CN113330070A - 防火聚氨酯涂层组合物以及包括防火聚氨酯涂层组合物的防火产品 - Google Patents
防火聚氨酯涂层组合物以及包括防火聚氨酯涂层组合物的防火产品 Download PDFInfo
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- CN113330070A CN113330070A CN201980089768.1A CN201980089768A CN113330070A CN 113330070 A CN113330070 A CN 113330070A CN 201980089768 A CN201980089768 A CN 201980089768A CN 113330070 A CN113330070 A CN 113330070A
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- polyurethane coating
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Abstract
本发明涉及一种防火聚氨酯组合物以及包括所述防火聚氨酯组合物的防火产品。所述防火聚氨酯涂层组合物包括:芳族异氰酸酯组分;多元醇组分;以及膨胀组分;其中聚氨酯主链中芳族结构含量≥24wt%。所述防火聚氨酯涂层组合物可以提供令人惊讶的良好膨胀层韧性以及良好的隔热性能。
Description
技术领域
本发明涉及一种防火聚氨酯涂层组合物以及包括所述防火聚氨酯涂层组合物的防火产品。
引言
防火安全是建筑材料和建筑行业的主要关注点之一。特别是对于易燃材料,如木材或承载建筑主要载荷的材料,需要用涂层进行保护,以延缓温升。尽管许多市面上的防火涂层产品可以帮助提高防火性能,但它们在延长木材或金属元件在发生火灾时承受结构载荷的持续时间方面并没有提供太大的改进。为了为建筑物中的人员提供更长的疏散时间,需要延长结构产品在发生火灾时承受结构载荷的持续时间。保护的延伸一般由涂层的膨胀来提供,即原位溶胀以产生可以隔离从外部到基材的热传递的泡沫结构。保护性能由三个因素决定:1)溶胀率,越高越好;2)泡沫结构,尺寸较小的闭孔比尺寸较大的开孔具有更好的隔热效果;3)膨胀层的韧性,韧性越大越好。溶胀率和泡沫结构决定了隔热性能,而膨胀层的韧性决定了保护耐久性。由于膨胀层具有一定的重量,如果层体不够坚韧,它往往会从基材上脱落,并且燃烧过程中的空气湍流增大了脱落的风险。一旦膨胀层脱落,就不能有效保护基材。
因此,需要开发一种用于木材、陶瓷或金属基材的涂层组合物,其可形成具有良好隔热性能和良好韧性的膨胀层,以确保更长的保护耐久性。
我们开发出了一种防火聚氨酯组合物,它可以提供令人惊讶的良好膨胀层韧性以及良好的隔热性能。
发明内容
本发明提供一种防火聚氨酯涂层组合物,以及包括所述防火聚氨酯涂层组合物的防火产品。
在第一方面,本发明提供一种防火聚氨酯涂层组合物,包括:
a.芳族异氰酸酯组分;
b.多元醇组分;以及
c.膨胀组分;
其中聚氨酯主链中芳族结构含量≥24wt%,其中“聚氨酯主链中芳族结构含量”被定义为前体中共轭平面环结构中所有原子的重量占前体总和的用于形成聚氨酯的百分比,且聚氨酯涂层组合物中的前体包括所有多元醇、异氰酸酯以及异氰酸酯的预聚物,如果存在的话。
在第二方面,本发明提供了一种包括基材和施用在基材上的防火聚氨酯涂层组合物的防火产品,所述防火聚氨酯涂层组合物包括:
a.芳族异氰酸酯组分;
b.多元醇组分;
c.膨胀成分;
其中聚氨酯主链中芳族结构含量≥24wt%,其中“聚氨酯主链中芳族结构含量”被定义为前体中共轭平面环结构中所有原子的重量占前体总和的用于形成聚氨酯的百分比,且聚氨酯涂层组合物中的前体包括所有多元醇、异氰酸酯以及异氰酸酯的预聚物,如果存在的话。
附图说明
图1示出垂直辐射热测试装置示意图(a)正视图;(b)侧视图;以及(c)俯视图。
图2示出本发明实施例1-4和比较例1-2的瓷砖背温。
图3示出本发明实施例5-11和比较例3的OSB背温曲线。
具体实施方式
如本文中所公开的,“和/或”意指“以及,或作为替代方案”。除非另外指示,否则所有范围都包括端点。
如本文中所公开的,词语“组合物”、“配制物”或“混合物”是指通过用物理手段简单地混合不同组分而获得的不同组分的物理掺合物。
“木制产品”用于指由木料,诸如方材(例如,板、规格材、实心锯材、托梁、集管、桁架、横梁、林木、线条、层积、指接或半成品方材)、复合木制产品或任何上述示例的组成部分制成的产品。“木质元件”一词用于指代任何类型的木制产品。
“复合木制产品”用于指一系列衍生木制产品,这些木制产品通过将木材的股线、颗粒、纤维或单板与粘合剂粘合在一起形成复合材料而制成。复合木制产品的示例包括但不限于平行胶合材(PSL)、定向胶合板(OSB)、定向胶合材(OSL)、单板层积材(LVL)、层积胶合材(LSL)、颗粒板、中密度纤维板(MDF),以及硬纸板。
“膨胀颗粒”是指暴露在火中时体积和烧焦物会膨胀的材料。
词语“涂层”、“组合物”以及“配制物”可以相互替换,并且它们对于本发明的目的具有相同的含义。
“芳族结构”一词被定义为共轭平面环,其中至少两个键伸出,以将此结构并入聚氨酯主链。共轭平面环可以是单六元环苯衍生物,也可以是稠合芳烃,如萘衍生物,也可以是多环芳烃,如蒽和菲衍生物。芳族结构可以来自异氰酸酯和多元醇部分,只要它位于聚氨酯主链中,而不是作为侧基。
“聚氨酯主链中芳族结构含量”一词被定义为前体中共轭平面环结构中所有原子的重量占前体总和的用于形成聚氨酯的百分比。聚氨酯涂层组合物中的前体包括所有多元醇、异氰酸酯以及异氰酸酯的预聚物,如果存在的话。
“基材”被定义为在其上施用涂层组合物的材料。
组合物中所有组分的重量百分比总和等于100wt%。
芳族异氰酸酯组分
芳族异氰酸酯可以是单一的芳族异氰酸酯或这些化合物的混合物。芳族异氰酸酯的示例包括甲苯二异氰酸酯(TDI)、单体亚甲基二苯基二异氰酸酯(MDI)、聚合亚甲基二苯基二异氰酸酯(pMDI)、1,5'-萘二异氰酸酯,以及TDI的预聚物、MDI的预聚物或pMDI的预聚物。TDI的预聚物、MDI的预聚物或pMDI的预聚物通常通过TDI、MDI或pMDI与少于化学计量的多官能多元醇的反应而制成。
芳族异氰酸酯组分的存在量可以是组合物重量的约10%至约30%,优选地是组合物重量的约12%至约25%,更优选地是组合物重量的约14%至约20%。
多元醇组分
优选地,多元醇组分包括芳族多元醇,更优选地是酚醛型多元醇组分。多元醇组分还可以包括选自非酚醛型聚醚多元醇、聚酯多元醇、蓖麻油、豆油基多元醇、它们的组合的其它多元醇组分。
酚醛型多元醇组分
酚醛型多元醇是芳族树脂引发的环氧丙烷-环氧乙烷多元醇,诸如,可从陶氏化学公司(Dow Chemical Company)购得的IP 585多元醇。
可以在催化剂存在下,以酚醛清漆酚为引发剂,将环氧丙烷或环氧乙烷烷氧基化而制得。方案描述如下,x=1~10,y,z=0~30,y+z=1~60。
酚醛型多元醇组分的存在量可以是组合物重量的约5%至约40%。在优选的实施方式中,酚醛型多元醇组分的存在量可以是组合物重量的约8%至约35%。在优选的实施方式中,酚醛型多元醇组分的存在量可以是组合物重量的约10%至约30%。
其他多元醇组分
组合物还可以包含括选自非酚醛型聚醚多元醇、聚酯多元醇、蓖麻油、豆油基多元醇、它们的组合等的其他多元醇。
非酚醛型聚醚多元醇可以是环氧乙烷、环氧丙烷、四氢呋喃以及环氧丁烷的加聚产物和接枝产物,多元醇的缩合产物,以及它们的任意组合。聚醚多元醇的合适示例包括但不限于聚丙二醇(PPG)、聚乙二醇(PEG)、聚丁二醇、聚四亚甲基醚二醇(PTMEG),以及它们的任意组合。在一些实施方式中,聚醚多元醇是PEG与选自上述加聚和接枝产物以及缩合产物的至少另一种聚醚多元醇的组合。在一些实施方式中,聚醚多元醇是PEG与PPG、聚丁二醇以及PTMEG中的至少一者的组合。
聚酯多元醇是二醇与二元羧酸及其衍生物的缩合产物或其衍生物。二醇的合适示例包括但不限于乙二醇、丁二醇、二甘醇、三甘醇、聚亚烷基二醇,诸如,聚乙二醇、1,2-丙二醇、1,3-丙二醇、2-甲基-1,3-丙二醇、1,3-丁二醇、1,4-丁二醇、1,6-己二醇、新戊二醇、3-甲基-1,5-戊二醇,以及它们的任意组合。为了实现大于2的多元醇官能度,也可以使用三醇和/或四醇。此类三醇的合适示例包括但不限于三羟甲基丙烷和甘油。此类四醇的合适示例包括但不限于赤藓糖醇和季戊四醇。二元羧酸选自芳族酸、脂族酸,以及它们的组合。芳族酸的合适示例包括但不限于邻苯二甲酸、间苯二甲酸,以及对苯二甲酸;而脂族酸的合适示例包括但不限于己二酸、壬二酸、癸二酸、戊二酸、四氯邻苯二甲酸、马来酸、富马酸、衣康酸、丙二酸、辛二酸、2-甲基琥珀酸、3,3-二乙基戊二酸,以及2,2-二甲基琥珀酸。同样可以使用这些酸的酸酐。出于本发明的目的,酸酐包含在“酸”一词的表述中。在一些实施方式中,脂族酸和芳族酸是饱和的,并且分别是己二酸和间苯二甲酸。应尽量减少或排除一元羧酸,诸如,苯甲酸和己烷羧酸。
聚酯多元醇也可以通过内酯与二醇、三醇和/或四醇的加聚反应来制备。内酯的合适示例包括但不限于己内酯、丁内酯,以及戊内酯。二醇的合适示例包括但不限于乙二醇、丁二醇、二甘醇、三甘醇、聚亚烷基二醇,诸如,聚乙二醇、1,2-丙二醇、1,3-丙二醇、2-甲基1,3-丙二醇、1,3-丁二醇、1,4-丁二醇、1,6-己二醇、新戊二醇、3-甲基1,5-戊二醇,以及它们的任意组合。三醇的合适示例包括但不限于三羟甲基丙烷和甘油。四醇的合适示例包括赤藓糖醇和季戊四醇。
蓖麻油是通过压榨蓖麻籽获得的甘油三酯化合物的混合物。甘油三酯化合物中约85%至约95%的侧链为蓖麻油酸,且约2%至6%为油酸,且约1%至5%为亚油酸。通常以约1%或更少的水平存在的其他侧链包括亚麻酸、硬脂酸、棕榈酸,以及二羟基硬脂酸。
天然油基多元醇是从种子油(如大豆)中获得的甘油三酯化合物的化学改性混合物。双键是指天然油经化学转化为多元醇,在一个分子中形成含有2个、3个或更多个羟基的化合物。
其它多元醇组分的存在量可以是组合物重量的约1%至约50%。在优选的实施方式中,其它多元醇组分的存在量可以是组合物重量的约3%至约45%。在优选的实施方式中,其它多元醇组分的存在量可以是组合物重量的约5%至约40%。在优选的实施方式中,其它多元醇组分的存在量可以是组合物重量的约5%至约30%。
膨胀组分
膨胀组分的存在量可以是总组合物重量的约1%至约50%。在优选的实施方式中,膨胀组分的存在量是组合物重量的约10%至约40%,或存在量是组合物重量的约15%至约35%。膨胀组分可以是膨胀颗粒。
适用于本发明的实施方式的膨胀颗粒包括可膨胀石墨,其是在构成石墨结构的碳的平行平面之间装载有酸性膨胀剂(一般称为“间充物”)的石墨。当处理过的石墨被加热到临界温度时,间充物分解成气态产物并使石墨发生显著的体积膨胀。可膨胀石墨的制造商包括格拉夫科技国际控股有限公司(GrafTech International Holding Incorporated)(俄亥俄州帕尔马市)。格拉夫科技(GrafTech)的特定可膨胀石墨产品包括称为Grafguard160-50、Grafguard 220-50以及Grafguard 160-80的产品。其他可膨胀石墨制造商包括HP材料解决方案公司(HP Materials Solutions,Incorporated)(加利福尼亚州伍德兰希尔斯市)。中国有多家可膨胀石墨制造商,且这些产品在北美由艾斯博瑞碳素公司(AsburyCarbons)(宾夕法尼亚州桑伯里市)和全球矿业公司(Global Minerals Corporation)(马里兰州贝塞达市)等公司分销。此外,本领域普通技术人员已知的其他类型的膨胀颗粒将适用于本发明的实施方式。优选地,膨胀组分不溶于水。
催化剂
催化剂可以包括氨基甲酸酯反应催化剂和异氰酸酯三聚反应催化剂。
三聚催化剂可以是本领域中已知的将催化有机异氰酸酯化合物的三聚反应的任何三聚催化剂。异氰酸酯的三聚可以在聚氨酯泡沫内部产生聚异氰脲酸酯化合物。在不受理论限制的情况下,聚异氰脲酸酯化合物可使聚氨酯泡沫更硬,并且提高对火的反应能力。三聚催化剂可以包括,例如,甘氨酸盐、叔胺三聚催化剂、碱金属羧酸盐,以及它们的混合物。在一些实施方式中,可以采用N-2-羟基-5-壬基苯基-甲基-N-甲基甘氨酸钠。在使用时,三聚催化剂的存在量可以是“多元醇包”的0.5-2wt%,优选地是0.8-1.5wt%。
叔胺催化剂包括含有至少一个叔氮原子并且能够催化异氰酸酯组分与异氰酸酯反应混合物之间的羟基/异氰酸酯反应的有机化合物。举例而言而非限制,叔胺催化剂可以包括三亚乙基二胺、四甲基乙二胺、五甲基二亚乙基三胺、双(2-二甲基氨基乙基)醚、三乙胺、三丙胺、三丁胺、三戊胺、吡啶、喹啉、二甲基哌嗪、哌嗪、N-乙基吗啉、2-甲基丙烷二胺、甲基三亚乙基二胺、2,4,6-三二甲基氨基-甲基)苯酚、N,N',N”-三(二甲基氨基-丙基)均-六氢三嗪,以及它们的混合物。在使用时,叔胺催化剂的存在量可以是“多元醇包”的0.5-2wt%,优选地是0.8-1.5wt%。
本发明的组合物还可以包括以下催化剂:叔膦,诸如,三烷基膦和二烷基苄基膦;各种金属的螯合物,诸如,乙酰丙酮、苯甲酰丙酮、三氟乙酰丙酮、乙酰乙酸乙酯等与金属(诸如,Be、Mg、Zn、Cd、Pd、Ti、Zr、Sn、As、Bi、Cr、Mo、Mn、Fe、Co和Ni)的螯合物;强酸的酸性金属盐,诸如,氯化铁、氯化锡;有机酸与各种金属(诸如,碱金属、碱土金属、Al、Sn、Pb、Mn、Co、Ni和Cu)的盐;有机锡化合物,诸如,有机羧酸的锡(II)盐,例如,二乙酸锡(II)、二辛酸锡(II)、二乙基己酸锡(II)和二月桂酸锡(II),以及有机羧酸的二烷基锡(IV)盐,例如,二乙酸二丁基锡、二月桂酸二丁基锡、马来酸二丁基锡和二乙酸二辛基锡;有机羧酸的铋盐,例如,辛酸铋;三价和五价As、Sb和Bi的有机金属衍生物以及铁和钴的金属羰基化合物。
本文所用的催化剂组分的总量总体而言可以是组合物重量的约0.01wt%至约10wt%,优选地是组合物重量的0.5wt%至约5wt%。
其它添加剂
其他可选的化合物或添加剂可以添加到本发明的组合物中。
添加剂的存在量可以是组合物重量的约0%至约30%,优选地是组合物重量的约10%至约20%。
可掺入防火聚氨酯组合物中以实现有益效果的添加剂包括但不限于表面活性剂(通常为硅型)、润湿剂、遮光剂、着色剂、增粘剂、防腐剂、填料和颜料(在非限制性实施方式中包括硫酸钡、碳酸钙、石墨、炭黑、二氧化钛、氧化铁、微球、三水合氧化铝、硅灰石、玻璃纤维、聚酯纤维、其他聚合物纤维、它们的组合等)、流平剂、消泡剂、增稠剂,诸如,二氧化硅、稀释剂、水合化合物、卤化化合物、水分清除剂(例如,分子筛、醛亚胺或对甲苯磺酰异氰酸酯)、酸、碱、盐、硼酸盐、三聚氰胺和其他可能促进木制产品防火涂层的生产、储存、加工、施用、功能、成本和/或外观的添加剂。
可以在组合物中添加额外的阻燃组分以提高涂层的阻燃性能。例如,当涂层暴露于火中时,可以添加卤化阻燃剂,以减少火焰蔓延和烟雾的产生。卤化阻燃剂可防止氧气与从受热基材释放的可燃气体发生反应,并与自由基反应,以减缓自由基燃烧过程。合适的卤化阻燃化合物的示例包括氯化石蜡、可从雅宝公司(Albermarle Corporation)以商品名SAYTEX 102E购得的十溴二苯醚,以及也可从雅宝公司(Albermarle Corporation)以商品名SAYTEX BT-93购得的亚乙基双-四溴邻苯二甲酰亚胺。卤化阻燃化合物通常以涂层重量的0-5%的量添加到涂层中,但也可以使用更大的量。通常,希望将卤化阻燃化合物与增效剂结合使用,以提高卤化化合物的整体阻燃性能。合适的增效剂包括羟基锡酸锌和三氧化二锑。通常,这些增效剂以每2-3重量份卤化阻燃剂1份的量添加到涂层中,但也可以使用更多或更少。此外,含磷阻燃剂,诸如,聚磷酸铵,或三聚氰胺聚磷酸,或其他粉末状聚磷酸盐,或芳族缩合磷酸盐,诸如,间苯二酚双(二苯基磷酸酯)(RDP)和双酚A双(二苯基磷酸酯)(BPA-BDPP)或它们的组合也可以添加到组合物中,以增强涂层的阻燃性能。优选地,芳族缩合磷酸酯是间苯二酚双(二苯基磷酸酯)(RDP)。更优选地,本文所用的含磷阻燃剂的总量总体而言可以是组合物重量的约1wt%至约40wt%,优选地是组合物重量的5wt%至约30wt%,优选地是组合物重量的7wt%至约20wt%。
优选地,阻燃添加剂不溶于水。
令人惊讶地发现,只有当聚氨酯主链中总芳族结构含量≥24wt%时,在火中产生的膨胀层才能提供足够的韧性,以提供持久的隔热保护。对于芳族结构含量<24wt%的PU组合物,膨胀的烧焦物没有足够的机械强度来承受任何机械冲击,如摇动或空气湍流,因此,在真实火灾事件中的持久性较差。优选地,聚氨酯主链中芳族结构含量≥25wt%、≥26wt%、≥27wt%、≥28wt%、≥29wt%、≥30wt%、≥32wt%,或≥35wt%。聚氨酯主链中芳族结构含量小于70wt%,优选地是小于60wt%,优选地是小于50wt%或小于45wt%。
组合物的制备
可以使用多种不同的技术来组合上述组分。在一些实施方式中,膨胀颗粒与其他添加剂一起分散在多元醇中,以形成相对稳定的悬浮液,其可以运输和储存一段时间,直到准备使用。这种混合物在本发明中可称为“多元醇组分”。芳族异氰酸酯组分(例如,芳族异氰酸酯或芳族异氰酸酯的混合物)总体而言是稳定的,只要保护它免受水和其他亲核化合物的影响,就可以长时间运输和储存。这种混合物在本发明中可称为“芳族异氰酸酯组分”。在施用之前,这两种组分可以混合在一起。这种特殊的配制策略使聚氨酯基质具有合适的弹性水平,可用作防火涂层。此外,在一些实施方式中,可以实现其他优点。例如,TDI或pMDI的预聚物可以对聚合物基质的弹性产生有益的效果,它们可以改变未固化液体组分的表面张力,从而使膨胀颗粒在多元醇和异氰酸酯组分在施用之前组合时倾向于保持更均匀的悬浮。
在将组合物施用到基材上之前,应将反应组分混合,尤其是多元醇和芳族异氰酸酯化合物。在一个实施方式中,膨胀颗粒可与其他组合物添加剂一起悬浮在多元醇中,以制备稳定的液体悬浮液,其随后可与芳族异氰酸酯化合物组合。因此,两种液体组分可以以适当的比例组合并通过使用计量混合设备(诸如,可从威拉米特山谷公司(The WillametteValley Company)(俄勒冈州尤金市)或固瑞克公司(GRACO Incorporated)(明尼苏达州明尼阿波利斯市)或ESCO(艾吉糖果公司)购得的设备)进行混合。在一些实施方式中,三种或更多种组分(异氰酸酯反应组分、膨胀以及芳族异氰酸酯)都可以在施用之前使用粉末/液体混合技术进行组合。在一些实施方式中,配制物具有有限的“适用期”,并且应在制备后不久施用。配制物随后固化以形成保护涂层,此涂层表现出作为木制产品防火涂层的性能属性。
在不存在催化剂的情况下,可以在制备后约30分钟内将完整的配制物施用到基材上。可以通过降低配制物混合物的温度或使用稀释剂或稳定剂(诸如,磷酸)来延长混合适用期。当在配制物中使用催化剂时,混合适用期会在约30分钟内。催化剂的示例包括有机金属化合物,诸如,二月桂酸二丁基锡、辛酸亚锡、硫醇二丁基锡、辛酸铅、乙酸/辛酸钾,以及乙酰丙酮铁;和叔胺催化剂,诸如,N,N-二甲基乙醇胺、N,N-二甲基环己胺、1,4-重氮双环[2.2.2]辛烷、1-(双(3-二甲基氨基丙基)氨基-2-丙醇、N,N-二乙基哌嗪、DABCO TMR-7,以及TMR-2。
组合物的施用
根据本发明的实施方式的组合物可以施用于基材,诸如,木制产品、复合木制产品,或陶瓷。总体而言,根据本发明的实施方式的组合物以约0.05至约3.0lb/ft2(优选地是约0.1至约2.0lb/ft2,优选地是约0.1至约0.5lb/ft2)的施用水平施用至基材的一个或多个表面。本发明的组合物可以多种方式施用,诸如,喷涂、辊衬刀涂,或使用加得科铸造刀薄膜施用器(Gardco Casting Knife Film Applicator)刮涂。
包括本申请的防火聚氨酯涂层组合物的防火产品选自木材、金属、陶瓷、聚合物材料,或混凝土。
实施例
现将在以下实施例中描述本发明的一些实施方式,除非另外说明,否则其中所有份数和百分比都按重量计。
I.原材料
本发明防火聚氨酯涂层组合物所用原材料及组分列于表1中。
表1:本发明所用原材料
本发明实施例1-4和比较例1-2(瓷砖涂层)
向内径4.5cm、高6.3cm、配备有外径3.5cm高速混合器的120ml聚乙烯杯中依次添加多元醇、可膨胀石墨、RDP、TiO2、表面活性剂、ATH,以及催化剂。为了使粉末在液体中均匀分布,将混合器速度调节到300rpm。运行3分钟后,将混合器速度提高到1500rpm并运行5分钟。添加异氰酸酯,且混合器在1000rpm下再运行1分钟。
混合后立即将浆液施用在10cm X 10cm X 0.6cm的瓷砖上。组合物用湿膜涂层厚度为1.5mm的刮刀施用。在室温(25±2℃)和约50%的相对湿度下,将涂覆的瓷砖置于通风橱中至少连续3天。
本发明实施例1-4和比较例1-2的配制物列于表2中。
表2.本发明实施例1-4和比较例1-2的配制物
注:芳烃含量计算如下:
Voranol IP585的芳烃含量计算:
OH当量=286
对于一个OH基团,有一个苄基环,Mw=76
IP585中的苄基环=76/286=0.2657。
对于pMDI
NCO当量=133.5
对于一个NCO基团,有一个苄基环,Mw=76
IP585中的苄基环=76/133.5=0.5693。
对于MDI OP50
NCO当量=126.5
对于一个NCO基团,有一个苄基环,Mw=76
IP585中的苄基环=76/126.5=0.6008。
本发明实施例1中的芳烃含量:
Voranol 2140贡献=0
Voranol IP-585贡献=14.5*0.2657=3.8527
MDI IP50贡献=14.6*0.6008=8.7717
总芳烃贡献=3.8527+8.7717=12.6244
配制物中的总聚氨酯主链=10.9+14.5+14.6=40
聚氨酯前体中总芳烃含量=12.6244/40*100=31.56%
以上所有都是以重量计算的。
本发明实施例5-11和比较例3(OSB板涂层)
向内径4.5cm、高6.3cm、配备有外径3.5cm高速混合器的120ml聚乙烯杯中依次添加多元醇、可膨胀石墨、RDP、TiO2、表面活性剂、ATH,以及催化剂。为了使粉末在液体中均匀分布,将混合器速度调节到300rpm。运行3分钟后,将混合器速度提高到1500rpm并运行5分钟。添加异氰酸酯,且混合器在1000rpm下再运行1分钟。
混合后立即将浆料施用到10cm X 10cm X 0.9cm的松木OSB板(定向胶合板)上。组合物用湿膜涂层厚度为1.5mm的刮刀施用。在室温(25±2℃)和约50%的相对湿度下,将涂覆的OSB板置于通风橱中至少连续3天。
本发明实施例5-11和比较例3的配制物列于表3中。
表3:本发明实施例5-11和比较例3的配制物
PU涂层组合物防火性能的评估方法
设计并制造了一种用于防火评估的垂直辐射加热器专用装置。装置的方案如图1所示。整个装置安装在配备有强制通风装置的阻燃室中,以排出测试中产生的烟雾和气体。加热器(如红色方块所示)输出功率为3000W,由Fe-Ni合金灯丝组装成18cm X 28cm面板制成。辐射面板固定在不锈钢台上,面向待测样品。样品架设计成用于将样品面对辐射面板固定在其上,面对面距离为10cm。样品架可以放下30°,使样品远离辐射(“关(OFF)”位置)并面对辐射面板直立开始测试(“开(ON)”位置)。热电偶放置在基材背面的中心,以记录辐射加热过程中的背温。辐射一段时间后,以每分钟60-120次的频率水平地摇动样品架,检查膨胀层是否会掉落。如果膨胀层的内聚力或膨胀层与基材的粘合力不足以固定层体,则它会像附面层的一部分的方形附面层一样掉落。记录摇动过程中发生的现象。摇动后,放下样品架,停止测试。将残留的膨胀层与基材一起冷却。冷却的膨胀层被手指破坏。视破坏膨胀层的力而定,其韧性从等级1到10排列。1表示非常软,手指轻轻一碰就碎,经不起任何明显的力。10表示非常坚韧,具有明显的模量和弹性,会被相当大的力破坏。摇动现象和韧性等级都用于评估膨胀层的韧性。
PU涂层组合物对瓷砖的防火性能
根据设计的评估方法,对本发明实施例1-4和比较例1-2中所述的PU涂覆瓷砖进行了测试。15分钟辐射后摇动过程中膨胀层掉落现象、膨胀层韧性等级,以及120秒、300秒、600秒和900秒时的背温分别记录在表4中。所有样品的背温曲线如图2所示。
表4.本发明实施例1-4和比较例1-2的防火性能
*附面层掉落:面向辐射面板的膨胀层像附面层一样呈方形(10cm X 10cm)掉落。
在辐射加热测试过程中,所有样品上的涂层均发生溶胀并产生膨胀层,从而保护了陶瓷基材并延缓了热传递。辐射15分钟后,摇动样品架,所有两个对照样品的总芳烃低于24wt%,且不含酚醛型多元醇(Voranol IP585),顶部膨胀层像附面层一样掉落(整个方形摇动)。此后,由于膨胀层掉落,隔热保护性能下降,背温曲线迅速上升。冷却后发现膨胀层很松软,经不起手指用很小的力按压。
相反,本发明的样品在摇动期间均未显示出有任何变化。Voranol IP585代替Voranol 2140,随着聚氨酯主链中芳烃含量的增加,膨胀层的韧性显著提高,从2级(比较例2)提高到8级(本发明实施例1),膨胀层变得非常坚韧,显示出一定的弹性。如本发明实施例2、3和4所示,无论添加催化剂或酸来微调固化动力学,随着聚氨酯主链中芳烃含量的进一步增加,膨胀层的韧性也相应增加。
PU涂层组合物对OSB木板的防火性能
在垂直辐射测试过程中,OSB板上的所有PU涂层都溶胀并形成膨胀层。然而,比较例3显示,即使没有摇动,附面层也会逐层掉落。掉落的材料塌在台上。辐射后的摇动去掉了一些膨胀的烧焦物,OSB基材上几乎没有烧焦物残留。冷却后用手指触摸检查烧焦物韧性,经不起手指用很小的力按压,因此评级为“2”。相反,如本发明实施例所示,通过在配制物中加入酚醛型多元醇,通过将非芳族聚醚多元醇替换为芳族聚醚多元醇(本发明实施例5、6、9、10、11),将聚氨酯主链中的芳烃含量提高到24wt%以上),或增加芳族异氰酸酯的用量(本发明实施例7、8),膨胀层的韧性显著增加。所有本发明实施例在辐射过程中或辐射后摇动过程中均未显示出膨胀层掉落。
表5.本发明实施例5-11和比较例3的防火性能
由于膨胀层韧性增加,泡沫烧焦物可以承受OSB基材可能发生的变形,并提供更好的保护耐久性。本发明实施例在900秒时的OSB背温显著低于比较例3的背温。图3为本发明实施例5-11和比较例3的OSB背温曲线。所有本发明实施例在380秒后显示出缓慢的温度升高。相反,比较例3由于其聚氨酯主链中芳烃含量较低,因此在600秒后显示出升高,因此烧焦物逐层掉落,这意味着保护耐久性变差。
由本发明实施例与比较例的对比发现,在以可膨胀石墨为溶胀型添加剂的PU涂层组合物中,只有当聚氨酯主链中总芳族结构含量≥24wt%时,火中产生的膨胀层才能提供足够的韧性,以提供具有持久性的隔热保护。对于芳族结构含量<24wt%的PU组合物,膨胀的烧焦物太松软,无法承受任何机械冲击,如摇动或空气湍流,因此保护耐久性较差。
Claims (13)
1.一种防火聚氨酯涂层组合物,包括:
a.芳族异氰酸酯组分;
b.多元醇组分;以及
c.膨胀组分;
其中聚氨酯主链中芳族结构含量≥24wt%,其中“聚氨酯主链中芳族结构含量”被定义为前体中共轭平面环结构中所有原子的重量占前体总和的用于形成聚氨酯的百分比,且所述聚氨酯涂层组合物中的前体包括所有多元醇、异氰酸酯以及异氰酸酯的预聚物,如果存在的话。
2.根据权利要求1所述的防火聚氨酯涂层组合物,其中,所述芳族异氰酸酯选自甲苯二异氰酸酯(TDI)、亚甲基二苯基二异氰酸酯(MDI)、聚合亚甲基二苯基二异氰酸酯(pMDI)、1,5'-萘二异氰酸酯、TDI的预聚物、MDI的预聚物,以及pMDI的预聚物。
3.根据权利要求1所述的防火聚氨酯涂层组合物,其中芳族异氰酸酯组分的存在量是所述组合物重量的约10%至约30%。
4.根据权利要求1所述的防火聚氨酯涂层组合物,其中所述多元醇组分包括芳族多元醇,且所述芳族多元醇优选地是酚醛型多元醇组分。
5.根据权利要求1所述的防火聚氨酯涂层组合物,其中所述多元醇组分包括酚醛型多元醇组分。
6.根据权利要求5所述的防火聚氨酯涂层组合物,其中所述酚醛型多元醇组分的存在量是所述组合物重量的约5%至约40%。
7.根据权利要求1所述的防火聚氨酯涂层组合物,其中,所述组合物还包括选自非酚醛型聚醚多元醇、聚酯多元醇或它们的组合的其他多元醇。
8.根据权利要求1所述的防火聚氨酯涂层组合物,其中所述膨胀组分的存在量是总组合物重量的约1%至约50%。
9.根据权利要求1所述的防火聚氨酯涂层组合物,其中所述膨胀组分包括可膨胀石墨或为可膨胀石墨。
10.根据权利要求1所述的防火聚氨酯涂层组合物,其中所述涂层组合物还包括催化剂。
11.根据权利要求1所述的防火聚氨酯涂层组合物,其中,所述涂层组合物还包括选自表面活性剂、润湿剂、遮光剂、着色剂、增粘剂、防腐剂、填料和颜料、流平剂、消泡剂、增稠剂、稀释剂、水合化合物、卤化化合物、水分清除剂、酸、碱、盐、硼酸盐、三聚氰胺以及含磷阻燃剂的添加剂。
12.一种防火产品,包括基材和施用在所述基材上的防火聚氨酯涂层组合物,所述防火聚氨酯涂层组合物包括:
a.芳族异氰酸酯组分;
b.多元醇组分;
c.膨胀组分;
其中聚氨酯主链中芳族结构含量≥24wt%,其中“聚氨酯主链中芳族结构含量”被定义为前体中共轭平面环结构中所有原子的重量占前体总和的用于形成聚氨酯的百分比,且所述聚氨酯涂层组合物中的前体包括所有多元醇、异氰酸酯以及异氰酸酯的预聚物,如果存在的话。
13.根据权利要求12所述的防火产品,其中所述基材选自木材、金属、陶瓷、聚合材料或混凝土。
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US (1) | US20220017772A1 (zh) |
EP (1) | EP3924426A1 (zh) |
CN (1) | CN113330070A (zh) |
BR (1) | BR112021014278A2 (zh) |
CA (1) | CA3128976A1 (zh) |
MX (1) | MX2021008996A (zh) |
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Also Published As
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WO2020163981A1 (en) | 2020-08-20 |
EP3924426A1 (en) | 2021-12-22 |
BR112021014278A2 (pt) | 2021-09-28 |
US20220017772A1 (en) | 2022-01-20 |
CA3128976A1 (en) | 2020-08-20 |
MX2021008996A (es) | 2021-08-19 |
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