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CN112480603B - 一种低烟成碳型阻燃剂及其在制备阻燃聚氨酯弹性体中的应用 - Google Patents

一种低烟成碳型阻燃剂及其在制备阻燃聚氨酯弹性体中的应用 Download PDF

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CN112480603B
CN112480603B CN202011242771.3A CN202011242771A CN112480603B CN 112480603 B CN112480603 B CN 112480603B CN 202011242771 A CN202011242771 A CN 202011242771A CN 112480603 B CN112480603 B CN 112480603B
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郭嘉昒
马慧
胡秀强
周艳明
钟伦超
王晓丹
邓俊
李为民
张琳
冯发维
廖堃
吕利刚
张东明
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Chengdu University
Chengdu Univeristy of Technology
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Abstract

本发明属阻燃聚氨酯弹性体材料技术领域，为解决目前缺乏对于磷、氮、碳三元素协同阻燃聚氨酯弹性体，提供一种低烟成碳型阻燃剂及其在制备阻燃聚氨酯弹性体中的应用。由磷酸、三聚氰胺、尿素、双酚A型环氧树脂E‑12合成的阻燃剂，调节聚氨酯体系的碳、氧含量而制备的一种低烟复合阻燃型聚氨酯弹性体，燃烧性能满足ISO340‑2004阻燃标准；减少了因燃烧而对人体及环境造成的危害；不会释放出任何腐蚀性的气体，不会对环境及周围的设备造成不良影响；有优异的成碳性，燃烧时在材料表面迅速形成一层致密的微泡碳层而自熄，不产生融滴现象，有优异的阻燃性能；制备方法、工艺简单、易于操作，实际应用价值高，环境友好，适合工业化大规模生产。

Description

一种低烟成碳型阻燃剂及其在制备阻燃聚氨酯弹性体中的应用
技术领域
本发明属于阻燃聚氨酯弹性体材料技术领域，具体涉及一种低烟成碳型阻燃剂及其在制备阻燃聚氨酯弹性体中的应用。
背景技术
聚氨酯弹性体（TPU）是指聚氨酯分子链上含有较多氨基甲酸酯基团的一类弹性体高分子聚合物材料，它具有许多优良特性，如高弹性、耐磨性、耐低温性、耐溶剂性以及良好的电绝缘性等，因而被广泛用于各个行业。但其含氧指数仅在18％左右，属于易燃材料。TPU本身不具备阻燃性能，燃烧时火焰剧烈且伴有浓烈黑烟以及严重的滴流现象。为了使TPU具有良好的阻燃性，通常添加大量的无机阻燃剂或者卤素阻燃剂，虽然提高了TPU阻燃性，但燃烧时仍伴有浓烈黑烟和有毒气体，而有毒气体往往是火灾中致人死亡的一个重要因素，因此改善TPU阻燃性和低烟性，一直是聚氨酯领域十分活跃的研究课题。
目前，国内外对聚氨酯弹性体的阻燃研究十分活跃，主要集中在阻燃剂的选择上。通常可以分为三大类：无机阻燃、卤素阻燃、磷氮协同阻燃。无机阻燃剂主要包括如三氧化二锑、水合氧化铝、氢氧化镁、纳米级镁铝水滑等无机物；卤素阻燃主要包括如溴一氯烷基磷酸双酯、十溴联苯醚等含卤有机物；磷氮协同阻燃主要包括如聚磷酸铵、二乙基次磷酸钠，多聚磷酸铵、9，10- 二氢-9- 氧杂-10- 磷杂菲-10- 氧化物（DOPO）、三聚氰胺聚磷酸盐及复配的膨胀型阻燃剂(聚磷酸铵，季戊四醇，三聚氰铵)等含磷氮系的有机物。
另外含磷微胶囊化也是一个研究的热门，如中国专利ZL200910144 076 .0。而磷氮协同阻燃是目前研究中一款环保型阻燃剂，它低烟低毒，且同时具备了阻燃体系中的酸源和气源。酸源即磷，不但可以抑制燃烧过程中的·H，还可以促进成碳，形成碳层保护膜，气源即氮，也可以抑制燃烧过程中的·H，还可以释放出惰性气体阻隔并稀释氧气，降低燃烧速率。但上述的研究中采用无机阻燃剂的方法一般是阻燃剂进行复合混配，对阻燃剂与聚氨酯的相容性考虑不足；而微胶囊化的阻燃和磷氮协同阻燃虽然解决了与聚氨酯的相容性，兼具阻燃剂中的磷源和氮源，但碳源考虑不足。众所周知，成碳是高分子材料阻燃的一个非常重要指标，在燃烧时成碳可以在材料表面形成一层碳化层，碳化层可以阻隔热量的传递、火焰的烧蚀及氧气的浸入使火焰在空气中自熄。同时在受热膨胀过程中还可以有效起到抗滴落的效果。
目前的研究中，尚未多见对于磷、氮、碳三元素协同阻燃聚氨酯弹性体的报道。
发明内容
本发明为了解决目前缺乏对于磷、氮、碳三元素协同阻燃聚氨酯弹性体，提供了一种低烟成碳型阻燃剂及其在制备阻燃聚氨酯弹性体中的应用。采用本发明所述的低烟成碳型阻燃剂制备的聚氨酯弹性体具有优异的阻燃性能和低烟特性，同时具有良好的加工性能和优异的力学性能。
本发明由如下技术方案实现的：一种低烟成碳型阻燃剂，由如下重量份的原料制备而成：磷酸110-115 份、三聚氰胺60-65份、尿素40-45 份、双酚A型环氧树脂E-12 15~25份、Ⅱ型聚磷酸铵40-45份。
制备所述的一种低烟成碳型阻燃剂的方法，步骤如下：将磷酸、三聚氰胺在120-125℃，真空度为-0.085MPa下反应1.5h，加入尿素在≤132℃下反应1h，再加入的双酚A型环氧树脂E-12，环氧树脂E12需要粉碎成粉末，过200目的筛，将其逐步添加进去，确保环氧树脂在体系中均匀分散并开环反应；110-115℃反应1h后，停真空，出料，得到白色的固体块状物，混合Ⅱ型聚磷酸铵将其粉碎后过300目的筛，得到低烟成碳型阻燃剂。
所述磷酸和三聚氰胺反应后加入尿素的反应温度优选为115-120℃。所述双酚A型环氧树脂E-12先粉碎成末，过200目筛，然后再加入反应体系中。
利用所述的一种低烟成碳型阻燃剂制备的阻燃聚氨酯弹性体，由如下重量份的原料制成：固化剂5-8份、聚氨酯预聚体50-55份、低烟成碳型阻燃剂20-25份、催化剂0.02-0.05份、脱水剂碳化二亚胺0.04-0.06份、有机硅流平剂0.04-0.06份；其中，所述聚氨酯预聚体由如下重量份的原料制成：聚酯PPA 20份、聚醚PTEMG 10份、聚醚N220 20份、二异氰酸酯15份、HDI三聚体3-4份、催化剂0.03-0.05份。
所述的聚氨酯预聚体固化剂为MSDS一缩二乙二醇或TEG二缩三乙二醇中的一种或两种混合；Mn =106；所述的聚酯PPA为聚己二酸1.4-异丁二醇酯二元醇，Mn=2000；聚醚PTEMG为聚四氢呋喃二醇,Mn=2000；聚醚N220 为聚氧化丙烯二元醇, Mn =2000；所述二异氰酸酯为IPDI异佛尔酮二异氰酸酯或ＨＭＤＩ二环己基甲烷二异氰酸酯中的一种或两种混合；所述催化剂为有机铋催化剂、有机锡催化剂或有机锌催化剂中的任意一种。
制备所述的阻燃聚氨酯弹性体的方法，步骤如下：
（1）合成聚氨酯预聚体：将聚酯PPA、聚醚PTEMG、聚醚N220在100-105℃下，在真空度-0.085MPA下脱水1.5h，加入二异氰酸酯和 HDI三聚体，再加入催化剂，在80-85℃下反应1.5h，得到聚氨酯预聚体。
（2）合成低烟阻燃型聚氨酯弹性体：将固化剂在100-105℃，真空度为-0.085MPa下脱水1.5h；将处理好的固化剂、低烟成碳型阻燃剂催化剂和脱水剂按比例混合，在三辊研磨机上将其研磨均匀，再加入聚氨酯预聚体、有机硅流平剂，在三辊研磨机上将其混合、研磨均匀后流到聚四氟乙烯平板模具上，固化后即得低烟阻燃型聚氨酯弹性体。
本发明以磷酸、聚磷酸铵为酸源，以三聚氰胺、尿素为氮源和抑烟剂，以双酚A型环氧树脂E-12为碳源，在材料燃烧时酸源将碳源碳化，配和燃烧过程中所形成的气体迅速形成一层具有微孔结构且致密的碳层，隔绝的热量的传递，阻断氧气和可燃基材的接触，同时消耗掉大量的·H，来达到阻燃的目的。
聚氨酯弹性体的燃烧要达到低烟的目的就必须调节聚氨酯所用的材料的碳/氧比和碳/氢比，为同时兼顾材料的力学性能，本发明选用聚酯PPA（聚己二酸1.4-异丁二醇酯二元醇）调节材料的抗撕裂性能和拉伸强度，选用聚醚PTEMG (聚四氢呋喃二醇) 调节材料的拉伸强度和断裂伸长率，聚醚N220 (聚氧化丙烯二元醇) 调节聚氨酯合成过程中的粘度，同时兼顾了材料的碳/氧比。选用二异氰酸酯IPDI(异佛尔酮二异氰酸酯)赋予材料较高的碳/氢比；选用HDI三聚体赋予材料一定的交联度，赋予材料一定的交联，即提高了拉伸强度、抗撕裂性能，同时促进一定的成碳，也可改进材料燃烧时的熔滴现象。
与现有技术相比，本发明所制备的低烟阻燃聚氨酯弹性体燃烧性能满足ISO340-2004阻燃标准；燃烧时只会释放出轻微的白烟，达到低烟的效果，减少了因燃烧而对人体及环境造成的危害；在燃烧过程中不会释放出任何腐蚀性的气体，因此不会对环境及周围的设备造成不良影响；在燃烧过程中具有优异的成碳性，在燃烧时可以在材料表面迅速形成一层致密的微泡碳层而自熄，且不产生融滴现象，具有优异的阻燃性能；本发明的制备方法、工艺简单、易于操作，阻燃剂与聚氨酯的相容性、匹配性好，实际应用价值高，环境友好，适合工业化大规模生产。
附图说明
图1为阻燃聚氨酯弹性体燃烧时的照片；
图2为阻燃聚氨酯弹性体燃烧后的照片；
图3为阻燃聚氨酯弹性体燃烧后的碳层电镜图片；
图4为低烟成碳型阻燃剂烧蚀后的电镜图片。
具体实施方式
下面，通过具体实施例对本发明的技术方案进行详细说明。
实施例1：将115份的磷酸、65份三聚氰胺在125℃，真空度-0.085MPa下反应1.5h，再入40份的尿素在115℃反应1h再加入15份的双酚A型环氧树脂E-12，在115℃反应1h后，停真空，出料，得到白色的固体块状物，混合40份的Ⅱ型聚磷酸铵将其粉碎后过300目的筛，得到低烟成碳型阻燃剂。
将20份的聚酯PPA、10份的聚醚PTEMG、20份的聚醚N220，在100~105℃，真空度-0.085MPa下脱水1.5h，加入15份的二异氰酸酯IPDI和3份的HDI三聚体，再加入0.04份的催化剂（有机铋），在85℃下反应1.5h，得到聚氨酯预聚体。
将聚氨酯预聚体的固化剂MSDS在100~105℃，真空度-0.085MPa下脱水1.5h。取其5.2份取25份的低烟成碳型阻燃剂，再加入0.03份的催化剂和脱水剂碳化二亚胺0.05份，在三辊研磨机上将其研磨均匀，再取聚氨酯预聚体55份，加入有机硅流平剂0.5份，在三辊研磨机上将其混合、研磨均匀后流到聚四氟乙烯平板模具上，在40~50℃下固化3~4h得产品。
实施例2：将110份的磷酸、60份三聚氰胺在125℃，真空度-0.085MPa下反应1.5h，再入45份的尿素在115℃反应1h再加入25份的双酚A型环氧树脂E-12，在115℃反应1h后，停真空，出料，得到白色的固体块状物，混合45份的Ⅱ型聚磷酸铵将其粉碎后过300目的筛，得到低烟成碳型阻燃剂。
将20份的聚酯PPA、10份的聚醚PTEMG、20份的聚醚N220，在100~105℃，真空度-0.085MPa下脱水1.5h，加入15份的二异氰酸酯IPDI和4份的HDI三聚体，再加入0.04份的催化剂（有机铋），在85℃下反应1.5h，得到聚氨酯预聚体。
将聚氨酯预聚体的固化剂TEG在100~105℃，真空度-0.085MPa下脱水1.5h。取其8份取20份的低烟成碳型阻燃剂，再加入0.03份的催化剂和脱水剂碳化二亚胺0.05份，在三辊研磨机上将其研磨均匀，再取聚氨酯预聚体50份，加入有机硅流平剂0.5份，在三辊研磨机上将其混合、研磨均匀后流到聚四氟乙烯平板模具上，在40~50℃下固化3~4h得产品。
空白比较例：将20份的聚酯PPA、10份的聚醚PTEMG、20份的聚醚N220，在100~105℃，真空度-0.085MPa下脱水1.5h，加入15份的二异氰酸酯IPDI和3份的HDI三聚体，再加入0.04份的催化剂（有机铋），在85℃下反应1.5h，得到聚氨酯预聚体。
将聚氨酯预聚体的固化剂MSDS在100~105℃，真空度-0.085MPa下脱水1.5h。取其5.2份，再加入0.03份的催化剂和脱水剂碳化二亚胺0.05份，在三辊研磨机上将其研磨均匀，再取聚氨酯预聚体55份，加入有机硅流平剂0.5份，在三辊研磨机上将其混合、研磨均匀后流到聚四氟乙烯平板模具上，在40~50℃下固化3~4h得产品。
上述样品测试方法：性能测试：氧指数按GB/T2406-1993测试，样品尺寸85mm×10mm×1 .6mm；《GB/T8627-2007 建筑材料燃烧或分解的烟密度测试方法》；拉伸强度和断裂伸长率按GB/T528-1998测试；邵A硬度按GB/T531-1992测试。
以上检验依据及方法为：《ISO340-2004 燃烧性能－要求和测试方法》。
测试结果见表1
表1
注：阻燃聚氨酯弹性体的阻燃性能测试委托苏州美标检测技术有限公司检测中心进行检测。
本发明所述低烟成碳型阻燃剂制备的阻燃聚氨酯弹性体进行燃烧试验，如图1所示，从图１中可以看出，阻燃聚氨酯弹性体在火焰中燃烧时迅速形成一层焦黑的碳化层，碳化层阻隔了聚氨酯弹性体的进一步燃烧。在图1中可以看出，阻燃聚氨酯弹性体在火焰中燃烧处于低烟或基本无烟的状态，而且不存在任何融滴现象。
阻燃聚氨酯弹性体燃烧后如图2所示，在图2中可以看出，阻燃聚氨酯弹性体在离开火焰后自熄，在阻燃聚氨酯弹性体烧蚀表面有一层焦黑的碳层，碳层保护着聚氨酯弹性体样条的外形，基本与烧蚀前没有大的变化，只是有轻微的膨胀，离开火焰后迅速自熄，且在自熄时无黑烟冒出，属于低烟或无烟的自熄。
阻燃聚氨酯弹性体燃烧后的碳层电镜图片如图3所示，从图3中可以看出，阻燃聚氨酯弹性体在烧蚀后表面碳层为致密的多空结构，此结构具有良好的隔热性能，隔绝火焰进一步向基体烧蚀，也隔绝了热量向集体的传递，从而赋予了阻燃聚氨酯弹性体优异的阻燃性能。
上述的低烟成碳型阻燃剂烧蚀后的电镜图片见图4，从图4中可以看出，低烟成碳型阻燃剂在烧蚀后形成了一层优异的碳化层，碳化层表面鼓起了致密的微泡，此微泡是低烟成碳型阻燃剂中尿素、三聚氰胺、环氧树脂的成分在在高温烧蚀时裂解成小分子的气态物质而鼓起的微泡，此微泡具有非常好的隔热，隔氧等作用，配合酸源的脱水至成碳作用，可以形成一层微泡沫状的琉璃层，提供了良好阻燃低烟的作用。

Claims (6)

1.一种低烟成碳型阻燃剂，其特征在于：由如下重量份的原料制备而成：磷酸110-115份、三聚氰胺60-65份、尿素40-45 份、双酚A型环氧树脂E-1215~25份、Ⅱ型聚磷酸铵40-45份；
制备该低烟成碳型阻燃剂的方法，步骤如下：将磷酸、三聚氰胺在120-125℃，真空度为-0.085MPa下反应1.5h，加入尿素在115-132℃下反应1h，再加入的双酚A型环氧树脂E-12，110-115℃反应1h后，停真空，出料，得到白色的固体块状物，混合Ⅱ型聚磷酸铵将其粉碎后过300目的筛，得到低烟成碳型阻燃剂。
2.根据权利要求1所述的一种低烟成碳型阻燃剂，其特征在于：所述磷酸和三聚氰胺反应后加入尿素的反应温度为115-120℃。
3.根据权利要求1所述的一种低烟成碳型阻燃剂，其特征在于：所述双酚A型环氧树脂E-12先粉碎成末，过200目筛，然后再加入反应体系中。
4.利用权利要求1所述的一种低烟成碳型阻燃剂制备的阻燃聚氨酯弹性体，其特征在于：由如下重量份的原料制成：固化剂5-8份、聚氨酯预聚体50-55份、低烟成碳型阻燃剂20-25份、催化剂0.02-0.05份、脱水剂碳化二亚胺0.04-0.06份、有机硅流平剂0.04-0.06份；其中，所述聚氨酯预聚体由如下重量份的原料制成：聚酯PPA 20份、聚醚PTEMG 10份、聚醚N220 20份、二异氰酸酯15份、HDI三聚体3-4份、催化剂0.03-0.05份。
5.根据权利要求4所述的一种低烟成碳型阻燃剂制备的阻燃聚氨酯弹性体，其特征在于：所述聚氨酯预聚体的固化剂为MSDS一缩二乙二醇或TEG二缩三乙二醇中的一种或两种混合；所述的聚酯PPA的Mn=2000；聚醚PTEMG 为聚四氢呋喃二醇,Mn=2000；聚醚N220 为聚氧化丙烯二元醇, Mn =2000；所述二异氰酸酯为IPDI异佛尔酮二异氰酸酯或ＨＭＤＩ二环己基甲烷二异氰酸酯中的一种或两种混合；所述催化剂为有机铋催化剂、有机锡催化剂或有机锌催化剂中的任意一种。
6.制备权利要求4所述的阻燃聚氨酯弹性体的方法，其特征在于：步骤如下：
（1）合成聚氨酯预聚体：将聚酯PPA、聚醚PTEMG、聚醚N220在100-105℃下，在真空度为-0.085MPA下脱水1.5h，加入二异氰酸酯和 HDI三聚体，再加入催化剂，在80-85℃下反应1.5h，得到聚氨酯预聚体；
（2）合成低烟阻燃型聚氨酯弹性体：将固化剂在100-105℃，真空度为-0.085MPa下脱水1.5h；将处理好的固化剂、低烟成碳型阻燃剂、催化剂和脱水剂按比例混合，在三辊研磨机上将其研磨均匀，再加入聚氨酯预聚体、有机硅流平剂，在三辊研磨机上将其混合、研磨均匀后流到聚四氟乙烯平板模具上，固化后即得低烟阻燃型聚氨酯弹性体。
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