CN104497268B - 一种阻燃导电聚氨酯材料及其制备方法 - Google Patents
一种阻燃导电聚氨酯材料及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种阻燃导电聚氨酯材料及其制备方法，其中本阻燃导电聚氨酯材料所需的原料包括如下重量百分比的物质：石墨烯0.1～10％；阻燃剂5～20％；离子液体1～20％；含磷含氮多元醇24.5～50％；多元异氰尿酸酯24.5～50％。本聚氨酯材料同时具有较优的导电性和阻燃性，扩大了其应用范围；另外，本制备方法所需的原料易得，设备工艺简单，易于操作，适合于大规模生产。
Description
技术领域
本发明涉及一种聚氨酯复合材料，尤其涉及一种阻燃导电聚氨酯材料，本发明还涉及一种阻燃导电聚氨酯材料的制备方法。
背景技术
聚氨酯全称为聚氨基甲酸酯，是主链上含有氨基甲酸酯官能团的聚合物。聚氨酯材料具有优异的耐磨性、耐候性和力学性能，已经被广泛应用于汽车产业、航天军工、建筑业等领域，具有广阔的市场前景。
为了拓展聚氨酯材料的应用领域，需要向聚氨酯复合材料中添加一些辅助材料，例如导电材料、阻燃材料等，从而使得聚氨酯复合材料具有导电性或阻燃性。
例如现有技术公开了一种聚氨酯吸波凝胶材料的制备，该吸波材料以聚醚多元醇，多异氰酸酯，二氧化硅气凝胶颗粒，去离子水，无卤阻燃剂，导电炭黑，铁氧体份，阻燃消烟剂，复合催化剂，泡沫稳定剂，物理发泡剂为原料，通过聚合反应制备得到，该方法制备材料的导电性和阻燃性不高。
又如现有技术公开了一种煤矿用阻燃抗静电耐磨聚氨酯输送带，其采用聚氨酯弹性体为覆盖胶，聚氨酯弹性体具体是指低聚物多元醇/甲苯二异氰酸酯体系或低聚物多元醇/二苯基甲烷二异氰酸酯体系；并对聚氨酯配方进行优化和改性，即合成时加入磷系阻燃剂或卤系阻燃剂或磷－卤复合阻燃剂，阻燃剂用量为预聚体质量的5～20％之间；聚氨酯弹性体覆盖胶浇注时加入季铵盐型表面活性剂或导电碳黑作抗静电剂，其用量为预聚体质量的2～8％之间。该输送带的导电性和阻燃性同样有待提高。
发明内容
本发明所要解决的第一个技术问题是针对技术现状提供一种具有良好导电、阻燃性能的聚氨酯复合材料。
本发明所要解决的第二个技术问题是提供一种简单、易于操作的聚氨酯复合材料的制备方法，由该方法制备的聚氨酯复合材料具有良好的导电性和阻燃性。
本发明解决上述第一个技术问题所采用的技术方案为：一种阻燃导电聚氨酯材料，所需原料包括如下重量百分比的物质：
其中，阻燃导电聚氨酯材料所需原料还包括重量百分比为0.01％～0.5％的催化剂，例如0.05％、0.1％、0.15％、0.2％、0.25％、0.3％、0.35％、0.4％、0.45％；
优选的，所述催化剂为二月桂酸二正丁基锡或三乙烯二胺。
其中，所述石墨烯为片状结构，所述石墨烯的厚度为0.35～100nm，例如0.5nm、1nm、5nm、10nm、20nm、30nm、50nm、70nm、100nm；
优选的，所述石墨烯的边长尺寸为0.1～100μm，例如0.5μm、1μm、10μm、20μm、30μm、50μm、60μm、70μm；
优选的，所述石墨烯的厚度为0.35～50nm，例如0.5nm、1nm、5nm、10nm、15nm、20nm、30nm、40nm。
其中，所述阻燃剂为氰尿酸三聚氰胺、氰尿酸聚磷酸盐、三聚氰胺、氢氧化铝、氢氧化镁、间苯二酚双(二苯基磷酸酯)(即RDP)、双酚A-双(二苯基磷酸酯)(即BDP)、次磷酸盐、红磷中的一种或两种以上。
优选的，离子液体为1-羟乙基-3-甲基咪唑四氟硼酸盐、1-甲基-3-乙基咪唑四氟硼酸盐、1-羧甲基-4甲基咪唑四氟硼酸盐或1-羧甲基-3-甲基咪唑六氟磷酸盐。
其中，所述含磷含氮多元醇为二乙基-N,N-(2-羟乙基)胺甲基磷酸酯。
其中，所述多元异氰尿酸酯为三羟乙基异氰尿酸酯、三烯丙基异氰尿酸酯或三缩水甘油异氰尿酸酯。
本发明解决上述第二个技术问题所采用的技术方案为：一种阻燃导电聚氨酯材料的制备方法，包括如下步骤：
(1)将离子液体、含磷含氮多元醇按配比混合，获得混合液，按配比分别将石墨烯、阻燃剂分散于所述混合液中，制得混合体系；
(2)向所述混合体系中按配比加入多元异氰尿酸酯，在室温或加热条件下进行固化反应，制得阻燃导电聚氨酯材料。
步骤(2)中，进行固化反应的加热温度为35～100℃，例如40℃、45℃、50℃、60℃、70℃、80℃、90℃、95℃；
优选的，步骤(2)中，进行固化反应时，向所述混合体系中加入重量百分比为0.01～0.5％的催化剂，例如0.05％、0.1％、0.2％、0.3％、0.4％、0.45％。
与现有技术相比，本发明的优点在于：通过向多元异氰尿酸酯中加入石墨烯、离子液体、含磷含氮多元醇、阻燃剂等，并调节各个组分所占的配比，使得最终制得的聚氨酯材料同时具有较优的导电性和阻燃性，扩大了其应用范围。
另外，本聚氨酯材料的制备方法所需的原料易得，设备工艺简单，易于操作，适合于大规模生产。
具体实施方式
以下结合实施例对本发明作进一步详细描述。
实施例1
本实施例的阻燃导电聚氨酯材料，所需的原料包括如下重量百分比的物质：
其中，石墨烯为片状结构，其厚度为0.35～100nm，石墨烯的边长尺寸为0.1～100μm；离子液体为1-羟乙基-3-甲基咪唑四氟硼酸盐、1-甲基-3-乙基咪唑四氟硼酸盐、1-羧甲基-4甲基咪唑四氟硼酸盐或1-羧甲基-3-甲基咪唑六氟磷酸盐，本实施例的离子液体具体为1-甲基-3-乙基咪唑四氟硼酸盐。
本实施例的阻燃导电聚氨酯材料的制备方法，包括如下步骤：
(1)按配比混合离子液体、含磷含氮多元醇——二乙基-N,N-(2-羟乙基)胺甲基磷酸酯，获得混合液，按配比分别将石墨烯、阻燃剂——三聚氰胺均匀分散于混合液中，制得混合体系；
(2)向混合体系中按配比加入多元异氰尿酸酯——三缩水甘油异氰尿酸酯，在催化剂——二月桂酸二正丁基锡存在下，在室温或35℃～100℃下进行固化反应，制得阻燃导电聚氨酯材料。
经测试，本实施例阻燃导电聚氨酯材料的电导率为7.5×1010Ω·cm，其阻燃性可达到UL94-V2的等级要求。
实施例2
本实施例的阻燃导电聚氨酯材料所需的原料包括如下重量百分比的物质：
其中，石墨烯的尺寸参考实施例1，本实施例的离子液体优选为1-羧甲基-4甲基咪唑四氟硼酸盐。
同时，本实施例的阻燃导电聚氨酯材料的制备方法参考实施例1。
经测试，本实施例阻燃导电聚氨酯材料的电导率为3.6×104Ω·cm，其阻燃性可达到UL94-V0的等级要求。
实施例3
本实施例的阻燃导电聚氨酯材料所需的原料包括如下重量百分比的物质：
本实施例中，离子液体具体为1-羟乙基-3-甲基咪唑四氟硼酸盐。
石墨烯的尺寸以及阻燃导电聚氨酯材料的制备方法参考实施例1。
经测试，本实施例阻燃导电聚氨酯材料的电导率为3.1×102Ω·cm，其阻燃性可达到UL94-V0的等级要求。
以上内容仅为本发明的较佳实施例，对于本领域的普通技术人员，依据本发明的思想，在具体实施方式及应用范围上均会有改变之处，本说明书内容不应理解为对本发明的限制。
Claims (12)
1.一种阻燃导电聚氨酯材料，其特征在于，所需原料包括如下重量百分比的物质：
石墨烯 0.1~10%；
阻燃剂 5~20%；
离子液体 1~20%；
含磷含氮多元醇 24.5~50%；
多元异氰尿酸酯 24.5~50%；
所述离子液体为1-羟乙基-3-甲基咪唑四氟硼酸盐、1-甲基-3-乙基咪唑四氟硼酸盐、1-羧甲基-4-甲基咪唑四氟硼酸盐或1-羧甲基-3-甲基咪唑六氟磷酸盐。
2.根据权利要求1所述的阻燃导电聚氨酯材料，其特征在于：所需原料还包括重量百分比为0.01%~0.5%的催化剂。
3.根据权利要求2所述的阻燃导电聚氨酯材料，其特征在于：所述催化剂为二月桂酸二正丁基锡或三乙烯二胺。
4.根据权利要求1所述的阻燃导电聚氨酯材料，其特征在于：所述石墨烯为片状结构，所述石墨烯的厚度为0.35~100nm。
5.根据权利要求1所述的阻燃导电聚氨酯材料，其特征在于：所述石墨烯的边长尺寸为0.1~100μm。
6.根据权利要求1所述的阻燃导电聚氨酯材料，其特征在于：所述石墨烯的厚度为0.35~50nm。
7.根据权利要求1所述的阻燃导电聚氨酯材料，其特征在于：所述阻燃剂为氰尿酸三聚氰胺、氰尿酸聚磷酸盐、三聚氰胺、氢氧化铝、氢氧化镁、间苯二酚双（二苯基磷酸酯）、双酚A-双(二苯基磷酸酯)、次磷酸盐、红磷中的一种或两种以上。
8.根据权利要求1所述的阻燃导电聚氨酯材料，其特征在于：所述含磷含氮多元醇为二乙基-N,N-（2-羟乙基）胺甲基磷酸酯。
9.根据权利要求1所述的阻燃导电聚氨酯材料，其特征在于：所述多元异氰尿酸酯为三羟乙基异氰尿酸酯、三烯丙基异氰尿酸酯或三缩水甘油异氰尿酸酯。
10.一种根据权利要求1所述的阻燃导电聚氨酯材料的制备方法，其特征在于，包括如下步骤：
(1)将离子液体、含磷含氮多元醇按配比混合，获得混合液，按配比分别将石墨烯、阻燃剂分散于所述混合液中，制得混合体系；
(2)向所述混合体系中按配比加入多元异氰尿酸酯，在室温或加热条件下进行固化反应，制得阻燃导电聚氨酯材料。
11.根据权利要求10所述的制备方法，其特征在于：步骤(2)中，进行固化反应的加热温度为35~100℃。
12.根据权利要求10所述的制备方法，其特征在于：步骤(2)中，进行固化反应时，向所述混合体系中加入重量百分比为0.01~0.5%的催化剂。
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| CN106832183B (zh) * | 2016-12-14 | 2019-12-24 | 武汉科利尔新材料有限公司 | 一种石墨烯改性阴极聚氨酯电泳树脂及其电泳漆组合物 |
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| CN108559107B (zh) * | 2018-04-28 | 2020-09-04 | 合肥工业大学 | 一种具有电磁屏蔽功能的石墨烯纳米片/离子液体封端的水性聚氨酯复合乳液的制备方法 |
| CN109232849A (zh) * | 2018-06-08 | 2019-01-18 | 青岛海尔股份有限公司 | 阻燃多元醇组合物及其制备方法、应用 |
| CN109054306A (zh) * | 2018-07-17 | 2018-12-21 | 安徽长淮新材料有限公司 | 一种阻燃抗静电聚酯材料及其制备方法 |
| CN110862671B (zh) * | 2018-08-27 | 2021-02-19 | 北京化工大学 | 一种金属有机框架材料/聚氨酯吸波材料及其制备方法 |
| CN110804152A (zh) * | 2019-10-14 | 2020-02-18 | 江苏华大新材料有限公司 | 一种革用湿法石墨烯聚氨酯树脂及其制备方法和应用 |
| CN111718464A (zh) * | 2020-08-04 | 2020-09-29 | 湖南省普瑞达内装材料有限公司 | 一种高密度导电聚氨酯泡棉及其制备方法、及胶带 |
| CN114181433B (zh) * | 2021-12-14 | 2023-09-05 | 安徽长淮新材料有限公司 | 一种聚氨酯基离子液体聚合物包覆红磷阻燃材料的制备方法 |
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