石墨烯。获得的氧化石墨烯粉末加入到氧化锌溶液中。强力搅拌4h,超声60min,快速加热到200℃,获得石墨烯和金属氧化锌的复合样品。
(3)高导热光固化涂料的制备:称取50g树脂,加入2g左右的导热填料,强烈搅拌4h,超声60min,加入0.5g流平助剂、2g成膜助剂、0.5g分散剂、0.5g消泡剂紫外灯下固化成膜。
实施例2
(1)可光固化树脂的制备:在氮气氛围下将24.58g聚己内酯二元醇及0.1g二月桂酸二丁基锡加入到三口烧瓶中,在70℃温度范围内搅拌滴加11.24g HDI三聚体反应4h,得到溶液A；在氮气氛围下将11.48g甲苯二异氰酸酯(TDI)、5.2g 2,2'-二羟甲基丁酸(DMBA)、14.25g硅油和0.2g二月桂酸二丁基锡加入到三口烧瓶中,在60℃搅拌反应3h,得到溶液B；在氮气氛围下将12.36g二异氰酸酯为甲苯二异氰酸酯(TDI)、16.23g季戊四醇三丙烯酸酯、0.29二月桂酸二丁基锡加入到三口烧瓶中,在40℃温度范围内搅拌反应5h,得到溶液C；将得到的A溶液温度升高至70℃,然后将溶液C慢慢滴加到A内,反应5h,采用丙酮调节体系的粘度,得到溶液D。将得到的溶液B缓慢滴加到溶液D中,得到溶液E,在溶液E中加入0.19对对苯二酚,然后将12.129季戊四醇三丙烯酸酯滴加到溶液E中,保持温度不变,反应时间3h；将得到的溶液E降低温度至50℃,加7.18g三乙胺中和,加入去离子水,搅拌1.5h,制得有机硅改性的水性光固化聚氨酯。
(2)导热填料的制备:将一定量的石墨烯和NaNO3放到烧杯中,加入50mL浓硫酸。将混合物室温搅拌1.5h,转移至70℃水浴锅,放置2h。接着将混合物放置于冰浴中,用2h将15g高锰酸钾缓慢加入到混合物中,在冰浴中继续搅拌3h,再将混合物放在40℃水浴中搅拌3小时,混合物的颜色变化为黑一绿一深棕一砖棕。往混合物中倒入1000mL去离子水,并将其温度控制在70℃保持60min。当混合物的温度降至70℃时,加入15mL的H2O2,溶液颜色迅速变为亮黄色。将混合物用酸洗通过搅拌、离心洗涤4次,用去离子水重复此过程4次,直到离心的上层清夜。将所得沉淀转移至70℃干燥箱干燥24h,所得产物即为氧化石墨。将所制备的氧化石墨样品,放置于超声机中8小时,得到棕色均一液体,转移至干燥箱中,条件也为70℃反应24h,所得产物即为氧化石墨烯。获得的氧化石墨烯粉末加入到氧化铝溶液中。强力搅拌3h,超声60min,快速加热到250℃,获得石墨烯和金属氧化铝的复合样。
(3)高导热光固化涂料的制备:称取50g树脂,加入4g左右的导热填料,强烈搅拌3h,超声60min,加入1g流平助剂、3g成膜助剂、0.5g分散剂、0.5g消泡剂紫外灯下固化成膜。

Claims (7)

1.一种高导热光固化功能涂料的制备方法，其特征步骤如下：
(1)可光固化树脂的制备：在氮气氛围下将聚酯二元醇及催化剂加入到三口烧瓶中，在60～80℃温度范围内搅拌滴加二异氰酸酯三聚体反应3～5h，得到溶液A；在氮气氛围下将二异氰酸酯、多羟基羧酸、端羟基硅油和催化剂加入到三口烧瓶中，在30～50℃温度范围内搅拌反应2～4h，得到溶液B；在氮气氛围下将二异氰酸酯、一端含羟基，一端含紫外光敏基团的化合物、催化剂加入到三口烧瓶中，在30～50℃温度范围内搅拌反应2～4h，得到溶液C；将得到的A溶液温度升高至60～80℃，然后将溶液C慢慢滴加到A内，反应4～6h，采用丙酮调节体系的粘度，得到溶液D，将得到的溶液B缓慢滴加到溶液D中，得到溶液E，在溶液E中加入一点阻聚剂，然后将一端含羟基，一端含紫外光敏基团的化合物滴加到溶液E中，保持温度不变，反应时间2～4h；将得到的溶液E降低温度至40～60℃，加入胺中和，加入去离子水，搅拌1～1.5h，制得有机硅改性的水性光固化聚氨酯；
(2)导热填料的制备：将一定量的石墨烯和NaNO3放到烧杯中，加入一定量的浓硫酸，将混合物室温搅拌1～3h，转移至80～100℃水浴锅，放置1～2h，接着将混合物放置于冰浴中，用1～3h将一定量的强氧化剂缓慢加入到混合物中，在冰浴中继续搅拌2～4h，再将混合物放在50～80℃水浴中搅拌数小时，混合物的颜色变化为黑-绿-深棕-砖棕，往混合物中倒入去离子水，并将其温度控制在80～95℃保持30～60min，当混合物的温度降至60～80℃时，加入一定量的氧化剂， 溶液颜色迅速变为亮黄色，将混合物用酸洗通过搅拌、离心洗涤3～5次，用去离子水重复此过程3～5次，直到离心的上层清夜，将所得沉淀转移至60～80℃干燥箱干燥24～48h，所得产物即为氧化石墨；将所制备的氧化石墨样品，放置于超声机中数小时，得到棕色均一液体，转移至干燥箱中，条件也为60～80℃反应24～48h，所得产物即为氧化石墨烯，获得的氧化石墨烯粉末加入到金属氧化物或氮化物溶液中，强力搅拌2～4h，超声30～60min，快速加热到一定温度，获得石墨烯和金属氧化物或氮化物的复合样品；
(3)高导热光固化涂料的制备：称取一定量的树脂，加入一定量的导热填料，强烈搅拌2～4h，超声30～60min，加入一定量的流平助剂、成膜助剂、分散剂、消泡剂紫外灯下固化成膜。
2.如权利要求1所述一种高导热光固化功能涂料的制备方法,其特征是:A溶液中二异氰酸酯三聚体为己二异氰酸酯(HDI)三聚体、异佛尔酮二异氰酸酯(IPDI)三聚体、甲苯二异氰酸酯(TDI)三聚体中的至少一种,聚酯二元醇为聚碳酸酯二元醇、聚己内酯二元醇、己二酸聚酯二元醇中的一种或几种的混合物,聚酯二元醇与二异氰酸酯三聚体的摩尔比为:n(二异氰酸酯三聚体)/n(聚酯二元醇)＝1:(1.5～3)。
3.如权利要求1所述一种高导热光固化功能涂料的制备方法,其特征是:B溶液中的端羟基硅油为端羟甲基硅油、端羟乙基硅油、端羟丙基硅油、端羟丁基硅油中的一种或几种的混合物,端羟基硅油的分子量在500-2000,二异氰酸酯为甲苯二异氰酸酯(TDI)、异佛尔酮二异氰酸酯(IPDI)、己二异氰酸酯(HDI)、4,4'-二苯基甲烷二异氰酸酯中的一种或几种的混合物；多羟基羧酸为2,2'一二羟甲基丙酸(DMPA)、2,2'-二羟甲基丁酸(DMBA)中的一种或几种的混合物,二异氰酸酯与多羟基羧酸的物质的量比:n(二异氰酸酯)/n(多羟基羧酸)＝(4-6):1；羟基硅油与二异氰酸酯的物质的量的比:n(羟基硅油)/n(二异氰酸酯)＝1:(2-4),催化剂为二月桂酸二丁基锡(DBTDL),催化剂的质量百分含量为0.1-0.3％。
4.如权利要求1所述一种高导热光固化功能涂料的制备方法，其特征是：C溶液中的一端含羟基，一端含紫外光敏基团的化合物为羟基丙烯酸酯为季戊四醇三丙烯酸酯(PETA)或甲基丙烯酸羟乙酯(HEMA)或丙烯酸羟乙酯(HEA)一种或几种的混合物，阻聚剂为对苯二酚或对甲氧基酚中的一种或几种的混合物，羟基丙烯酸酯与二异氰酸酯比为：n(羟基丙烯酸酯)/n(二异氰酸酯)＝1：(1～3)。
5.如权利要求1所述一种高导热光固化功能涂料的制备方法，其特征是：溶液E中的阻聚剂为对苯二酚、对甲氧基苯酚、对羟基苯甲醚中的一种或几种混合物，胺为三乙胺或二甲氨基乙醇中的一种或几种的混合物，三乙胺的物质的量与羧基的摩尔比：n(三乙胺)/n(羧基含量)＝(0.6～1.1)：1；去离子水的加入的质量分数为树脂的30～60％。
6.如权利要求1所述导热填料的制备方法，其特征是：强氧化剂为高锰酸钾，氧化剂为高锰酸钾、H2O2中的一种或几种的混合物，酸为盐酸、硫酸、醋酸、硝酸中的一种或几种的混合物，金属氧化物为氧化铁、氧化锌、氧化铜、氧化铝和金属氮化物氮化铝中的一种或几种的混合物。
7.如权利要求1所述可光固化的导热涂料的制备方法，其特征是：树脂的质量与填料的质量比为：100：(1～40)。
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