CN115028891A - 一种阻燃导热剂、其制备方法及其在橡胶复合材料中的应用 - Google Patents
一种阻燃导热剂、其制备方法及其在橡胶复合材料中的应用 Download PDFInfo
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Abstract
本发明为阻燃导热材料领域，具体涉及一种阻燃导热剂，采用的技术方案为：在氮化硼表面原位合成焦磷酸哌嗪，得到改性氮化硼即为阻燃导热剂。本发明还涉及上述阻燃导热剂的制备方法。采用上述方案，通过在氮化硼表面原位合成焦磷酸哌嗪得到改性后的氮化硼纳米材料。本发明得到的改性氮化硼，一方面具有较高的热导率可以提高橡胶复合材料的导热性能；另一方面在其表面含有的焦磷酸哌嗪结构具有催化成炭的效果，能够提高可膨胀石墨形成的膨胀炭层的致密性。将可膨胀石墨和改性氮化硼共同添加到橡胶中可以制得具有优异的阻燃和导热性能的橡胶复合材料。
Description
技术领域
本发明为阻燃导热材料领域，具体涉及一种阻燃导热剂、其制备方法及其在橡胶复合材料中的应用。
背景技术
通用橡胶如天然橡胶、丁苯橡胶、顺丁橡胶等有着良好的物理性能和化学性能，被广泛应用于轮胎和输送带等制品。但其容易燃烧并且热导率低，从而限制了其使用范围。因此开发一种具有阻燃和导热功能的橡胶复合材料具有重要意义。
六方氮化硼是一种具有片层结构的无机材料，导热率高。但是未改性的氮化硼阻燃效率低，因此需要对其表面改性以提高阻燃性能。焦磷酸哌嗪是一种含有P、N元素的膨胀型阻燃剂，现有技术中有将其与氮化硼联合使用，以提高材料的阻燃和导热性能。但是其是简单的物理共混，在基体中的分散性较差，所以导致力学性能较差和阻燃效率较低。
可膨胀石墨是一种层状的材料，在受热会分解形成膨胀的炭层，覆盖在基体表面从而起到阻燃作用，但是其形成的膨胀炭层疏松多孔，难以有效地阻隔热量的传递，故其单独使用时阻燃效率低。
本发明通过氮化硼上原位合成焦磷酸哌嗪并与可膨胀石墨协效，一方面通过表面改性提高了氮化硼在基体中的分散性，改善了其力学性能；另一方面两者协效在提高可膨胀石墨碳层密度，增强其阻燃效率的同时，进一步提高了复合材料的导热性能。
发明内容
本发明的目的在于开发一种性能优异的阻燃导热剂，采用的技术方案为：在氮化硼表面原位合成焦磷酸哌嗪，得到改性氮化硼即为阻燃导热剂。
上述阻燃导热剂的制备方法为：
(a)羟基化氮化硼的制备：将氮化硼水浴超声处理18-24h，并将上层清液离心、干燥处理，即得到单层或者少层的羟基化的氮化硼；
(b)焦磷酸哌嗪改性氮化硼的制备：将羟基化氮化硼、磷酸和无水乙醇混合并分散均匀，得A液；将哌嗪溶解在乙醇溶液中得到B液；将B液缓慢滴加到温度升至140～160℃的A液中，反应0.5～2h得到中间产物，将中间产物抽滤、无水乙醇清洗后，置于马弗炉中升温至260～300℃反应2～2.5h，得到焦磷酸哌嗪改性氮化硼即为阻燃导热剂。
具体地，所述步骤(a)中，在超声水浴条件下，氮化硼片层会断裂和分离，缺陷位点的B-N会受到水中氧原子的攻击，进而形成羟基化氮化硼。
步骤(b)中羟基化氮化硼、磷酸和哌嗪的摩尔比为20:2:1。所述中间产物置于马弗炉处理过程在氮气保护下进行。
焦磷酸哌嗪是一种含有P、N元素的膨胀型阻燃剂，其可以在氮化硼表面的活性位点进行原位聚合，经过焦磷酸哌嗪改性后的氮化硼具有优异的阻燃和导热性能。
本发明的另一目的是提供一种利用上述阻燃导热剂制备橡胶复合材料的方法，具体是将所述阻燃导热剂与可膨胀石墨复配添加到橡胶中制备橡胶复合材料。
所述橡胶复合材料按照以下质量份数制备而成：橡胶100份，炭黑40～50份，氧化锌5份，硬脂酸1～2份，促进剂NS 1～1.5份，促进剂M1～1.5份，硫磺2～2.5份，防老剂RD 1～1.5份，改性氮化硼3～7份，可膨胀石墨18～25份。
其制备方法为：向密炼机中依次加入橡胶、氧化锌、硬脂酸、防老剂RD、促进剂NS、促进剂NS、炭黑、改性氮化硼、可膨胀石墨、硫磺，混炼均匀后在开炼机压制成片，用平板硫化机硫化，硫化条件为：155-165℃/5-8MPa×(15-20min)。
所述橡胶为天然橡胶、丁苯橡胶、顺丁橡胶中的至少一种。
上述方案，通过在氮化硼表面原位合成焦磷酸哌嗪得到改性后的氮化硼纳米材料。本发明得到的改性氮化硼，一方面具有较高的热导率可以提高橡胶复合材料的导热性能；另一方面在其表面含有的焦磷酸哌嗪结构具有催化成炭的效果，能够提高可膨胀石墨形成膨胀炭层的致密性，同时可以改善氮化硼在基体中的分散性。将可膨胀石墨和改性氮化硼共同添加到橡胶中可以制得具有优异的阻燃和导热性能的橡胶复合材料。
附图说明
图1为实施例1中试样的热释放速率曲线；
图2为实施例1中试样的热释放总量曲线。
具体实施方式：
下面结合实例对本发明的技术方案作进一步详细描述。
实施例1
一、焦磷酸哌嗪改性氮化硼的制备
(a)羟基化氮化硼的制备：将40g氮化硼在水浴超声处理18h，并将上层清液离心后干燥，即得到单层或者少层的羟基化的氮化硼。
(b)将25g羟基化氮化硼置于马弗炉中将25g BN分散在11.5毫升磷酸和100毫升无水乙醇溶液中，得混合液A，随后将4.3g的哌嗪溶解在200乙醇溶液中得到混合液B。将混合液A升温至150℃后，将混合液B缓慢滴加到混合液A中反应1h得到二磷酸哌嗪改性后的氮化硼，随后将该产物抽滤，用无水乙醇洗去未反应的哌嗪和磷酸，最后将该产物置于马弗炉在氮气保护的条件下升温至260℃反应2.5h得到焦磷酸哌嗪改性氮化硼。
二、橡胶复合材料的制备及性能测试
1试样制备
试样配方如表1所示，混炼方法为在密炼机中依次加入橡胶、氧化锌、硬脂酸、防老剂RD、促进剂NS、促进剂NS、炭黑、改性氮化硼、可膨胀石墨、硫磺；混炼均匀后在开炼机压制成片，用平板硫化机硫化，硫化条件为：155℃/8MPa×20min。
表1不同试样的配方表(质量份)
2橡胶复合材料性能测试
极限氧指数测试按照ASTM D2863进行，微型量热仪：采用美国Govmark MCC-2微型量热仪对样品进行热释放测试；力学性能测试照GB/T6344-2008标准进行，试样的拉伸速率为500mm/min，热导率测试；在室温下使用TC3100热导率仪进行测试。表2显示了试样一、二、三和四的极限氧指数LOI、热释放峰值(PHRR)、拉伸强度、断裂伸长率以及热导率。图1和图2分别是样品一、二、三、四的HRR和THR曲线
表2橡胶复合材料的性能测试数据
由上表数据可知，同时添加了可膨胀石墨和采用本发明方案制备的改性氮化硼后，橡胶复合材料的热释放峰值(PHRR)和热释放总量(THR)大幅度降低，而单独添加可膨胀石墨或将其于氮化硼复配试样，橡胶复合材料的PHRR和THR虽然也有所降低，然而在添加质量不变的情况下，显然可膨胀石墨与本发明方案制备的改性氮化硼二者协同使用阻燃效果更优；从导热率数据可以看出，二者协同使用，还可以大大提高橡胶复合材料的导热性能。这也证明了本发明方案制备的改性氮化硼与可膨胀石墨协效，可以制备具有阻燃、导热性能优异的橡胶复合材料。
实施例2
一焦磷酸哌嗪改性氮化硼的制备
(a)羟基化氮化硼的制备：将35g氮化硼在水浴超声处理21h，并将上层清液离心后干燥，即得到单层或者少层的羟基化的氮化硼。
(b)将12.5g羟基化氮化硼分散在5.8毫升磷酸和100毫升无水乙醇溶液中，得混合液A，随后将2.2g的哌嗪溶解在200乙醇溶液中得到混合液B。将混合液A升温至150℃后，将混合液B缓慢滴加到混合液A中反应1h得到二磷酸哌嗪改性后的氮化硼，随后将该产物用抽滤，用无水乙醇洗去未反应的哌嗪和磷酸，最后将该产物置于马弗炉在氮气保护的条件下升温至280℃反应2.2h得到焦磷酸哌嗪改性氮化硼。
二橡胶复合材料的制备及性能测试
1试样制备
试样配方如表3所示，混炼方法为在密炼机中依次加入橡胶、氧化锌、硬脂酸、防老剂RD、促进剂NS、促进剂NS、炭黑、改性氮化硼、可膨胀石墨、硫磺；混炼均匀后在开炼机压制成片，用平板硫化机硫化，硫化条件为：160℃/6.5MPa×18min。
表3不同试样的配方表(质量份)
2橡胶复合材料性能测试
极限氧指数测试按照ASTM D2863进行，微型量热仪：采用美国Govmark MCC-2微型量热仪对样品进行热释放测试；力学性能测试照GB/T6344-2008标准进行，试样的拉伸速率为500mm/min，热导率测试；在室温下使用TC3100热导率仪进行测试。表4显示了试样五和试样六的极限氧指数LOI、热释放峰值(PHRR)、拉伸强度、断裂伸长率以及热导率。由数据可知，本发明制备的阻燃、导热橡胶具有良好的阻燃性能和导热性能。
表4不同试样的性能测试数据
实施例3
一焦磷酸哌嗪改性氮化硼的制备
(a)羟基化氮化硼的制备：将30g氮化硼在水浴超声处理24h，并将上层清液离心后干燥，即得到单层或者少层的羟基化的氮化硼。
(b)将16.7g BN分散在7.6毫升磷酸和100毫升无水乙醇溶液中，得混合液A，随后将2.9g的哌嗪溶解在200乙醇溶液中得到混合液B。将混合液A升温至150℃后，将混合液B缓慢滴加到混合液A中反应1h得到二磷酸哌嗪改性后的氮化硼，随后将该产物用抽滤，用无水乙醇洗去未反应的哌嗪和磷酸，最后将该产物置于马弗炉在氮气保护的条件下升温至300℃反应2.0h得到焦磷酸哌嗪改性氮化硼。
二橡胶复合材料的制备及性能测试
1试样制备
试样配方如表5所示，混炼方法为在密炼机中依次加入橡胶、氧化锌、硬脂酸、防老剂RD、促进剂NS、促进剂NS、炭黑、改性氮化硼、可膨胀石墨、硫磺；混炼均匀后在开炼机压制成片，用平板硫化机硫化，硫化条件为：165℃/5MPa×15min。
表5不同试样的配方表(质量份)
2橡胶复合材料性能测试
极限氧指数测试按照ASTM D2863进行，微型量热仪：采用美国Govmark MCC-2微型量热仪对样品进行热释放测试；力学性能测试照GB/T6344-2008标准进行，试样的拉伸速率为500mm/min，热导率测试；在室温下使用TC3100热导率仪进行测试。表6显示了试样七和试样八的极限氧指数LOI、热释放峰值(PHRR)、拉伸强度、断裂伸长率以及热导率。由数据可知，本发明制备的阻燃、导热橡胶具有良好的阻燃性能和导热性能。
表6不同实验的性能测试数据
另外，经由申请人大量试验验证，本发明方案制备的焦磷酸哌嗪改性氮化硼，与普通氮化硼相比，其与基体之间的相容性大大提高，而若焦磷酸哌嗪与氮化硼仅物理混合复配使用，并不能改善氮化硼的分散性，且阻燃效果较差；而若单独用焦磷酸哌嗪与可膨胀石墨复配，虽然阻燃效果有一定提高，然导热性能较差。由此可见，采用本发明技术方案制备的焦磷酸哌嗪改性氮化硼与可膨胀石墨协效，可以大大提高橡胶复合材料的阻燃、导热性能。
Claims (8)
1.一种阻燃导热剂，其特征在于：在氮化硼表面原位合成焦磷酸哌嗪，得到改性氮化硼即为阻燃导热剂。
2.一种如权利要求1所述阻燃导热剂的制备方法，包括以下步骤：
(a)羟基化氮化硼的制备：将氮化硼水浴超声处理18-24h，并将上层清液离心、干燥处理，即得到单层或者少层的羟基化的氮化硼；
(b)焦磷酸哌嗪改性氮化硼的制备：将羟基化氮化硼、磷酸和无水乙醇混合并分散均匀，得A液；将哌嗪溶解在乙醇溶液中得到B液；将B液缓慢滴加到温度升至140～160℃的A液中，反应0.5～2h得到中间产物，将中间产物抽滤、无水乙醇清洗后，置于马弗炉中升温至260～300℃反应2～2.5h，得到焦磷酸哌嗪改性氮化硼即为阻燃导热剂。
3.根据权利要求2所述阻燃导热剂的制备方法，其特征在于：所述步骤(b)中，氮化硼、磷酸和哌嗪的摩尔比为20:2:1。
4.根据权利要求2所述阻燃导热剂的制备方法，其特征在于：所述步骤(b)中，中间产物置于马弗炉处理过程在氮气保护下进行。
5.一种如权利要求1-4任一所述阻燃导热剂制备橡胶复合材料的方法，其特征在于：将所述阻燃导热剂与可膨胀石墨复配添加到橡胶中制备橡胶复合材料。
6.根据权利要求5所述橡胶复合材料的制备方法，其特征在于：所述橡胶复合材料按照以下质量份数制备而成：橡胶100份，炭黑40～50份，氧化锌5份，硬脂酸1～2份，促进剂NS 1～1.5份，促进剂M 1～1.5份，硫磺2～2.5份，防老剂RD 1～1.5份，改性氮化硼3～7份，可膨胀石墨18～25份。
7.根据权利要求6所述橡胶复合材料的制备方法，其特征在于：其制备方法为：向密炼机中依次加入橡胶、氧化锌、硬脂酸、防老剂RD、促进剂NS、促进剂NS、炭黑、改性氮化硼、可膨胀石墨、硫磺，混炼均匀后在开炼机压制成片，用平板硫化机硫化，硫化条件为：155-165℃/5-8MPa×(15-20min)。
8.根据权利要求5或6或所述橡胶复合材料的制备方法，其特征在于：所述橡胶为天然橡胶、丁苯橡胶、顺丁橡胶中的至少一种。
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105367955A (zh) * | 2015-11-27 | 2016-03-02 | 安徽锦洋氟化学有限公司 | 一种耐热高阻燃氟橡胶复合材料 |
| CN109384967A (zh) * | 2018-10-25 | 2019-02-26 | 北京石油化工学院 | 一种高导热氮化硼/天然橡胶复合材料及其制备方法 |
| CN112210131A (zh) * | 2020-10-16 | 2021-01-12 | 马海社 | 一种阻燃橡胶及其制备方法 |
| CN114015229A (zh) * | 2021-12-20 | 2022-02-08 | 平顶山学院 | 一种尼龙阻燃导热复合材料及其制备方法 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105367955A (zh) * | 2015-11-27 | 2016-03-02 | 安徽锦洋氟化学有限公司 | 一种耐热高阻燃氟橡胶复合材料 |
| CN109384967A (zh) * | 2018-10-25 | 2019-02-26 | 北京石油化工学院 | 一种高导热氮化硼/天然橡胶复合材料及其制备方法 |
| CN112210131A (zh) * | 2020-10-16 | 2021-01-12 | 马海社 | 一种阻燃橡胶及其制备方法 |
| CN114015229A (zh) * | 2021-12-20 | 2022-02-08 | 平顶山学院 | 一种尼龙阻燃导热复合材料及其制备方法 |
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