CN114835951B - 一种mq表面改性导热粉体及其制备方法和应用 - Google Patents
一种mq表面改性导热粉体及其制备方法和应用 Download PDFInfo
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Abstract
本发明涉及一种MQ表面改性导热粉体及其制备方法和应用,所述改性粉体的制备方式为采用硅酸酯、六甲基二硅氧烷、四甲基二乙烯基硅氧烷等为原料,在烃类溶剂、醇类溶剂、水、导热粉等混合相溶剂中,以酸为催化剂,反应生成MQ树脂湿法改性导热粉体,得到的导热粉体经过干燥、挥脱小分子处理后与端乙烯基硅油、端侧含氢等进行混合、压延、加热硫化等工艺过程制备导热垫片。本发明的MQ表面改性导热粉体与有机硅基体的相容性好、结合力强,所制备的导热垫片具有低热阻、低挥发、高回弹性等优点,可广泛应用于5G、视频监控等领域,与散热部件紧密贴合,既能起到良好的导热散热作用,又不会造成硅污染等。
Description
技术领域
本发明属于粉体表面处理和导热有机硅复合材料领域,具体涉及一种MQ表面改性导热粉体的制备方法及其在有机硅垫片中的应用。
背景技术
导热粉体因其具有优良的热导率和绝缘性,将其添加在高分子树脂基体中,能够有效赋予高分子树脂优异的导热性能,是目前制备绝缘型导热高分子材料应用最为广泛的方法。以乙烯基硅油为树脂基体、含氢硅油为固化剂添加导热粉来制备导热垫片是导热粉体最为重要的应用方式。导热垫片以其较高的导热系数、低的热阻率、良好柔韧性、回弹性,广泛应用于智能手机、新能源汽车、工业自动化、电力能源、无人机、5G通讯终端等领域的发热器件和散热器件间的缝隙填充和链接,提高发热器件多余热量的传递效率。
导热垫片是填充型导热复合材料,通过导热填料的的大量添加实现其高的热导率,导热填料的大量添加实现高的热导率的同时也带来了导热垫片如回弹性、表面黏性、物理机械性能等变差的问题。为解决上述因导热填料的添加所带来的问题,常在导热垫片配方中添加高粘度的乙烯基硅油、甲基乙烯基硅橡胶、气相二氧化硅、MQ树脂等方式来改善导热垫片的综合性能。
研究表明,采用添加高粘度的乙烯基硅油或甲基乙烯基硅橡胶能够明显改善垫片回弹性等性能,但高粘度硅油会影响导热填料的添加量,无法达到较高的热导率,即使通过其他强烈机械力分散达到热导率要求,后期垫片的成型加工也会受到严重影响,造成垫片压延成型困难、废品率高等问题。其次,作为常用的有机硅补强填料气相二氧化硅也被尝试用于垫片的补强及性能改善,但由于气相二氧化硅表面羟基多、结构化明显,添加后会导致有机硅体系粘度徒增,影响材料的加工和成型性,且添加气相二氧化硅补强导致导热垫片硬度上升明显,影响垫片表面粘度及垫片与热源及散热部件的贴合,导致热阻上升,影响导热效率。
MQ硅树脂因其优良的特性常作为基体树脂用于制备有机硅橡胶,例如专利号CN202010356317.4公开了一种高撕裂强度导热硅胶材料及其制备方法,以表面活性剂改性导热粉体,以高用量的MQ硅树脂与液体硅橡胶复配作为导热填料的载体,与含氢交联剂加成反应后制备出具有高撕裂强度和机械性能的导热硅胶材料。专利号为CN113402887A公开了一种高附着性导热硅胶片及其制备工艺,通过将甲基乙烯基MQ高粘度硅树脂以基体树脂的方式添加到没有导热填料的A组分中,此种方式添加能够较为有效的体现MQ树脂优异的强度和附着力等特性,但是导热填料与基体树脂的结合性和相容性未得到明显改善,垫片热阻偏高。通过上述分析,以MQ硅树脂作为部分基体树脂可有效改善导热硅橡胶材料的各项机械性能,但无法改善基体树脂和导热填料相容性的问题,为保证导热粉体的添加量,还需采用常规表面改性剂如长链硅烷偶联剂等对导热粉体表面进行处理,此种粉体表面处理方式虽然对粉体添加量改善明显,但对体系的回弹性帮助甚小,并且同时还会带来一些可挥发性小分子,长期使用会对如视频监控设备、5G等高精尖领域产生硅污染。
发明内容
本发明旨在解决现有技术中采用添加高粘度乙烯基硅油、甲基乙烯基硅橡胶、MQ树脂、气相二氧化硅等方式改善导热垫片回弹性等性能,所存在的体系粘度高、加工性能差、成品率不高、垫片热阻高等问题以及常规长链硅烷改性导热粉体所带来的硅污染。提供一种MQ表面改性导热粉体的制备方法,该方法制备的导热粉体,既能保持其良好的导热率和添加性,添加到有机硅体系制备的导热垫片还具有回弹性良好、热阻低、无硅污染等优点。
本发明所述一种MQ表面改性导热粉体,其制备工艺为:
将硅酸酯、水、烃类溶剂、醇类溶剂、导热粉等加入到带有感温探头、搅拌桨、通气装置等的反应釜反应1-2h,然后加入计量的六甲基二硅氧烷(MM),四甲基二乙烯基硅烷(viMMvi),升高温度至50-70℃反应3-5h,待反应终止后,将反应结束后的混合物进行过滤、洗涤至pH至5-7,将其放置在通风橱中24h以挥脱可挥发性溶剂,再将改性后的粉体在真空干燥箱中100-120℃,干燥24h,即得到MQ改性导热粉体,其反应过程如下:
所述的各个组分按重量份占比为:硅酸酯100份、烃类溶剂20-40份、六甲基二硅氧烷10-20份、四甲基二乙烯基硅烷1-30份、醇类溶剂5-10份、酸性催化剂2.8-3.5份、水1200-200000份、导热粉体400-20000份;导热粉体的添加量与制备形成的甲基乙烯基MQ树脂和水成比例,具体如下:甲基乙烯基MQ树脂与导热粉体的质量百分比为0.5-10:100,水与导热粉体的比例为3-10:1,以确保导热粉体能够在水相中呈均匀的浆料分散。
所述硅酸酯为硅酸甲酯、硅酸乙酯、硅酸丙酯或它们的缩聚物中的至少一种。
所述烃类溶剂为甲苯、二甲苯、环己烷、正庚烷中的至少一种。
所述醇类溶剂为甲醇、乙醇、异丙醇中的至少一种。
所述酸性催化剂为36%浓盐酸、98%浓硫酸、99%三氟甲磺酸、对甲苯磺酸、全氟磺酸树脂中的至少一种。
所述导热粉体为氧化铝、氧化锌、氮化硼、氮化铝、氮化硅、金刚石中的至少一种,其中位径D50为0.8-150微米。
将制备所得的MQ表面改性导热粉体应用于有机硅导热垫片,所述导热垫片的制备方法为:将粘度为50-5000mPa*s的端乙烯基聚甲基乙烯基硅氧烷1-15%、MQ树脂改性导热粉体80-96%加入真空捏合机中,升温至120℃,捏合并抽真空,捏合时间为1-4h,真空度为0.96-0.98,挥脱小分子结束后降温至25-45℃,加入含氢量为0.18-1.0%、粘度为80-240mPa*s的的端侧含氢硅油0.1-3%、炔醇类抑制剂0.001-0.05%、铂金催化剂0.001-0.05%维持原有真空度捏合均匀后用压延机压延定型成要求厚度及宽度的制品,并过隧道炉进行硫化、裁切成成品。
相比于现有技术,本发明有益效果在于所制备的MQ表面改性导热粉体既可以改善与有机树脂的相容性,同时提高制备导热垫片机械性能等综合性能,具体如下:
(1)相对于常规技术添加其他助剂(气相二氧化硅、高粘度乙烯基硅油、甲基乙烯基硅橡胶)等方式改善导热垫片性能,本发明采用的甲基乙烯基MQ树脂湿法处理导热粉体得到的改性导热粉体,不仅改善了与基体树脂的结合性和相容性获得低粘度的有机硅体系,所制备的导热垫片具有热阻低、附着力高、回弹性好等性能;
(2)MQ表面改性导热粉体的表面含有乙烯基基团,与端侧含氢硅油交联形成网状结构,使得导热粉体均匀稳定的包裹在有机硅树脂的网状体系中,减少了硅油的析出;相对于常规使用分子量较小的长链硅烷偶联剂,长期使用可避免小分子硅化合物的污染。
具体实施方式
为更为详尽的介绍本发明,结合以下实施例对本发明作进一步的阐述和说明。
对比例1
(1)MQ改性导热粉体的制备:
将十二烷基三乙氧基硅烷20g、水6000g、甲苯10g、甲醇5g、氧化铝2100g加入到带有感温探头、搅拌桨、通气装置等的反应釜中反应3h。将其放置在通风橱中24h以挥脱可挥发性溶剂,再将改性后的粉体在真空干燥箱中100℃,干燥24h,备用。
(2)导热垫片的制备:
将500mPa*s端乙烯基聚甲基乙烯基硅氧烷70g、步骤1制备的导热粉体930g加入真空捏合机中,升温至120℃,捏合并抽真空,捏合时间为2h,真空度为0.97,挥脱小分子结束后降温至30℃,加入含氢量为0.36%的端侧含氢硅油1.5g、抑制剂0.23g、铂金催化剂0.23g维持原有真空度捏合均匀后用压延机压延定型成要求厚度及宽度的制品,并过隧道炉进行硫化裁切成成品。
对比例2
(1)MQ改性导热粉体的制备:
将十二烷基三乙氧基硅烷20g、水6000g、甲苯10g、甲醇5g、氧化铝2100g加入到带有感温探头、搅拌桨、通气装置等的反应釜中反应3h。将其放置在通风橱中24h以挥脱可挥发性溶剂,再将改性后的粉体在真空干燥箱中100℃,干燥24h,备用。
(2)导热垫片的制备:
将500mPa*s端乙烯基聚甲基乙烯基硅氧烷69g、甲基乙烯基MQ树脂1g、步骤1制备的导热粉体930g加入真空捏合机中,升温至120℃,捏合并抽真空,捏合时间为2h,真空度为0.97,挥脱小分子结束后降温至30℃,加入含氢量为0.36%的端侧含氢硅油1.5g、抑制剂0.23g、铂金催化剂0.23g维持原有真空度捏合均匀后用压延机压延定型成要求厚度及宽度的制品,并过隧道炉进行硫化裁切成成品。
实施例1
(1)MQ改性导热粉体的制备:
将正硅酸乙酯50g、水6000g、甲苯10g、甲醇5g、氧化铝2100g加入到带有感温探头、搅拌桨、通气装置等的反应釜中,进行混合搅拌10min;加入36%浓盐酸1.5g,并维持温度30℃,反应1h;加入六甲基二硅氧烷MM 5g、四甲基二乙烯基硅烷viMMvi 1g,并升高温度至50℃,维持此温度不变,反应3h。将反应结束后的混合物进行过滤、洗涤至pH至5-7,将其放置在通风橱中24h以挥脱可挥发性溶剂,再将改性后的粉体在真空干燥箱中100℃,干燥24h,备用。
(2)导热垫片的制备:
将500mPa*s端乙烯基聚甲基乙烯基硅氧烷70g、步骤1制备的导热粉体930g加入真空捏合机中,升温至120℃,捏合并抽真空,捏合时间为2h,真空度为0.97,挥脱小分子结束后降温至30℃,加入含氢量为0.36%的端侧含氢硅油1.5g、抑制剂0.23g、铂金催化剂0.23g维持原有真空度捏合均匀后用压延机压延定型成要求厚度及宽度的制品,并过隧道炉进行硫化裁切成成品。
实施例2
(1)MQ改性导热粉体的制备:
将正硅酸乙酯100g、水10000g、甲苯30g、乙醇6g、氧化铝4000g加入到带有感温探头、搅拌桨、通气装置等的反应釜中,进行混合搅拌10min;加入36%浓盐酸1.5g,并维持温度30℃,反应1.5h;加入六甲基二硅氧烷MM 5g、四甲基二乙烯基硅烷viMMvi 3g,并升高温度至60℃,维持此温度不变,反应3h。将反应结束后的混合物进行过滤、洗涤至pH至5-7,将其放置在通风橱中24h以挥脱可挥发性溶剂,再将改性后的粉体在真空干燥箱中120℃,干燥24h,备用。
(2)导热垫片的制备:
将500mPa*s端乙烯基聚甲基乙烯基硅氧烷70g、步骤1制备的导热粉体930g加入真空捏合机中,升温至120℃,捏合并抽真空,捏合时间为2h,真空度为0.98,挥脱小分子结束后降温至30℃,加入含氢量为0.36%的端侧含氢硅油2.2g、抑制剂0.26g、铂金催化剂0.26g维持原有真空度捏合均匀后用压延机压延定型成要求厚度及宽度的制品,并过隧道炉进行硫化裁切成成品。
实施例3
(1)MQ改性导热粉体的制备:
将正硅酸乙酯100g、水10000g、甲苯40g、乙醇6g、氧化铝+金刚石(质量比9:1)5000g加入到带有感温探头、搅拌桨、通气装置等的反应釜中,进行混合搅拌10min;加入对甲苯磺酸2.5g,并维持温度40℃,反应2.5h;加入六甲基二硅氧烷MM 20g、四甲基二乙烯基硅烷viMMvi 15g,并升高温度至65℃,维持此温度不变,反应3h。将反应结束后的混合物进行过滤、洗涤至pH至5-7,将其放置在通风橱中24h以挥脱可挥发性溶剂,再将改性后的粉体在真空干燥箱中120℃,干燥24h,备用。
(2)导热垫片的制备:
将1000mPa*s端乙烯基聚甲基乙烯基硅氧烷150g、步骤1制备的导热粉体850g加入真空捏合机中,升温至120℃,捏合并抽真空,捏合时间为1.5h,真空度为0.98,挥脱小分子结束后降温至30℃,加入含氢量为0.36%的端侧含氢硅油2.0g、抑制剂0.32g、铂金催化剂0.32g维持原有真空度捏合均匀后用压延机压延定型成要求厚度及宽度的制品,并过隧道炉进行硫化裁切成成品。
实施例4
(1)MQ改性导热粉体的制备:
将正硅酸乙酯100g、水10000g、甲苯40g、乙醇6g、氧化铝+氧化锌+氮化硼(质量比85:1:5)3000g加入到带有感温探头、搅拌桨、通气装置等的反应釜中,进行混合搅拌10min;加入对甲苯磺酸2.5g,并维持温度40℃,反应2.5h;加入六甲基二硅氧烷MM 20g、四甲基二乙烯基硅烷viMMvi 15g,并升高温度至65℃,维持此温度不变,反应3h。将反应结束后的混合物进行过滤、洗涤至pH至5-7,将其放置在通风橱中24h以挥脱可挥发性溶剂,再将改性后的粉体在真空干燥箱中120℃,干燥24h,备用。
(2)导热垫片的制备:
将1000mPa*s端乙烯基聚甲基乙烯基硅氧烷150g、步骤1制备的导热粉体850g加入真空捏合机中,升温至120℃,捏合并抽真空,捏合时间为1.5h,真空度为0.98,挥脱小分子结束后降温至30℃,加入含氢量为0.36%的端侧含氢硅油2.0g、抑制剂0.32g、铂金催化剂0.32g维持原有真空度捏合均匀后用压延机压延定型成要求厚度及宽度的制品,并过隧道炉进行硫化裁切成成品。
实施例5
(1)MQ改性导热粉体的制备:
将正硅酸乙酯100g、水15000g、甲苯40g、乙醇6g、氧化锌+金刚石(质量比30:70)3000g加入到带有感温探头、搅拌桨、通气装置等的反应釜中,进行混合搅拌10min;加入对甲苯磺酸2.5g,并维持温度40℃,反应2.5h;加入六甲基二硅氧烷MM 18g、四甲基二乙烯基硅烷viMMvi 15g,并升高温度至65℃,维持此温度不变,反应4h。将反应结束后的混合物进行过滤、洗涤至pH至5-7,将其放置在通风橱中24h以挥脱可挥发性溶剂,再将改性后的粉体在真空干燥箱中120℃,干燥24h,备用。
(2)导热垫片的制备:
将2000mPa*s端乙烯基聚甲基乙烯基硅氧烷200g、步骤1制备的导热粉体800g加入真空捏合机中,升温至120℃,捏合并抽真空,捏合时间为1.5h,真空度为0.98,挥脱小分子结束后降温至30℃,加入含氢量为0.36%的端侧含氢硅油1.2g、抑制剂0.15g、铂金催化剂0.15g维持原有真空度捏合均匀后用压延机压延定型成要求厚度及宽度的制品,并过隧道炉进行硫化裁切成成品。
垫片性能测试标准及方法
导热系数和热阻测试:利用热流法导热测试仪,按照ASTME D5470-6标准,在环境温度为25℃下测试,测试压力为10psi,热端温度:80℃,样品尺寸26mm*26mm,厚度2mm,叠加不同厚度测试时热阻和导热率;
垫片渗油率测试:将Ф=30mm,厚度2mm的样品放置在干燥的白色滤纸上,一起称重后放置于两块钢化玻璃中间,将样品置于模框中,通过控制四角固定螺丝位的限位柱,调整压缩比为30%并锁紧螺丝,将整体装置放于温度设定为125℃的鼓风干燥箱中,48h取出,通过测试烘烤前后样品的重量及油圈直径,计算样品的出油率;
垫片高温永久变形测定:测试样品尺寸:26mm*26mm*2mm,量取样品的初始厚度为t0,将样品放置表面平整的铝板之间,通过限位柱控制样品的压缩率为30%,并用螺丝固定,样品在压缩状态下,150℃烘烤24h,随后室温冷却30min,待样品恢复常温后,拆除限位装置,将样品静置2h,测试时样品的厚度为t1,计算
实施例与对比例的垫片性能测试结果如表1
表1:垫片性能测试结果
说明:渗油率和回弹性体现在改性导热粉体应用于制备成导热垫片的物理性能,渗油率较高,则会导致垫片变硬、回弹性变差,影响垫片与散热部件的紧密贴合,同时造成硅污染。
最后应当说明的是,以上实施例仅用以说明本发明的技术方案,而非对本发明保护范围的限制,尽管参照较佳实施例对本发明作了详细地说明,本领域的普通技术人员应当理解,可以对本发明的技术方案进行修改或者等同替换,而不脱离本发明技术方案的实质和范围。
Claims (4)
1.一种MQ表面改性导热粉体,其制备工艺为:将硅酸酯、水、烃类溶剂、醇类溶剂、导热粉加入到带有感温探头、搅拌桨、通气装置的反应釜,再加入酸性催化剂反应1-2h,然后加入计量的六甲基二硅氧烷、四甲基二乙烯基硅烷,升高温度至50-70℃反应3-5h,待反应终止后,将反应结束后的混合物进行过滤、洗涤至pH至5-7,将其放置在通风橱中24h以挥脱可挥发性溶剂,再将改性后的粉体在真空干燥箱中100-120℃干燥24h,即得到MQ改性导热粉体;
其中,所述的各个组分按重量份占比为:硅酸酯100份、烃类溶剂20-40份、六甲基二硅氧烷10-20份、四甲基二乙烯基硅烷1-30份、醇类溶剂5-10份、酸性催化剂2.8-3.5份、水10000-15000份、导热粉体3000-5000份;
所述导热粉体为氧化铝、氧化锌、氮化硼、氮化铝、氮化硅、金刚石中的至少一种,其中位径D50为0.8-150微米;
所述酸性催化剂为36%浓盐酸、对甲苯磺酸中的至少一种;
所述硅酸酯为硅酸乙酯。
2.根据权利要求1所述的MQ表面改性导热粉体,其特征在于,所述烃类溶剂为甲苯、二甲苯、环己烷、正庚烷中的至少一种。
3.根据权利要求1所述的MQ表面改性导热粉体,其特征在于,所述醇类溶剂为甲醇、乙醇、异丙醇中的至少一种。
4.如权利要求1所述的MQ表面改性导热粉体应用于有机硅导热垫片。
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