CN113302240A - 阻燃环氧组合物及其使用方法 - Google Patents
阻燃环氧组合物及其使用方法 Download PDFInfo
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- CN113302240A CN113302240A CN201980089199.0A CN201980089199A CN113302240A CN 113302240 A CN113302240 A CN 113302240A CN 201980089199 A CN201980089199 A CN 201980089199A CN 113302240 A CN113302240 A CN 113302240A
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- flame retardant
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Abstract
一种低密度、不含卤素的环氧组合物,其在固化后具有阻燃性并且适合用作灌注化合物。所述环氧组合物包含:(a)环氧组分;(b)至少一种固化剂;(c)至少一种潜在的固化促进剂;(d)包含粒度小于1微米的纳米尺寸核壳橡胶(CSR)颗粒的增韧组分;(e)不含卤素的阻燃组分;以及(f)用于降低所述组合物的密度的空心微球。所述阻燃组分包含以下的混合物:(i)至少一种聚磷酸盐;(ii)至少一种金属硼酸盐;以及(iii)至少一种选自碱土金属氢氧化物和氢氧化铝的化合物。
Description
本申请要求于2018年12月18日提交的在先的美国临时申请号62/781,190的权益,将该临时申请的内容以其全文通过援引方式并入本申请。
蜂窝夹层板用于诸如航空器内部的地板和墙壁等结构中,以保持强度和刚度,同时最小化结构的重量。蜂窝夹层板通常由插入两个预浸料面板之间的蜂窝芯组成。预浸料面板由浸渍有可固化树脂(例如,基于环氧树脂的组合物)的增强纤维构成。通过在每个预浸料面板与蜂窝芯的一侧之间施加可固化胶粘剂膜,将预浸料面板粘合层压到蜂窝芯上。
通常,将灌注化合物插入用于特定应用的蜂窝结构的芯以改善结构性能并增强粘合。此外,通过用边缘灌注化合物密封蜂窝芯夹层板的暴露边缘,可以减少或有效消除进入蜂窝芯的空隙的湿气,该边缘灌注化合物可以与蜂窝芯夹层板共固化。经常,用于此目的的此类灌注化合物被称为“单组分(one-part)”,即它们在一个步骤中进行预混合和施用。单组分灌注化合物通常是高粘度、类似油灰的化合物。通常,可以使用抹刀或镘刀手动将此类灌注化合物施用于复合孔结构。可替代地,此类灌注化合物还可以通过机器人或自动化系统施用,其中材料被泵送并插入蜂窝芯中。
环氧树脂由于其有吸引力的特性而被广泛用作各种应用中的基质树脂,这些特性如高强度和模量、对基底的高粘附性、良好的耐化学性和耐腐蚀性、优异的尺寸稳定性和电特性。特别地,环氧树脂已被用于航空航天应用,其中它们与增强纤维结合形成用于制造航空器部件的复合材料或用作结构膜胶粘剂的材料。已发现环氧树脂可用于其中的一个领域是作为用于填充蜂窝夹层板的空隙的灌注化合物。
此外,用于在航空航天工业(例如航空器内部)中应用的材料通常需要满足各个监管机构规定的某些关键要求。此类要求经常由航空器的原始设备制造商(OEM)提供,并且经常源自联邦航空要求,如美国联邦航空管理局(FAA)提出的要求,或者源自OEM所希望的性能特征。要求包括机械性能,如高抗压强度、高阻燃性和在燃烧过程中低的烟和有毒气体排放。机械性能和阻燃性的要求需要在相对较低的重量下实现;因此,阻燃组合物在其固化形式下需要具有低密度。最后,在商业环境中对所述材料的加工必须能够通过常规加工技术,比如挤出进行。
传统上,旨在满足可燃性要求的基于环氧树脂的组合物包含基于卤素的阻燃剂。由于溴或其他卤素的存在,已知此类阻燃的、基于环氧树脂的组合物是危险和有毒的。因此,需要能够满足与基于卤素的材料相同的可燃性要求的不含卤素的组合物。然而,在不使用所述基于卤素的阻燃剂的情况下实现所希望的可燃性特性是困难的,尤其是对于由芳族环氧树脂构成的树脂。
此外,已经发现常规的阻燃的基于环氧树脂的组合物,尤其是当用作蜂窝芯填充应用的灌注化合物时,在固化时展示出细小的微裂纹。这种微裂纹是由于在典型的固化循环中加热和随后冷却而在环氧树脂基质内形成的内部应力的结果。微裂纹对包含蜂窝芯的经固化的复合结构的性能特性具有有害影响。这些微裂纹经常沿蜂窝芯的孔壁存在,使湿气和水进入芯中。
因此,仍然需要一种低密度、不含卤素的阻燃环氧组合物,其可以用作蜂窝夹层板的灌注化合物,并且其在固化时能够抵抗微裂纹以便提高经固化的材料的耐湿性。
本文披露了一种低密度的阻燃环氧组合物,其不含卤化物质并且其在固化时能够抵抗微裂纹,从而提高经固化的材料的耐湿性并提高材料的随着时间推移的整体机械性能。
总体上,本披露的不含卤素的阻燃环氧组合物包含:
a)包含至少一种环氧化物官能度为至少1的环氧化物化合物的环氧组分,
b)至少一种固化剂(或硬化剂),
c)至少一种促进剂,
d)包含纳米尺寸核壳橡胶(CSR)颗粒的增韧组分,
e)不含卤素的阻燃组分,以及
f)用于降低组合物的密度的低密度填料组分。
基于组合物的总重量,环氧组合物中组分的重量百分比(wt%)的相对量可以如下:
a)5至60wt%、优选20至45wt%的环氧组分,
b)总共1至50wt%、优选20至30wt%的一种或多种固化剂,
c)0.5至1wt%的促进剂,
d)2至40wt%、优选8至18wt%的增韧组分,
e)3至50wt%、优选25至40wt%的不含卤素的阻燃组分,以及
f)5至50wt%、优选15至22wt%的低密度填料组分。
在一些实施例中,环氧组分的重量百分比小于总组合物的50wt%,并且环氧组分(e)与低密度填料组分(f)的重量比(e/f)为1比1.1。
本文披露的阻燃环氧组合物的特征为可以具有低密度,这使其能够用于希望具有轻质结构的应用中。本文中,术语“低密度”定义为重量/体积为1g/cm3或更小的组合物。在阻燃环氧组合物固化后,经固化的材料的密度小于0.8g/cm3,在一些实施例中,小于0.7g/cm3,或小于0.6g/cm3。这种低密度是由于环氧组合物中低密度填料组分的比例高。密度可以通过将环氧组合物浇铸到模具中并在250°F下固化60分钟来测量。从模具中取出经固化的样品并确定它们的精确尺寸。称重每个样品并以g/cm3计算密度。
本文披露的阻燃环氧组合物可以被称为“单组分”体系,因为它在其中包含固化剂(或硬化剂),因此,它可以按原样固化。与单组分体系相比,“两组分”体系需要将固化剂组分和环氧组分分开储存并且需要在使用时混合。
本披露的环氧组合物可通过多种常规的混合和共混技术制备。例如,环氧组合物的组分可以在环境条件下使用标准混合设备如罗斯(Ross)混合器添加和共混。取决于特定组合物的特性,在混合期间可以任选地加热或冷却组分。此外,可以对组合物抽真空以控制组合物的粘度和密度。优选地,首先将环氧树脂共混从5至60分钟的设定时间,然后添加橡胶添加剂和固化剂。低密度填料组分通常作为最终成分添加。继续混合直至达到均匀。
环氧组分
可用于阻燃环氧组合物的有机环氧化物化合物是具有通过开环可聚合的环氧乙烷环的任何有机化合物。此类环氧化物化合物(在本领域中称为环氧化物)可以包括单体和聚合的环氧化合物并且可以是脂族、芳族、脂环族或杂环的。环氧化物化合物可以选自具有一或更大并且更优选地从二至四的官能度的宽范围的脂族和芳族环氧树脂。适用于本发明的环氧化物化合物衍生自但不限于双酚A、双酚F、双酚S和双酚Z环氧树脂。更优选地,本发明的环氧化物化合物衍生自双酚A、双酚F、双酚S和双酚Z的二缩水甘油醚。
特别合适的是每分子具有多个环氧化物官能团的多官能环氧树脂(或聚环氧化物)。聚环氧化物可以是饱和的、不饱和的、环状的、或非环状的、脂族的、芳族的、或杂环的聚环氧化物化合物。合适的聚环氧化物的实例包括通过在碱存在下表氯醇或表溴醇与多酚的反应制备的聚缩水甘油醚。因此,合适的多酚是例如间苯二酚、邻苯二酚、对苯二酚、双酚A(双(4-羟苯基)-2,2-丙烷)、双酚F(双(4-羟苯基)甲烷)、氟4,4'-二羟基二苯甲酮、双酚Z(4,4'-亚环己基双酚)和1,5-羟基萘。作为聚缩水甘油醚的基础的其他合适的多酚是已知的酚醛清漆树脂类型的苯酚和甲醛或乙醛的缩合产物。
合适的环氧树脂的实例包括双酚A或双酚F的二缩水甘油醚,例如从陶氏化学公司(Dow Chemical Co.)可获得的EPONTM 828(液体环氧树脂),D.E.R.331、D.E.R.661(固体环氧树脂);氨基酚的三缩水甘油醚,例如来自亨斯迈公司(Huntsman Corp.)的MY 0510、MY 0500、MY 0600、MY 0610;和从迈图公司(Momentive)可获得的158。另外的实例包括基于苯酚的酚醛清漆环氧树脂,从陶氏化学公司以DEN428、DEN 431、DEN 438、DEN 439和DEN 485可商购;从汽巴-嘉基公司(Ciba-Geigy Corp.)以ECN 1235、ECN 1273和ECN 1299可商购的基于甲酚的酚醛清漆环氧树脂;从亨斯迈公司以71756、556和756可商购的烃类酚醛清漆环氧树脂。
固化剂和促进剂
如本文披露的环氧硬化剂,也称为固化试剂、催化剂或固化剂,是能够与环氧官能团反应或使环氧官能团聚合的反应性材料。由于阻燃环氧组合物优选为单组分体系,它包含一种或多种环氧硬化剂,当加热组合物时,该一种或多种环氧硬化剂能够完成组合物中的环氧树脂的交联或固化。如本文详述的硬化剂可以以催化方式起作用,或者在一些实施例中,通过与一种或多种环氧树脂反应而直接参与固化过程。在一些实施例中,使用两种或三种硬化剂的组合。
可用于阻燃环氧组合物的硬化剂的具体实例包括但不限于脂族和芳族伯胺、脂族和芳族叔胺、三氟化硼络合物、胍(包括取代的胍)和双脲。具体实例包括双氰胺(DICY)、2,4-甲苯双-(二甲基脲)(例如,来自CVC热固性特种材料公司(CVC Thermoset Specialties)的CA 150)、4,4'-亚甲基双-(苯基二甲基脲)(例如,来自CVC热固性特种材料公司的CA152)、3,3'-二氨基二苯砜(3,3-DDS)和4,4'-二氨基二苯砜(4,4-DDS)。可以存在一种或多种固化试剂。
在优选实施例中,环氧硬化剂选自酸酐硬化剂,如4-甲基四羟基邻苯二甲酸酐、甲基纳迪克酸酐、5-甲基-2,3-二羧基降冰片烯酸酐、邻苯二甲酸酐和四氢甲基邻苯二甲酸酐。
为了改善灌注化合物的固化条件,标准是使用促进剂。促进剂,其与环氧硬化剂可能相同或可能不同,通常存在于组合物中以提高环氧化物固化反应发生的速率。此类促进剂的实例包括但不限于芳族叔胺、咪唑、咪唑衍生物、类似咪唑的化合物等。具体实例包括例如2-(2-(2-甲基咪唑基)-乙基)-4,6-二氨基-s-三嗪。然而,此类促进剂具有使最终环氧组合物的潜伏状态(latency)变差,从而导致适用期(或贮存期)短的倾向。在制造环境中,此类材料在很短的时间段内变得无法使用。
已经发现,将某些胺加合物作为潜在的固化促进剂添加到本披露的阻燃环氧组合物中可以改变固化动力学并允许更长的适用期(或贮存期)。此类促进剂包括胺-环氧加合物、胺-脲基加合物和胺-氨基甲酸乙酯加合物。这些胺加合物在室温(21℃-25℃)下是固体且不溶于环氧组分。在升高的温度下,胺加合物溶解到周围的环氧树脂中并起到促进剂的作用。
胺-环氧加合物可以通过使具有多于一个环氧基的环氧化合物与分子中具有叔氨基和至少一个选自由OH、SH、NH、NH2、COOH和CONHNH2组成的组的官能团的化合物反应来合成。此种胺-环氧加合物促进剂是优选的,因为它们具有加速环氧固化的速率而不导致适用期下降的能力。
胺-脲基加合物是通过使胺与脲、硫脲或其衍生物反应制备的。例如,胺-脲基加合物可通过使胺与亚乙基脲和甲醛反应来制备,并且反应在基于水的介质中进行。胺-氨基甲酸乙酯加合物是通过使胺与异氰酸酯反应制备的,如异氰酸正丁酯、异氰酸异丙酯、异氰酸苯酯和异氰酸苄酯,包括多官能异氰酸酯化合物,如六亚甲基二异氰酸酯、甲苯二异氰酸酯、1,5-萘二异氰酸酯、二苯基甲烷-4,4'-二异氰酸酯、异佛尔酮二异氰酸酯、苯二甲基二异氰酸酯、对苯二异氰酸酯、1,3,6-六亚甲基三异氰酸酯和双环庚烷三异氰酸酯。
任何胺化合物可用于合成胺加合物促进剂,包括具有伯氨基、仲氨基或叔氨基的胺。合适的胺化合物的实例包括脂族胺,如二亚乙基三胺、三亚乙基四胺、正丙胺、2-羟乙基氨基丙胺、环己胺和4,4'-二氨基二环己基甲烷;芳族胺化合物,如4,4'-二氨基二苯基-甲烷和2-甲基苯胺;以及含氮原子的杂环化合物,如2-乙基-4-甲基咪唑、2-乙基-4-甲基咪唑啉、2,4-二甲基咪唑啉、哌啶和哌嗪。
增韧组分
本披露的阻燃环氧组合物包含增韧组分,该增韧组分包含纳米尺寸核-壳橡胶(CSR)颗粒。如本文所用的术语“纳米尺寸”是指在小于1微米的纳米范围内的尺寸。增韧组分提高源自固化环氧组合物的经固化的环氧树脂基质的机械强度。此外,已经发现这种增韧组分的存在消除了经固化的材料中微裂纹的形成,从而降低材料吸湿的倾向。
在优选实施例中,增韧组分进一步包含弹性体材料(或弹性体)。通过纳米尺寸CSR颗粒和弹性体材料的组合产生了协同效应。纳米尺寸CSR颗粒的作用是通过从基质脱粘,接着是伴随着剪切带屈服的大规模塑性空隙增长来使脆性的经固化的环氧树脂基质增韧。弹性体材料的作用是有效地在CSR颗粒与基质之间传递应力。
包含纳米尺寸CSR颗粒和弹性体材料的增韧组分以总环氧组合物的8wt%至18wt%范围内的量存在。术语“wt%”是指重量百分比。在一些实施例中,增韧组分中CSR颗粒(A)与弹性体材料(B)的重量比(A/B)为1至2,优选1至1.5。
如使用激光散射粒度分布分析仪通过激光散射技术测定的,纳米尺寸CSR颗粒的粒度可以在从10nm至300nm的范围内。CSR颗粒可以具有由具有弹性体或似橡胶的特性(即,玻璃化转变温度(Tg)小于约0℃,例如,小于约-30℃)的聚合物材料构成的软核,该软核被由非弹性体聚合物材料(即,具有大于环境温度(例如,大于约50℃)的Tg的热塑性或热固性/交联聚合物)构成的硬壳包围。例如,核可以由例如二烯均聚物或共聚物(例如,丁二烯或异戊二烯的均聚物,丁二烯或异戊二烯与一种或多种烯键式不饱和单体(如乙烯基芳族单体、(甲基)丙烯腈、(甲基)丙烯酸酯或类似物)的共聚物)构成,而壳可以由一种或多种单体(如(甲基)丙烯酸酯(例如,甲基丙烯酸甲酯)、乙烯基芳族单体(例如,苯乙烯)、乙烯基氰化物(例如,丙烯腈)、不饱和酸和酸酐(例如,丙烯酸)、(甲基)丙烯酰胺以及具有适当高的玻璃化转变温度的类似物)的聚合物或共聚物构成。壳中使用的聚合物或共聚物可具有通过金属羧酸盐形成(例如,通过形成二价金属阳离子的盐)而离子交联的酸基团。壳聚合物或共聚物还能够通过使用每分子具有两个或更多个双键的单体而共价交联。其他弹性体聚合物也可以适用于核,包括聚丙烯酸丁酯或聚硅氧烷弹性体(例如,聚二甲基硅氧烷,特别是交联的聚二甲基硅氧烷)。
CSR颗粒可以由多于两个层构成(例如,一种弹性体材料的中心核可以被不同弹性体材料的第二核包围,或者核可以被不同组成的两个壳包围,或者颗粒可以具有软核/硬壳/软壳/硬壳的结构)。通常,核占颗粒的按重量计从约50%至约95%,而壳占颗粒的按重量计从约5%至约50%。CSR颗粒可以预分散在液体树脂基质体系中,如从钟渊德州公司(Kaneka Texas Corporation)以商标Kane AceTM MX可获得的那些。优选将核-壳橡胶颗粒预分散在要用于树脂组分(A)的双官能、三官能和四官能环氧树脂中的一种中。作为举例,合适的含有CSR颗粒的树脂基质体系包括MX 120(具有约25wt.%CSR的液体双酚A环氧树脂)、MX 125(具有约25wt.%CSR的液体双酚A环氧树脂)、MX 153(具有约33wt.%CSR的液体双酚A环氧树脂)、MX 156(具有约25wt.%CSR的液体双酚A环氧树脂)、MX 130(具有约25wt.%CSR的液体双酚F环氧树脂)、MX 136(具有约25wt.%CSR的液体双酚F环氧树脂)、MX257(具有约37wt.%CSR的液体双酚A环氧树脂)、MX 416和MX 451(具有约25wt.%CSR的液体多官能环氧树脂)、MX 215(具有约25wt.%CSR的环氧化苯酚酚醛清漆)和MX 551(具有约25wt.%CSR的脂环族环氧树脂)。
增韧组分中使用的弹性体包括但不限于天然橡胶、苯乙烯丁二烯、聚异戊二烯、聚异丁烯、聚丁二烯、异戊二烯-丁二烯共聚物、氯丁橡胶、丁腈、聚硫化物弹性体、丙烯酸弹性体、丙烯腈弹性体、硅酮橡胶、聚硅氧烷、聚酯橡胶、二异氰酸酯连接的缩合弹性体、乙烯-丙烯二烯橡胶(EPDM)、氯磺化聚乙烯、氟化烃等。在一些实施例中,弹性体选自液体弹性体,如胺封端的丁二烯丙烯腈(ATBN)、羧基封端的丁二烯丙烯腈(CTBN)和羧基封端的丁二烯(CTB)。
还合适的是环氧-弹性体加合物。通常,将弹性体和环氧树脂混合,例如在高剪切混合器中,以形成作为基本上均匀混合物的加合物。用于加合物的弹性体可以选自先前披露的弹性体。在一个实施例中,环氧-弹性体加合物是环氧树脂、双酚和液体弹性体聚合物(在室温20℃-25℃下呈液体形式)的反应产物。用于形成加合物的合适的液体弹性体包括先前提到的那些,特别是ATBN、CTBN和CTB。
作为选择,增韧组分可以包含热塑性聚合物。合适的热塑性聚合物包括无定形聚砜,即主要包含散布在亚芳基残基之间的醚和砜基团的那些聚合物。此类聚砜包括聚醚砜(PES)。除了砜基团之外还包含醚和亚烷基基团的聚砜主要是无定形的,并且适用于本文的目的。同样合适的是具有胺端基的聚醚砜-聚醚醚砜(PES-PEES)共聚物,如美国专利号7084213中所述。这种共聚物的Tg高于150℃,例如180℃-200℃。如果存在,则热塑性材料(TP)相对于组合的CSR和弹性体的比例(或TP/(CSR+弹性体))为0.133至0.333。
本文披露的玻璃化转变温度(Tg)通过差示扫描量热法(DSC)以5℃/min的斜坡速率测量。
阻燃组分
不含卤素的阻燃组分包含以下的混合物:
1)至少一种聚合磷基阻燃材料;
2)至少一种选自包含金属硼酸盐的组的化合物;以及
3)至少一种选自包含碱土金属氢氧化物和铝族氢氧化物的组的化合物。
合适的聚合磷基材料或聚磷酸盐可以由环状或线性链构成,其中聚合氧阴离子由通过共享氧原子连接在一起的四面体磷酸盐结构单元形成。如在此上下文中使用的术语“磷基”意指含有磷。此类聚磷酸盐材料的实例包括但不限于聚磷酸三聚氰胺、聚磷酸铵和聚磷酸盐的金属盐,如聚磷酸钠、聚磷酸钙和聚磷酸钾。聚磷酸盐以环氧组合物的总重量的范围为按重量计从3%至12%、优选6%至8%的量存在于环氧组合物中。
使用元素红磷来生产阻燃材料是已知的。然而,由于红磷的易燃性和对氧化剂的反应性,使用元素红磷确实引起了健康和环境顾虑。因此,将有益的是阻止其在产生有毒烟雾令人担忧的行业如航空航天中使用。虽然易燃,但红磷在与其他协同阻燃剂组合时提供卓越的阻燃特性,并且经常阻燃组合物、尤其是基于环氧树脂的组合物中不包括红磷导致不燃烧特性的损失。已经发现聚磷酸盐(聚合物材料)与其他阻燃化合物的组合使用提供了类似于或优于基于红磷的体系的阻燃特性。此外,就不燃烧特性而言,聚磷酸盐提供优于非聚合磷材料的明显优势。已经发现,使用聚磷酸盐如聚磷酸三聚氰胺产生了改进的火焰传播耐受性并且还产生了具有较低的产生烟雾倾向的材料。此外,发现聚磷酸三聚氰胺的表现不同于磷酸三聚氰胺。
阻燃组分中的金属硼酸盐可包括但不限于硼酸锌、硼酸铝、硼酸镁及其混合物。在优选的实施例中,使用硼酸锌。金属硼酸盐以环氧组合物的总重量的范围为按重量计从约0.1%至约15%的量存在于环氧组合物中。在优选的实施例中,金属硼酸盐以环氧组合物的总重量的范围为按重量计从1%至10%的量存在。
碱土金属氢氧化物和铝族氢氧化物包括但不限于三水合铝和氢氧化镁。通常,金属氢氧化物以组合物的总重量的范围为按重量计从1%至20%、优选范围为按重量计从5%至20%、或按重量计10%至20%的量存在。
低密度填料组分
阻燃环氧组合物的低密度填料组分选自空心无机微球或微球体。微球是小的、球形的空心体。每个微球由包围空心芯的外壳组成。直径范围为数百微米和更小且壁厚为约11/2微米的微球是可商购的。优选地,用于当前阻燃组合物的直径范围为从5至150微米。微球可由各种材料制成,包括玻璃、二氧化硅(SiO2)、氧化锆、陶瓷和碳。合适的偶联剂如官能取代的硅氧烷(例如,来自道康宁公司(Dow Corning)的Z-6020和Z-6040)可用于涂覆微球体表面以增强其特性。作为举例,从特瑞堡公司(Trelleborg)以商标可获得的二氧化硅微球适用于本文披露的目的。
适用于本文目的的微球展示出小于0.5g/cm3的密度,在一些实施例中,在0.1至0.4g/cm3或0.1至0.3g/cm3的范围内的密度。微球的粒度范围可以是从1μm至300μm,并且在一些实施例中,在40μm-60μm的范围内。微球粒度测量可以通过在光学显微镜或扫描电子显微镜(SEM)下分析统计上显著的微球样品来进行。
阻燃环氧组合物的密度可以通过添加第二类型的低密度空心微球来进一步降低,该第二类型的低密度空心微球的密度低于第一类型的低密度空心微球。第二类型的低密度空心微球的密度在0.01-0.03g/cm3范围内。第二类型的低密度空心微球的粒度可以在20μm-100μm并且优选35μm-55μm的范围内。
在一些实施例中,微球(总计)以总环氧组合物的按重量计15%至25%的量存在。
特性和应用
本披露的阻燃、不含卤素的环氧组合物的特征可以在于具有希望的加工性能,因为它可以通过挤出加工,这是由于它的初始粘度低以及随时间推移的粘度增加最小。粘度增加可能限制阻燃组合物的贮存期和使用。初始挤出速率,定义为材料刚制成后的挤出速率,随着时间的推移会显著降低,这限制了材料的贮存期和加工性能。例如,环氧组合物在其配制后一天或两天后展示出较低的挤出速率是常见的。本披露的阻燃环氧组合物在组分混合后最初展示出大于100g/min的挤出速率并且在此后保持该速率长达8天。
由于其优异的加工特性,本披露的阻燃环氧组合物可以以多种不同的形式供应和/或使用,这些形式包括但不限于糊剂、膜、粘性树脂等。
本披露的阻燃环氧组合物是可热固化的,即在加热时组合物经历固化。固化条件可根据应用以及还有组合物中所用的固化试剂的选择而变化。在一些实施例中,环氧组合物在100℃至180℃范围内的温度下可固化,固化周期从5分钟至240分钟变化。
在一些实施例中,通过阻燃环氧组合物的热固化获得的硬化材料展示出以阻燃为特征的良好平衡特性,包括:低烟雾产生和低燃烧时间。这种经固化的材料在燃烧过程中还释放很少有毒气体至不释放有毒气体。例如,硬化、固化的材料可以提供以下:
1.90秒后小于100且240秒后小于200的火焰烟雾密度;
2.在60秒垂直燃烧测试中小于152mm的燃烧长度;
3.在60秒垂直燃烧测试中小于15秒的火焰时间;以及
4.小于3秒的滴液燃烧时间。
在一些实施例中,经固化的材料在室温(20℃-25℃)下具有至少2500psi(17.2MPa)、例如2500psi至5000psi(17.2MPa至34.5MPa)的抗压强度。这种抗压强度是根据ASTM D 695确定的。已经发现,添加本文披露的增韧组分(特别地,CSR颗粒和弹性体材料的组合)可以增加所得组合物的抗压强度。这种增韧组分的存在提供了对在例如在使用过程中遇到恒定负荷和力的结构部件的整个生命周期中出现的压缩力下的微裂纹的耐受性。
由于其低密度,本披露的阻燃环氧组合物适用于希望具有轻质结构的结构部件。该组合物特别可用于航空航天应用,例如,作为用于航空器内部的材料以及通常用于粘合、密封和/或绝缘部件的材料。特别合适的应用是其用作用于填充夹层板的蜂窝芯中的一个或多个空隙的灌注化合物,如密封蜂窝夹层板的边缘,或修复板内的损坏区域。夹层板的损坏可以通过将灌注化合物施用到受损区域的蜂窝芯中来修复。灌注化合物的施用可以通过常规技术(如注射、涂覆或抹涂)进行。
Claims (19)
1.一种用于填充蜂窝夹层板的空隙的方法,所述方法包括:
提供蜂窝夹层板,所述蜂窝夹层板包括布置在两片复合材料之间的蜂窝芯,所述蜂窝芯包括要用灌注组合物填充的一个或多个空隙;
将灌注组合物引入所述蜂窝芯的所述一个或多个空隙中;
用所述灌注组合物固化所述蜂窝夹层板,
其中所述灌注组合物是不含卤素的、可固化的环氧组合物,其包含:
a)包含至少一种环氧化物官能度为至少1的环氧化物化合物的环氧组分;
b)至少一种固化剂;
c)至少一种潜在的固化促进剂;
d)包含粒度小于1微米的纳米尺寸核壳橡胶(CSR)颗粒的增韧组分;
e)不含卤素的阻燃组分;以及
f)用于降低所述组合物的密度的空心微球;
其中所述潜在的固化促进剂选自在室温(21℃-25℃)下不溶于所述环氧组分的胺加合物,
其中所述阻燃组分包含以下的混合物:(i)至少一种聚磷酸盐;(ii)至少一种金属硼酸盐;以及(iii)至少一种选自碱土金属氢氧化物和氢氧化铝的化合物,并且
其中,固化后,经固化的灌注组合物的密度小于0.8g/cm3。
2.如权利要求1所述的方法,其中,所述增韧组分进一步包括弹性体材料。
3.如权利要求1所述的方法,其中,所述增韧组分进一步包括热塑性聚合物。
4.如权利要求1所述的方法,其中,所述增韧组分进一步包括弹性体材料和热塑性聚合物。
5.如权利要求2或4所述的方法,其中,弹性体材料选自:天然橡胶、苯乙烯丁二烯、聚异戊二烯、聚异丁烯、聚丁二烯、异戊二烯-丁二烯共聚物、氯丁橡胶、丁腈、聚硫化物弹性体、丙烯酸弹性体、丙烯腈弹性体、硅酮橡胶、聚硅氧烷、聚酯橡胶、二异氰酸酯连接的缩合弹性体、乙烯-丙烯二烯橡胶(EPDM)、氯磺化聚乙烯、氟化烃、及其组合。
6.如权利要求2或4所述的方法,其中,所述弹性体材料选自液态弹性体,优选胺封端的丁二烯丙烯腈(ATBN)、羧基封端的丁二烯丙烯腈(CTBN)和羧基封端的丁二烯(CTB)。
7.如权利要求2或4所述的方法,其中,所述弹性体材料是环氧-弹性体加合物。
8.如权利要求3或4所述的方法,其中,所述热塑性聚合物选自无定形聚砜,包括聚醚砜(PES)。
9.如权利要求3或4所述的方法,其中,所述热塑性聚合物是聚醚砜-聚醚醚砜(PES-PEES)共聚物。
10.如前述权利要求中任一项所述的方法,其中,所述潜在的固化促进剂选自胺-环氧加合物、胺-脲基加合物和胺-氨基甲酸乙酯加合物,优选胺-环氧加合物。
11.如前述权利要求中任一项所述的方法,其中,所述纳米尺寸CSR颗粒具有如通过激光散射技术测定的在从10nm至300nm范围内的粒度。
12.如前述权利要求中任一项所述的方法,其中,所述空心微球包括具有不同密度的微球。
13.如权利要求12所述的方法,其中,所述空心微球的一部分的密度在0.1-0.4g/cm3范围内,并且所述空心微球的另一部分的密度在0.01-0.03g/cm3范围内。
14.如前述权利要求中任一项所述的方法,其中,所述灌注组合物包含以基于组合物的总重量的重量百分比(wt%)计的以下项:
a)5至60wt%、优选20至45wt%的环氧组分,
b)总共1至50wt%、优选20至30wt%的一种或多种固化剂,
c)0.5至1wt%的潜在的固化促进剂,
d)2至40wt%、优选8至18wt%的增韧组分,
e)3至50wt%、优选25至40wt%的阻燃组分,以及
f)5至50wt%、优选15至22wt%的空心微球。
15.一种在固化后具有阻燃性的低密度、不含卤素的环氧组合物,所述组合物包含:
a)包含至少一种环氧化物官能度为至少1的环氧化物化合物的环氧组分;
b)至少一种固化剂;
c)至少一种潜在的固化促进剂;
d)包含粒度小于1微米的纳米尺寸核壳橡胶(CSR)颗粒的增韧组分;
e)不含卤素的阻燃组分;以及
f)用于降低所述组合物的密度的空心微球;
其中
所述潜在的固化促进剂选自在室温(21℃-25℃)下不溶于所述环氧组分的胺加合物,
所述阻燃组分包含以下的混合物:(i)至少一种聚磷酸盐;(ii)至少一种金属硼酸盐;以及(iii)至少一种选自碱土金属氢氧化物和氢氧化铝的化合物,
所述空心微球的密度小于0.5g/cm3。
16.如权利要求15所述的低密度、不含卤素的环氧组合物,其中,环氧组分(a)与空心球(f)的重量比(a)/(f)是1比1.1并且所述环氧组分的重量百分比小于总组合物的50%。
17.如权利要求15或16所述的低密度、不含卤素的环氧组合物,其中,所述增韧组分进一步包括弹性体或环氧-弹性体加合物。
18.如权利要求15至17中任一项所述的低密度、不含卤素的环氧组合物,其中,所述增韧组分进一步包括热塑性聚合物。
19.如权利要求15至18中任一项所述的低密度、不含卤素的环氧组合物,其中,所述促进剂选自胺-环氧加合物、胺-脲基加合物和胺-氨基甲酸乙酯加合物,优选胺-环氧加合物。
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EP3898836A1 (en) | 2021-10-27 |
CA3123577A1 (en) | 2020-06-25 |
JP7539886B2 (ja) | 2024-08-26 |
JP2022514530A (ja) | 2022-02-14 |
AU2019406816A1 (en) | 2021-07-01 |
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