CN111295407B - 树脂组合物及树脂灌注方法 - Google Patents

树脂组合物及树脂灌注方法 Download PDF

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CN111295407B
CN111295407B CN201880069615.6A CN201880069615A CN111295407B CN 111295407 B CN111295407 B CN 111295407B CN 201880069615 A CN201880069615 A CN 201880069615A CN 111295407 B CN111295407 B CN 111295407B
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J.E.米根
M.奥里利亚
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Abstract

披露了适合用于液体树脂灌注方法的可固化环氧树脂组合物。在一个实施例中，该树脂组合物含有(a)至少两种聚环氧化物，其中一种是三(羟苯基)甲烷的三缩水甘油醚，(b)芳香族胺固化剂，以及(c)核‑壳橡胶颗粒。在另一个实施例中，该树脂组合物含有(a)至少两种聚环氧化物，其中一种是双(羟苯基)芴的二缩水甘油醚，(b)芳香族胺固化剂，以及(c)核‑壳橡胶颗粒。

Description

树脂组合物及树脂灌注方法
本披露总体上涉及通过树脂灌注方法(如树脂传递模制(RTM))制造纤维增强复合结构，以及适合用于此种树脂灌注方法的树脂组合物。
具体实施方式
可以使用不同的方法制造三维纤维增强复合零件，这些方法之一是液体树脂灌注。树脂传递模制(RTM)和真空辅助RTM(VARTM)是涉及将液体树脂注入纤维预成型件中的制造方法的实例。在RTM方法期间，将预成型件置于封闭模具腔体中，并且将树脂在压力下注入该腔体中。经常将具有预成型件的模具置于真空下，使得真空去除该预成型件中的所有截留空气并且加速RTM方法。一旦液体树脂充满模具腔体，则将该树脂固化，导致形成复合零件。VARTM类似于RTM，除了单面机床通常与真空装袋一起使用，并且压力梯度将液体树脂推进预成型件中。该纤维预成型件是干增强纤维的组件，通常呈以堆叠布置的形式铺放的织物层形式。这些技术非常适合用于在许多情况下以合理的生产速率制造非常复杂形状的零件。
热固性树脂，特别是环氧树脂，由于其令人希望的特性如耐热性和耐化学性、粘附性和耐磨性，已经被广泛用作此类纤维增强复合零件的基质树脂。对于RTM加工，固化剂溶解到树脂相中促进简单的“加热、注射/浸湿和固化”工艺方法，其中理解和权衡的是由于树脂和固化剂的紧密混合，树脂组合物即使在环境温度下也显示出少许自反应性。与环氧树脂广泛使用以生产纤维增强复合材料的固化剂尤其包括脂肪族胺和芳香族胺。固化剂的结构及其官能团的反应性经常被用于控制树脂组合物的反应速率和可加工性。
当设计用于结构应用(如航空航天应用)的纤维增强聚合物复合材料时，希望增加固化的聚合物基质的玻璃化转变温度(Tg)、特别是湿Tg并且降低固化速率同时维持聚合物基质中的高水平的韧性和固化的复合材料中的高水平的抗损伤性。此类特性对于制造其中要求高韧性或高速撞击耐受性的航空航天结构(如风扇叶片、发动机舱和包容机匣(containment casing))将是特别令人希望的。来源于纤维增强聚合物的航空航天复合零件可以被环境侵蚀(如水分扩散)所降解。湿Tg是指固化的材料在其中材料(以测试试样的形式)被水分所饱和的条件下的玻璃化转变温度，此类条件被认为是在使用环境中的指示。还希望来源于纤维增强聚合物的航空航天复合零件在其使用时间内对材料特性的变化示出抗性。用于表征这种行为的一种方法是将固化的树脂体系保持在升高的温度下，并追踪在升高的温度下玻璃化转变温度随时间变化的演变。
本披露提供了可固化树脂组合物，其适合用于液体树脂灌注方法、特别是RTM和VARTM。
根据一个实施例，该可固化树脂组合物含有以下组分：
(A)至少两种聚环氧化物，其中一种是双官能环氧化物并且另一种是由式I表示的三(羟苯基)甲烷的三缩水甘油醚：
Figure BDA0002465677400000021
(B)至少一种由式II表示的芳香族胺固化剂：
Figure BDA0002465677400000022
其中A是由-NHR表示的胺基，R独立地选自氢、具有1至6个碳原子(C1-C6)的直链和支链烷基，优选A是NH2；
B选自：
Figure BDA0002465677400000031
C选自C1-C6烷基和异丙基；并且X是选自Cl、Br、F和I的卤素或氢(H)；以及
(C)核-壳橡胶颗粒。
具有式I的三(羟苯基)甲烷的三缩水甘油醚是以基于该组合物的总重量按重量计大于0％并且最高达18％，例如2％至10％的量存在。涵盖在式I中的可商购的聚环氧化物是来自亨斯迈公司(Huntsman)的
Figure BDA0002465677400000032
742。
合适的具有式II的芳香族胺固化剂包括分别具有下式1和2的9,9-双(3-氯-4-氨基苯基)芴(或CAF)和9,9-双(4-氨基苯基)芴：
(1)
Figure BDA0002465677400000033
(2)
Figure BDA0002465677400000034
其他合适的具有式II的芳香族胺包括：
4-甲基-9,9-双(4-氨基苯基)芴、
4-氯-9,9-双(4-氨基苯基)芴、
2-乙基-9,9-双(4-氨基苯基)芴、
2-碘-9,9-双(4-氨基苯基)芴、
3-溴-9,9-双(4-氨基苯基)芴、
9-(4-甲基氨基苯基)-9-(4-乙基氨基苯基)芴、
1-氯-9,9-双(4-氨基苯基)芴、
2-甲基-9,9-双(4-氨基苯基)芴、
2,6-二甲基-9,9-双(4-氨基苯基)芴、
1,5-二甲基-9,9-双(4-氨基苯基)芴、
2-氟-9,9-双(4-氨基苯基)芴、
1,2,3,4,5,6,7,8-八氟-9,9-双(4-氨基苯基)芴、
2,7-二硝基-9,9-双(4-氨基苯基)芴、
2-氯-4-甲基-9,9-双(4-氨基苯基)芴、
2,7-二氯-9,9-双(4-氨基苯基)芴、
2-乙酰基-9,9-双(4-氨基苯基)芴、
2-甲基-9,9-双(4-甲基氨基苯基)芴、
2-氯-9,9-双(4-乙基氨基苯基)芴、
2-叔丁基-9,9-双(4-甲基氨基苯基)芴。
还合适的是4,4’-亚甲基-双-(3-氯-2,6-二乙基苯胺)(MCDEA)；4,4’-亚甲基-双-(2-异丙基-6-甲基苯胺)(MMIPA)。其他具有式II的芳香族胺(其中B是O＝S＝O)包括分别由式3和4表示的4,4’-二氨基二苯砜(4,4’-DDS)和3,3’-二氨基二苯砜(3,3’-DDS)：
(3)
Figure BDA0002465677400000051
4,4’-DDS
(4)
Figure BDA0002465677400000052
3,3’-DDS
术语“聚环氧化物”是指含有多于一个环氧基团的化合物：
Figure BDA0002465677400000053
双官能环氧化物是具有两个官能团的聚环氧化物。合适的双官能环氧化物包括在室温下具有低粘度(例如在25℃下<1000cP)的那些。双官能环氧化物的具体实例是双酚或二烯烃化合物的环氧化反应产物(如双酚F、双酚A或双酚Z的二缩水甘油醚)；丁二醇的二缩水甘油醚(例如来自亨斯迈公司的
Figure BDA0002465677400000054
DY-D)；环氧含量为6.8-8.0当量/kg且在25℃下粘度为100-600cP的低粘度的脂环族环氧树脂(例如来自亨斯迈公司的/>
Figure BDA0002465677400000055
CY179)。
其他合适的双官能环氧化物包括具有下式5和6的化合物(或单体)：
(5)
Figure BDA0002465677400000056
(6)
Figure BDA0002465677400000061
双官能环氧化物可以以基于组合物的总重量按重量计最高达50wt％，例如24％至38％的量存在。
看起来，当与没有具有式I的聚环氧化物的相同的树脂组合物相比时，树脂组合物中具有式I的聚环氧化物和具有式II的芳香族胺(CAF)的存在有助于增加固化的树脂基质的湿Tg同时维持高水平的韧性。此外，当与其他众所周知的多官能树脂(如来自亨斯迈公司的
Figure BDA0002465677400000062
MY0510(三缩水甘油基对氨基苯酚)、MY0610(三缩水甘油基间氨基苯酚)和MY721(四缩水甘油基二氨基二苯基甲烷))相比时，具有式I的聚环氧化物看起来在升高的温度下提供了Tg稳定性的改善。
以上披露的可固化树脂组合物可以进一步包括由式III表示的环氧酚醛清漆树脂：
Figure BDA0002465677400000063
其中n＝1至5，R＝H。
特别合适的环氧酚醛清漆树脂是由下式表示的：
Figure BDA0002465677400000071
此种环氧酚醛清漆树脂是从陶氏化学公司(Dow Chemical Co)作为D.E.N.TM 431可商购的。
环氧酚醛清漆树脂可以以基于组合物的总重量按重量计大于0％并且最高达18％，例如1％至7％的量存在。
以上披露的可固化树脂组合物可以进一步包括芴基环氧树脂，特别是由式IV表示的双(羟苯基)芴的二缩水甘油醚：
Figure BDA0002465677400000072
当存在时，该芴基环氧树脂可以以基于组合物的总重量按重量计大于0％并且最高达20％，例如4％至18％的量存在。
看起来，当与没有芴基环氧化物的相同的树脂组合物相比时，树脂组合物中具有式IV的芴基环氧化物和具有式II的芳香族胺(例如CAF)的存在有助于增加固化的树脂基质的湿Tg。在一些实施例中，环氧树脂组合物不含任何在其式中具有一个或多个萘环的基于萘的环氧树脂。
根据又另一个实施例，树脂组合物含有以下组分：
(A)至少两种聚环氧化物，其中一种是芴基环氧树脂，特别是以上披露的由式IV表示的化合物，并且另一种聚环氧化物是基于萘的环氧树脂；
(B)以上披露的由式II表示的芳香族胺固化剂；以及
(C)核-壳橡胶颗粒。
该基于萘的环氧树脂在其式中具有至少一个萘环结构(或苯环的稠合对)：
Figure BDA0002465677400000081
该基于萘的环氧树脂可以选自：1,6-二羟基萘的二缩水甘油醚；1,7-二羟基萘；1萘甲酚缩水甘油醚；1,2-二羟基萘；1,3-二羟基萘；1,4-二羟基萘；1,5-二羟基萘；2,3-二羟基萘；2,7-二羟基萘；及其组合。
该基于萘的环氧树脂可以以基于组合物的总重量按重量计大于0％并且最高达30％，例如21％-30％的量存在。
在本文对于可固化树脂组合物所述的不同实施例中，所有芳香族胺(“A”)的组合与聚环氧化物(“B”)的摩尔比(A:B)，A/B可以是在1至2(1:1至2:1)、优选1.5至1.6(15:10至16:10)的范围内。
本文所述的环氧树脂组合物优选在90℃至160℃范围内的温度下具有小于10泊、优选小于5泊或小于3泊的粘度。
本披露中的术语“固化(curing)”或“固化(cure)”是指通过加热、化学反应或照射引起的热固性材料(预聚物或树脂或单体)的硬化。固化过程将树脂改变成不熔性、不溶性的交联聚合物网络。在可固化树脂组合物的上下文中，术语“可固化的”意指组合物能够经受将使该组合物由粘性液体状态转变为硬化状态的条件(如加热)。
核-壳颗粒
核-壳橡胶(CSR)颗粒在环氧基树脂组合物中用作增韧剂。优选地，核-壳橡胶颗粒具有小于800nm，例如100nm至200nm的粒度(d90)。CSR颗粒在树脂组合物中的相对量可以是基于组合物的总重量按重量计1％至20％，在一些实施例中是0.3％至10％。
CSR颗粒具有内核部分和基本上包住内核部分的外壳部分。核部分优选是具有弹性体或橡胶特性的聚合物材料，即相对低的玻璃化转变温度(特别是相对于外壳部分的材料)并且优选小于约0℃，例如小于约-30℃。外壳部分优选为玻璃状聚合物材料，即，具有高于环境温度(20℃)、优选高于约50℃的玻璃化转变温度的热塑性或交联的热固性聚合物。
CSR颗粒的核可以是类似于橡胶化合物的丁二烯/苯乙烯共聚物，并且壳可以是丙烯酸酯，例如甲基丙烯酸甲酯的均聚物或共聚物。
在一些实施例中，该树脂组合物不含任何热塑性聚合物，如聚芳砜(包括聚醚砜(PES)、聚芳醚醚砜(PEES)、及其共聚物)、聚芳醚、聚芳基硫醚以及聚苯醚(PPO)，以便将粘度维持在希望的低水平下。
任选的添加剂
可固化树脂组合物可以包括任选的添加剂，如纳米尺寸的无机颗粒(如二氧化硅)。无机颗粒具有在从约2.0nm至约800nm范围内的粒度，优选不超过500nm，在一些实施例中，不超过100nm。此类任选的添加剂的量不超过可固化树脂组合物的按重量计5.0％。
树脂灌注方法和模制制品的制造
本披露的可固化的环氧基树脂组合物适合用于包括RTM和VaRTM的液体树脂灌注。模制制品可以通过以下来生产：提供纤维预成型件，用本文披露的可固化环氧树脂组合物灌注该纤维预成型件，以及固化该树脂灌注的预成型件。该纤维预成型件是多孔的并且对于液体树脂组合物是可渗透的。为了形成该预成型件，将纺织材料的多个层铺放到希望的厚度。
在树脂灌注之前可以将该预成型件置于封闭模具中。将模具加热至初始温度并且将具有足够低的粘度的树脂组合物注入该模具中以用树脂灌注该预成型件。然后在高于初始温度的固化温度(Tc)下固化该树脂灌注的预成型件持续足以形成硬化复合制品的时间段。
特性测量
粒度
在本披露中，粒度是通过动态光散射，例如使用Malvern Zetasizer 2000测量的。粒度(d90)定义了粒度分布(基于体积)，使得90％的颗粒具有低于这个值的粒度。
粘度
粘度测量是根据ASTM标准D2196在稳定条件下使用布氏粘度计进行的。
玻璃化转变温度
在本披露中，玻璃化转变温度(Tg)是通过差示扫描量热法(DSC)在5℃/min的斜坡速率下确定的。
实例
一些用于RTM方法的示例性树脂组合物在表1-表3中示出。
表1
Figure BDA0002465677400000101
表2
Figure BDA0002465677400000102
表3
Figure BDA0002465677400000111
PY 306、MY0816和LME10169是从亨斯迈先进材料公司(Huntsman AdvancedMaterials)可获得的。

Claims (5)

1.一种适合用于液体树脂灌注的可固化环氧树脂组合物，其包含：(A)由以下组成的聚环氧化物的组合：
(i)由式I表示的三(羟苯基)甲烷的三缩水甘油醚：
Figure FDA0004096691660000011
(ii)双酚F或双酚A的二缩水甘油醚；
(iii)由以下式II表示的双官能环氧化物：
Figure FDA0004096691660000012
和
(iv)由以下式III表示的环氧酚醛清漆树脂：
Figure FDA0004096691660000013
其中n＝1至5，R＝H
(B)9,9-双(4-氨基-3-氯苯基)芴或9,9-双(4-氨基苯基)芴，以及
(C)核-壳橡胶颗粒，
其中基于该环氧树脂组合物的总重量，所述聚环氧化物的重量百分比如下：2％至10％聚环氧化物(i)；24％至38％聚环氧化物(ii)和(iii)合计；和1％至7％聚环氧化物(iv)，
其中组分(B)与组分(C)的摩尔比为1:1至2:1，
其中所述核-壳橡胶颗粒的量为0.3％重量至10％重量，基于该环氧树脂组合物的总重量计，和
其中所述可固化环氧树脂组合物不含任何热塑性聚合物。
2.如权利要求1所述的可固化环氧树脂组合物，其中，该环氧酚醛清漆树脂由下式表示：
Figure FDA0004096691660000021
3.如权利要求1所述的可固化环氧树脂组合物，其中，该可固化环氧树脂组合物在90℃至160℃范围内的温度下具有小于10泊的粘度。
4.一种用于生产模制制品的液体树脂灌注(LRI)制造方法，该方法包括以下步骤：提供被配置用于接收液体树脂的纤维预成型件，用权利要求1所述的可固化环氧树脂组合物灌注该纤维预成型件，以及在固化温度(Tc)下固化该树脂灌注的预成型件。
5.如权利要求4所述的方法，其进一步包括：
a.将该纤维预成型件置于封闭模具中；
b.将该模具加热至初始温度；
c.将该可固化环氧树脂组合物注入该模具中，以便用该环氧树脂组合物灌注该纤维预成型件；以及
d.在高于该初始温度的该固化温度(Tc)下固化该树脂灌注的预成型件持续足以形成硬化制品的时间段。
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