CN114573774A - 三聚氰胺硬泡闭孔材料及其制备方法与应用 - Google Patents
三聚氰胺硬泡闭孔材料及其制备方法与应用 Download PDFInfo
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Abstract
本发明涉及一种三聚氰胺硬泡闭孔材料及其制备方法与应用。三聚氰胺预聚体由液态的三聚氰胺、触发剂、阻燃剂和接枝剂制得；基于所述三聚氰胺预聚体的原料总重量，所述触发剂的添加量为2％‑6％。本发明制备的三聚氰胺硬泡闭孔材料，闭孔率达到90％以上，导热系数达到0.035以下，吸水率达到3.8％以下，防火等级达到A2级，具有优异的阻燃性能。
Description
技术领域
本发明涉及一种三聚氰胺硬泡闭孔材料及其制备方法与应用。
背景技术
三聚氰胺材料无卤、低毒、低烟、不腐蚀、对热和光稳定是良好的具有阻燃性能热固材料。
三聚氰胺由于有丰富的氮元素良好的阻燃性，以及发泡闭孔性。现有技术中美国KasowskiM M合成的三聚氰胺焦磷酸脂合成方法是在90℃下加热37.9克三聚氰胺和10.4克低聚甲醛(溶于170克水中)15-30min，然后将生成的羟甲基三聚氰胺溶液在3-5min内加入含有焦磷酸的水中，即生成三聚氰胺焦磷酸脂。此材料在发泡时开孔率极高，是很好的隔音材料，缺点是吸水率高达500％。保温隔热性能受到极大影响。
巴斯夫公司以三聚氰胺作为材料制备了三聚氰胺亲水、阻燃开孔软泡材料。
然而硬泡三聚氰胺硬质泡闭孔材料一直是世界上的空白。
发明内容
本发明人研究发现，在三聚氰胺闭孔发泡生产过程中，泡体成长时间与泡壁凝胶固化时间必须同步，泡壁凝胶固化时间提前则泡体在继续成长就会撑破泡壁形成开孔，使得闭孔发泡失败。反之泡壁凝胶固化时间延后则会出现炮孔过大，泡壁过薄，物理性能失去甚至出现塌泡现象。因此触发剂的介入，影响凝胶固化时间是本技术的关键。不同的触发剂活性不同，触发性还与不同的反应浓度、反应温度等各条件有关。例如三亚乙基二胺对芳香族异氰酸酯与羟基反应的触发催化作用比脂肪族的HDI及芳脂型异氰酸酯XDI高得多。试验发现证明，触发剂的添加量增加则反应速度加快；两种或多种不同的触发剂复合起来，触发性比单一触发剂活性强的多。
基于以上研究，本发明首先提供一种三聚氰胺预聚体，由液态的三聚氰胺、触发剂、阻燃剂和接枝剂制得；其中，基于所述三聚氰胺预聚体的原料总重量，所述触发剂的添加量为2％-6％。研究发现，若触发剂的添加量过高，则发泡速度过快，泡体固化时间小于成长时间，撑破泡闭造成开孔现象；若触发剂的含量过低，则发泡过慢，泡体固化时间大于成长时间，泡体过大，影响材料的物理性能。
根据本发明实施例，基于所述三聚氰胺预聚体的原料总重量，所述触发剂的添加量为2％-6％，优选2％-4％，例如2％、2.1％、2.2％、2.3％、2.5％、2.8％、3％、3.2％、3.5％、3.7％、3.8％、4％、4.5％、5％、5.9％、6％。
根据本发明实施例，所述触发剂选自：四甲基丁二胺、DMP-30(2,4,6—三(二甲胺基甲基)苯酚)、AK8805(聚氨酯硬泡硅油)、油酸钾、PC-5(五甲基二乙烯三胺)、PC-8(N,N-二甲基环己胺)、PC-41(三(二甲氨基丙基)六氢三嗪)等中的一种或几种；优选为DMP-30、PC-5中的一种或两种。
根据本发明实施例，所述触发剂为DMP-30和PC-5，二者重量比优选为(0.5:1)-(1:1.5)，例如1:1。
根据本发明实施例，所述液态的三聚氰胺可由现有方法制备，例如通过苯酚与甲醛在碱性溶液中加温缩聚蒸馏脱水制得；也可市购，例如“中原大化”提供的三聚氰胺生产线上的中间体。
根据本发明实施例，基于所述三聚氰胺预聚体的原料总重量，所述阻燃剂的添加量为15％-20％，例如17.4％
根据本发明实施例，所述阻燃剂包括但不限于：聚磷酸铵、多聚磷酸铵、三聚氰胺粉末、二氢二胺、尿素等高氮化合物中的一种或几种。
根据本发明实施例，所述阻燃剂为三聚氰胺粉末和二氢二胺，二者重量比优选为(0.5:1)-(1:1.5)，例如1:1。
根据本发明实施例，基于所述三聚氰胺预聚体的原料总重量，所述接枝剂的添加量为13％-18％，例如15.5％。
根据本发明实施例，所述接枝剂包括但不限于：聚醚4110、聚醚4110A、聚醚4110F、聚醚403、聚醚8239G、聚酯315A、聚酯320B、聚酯3304等可聚合高分子材料中的一种或几种。
根据本发明实施例，所述接枝剂为聚醚4110、聚醚403和聚酯315A，三者重量比优选为(0.5-1.5):(0.5-1.5):(0.5-1.5)，例如1:1:1。
根据本发明实施例，以重量份计，所述三聚氰胺预聚体由液态的三聚氰胺80-90份、触发剂3-8份、阻燃剂20-25份、接枝剂18-23份制得。
根据本发明实施例，以重量份计，所述三聚氰胺预聚体由液态的三聚氰胺85份、触发剂3-8份、阻燃剂23份、接枝剂20.5份制得。
根据本发明实施例，以重量份计，所述三聚氰胺预聚体由液态的三聚氰胺85份、触发剂4份、阻燃剂23份、接枝剂20.5份制得。
根据本发明实施例，制备所述三聚氰胺预聚体时的温度为25℃-35℃。研究发现，若温度过高，则发泡时间过快；若温度过低，则发泡时间过慢。
根据本发明实施例，制备所述三聚氰胺预聚体时压力为2-6个大气压，例如4个大气压。研究发现，若压力过高，则预聚时间过快，物料粘度过高；若压力过低，则预聚时间过慢。
通常情况下，将液态的三聚氰胺、触发剂、阻燃剂和接枝剂在上述条件下充分搅拌(例如搅拌30-60min)即可制得三聚氰胺预聚体。
本发明还提供上述三聚氰胺预聚体的制备方法，包括将液态的三聚氰胺、触发剂、阻燃剂和接枝剂在上述条件下充分搅拌。在一些优选方案中，在上述温度/压力条件下进行制备。
本发明还提供一种三聚氰胺硬泡闭孔材料，由上述三聚氰胺预聚体制得。
根据本发明实施例，所述三聚氰胺硬泡闭孔材料，由上述三聚氰胺预聚体和异氰酸酯制得
根据本发明实施例，所述三聚氰胺预聚体与异氰酸酯的重量比为(130-138):(40-45)，可选为(131-137):43，例如132.5:43。
根据本发明实施例，制备三聚氰胺硬泡闭孔材料时的温度可为21℃-25℃。
根据本发明实施例，将上述三聚氰胺预聚体与异氰酸酯充分混合后，喷入模具发泡，即可制得三聚氰胺硬泡闭孔材料。
本发明还提供上述三聚氰胺硬泡闭孔材料的制备方法，包括将上述三聚氰胺预聚体与异氰酸酯充分混合后，喷入模具发泡。
本发明还包括上述方法制备的三聚氰胺硬泡闭孔材料。
本发明还包括上述三聚氰胺硬泡闭孔材料在防火、保温、隔热、隔音、节能等领域的应用。
本发明制备的三聚氰胺硬泡闭孔材料，闭孔率达到90％以上，导热系数达到0.035以下，吸水率达到3.8％以下，防火等级达到A2级，具有优异的阻燃性能。
附图说明
图1-图3为实验例2的检测报告。
具体实施方式
以下实施例用于说明本发明，但不用来限制本发明的范围。实施例中未注明具体技术或条件者，按照本领域内的文献所描述的技术或条件，或者按照产品说明书进行。所用试剂或仪器未注明生产厂商者，均为可通过正规渠道商购买得到的常规产品。
以下液态的三聚氰胺为“中原大化”提供的三聚氰胺生产线上的中间体。
以下异氰酸酯为万华PM-200。
实施例1
将液态的三聚氰胺85克、触发剂4克(即DMP-30和PC-5各2克)、阻燃剂23克(即三聚氰胺粉末和二氢二胺各11.5克)与接枝剂20.5克(聚醚4110、聚醚403和聚酯315A等重量比例的混合物)在25℃环境4个大气压下充分搅拌30min制得三聚氰胺预聚体备用。
将三聚氰胺预聚体与异氰酸酯43克在21℃-25℃下充分混合搅拌2min，喷入模具发泡制得三聚氰胺硬泡闭孔材料。
实施例2
将液态的三聚氰胺85克、触发剂(DMP-30)4克、阻燃剂23克(即三聚氰胺粉末和二氢二胺各11.5克)与接枝剂20.5克(聚醚4110、聚醚403和聚酯315A等比例的混合物)在25℃环境4个大气压下充分搅拌30min制得三聚氰胺预聚体备用。
将三聚氰胺预聚体与异氰酸酯43克在21℃-25℃下充分混合搅拌2min，喷入模具发泡制得三聚氰胺硬泡闭孔材料。
实施例3
将液态的三聚氰胺85克、触发剂(PC-5)4克、阻燃剂23克(即三聚氰胺粉末和二氢二胺各11.5克)与接枝剂20.5克(聚醚4110、聚醚403和聚酯315A等比例的混合物)在25℃环境4个大气压下充分搅拌30min制得三聚氰胺预聚体备用。
将三聚氰胺预聚体与异氰酸酯43克在21℃-25℃下充分混合搅拌2min，喷入模具发泡制得三聚氰胺硬泡闭孔材料。
实施例4
将液态的三聚氰胺85克、触发剂3克(即DMP-30和PC-5各1.5克)、阻燃剂23克(即三聚氰胺粉末和二氢二胺各11.5克)与接枝剂20.5克(聚醚4110、聚醚403和聚酯315A等比例的混合物)在25℃环境4个大气压下充分搅拌30min制得三聚氰胺预聚体备用。
将三聚氰胺预聚体与异氰酸酯43克在21℃-25℃下充分混合搅拌2min，喷入模具发泡制得三聚氰胺硬泡闭孔材料。
实施例5
将液态的三聚氰胺85克、触发剂8克(即DMP-30和PC-5各4克)、阻燃剂23克(即三聚氰胺粉末和二氢二胺各11.5克)与接枝剂20.5克(聚醚4110、聚醚403和聚酯315A等比例的混合物)在25℃环境4个大气压下充分搅拌30min制得三聚氰胺预聚体备用。
将三聚氰胺预聚体与异氰酸酯43克在21℃-25℃下充分混合搅拌2min，喷入模具发泡制得三聚氰胺硬泡闭孔材料。
对比例1
将液态的三聚氰胺85克、触发剂2克(即DMP-30和PC-5各1克)、阻燃剂23克(即三聚氰胺粉末和二氢二胺各11.5克)与接枝剂20.5克(聚醚4110、聚醚403和聚酯315A等比例的混合物)在25℃环境4个大气压下充分搅拌30min制得三聚氰胺预聚体备用。
将三聚氰胺预聚体与异氰酸酯43克在21℃-25℃下充分混合搅拌2min，喷入模具发泡制得三聚氰胺硬泡闭孔材料。
对比例2
将液态的三聚氰胺85克、触发剂10克(即DMP-30和PC-5各5克)、阻燃剂23克(即三聚氰胺粉末和二氢二胺各11.5克)与接枝剂20.5克(聚醚4110、聚醚403和聚酯315A等比例的混合物)在25℃环境4个大气压下充分搅拌30min制得三聚氰胺预聚体备用。
将三聚氰胺预聚体与异氰酸酯43克在21℃-25℃下充分混合搅拌2min，喷入模具发泡制得三聚氰胺硬泡闭孔材料。
实验例
分别对以上实施例及对比例制备的三聚氰胺发泡材料进行检测，结果如下。
检测方法：
导热系数：GB/T 10294绝热材料稳态热阻及有关特性的测定防护热板法；
吸水率：GB/T 8810硬质泡沫塑料吸水率的测定；
防火等级：GB/T 8624-2012建筑材料及制品燃烧性能分级。
检测结果见下表：
| 实施例1 | 实施例2 | 实施例3 | 实施例4 | 实施例5 | 对比例1 | 对比例2 | |
| 闭孔率 | 98％ | 94％ | 91％ | 95％ | 94％ | 85％ | 88％ |
| 导热系数 | 0.027 | 0.030 | 0.031 | 0.035 | 0.034 | 0.045 | 0.050 |
| 吸水率 | 2.5％ | 3.2％ | 3.8％ | 3.3％ | 3.5％ | 5.5％ | 5.8％ |
| 防火等级 | A2级 | A2级 | A2级 | A2级 | A2级 | A2级 | A2级 |
结果表明，在防火等级不变的情况下。导热系数及闭孔率均能达到理想标准。注：材料的吸水率与闭孔率息息相关。
实验例2
以实施例1制备的三聚氰胺硬泡闭孔材料制成保温板，经河北省建筑工程质量检测中心有限公司进行检测，结果见图1-3。
虽然，上文中已经用一般性说明及具体实施方案对本发明作了详尽的描述，但在本发明基础上，可以对之作一些修改或改进，这对本领域技术人员而言是显而易见的。因此，在不偏离本发明精神的基础上所做的这些修改或改进，均属于本发明要求保护的范围。
Claims (10)
1.一种三聚氰胺预聚体，其特征在于，由液态的三聚氰胺、触发剂、阻燃剂和接枝剂制得；其中，基于所述三聚氰胺预聚体的原料总重量，所述触发剂的添加量为2％-6％。
2.根据权利要求1所述的三聚氰胺预聚体，其特征在于，基于所述三聚氰胺预聚体的原料总重量，所述触发剂的添加量为2％-4％；和/或，
基于所述三聚氰胺预聚体的原料总重量，所述阻燃剂的添加量为15％-20％；和/或，
基于所述三聚氰胺预聚体的原料总重量，所述接枝剂的添加量为13％-18％。
3.根据权利要求1或2所述的三聚氰胺预聚体，其特征在于，所述触发剂选自四甲基丁二胺、DMP-30、AK8805、油酸钾、PC-5、PC-8、PC-41中的一种或几种；优选为DMP-30、PC-5中的一种或两种；和/或，
所述阻燃剂包括但不限于：聚磷酸铵、多聚磷酸铵、三聚氰胺粉末、二氢二胺、尿素中的一种或几种；和/或，
所述接枝剂包括但不限于：聚醚4110、聚醚4110A、聚醚4110F、聚醚403、聚醚8239G、聚酯315A、聚酯320B、聚酯3304中的一种或几种。
4.根据权利要求1或2所述的三聚氰胺预聚体，其特征在于，所述触发剂为DMP-30和PC-5，二者重量比优选为(0.5:1)-(1:1.5)，可选为1:1；和/或，
所述阻燃剂为三聚氰胺粉末和二氢二胺，二者重量比优选为(0.5:1)-(1:1.5)，可选为1:1；和/或，
所述接枝剂为聚醚4110、聚醚403和聚酯315A，三者重量比优选为(0.5-1.5):(0.5-1.5):(0.5-1.5)，可选为1:1:1。
5.根据权利要求1-4任一项所述的三聚氰胺预聚体，其特征在于，以重量份计，所述三聚氰胺预聚体由液态的三聚氰胺80-90份、触发剂3-8份、阻燃剂20-25份、接枝剂18-23份制得；
可选地，以重量份计，所述三聚氰胺预聚体由液态的三聚氰胺85份、触发剂3-8份、阻燃剂23份、接枝剂20.5份制得；
可选地，以重量份计，所述三聚氰胺预聚体由液态的三聚氰胺85份、触发剂4份、阻燃剂23份、接枝剂20.5份制得。
6.根据权利要求1-5任一项所述的三聚氰胺预聚体，其特征在于，制备所述三聚氰胺预聚体时的温度为25℃-35℃；和/或，
制备所述三聚氰胺预聚体时压力为2-6个大气压，可选为4个大气压。
7.权利要求1-6任一项所述三聚氰胺预聚体的制备方法，其特征在于，包括将液态的三聚氰胺、触发剂、阻燃剂和接枝剂充分搅拌；
可选地，制备所述三聚氰胺预聚体时的温度为25℃-35℃；和/或，
可选地，制备所述三聚氰胺预聚体时压力为2-6个大气压，可选为4个大气压。
8.一种三聚氰胺硬泡闭孔材料，其特征在于，由权利要求1-6任一项所述三聚氰胺预聚体和异氰酸酯制得；
可选地，所述三聚氰胺预聚体与异氰酸酯的重量比为(130-138):(40-45)，可选为(131-137):43；和/或，
可选地，制备三聚氰胺硬泡闭孔材料时的温度为21℃-25℃。
9.权利要求8所述三聚氰胺硬泡闭孔材料的制备方法，其特征在于，包括将上述三聚氰胺预聚体与异氰酸酯充分混合后，喷入模具发泡。
10.权利要求8所述三聚氰胺硬泡闭孔材料在防火、保温、隔热、隔音、节能中任一领域的应用。
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