CN115044192B - 一种应用于聚酯类塑料的高填充导热母粒及其制备方法 - Google Patents
一种应用于聚酯类塑料的高填充导热母粒及其制备方法 Download PDFInfo
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Abstract
本发明提供了一种应用于聚酯类塑料的高填充导热母粒及其制备方法，包括以下重量百分比的组成：导热粉体90～97％，基体树脂2～7.5％，润滑分散剂0.5～3％。其制备步骤为：(1)基体树脂制备：在反应釜中加入多元醇进行脱水处理，通入保护气并滴加计算量的二异氰酸酯，恒温下搅拌制得端NCO封端的聚氨酯预聚体；再在温度为60～80℃的聚氨酯预聚体中加入计算量的环氧树脂，反应完全即得。(2)将(1)中的制得的基体树脂、导热粉体、润滑分散剂按照设定重量百分比加入密炼机在110～150℃密炼1～3h，再经过单螺杆挤出机挤出造粒。本发明所制备的导热母粒能够有效提高导热粉体的添加量，显著改善母粒的导热性能，同时提高导热母粒应用于聚酯类塑料中的力学强度和冲击韧性。
Description
技术领域
本发明涉及一种塑料用导热母粒，特别是涉及一种用于聚酯类塑料的高填充导热母粒及其制备方法。
背景技术
聚酯类塑料，是由多元酸和多元醇缩聚而得的塑料总称，主要包括聚对苯二甲酸乙二醇酯、聚对苯二甲酸丁二醇酯等，因其优良的结晶性能、力学性能、绝缘性能、耐热性能和加工性能等，广泛应用于工业零件、电子电器、汽车等领域。但聚酯类塑料本身导热在0.2W/m*K左右，难以满足导热领域的应用要求。
目前，常通过在树脂基体中添加适量的导热粉体，形成导热通路来使聚酯类材料获得导热性能。为使材料具有良好的导热性，往往需要添加较高质量份数的导热粉体才能获得较明显的导热性能提升，由于导热粉体与聚合物基体的极性差异，直接添加在基体中导致其难以在聚合物中分散、剥离，不仅不易形成有效的导热网链结构，还会造成生产成本的增加和力学性能的劣化；同时由于导热粉体与树脂之间存在粒径差异使得在挤出造粒时树脂粒子和导热粉体分层，会影响计量比例差异。为避免上述问题，常通过将导热粉体与其他树脂载体混合制备成导热母粒来解决，不仅如此制备成导热母粒还可解决直接添加导热粉体造成粉尘污染的问题。
例如，专利号CN 104559109 B公开了一种聚碳酸酯导热复合材料及其制备方法，采用先制备导热母粒，再将导热母粒与树脂挤出混合的两步法方法制备导热复合材料，其制备导热母粒时采用碳纳米管和石墨烯按比例计量，通过强气流分散法使石墨烯和碳纳米管均匀分散、吸附到载体炭黑上，制得导热母粒。但由于其制备导热过程采用强气流分散方式，存在严重扬尘等问题，收集困难；其次，碳纳米管、石墨烯、炭黑等导热粉体表面活性高、易团聚，与树脂间的极性差异难以实现高填充，即便可以高填充，材料在高填充状态下为避免下料困难需采用强制辅助喂料装置，这对设备的要求高，易出现出料不均、断条等问题。
导热填料的大比例添加会对聚酯类塑料的韧性产生影响明显，传统的解决方法多采用外加如POE-g-MAH等增韧剂的方式来改善材料的韧性，但会导致材料刚性和热变形温度下降等问题。专利号CN 111978615A公开了一种聚合物导热母粒及其制备方法，通过采用第一聚合物基体20％～70％、导热填料20％～80％、分散剂1％～10％、分散剂0～0.5％、增韧剂0～15％、加工助剂0.3％～5％制备出的导热母粒与聚合物共混可以得到具有较好导热性能和力学性能的复合导热材料。该发明中聚合物导热母粒虽然具有高填充、高导热、高强度等特点，但成分比例复杂，引入增韧剂、分散剂等加工助剂对材料性能存在不可控制的影响。因此，提供一种高填充、好加工、在树脂基体中易于分散、与树脂相容性好并且可以为聚酯类塑料提供良好增韧效果的导热母粒成为业内人士研究的焦点。
发明内容
本发明的目的在于克服现有技术中导热粉体受粉体种类、粒子形貌、粒径、粒径分布、粒子表面特性、水分含量等因素影响其在树脂基体中的流动性和分散性，直接添加易造成粉尘污染、计量不准等问题，以及现有导热母粒因使用其他树脂做载体，影响成品如耐热温度、冲击性等性能影响。本发明提供一种用于聚酯类塑料的高填充导热母粒及其制备方法，所制备的导热母粒具有导热粉体含量高、且树脂载体兼具环氧树脂和聚氨酯树脂的综合优点，对聚酯塑料提供增韧的同时缩水甘油醚的引入可对基体材料提供扩链效果，减少材料性能损失使成品材料具有优良导热性能的同时不影响其他物理性能。
一种应用于聚酯类塑料的高填充导热母粒及其制备方法，包括以下重量百分比的组成：导热粉体为90～97％，基体树脂为2～7.5％，润滑分散剂0.5～3％。
所述基体树脂为环氧基团封端的聚氨酯改性环氧树脂，其结构通式为：其
中n≥1。
所述基体树脂制备所用的多元醇为聚氧化丙烯多元醇、聚氧化丙烯-氧化乙烯共聚多元醇、聚丁二烯多元醇、聚丁二烯-丙烯腈多元醇、脂肪族聚酯多元醇及改性聚酯多元醇中的一种或几种其分子量为200～2000g/mol。
所述基体树脂制备所用的二异氰酸酯化合物为甲苯二异氰酸酯、苯二亚甲基二异氰酸酯、1,6-六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯中的一种或几种。
所述基体树脂制备所用的环氧树脂为双酚A型环氧树脂、双酚F型环氧树脂、氢化双酚A环氧树脂以及双酚A/F型环氧树脂中的一种或几种。
所述导热粉体为氧化铝、氧化镁、氢氧化铝、氢氧化镁、硅微粉、碳酸钙、氧化锌、氮化硼、氮化硅、碳化硅中一种或几种。
所述润滑分散剂为硬脂酸镁、硬脂酸锌、氧化乙烯蜡、乙撑双脂肪酸酰胺类润滑剂、椰油酸酯中一种或几种。
一种应用于聚酯类塑料的高填充导热母粒的制备方法，包括以下步骤：
(1)基体树脂制备：在装有搅拌装置、温度探头、保护气导管及减压装置的反应釜中加入多元醇加热升温至120～140℃，在真空度为0.090～0.099抽真空2～5h，脱除水分后降温至60～80℃，通入干燥保护气，滴加计算量的二异氰酸酯，恒温下搅拌制得端NCO封端的聚氨酯预聚体。再在温度为60～80℃的聚氨酯预聚体中加入计算量的环氧树脂，持续反应3～5h至分析证实无NCO存在，结束反应，得淡黄色均相树脂，即为所述基体树脂；
(2)将导热粉体、基体树脂、润滑分散剂按照设定重量百分比加入带底部出料装置，温度设定为110～150℃的密炼机中，进行密炼，密炼时间为1～3h，再经过单螺杆挤出机，温度设定为110～170℃，再经过单螺杆挤出机进行挤出造粒，可得应用于聚酯类塑料的高填充导热母粒；
其反应方程式如下：
本发明的优点在于：
(1)选用粘度低的多元醇与异氰酸酯、环氧树脂等反应，初始粘度低，在易于合成制备的同时对导热粉体有良好的混合吸附作用利于粉体的大比例添加；(2)缩水甘油醚基团的存在，载体树脂具有与聚酯类塑料的相容性好的同时还可作为聚酯类塑料的扩链剂，减少加工过程中因分子量断裂而影响材料的韧性，对材料物理性能影响小的同时赋予材料优异的导热性能；(3)基体树脂制备、母粒密炼及造粒全程密闭，避免了粉尘污染。所制得的母粒在树脂中易于分散、与树脂相容性好、在赋予材料导热性的同时对材料物理性能影响小，具有广泛的应用领域，解决了目前行业内所遇到的问题。
具体实施方式
结合具体实施方式对本发明做进一步说明，但本发明的实施方式不局限于此。
实施例1
在30000ml的反应釜中中添加1500g分子量为200的聚氧化丙烯二元醇，升温至120℃，抽真空至真空度为0.095，维持3h，降温至65℃，将2042gTDI逐步滴加入反应釜中，恒温65℃，检测NCO含量至10％时，加入E-51环氧树脂18350g反应3h，采用傅里叶红外光谱测试无异氰酸酯峰为反应终点。将氧化铝：372Kg、按照上述制备的基础树脂：20Kg、硬脂酸镁：8Kg，加入容积为500升的密炼机中密炼1h，再经过三段温度设定均为120℃的单螺杆挤出机进行挤出造粒，高填充导热母粒1#备用。
实施例2
在30000ml的反应釜中中添加4000g分子量为500的聚氧化丙烯-氧化乙烯共聚二元醇，升温至130℃，抽真空至真空度为0.097，维持4h，降温至60℃，将2470gTDI逐步滴加入反应釜中，恒温60℃，检测NCO含量至8％时，加入E-44环氧树脂14100g反应3h，采用傅里叶红外光谱测试无异氰酸酯峰为反应终点。将氧化镁：360Kg、按照上述制备的基础树脂：30Kg、椰油酸酯：10Kg，加入容积为500升的密炼机中密炼2h，再经过三段温度设定均为170℃的单螺杆挤出机进行挤出造粒，高填充导热母粒2#备用。
实施例3
在30000ml的反应釜中中添加5000g分子量为1000的聚丁二烯多元醇，升温至100℃，抽真空至真空度为0.097，维持5h，降温至65℃，将2685g1,6-六亚甲基二异氰酸酯逐步滴加入反应釜中，恒温65℃，检测NCO含量至12％时，加入E-35环氧树脂15500g反应5h，采用傅里叶红外光谱测试无异氰酸酯峰为反应终点。将氧化铝：375Kg、按照上述制备的基础树脂：18Kg、TAF：7Kg，加入容积为500升的密炼机中密炼2h，再经过三段温度设定均为150℃的单螺杆挤出机进行挤出造粒，高填充导热母粒3#备用。
实施例4
在30000ml的反应釜中中添加2000g分子量为2000的聚丁二烯-丙烯腈多元醇，升温至120℃，抽真空至真空度为0.093，维持3h，降温至65℃，将1720gTDI逐步滴加入反应釜中，恒温65℃，检测NCO含量至20％时，加入E-44环氧树脂20150g反应4h，采用傅里叶红外光谱测试无异氰酸酯峰为反应终点。将氧化镁：360Kg、按照上述制备的基础树脂：30Kg、硬脂酸锌：10Kg，加入容积为500升的密炼机中密炼1h，再经过三段温度设定均为150℃的单螺杆挤出机进行挤出造粒，高填充导热母粒4#备用。
实施例5
在30000ml的反应釜中中添加1000g分子量为1500的改性聚酯多元醇，升温至140℃，抽真空至真空度为0.097，维持5h，降温至60℃，将6250gTDI逐步滴加入反应釜中，恒温65℃，检测NCO含量至15％时，加入E-54环氧树脂20800g反应3h，采用傅里叶红外光谱测试无异氰酸酯峰为反应终点。将导热粉：368Kg、按照上述制备的基础树脂：27Kg、TAF：5Kg，加入容积为500升的密炼机中密炼1h，再经过三段温度设定均为170℃的单螺杆挤出机进行挤出造粒，高填充导热母粒5#备用。
对比样是在树脂中所添加的母粒为添加以20％的聚氧化乙烯为载体，添加80％氧化铝粉体在密炼机中密炼2h再经过三段温度设定均为120℃的单螺杆挤出机所制备的导热母粒，对比样母粒与树脂进行挤出造粒再制样后进行测试，并与实施例1和3进行对比。
导热聚酯塑料的制备：以质量百分比为48％的PBT为基体、其他助剂为2％与50％上述实施例1-5和对比样制备的导热母粒经过双螺杆挤出，制备出导热PBT。
对实施例1-5和对比样制备的导热PBT进行性能测试，结果如表1所示。
所采用的测试方法说明如下：
拉伸强度：参照标准GB/T 1040，采用承德市金建检测仪器有限公司的UTM-1422
万能实验机测试；
伸长率：参照标准GB/T 1040采用承德市金建检测仪器有限公司的UTM-1422万能实验机测试；
弯曲强度：参照标准GB/T 9341采用承德市金建检测仪器有限公司的UTM-1422万能实验机测试；
缺口冲击强度：参照标准GB/T 1043采用承德市金建检测仪器有限公司的XJUD摆锤冲击实验机测试；
熔融指数：参照标准GB/T 3682采用承德市金建检测仪器有限公司的MFI-1322熔体流动速率仪测试；
导热系数：参照标准ASTM D5470采用湘潭湘仪仪器有限公司的DRL-III导热系数测试仪测试，样品直径为3cm，厚度为2mm。
表1
从上表数据可以看出，添加导热母粒1#和3#所制备的导热塑料较直接添加导热粉体的对比样导热系数有所提升，是因为制备成的导热母粒比导热粉体分散性更佳可填充份数更多，进一步说明导热母粒法的优越性；其次，本发明的导热母粒在赋予材料导热性的同时对材料物理性能影响小，适用于多个应用领域。
上述实施例仅表达了本发明的几个实施方式，其描述较为具体和详细，但并不能因此而理解为对本发明的专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可做出若干的变形和改进，这些都属于本发明的保护范围。
Claims (4)
1.一种应用于聚酯类塑料的高填充导热母粒，其特征在于，包括以下重量百分比的组成：导热粉体90～97％，基体树脂2～7.5％，润滑分散剂0.5～3％，所述基体树脂为环氧基团封端的聚氨酯改性环氧树脂，其结构通式为：
其中n≥1；
所述基体树脂制备方法为：在装有搅拌装置、温度探头、保护气导管及减压装置的反应釜中加入多元醇加热升温至120～140℃，在真空度为0.090～0.099抽真空2～5h，脱除水分后降温至60～80℃，通入干燥保护气，滴加计算量的二异氰酸酯，恒温下搅拌制得端NCO封端的聚氨酯预聚体，再在温度为60～80℃的聚氨酯预聚体中加入计算量的环氧树脂，持续反应3～5h至分析证实无NCO存在，结束反应，得淡黄色均相树脂，即为所述基体树脂；
所述基体树脂制备所用的多元醇为聚氧化丙烯多元醇、聚氧化丙烯-氧化乙烯共聚多元醇、聚丁二烯多元醇、聚丁二烯-丙烯腈多元醇、脂肪族聚酯多元醇及改性聚酯多元醇中的一种或几种，其分子量为200～2000g/mol；
所述基体树脂制备所用的二异氰酸酯化合物为甲苯二异氰酸酯、苯二亚甲基二异氰酸酯、1,6-六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯中的一种或几种；
所述基体树脂制备所用的环氧树脂为双酚A型环氧树脂、双酚F型环氧树脂、氢化双酚A环氧树脂以及双酚A/F型环氧树脂中的一种或几种。
2.根据权利要求1所述的应用于聚酯类塑料的高填充导热母粒，其特征在于，所述导热粉体为氧化铝、氧化镁、氢氧化铝、氢氧化镁、硅微粉、碳酸钙、氧化锌、氮化硼、氮化硅、碳化硅中的一种或几种。
3.根据权利要求1所述的应用于聚酯类塑料的高填充导热母粒，其特征在于，所述润滑分散剂为硬脂酸镁、硬脂酸锌、氧化乙烯蜡、乙撑双脂肪酸酰胺类润滑剂、椰油酸酯中的一种或几种。
4.根据权利要求1～3中任一项所述的应用于聚酯类塑料的高填充导热母粒的制备方法，其特征在于，包括以下步骤：将导热粉体、基体树脂、润滑分散剂按照设定重量百分比加入带底部出料装置，温度设定为110～150℃的密炼机中，进行密炼，密炼时间为1～3h，再经过单螺杆挤出机，温度设定为110～170℃，再经过单螺杆挤出机进行挤出造粒，得应用于聚酯类塑料的高填充导热母粒。
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| CN104072966A (zh) * | 2014-06-10 | 2014-10-01 | 东莞上海大学纳米技术研究院 | 一种多元复合导热功能母粒及制备方法 |
| CN104559136A (zh) * | 2014-12-03 | 2015-04-29 | 华南理工大学 | 氧化铝/聚氨酯/环氧树脂导热复合材料及其制备方法 |
| CN105061999A (zh) * | 2015-08-06 | 2015-11-18 | 殷姝媛 | 一种高导热性能高分子复合材料 |
| CN105153680A (zh) * | 2015-09-09 | 2015-12-16 | 苏州晓谕精密机械股份有限公司 | 一种齿条用耐磨材料及制备方法 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104072966A (zh) * | 2014-06-10 | 2014-10-01 | 东莞上海大学纳米技术研究院 | 一种多元复合导热功能母粒及制备方法 |
| CN104559136A (zh) * | 2014-12-03 | 2015-04-29 | 华南理工大学 | 氧化铝/聚氨酯/环氧树脂导热复合材料及其制备方法 |
| CN105061999A (zh) * | 2015-08-06 | 2015-11-18 | 殷姝媛 | 一种高导热性能高分子复合材料 |
| CN105153680A (zh) * | 2015-09-09 | 2015-12-16 | 苏州晓谕精密机械股份有限公司 | 一种齿条用耐磨材料及制备方法 |
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