CN108290386B - 形成固化环氧材料的方法、由其形成的固化环氧材料及结合固化环氧材料的复合材料核 - Google Patents
形成固化环氧材料的方法、由其形成的固化环氧材料及结合固化环氧材料的复合材料核 Download PDFInfo
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- CN108290386B CN108290386B CN201680066740.2A CN201680066740A CN108290386B CN 108290386 B CN108290386 B CN 108290386B CN 201680066740 A CN201680066740 A CN 201680066740A CN 108290386 B CN108290386 B CN 108290386B
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- anhydride
- glycidyl ether
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- DUILGEYLVHGSEE-UHFFFAOYSA-N 2-(oxiran-2-ylmethyl)isoindole-1,3-dione Chemical compound O=C1C2=CC=CC=C2C(=O)N1CC1CO1 DUILGEYLVHGSEE-UHFFFAOYSA-N 0.000 claims description 3
- KFUSXMDYOPXKKT-UHFFFAOYSA-N 2-[(2-methylphenoxy)methyl]oxirane Chemical compound CC1=CC=CC=C1OCC1OC1 KFUSXMDYOPXKKT-UHFFFAOYSA-N 0.000 claims description 3
- SFJRUJUEMVAZLM-UHFFFAOYSA-N 2-[(2-methylpropan-2-yl)oxymethyl]oxirane Chemical compound CC(C)(C)OCC1CO1 SFJRUJUEMVAZLM-UHFFFAOYSA-N 0.000 claims description 3
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- DXEHULHXWHEJJD-UHFFFAOYSA-N 2-[(4-butylphenoxy)methyl]oxirane Chemical compound C1=CC(CCCC)=CC=C1OCC1OC1 DXEHULHXWHEJJD-UHFFFAOYSA-N 0.000 claims description 3
- HDPLHDGYGLENEI-UHFFFAOYSA-N 2-[1-(oxiran-2-ylmethoxy)propan-2-yloxymethyl]oxirane Chemical compound C1OC1COC(C)COCC1CO1 HDPLHDGYGLENEI-UHFFFAOYSA-N 0.000 claims description 3
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- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 claims description 3
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Abstract
一种形成固化的环氧材料的方法,包括在加入环氧树脂和固化促进剂之前使亚苯基醚低聚物与酸酐硬化剂预反应,然后将所得的组合物固化。相对于其中在添加硬化剂之前使亚苯基醚低聚物与环氧树脂预反应,以及其中同时混合所有组分的相应方法的相应方法,本方法提供了改善的耐热性和韧性的平衡。固化的环氧材料可以在铝导体复合材料核增强电缆的复合材料核中应用。
Description
技术领域
本发明涉及形成固化的环氧材料的方法、由其形成的固化的环氧材料、在该方法中有用的亚苯基醚低聚物-酸酐反应产物以及结合固化的环氧材料的复合材料核。
背景技术
提高热固性树脂中玻璃化转变温度(Tg)的重要途径是增加网络的交联密度。高官能度环氧树脂已用于增加交联密度并获得高Tg固化材料。Becker已经报道了四官能四缩水甘油基二氨基二苯基甲烷(TGDDM)和芳香族二胺如二乙基甲苯二胺(DETDA)可以生产Tg值大于200℃的固化材料(O.Becker,R.Varley,G.Simon,Polymer 2002,43卷,4365-4373页)。
通常,较高的交联密度限制了交联位置之间分子链的运动。这种受限制的运动也会导致不希望有的韧性下降。因此,在高Tg和韧性之间存在权衡。因此,配制多官能环氧树脂的挑战是获得高Tg材料,同时保持或增加韧性。
发明内容
一个实施方式是一种形成固化的环氧材料的方法,该方法包含:使亚苯基醚低聚物与酸酐硬化剂反应以形成第一产物;将环氧树脂加入到第一产物以形成第二产物;以及将第二产物固化以形成固化的环氧材料。
另一实施方式是通过权利要求1-17中任一项的方法形成的固化的环氧材料,其表现出通过差示扫描量热法测量的150至250℃的玻璃化转变温度,以及在23℃下通过ASTM D4812-11确定的在23℃下的80至200焦耳/米的无缺口悬臂梁冲击强度。
另一实施方式是使亚苯基醚低聚物与单酸酐反应的产物,其中亚苯基醚低聚物具有平均1.5至3个羟基基团/分子,其中亚苯基醚低聚物与单酸酐以有效于提供0.04:1至0.26:1羟基基团与酸酐基团的初始摩尔比的量反应,并且其中在产物中,亚苯基醚低聚物上至少75摩尔%的羟基已与单酸酐反应。
另一实施方式是一种用于铝导体复合材料核增强电缆的复合材料核,该复合材料核包含:选自由碳纤维、聚(对苯二甲酰对苯二胺)纤维、玄武岩纤维、玻璃纤维、芳香族聚酰胺纤维、硼纤维、液晶纤维和聚乙烯纤维组成的组的两种以上类型的纵向取向且基本上连续的增强纤维;和围绕增强纤维的固化的环氧材料,其中固化的环氧材料是包含亚苯基醚低聚物、酸酐硬化剂和环氧树脂的反应组分的产物;其中所述复合材料核具有至少50体积%的纤维。
以下详细描述这些和其他实施方式。
附图说明
图1是浸入80℃水中的固化样品的百分比重量增加对时间的曲线图。
图2是浸入80℃水中的固化样品的样品长度的百分比变化对时间的曲线图。
图3是亚苯基醚低聚物与环氧树脂的反应(比较例17)、环氧树脂与酸酐硬化剂的反应(比较例18)以及亚苯基醚低聚物与酸酐硬化剂的反应(实施例9)的反应程度对时间的曲线图。
图4是在不存在溶剂的条件下亚苯基醚低聚物与酸酐硬化剂反应的反应程度对时间的曲线图。
图5是用于铝导体复合材料核增强电缆的复合材料核(1)的示意性横截面图;玻璃纤维(2)和碳纤维(3)散布在固化的环氧材料(4)中。
图6是用于铝导体复合材料核增强电缆的复合材料核(1)的示意性横截面图;核包含处于固化的环氧材料(4)中的碳纤维(3)的中心区域和处于固化的环氧材料(4)中的玻璃纤维(2)的外周区域。
具体实施方式
本发明人已经确定,通过其中在加入环氧树脂之前使亚苯基醚低聚物与酸酐硬化剂预反应的方法而制备的固化的环氧材料表现出增加的耐热性。相对于缺乏亚苯基醚低聚物的相应环氧材料,通过本方法制备的固化的环氧材料还表现出增加的延展性。
一个实施方式是一种形成固化的环氧材料的方法,该方法包含:使亚苯基醚低聚物与酸酐硬化剂反应以形成第一产物;将环氧树脂加入到第一产物以形成第二产物;以及将第二产物固化以形成固化的环氧材料。
亚苯基醚低聚物可以具有0.02至0.25分升/克、特别是0.03至0.2分升/克、更特别是0.05至0.15分升/克的特性粘度。特性粘度可以通过乌伯洛德粘度计(乌式粘度计)在25℃在氯仿中确定。
亚苯基醚低聚物包括包含具有下式的重复结构单元的那些:
其中每次出现的Z1独立地为卤素、未取代的或取代的C1-C12烃基(条件是该烃基基团不是叔烃基)、C1-C12烃硫基、C1-C12烃氧基或C2-C12卤代烃氧基(其中至少两个碳原子分隔开卤素和氧原子);并且每次出现的Z2独立地为氢、卤素、未取代的或取代的C1-C12烃基(条件是该烃基基团不是叔烃基)、C1-C12烃硫基、C1-C12烃氧基或C2-C12卤代烃氧基(其中至少两个碳原子分隔开卤素和氧原子)。如本文所用的,术语“烃基”,不管是单独使用还是作为另一术语的前缀、后缀或片段,是指仅含有碳和氢的残基。残基可以是脂肪族或芳香族、直链、环状、双环、支化、饱和或不饱和的。其也可以含有脂肪族、芳香族、直链、环状、双环、支链、饱和和不饱和烃部分的组合。然而,当烃基残基被描述为取代的时,其可以任选地含有除了取代基残基的碳和氢成员之外还杂原子。因此,当具体地被描述为取代的时,烃基残基还可以含有一个或多个羰基基团、氨基基团、羟基基团等,或者它可以在烃基残基的骨架中含有杂原子。例如,Z1可以是通过末端3,5-二甲基-1,4-苯基与氧化聚合催化剂的二正丁胺组分反应形成的二正丁氨基甲基。
在一些实施方式中,亚苯基醚低聚物具有平均1.5-3个羟基基团/分子,特别是1.5至2.5个羟基基团/分子。这种亚苯基醚低聚物可通过一元酚诸如(2,6-二甲基苯酚或2,3,6-三甲基苯酚)与二元酚(诸如2,2-双(3,5-二甲基-4-羟苯基)丙烷)的共聚来制备。
酸酐硬化剂典型地具有98至400克/摩尔,特别是98至200克/摩尔的分子量,并且具有1至2个酸酐基团/分子的平均酸酐官能度。在一些实施方式中,酸酐硬化剂是单酸酐(即每分子具有一个酸酐基团)。
具体的酸酐硬化剂包括马来酸酐、琥珀酸酐、十二碳烯基琥珀酸酐、环己烷-1,2-二羧酸酐、顺-4-环己烯-1,2-二羧酸酐、4-甲基-4-环己烯-1,2-二羧酸酐、邻苯二甲酸酐、六氢化邻苯二甲酸酐、四氢邻苯二甲酸酐、甲基四氢邻苯二甲酸酐、偏苯三酸酐、二苯甲酮四羧酸二酐、乙二醇双(偏苯三酸酐)、甘油三(偏苯三酸酐)、5-降冰片烯-2,3-二羧酸酐、甲基-5-降冰片烯-2,3-二羧酸酐及它们的组合。
以使得亚苯基醚低聚物上的羟基基团与酸酐硬化剂上的酸酐基团的初始比率为0.03:1至0.27:1,特别是0.04:1至0.26:1的量使亚苯基醚低聚物与酸酐硬化剂典型地反应。
亚苯基醚低聚物与酸酐硬化剂的反应可以在不存在溶剂或存在溶剂的条件下进行。无论是否使用溶剂,反应温度可以是例如50至160℃。在此范围内,反应温度可以是60至120℃,特别是70至90℃。反应时间取决于反应温度,并且可以是例如10分钟至10小时。
当使用溶剂时,其作用是促进亚苯基醚低聚物、酸酐硬化剂和环氧树脂的溶解,促进亚苯基醚低聚物与酸酐硬化剂在溶剂的常压沸点下的反应,并且在组合物固化之前能容易并完全地从组合物中除去。在一些实施方式中,溶剂的常压沸点为50至160℃,特别是60至120℃,更特别地为70-90℃。在一些实施方式中,溶剂选自由C3-C8酮、C6-C8醚、C3-C6 N,N-二烷基酰胺、C6-C10芳香族烃、C1-C3氯代烃、C3-C6烷基烷酸酯、C2-C6烷基氰化物、C2-C4二烷基亚砜以及它们的组合组成的组。在一些实施方式中,溶剂选自由丙酮、甲基乙基酮、甲基异丁基酮、乙酸乙酯、乙酸异丙酯、乙酸丁酯、二噁烷、四氢呋喃、甲苯、苯甲醚以及它们的组合组成的组。
当将溶剂用于亚苯基醚低聚物与酸酐硬化剂的反应时,在将环氧树脂组合物固化之前应该除去溶剂。可以从第一产物(包含亚苯基醚低聚物和酸酐硬化剂的反应产物)、第二产物(包含环氧树脂和反应产物)或两者除去溶剂。
亚苯基醚低聚物与酸酐硬化剂的反应优选进行到使到亚苯基醚低聚物上的至少75摩尔%的酚羟基基团已与酸酐硬化剂反应的程度。在此范围内,优选85摩尔%,特别是95摩尔%的酚羟基基团已经反应。例如,可以通过质子核磁共振光谱法(1H NMR)来确定亚苯基醚低聚物上的酚羟基基团与酸酐硬化剂的反应程度。
另一实施方式是一种亚苯基醚低聚物与单酸酐反应的产物,其中亚苯基醚低聚物具有平均1.5至3羟基基团/分子,特别是1.5至2.5个羟基基团/分子,其中亚苯基醚低聚物和单酸酐以有效提供0.04:1至0.26:1羟基基团与酸酐基团的初始摩尔比的量进行反应,并且其中在产物中,亚苯基醚低聚物上至少75摩尔%,特别是至少85摩尔%,更特别是至少95摩尔%的羟基基团已经与单酸酐反应。
除了使亚苯基醚低聚物与酸酐硬化剂反应以形成第一产物的步骤,方法还包括将环氧树脂加入到第一产物以形成第二产物。在一些实施方式中,环氧树脂的平均环氧官能度为每分子1.5至10个环氧基团,并且环氧当量重量为90至500克/当量。在每分子1.5至10个环氧基团的范围内,平均环氧官能度可以是2至8个环氧基团/分子,特别是3至6个环氧基团/分子。在90至500克/当量的范围内,环氧当量重量可为100至400克/当量,具体为150至300克/当量。
在一些实施方式中,环氧树脂选自N-缩水甘油邻苯二甲酰亚胺、N-缩水甘油四氢邻苯二甲酰亚胺、苯基缩水甘油醚、对丁基苯基缩水甘油醚、苯乙烯氧化物、新己烯氧化物(neohexene oxide)、乙二醇二缩水甘油醚、聚乙二醇二缩水甘油醚、丙二醇二缩水甘油醚、聚丙二醇二缩水甘油醚、四亚甲基二醇二缩水甘油醚、聚四亚甲基二醇二缩水甘油醚、己二酸二缩水甘油酯、癸二酸二缩水甘油酯、邻苯二甲酸二缩水甘油酯、双酚A二缩水甘油醚、双酚F二缩水甘油醚、双酚S二缩水甘油醚、间苯二酚二缩水甘油醚、四缩水甘油基二氨基二苯基甲烷、前述化合物的低聚物、苯酚-甲醛酚醛清漆的缩水甘油醚、甲酚-甲醛酚醛清漆的缩水甘油醚、叔丁基苯酚-甲醛酚醛清漆的缩水甘油醚、仲丁基苯酚-甲醛酚醛清漆的缩水甘油醚、叔辛基苯酚-甲醛酚醛清漆的缩水甘油醚、枯基苯酚-甲醛酚醛清漆的缩水甘油醚、癸基苯酚-甲醛酚醛清漆的缩水甘油醚、溴苯酚-甲醛酚醛清漆的缩水甘油醚、氯苯酚-甲醛酚醛清漆的缩水甘油醚、苯酚-双(羟甲基)苯酚醛清漆的缩水甘油醚、苯酚-双(羟甲基联苯)酚醛清漆的缩水甘油醚、苯酚-羟基苯甲醛酚醛清漆的缩水甘油醚、苯酚-二环戊二烯酚醛清漆的缩水甘油醚、萘酚-甲醛酚醛清漆的缩水甘油醚、萘酚-双(羟甲基)苯酚醛清漆的缩水甘油醚、萘酚-双(羟甲基联苯)酚醛清漆的缩水甘油醚、萘酚-羟基苯甲醛酚醛清漆的缩水甘油醚、萘酚-二环戊二烯酚醛清漆的缩水甘油醚、对氨基苯酚的三缩水甘油醚、甲酚-甲醛酚醛清漆的缩水甘油醚、BPA酚醛清漆环氧树脂(双酚A酚醛清漆环氧树脂)、1,4-丁二醇的二缩水甘油醚、环氧化大豆油、环氧化蓖麻油、新戊二醇的二缩水甘油醚、2-乙基己基缩水甘油醚、丁基缩水甘油醚、苯基缩水甘油醚、叔丁基缩水甘油醚、邻甲苯基缩水甘油醚、壬基苯酚缩水甘油醚、环己烷二甲醇二缩水甘油醚、三羟甲基乙烷三缩水甘油醚、三羟甲基丙烷三缩水甘油醚、间二甲苯二胺的四缩水甘油醚、四苯酚乙烷的四缩水甘油醚、二环戊二烯二氧化物、3,4-环氧环己基甲基-3,4-环氧环己基羧酸酯、二羟基萘的二缩水甘油醚(d-羟基萘的二缩水甘油醚,diglycidyl ether of d-hydroxy naphthalene)以及它们的组合。
向第一产物加入环氧树脂是在足够高的温度下进行的,以促进混合并且温度不会太高到促进组分的化学反应。在一些实施方式中,向第一产物中加入环氧树脂是在60至120℃的温度下进行的,特别是70至100℃,更特别是70至90℃。该步骤可以在存在或不存在溶剂的情况下进行。
将环氧树脂加入到第一产物中的产物被称为第二产物。在一些实施方式中,第二产物是均匀的。在一些实施方式中,亚苯基醚低聚物上至少75摩尔%的酚羟基基团已与酸酐硬化剂反应。在此限度内,与酸酐硬化剂反应的酚羟基基团的摩尔百分比可以是至少85摩尔%,特别是至少95摩尔%。
在一些实施方式中,亚苯基醚低聚物的用量为5至40重量份,酸酐硬化剂的用量为20至40重量份,环氧树脂的用量为35至65重量份,全部基于亚苯基醚低聚物、酸酐硬化剂和环氧树脂总计100重量份。在5至40重量份的范围内,亚苯基醚低聚物的量可以是10至35重量份,特别是10至30重量份。在20至40重量份的范围内,酸酐硬化剂的量可以为25至35重量份。在35至65重量份的范围内,环氧树脂的量可以为40至60重量份。
如上,在一些实施方式中,亚苯基醚低聚物上的羟基基团与酸酐硬化剂上的酸酐基团的摩尔比是0.03:1至0.27:1,特别是0.04:1至0.26:1。在一些实施方式中,亚苯基醚低聚物上的羟基基团与环氧树脂上的环氧基的摩尔比为0.03:1至0.14:1,特别是0.04:1至0.12:1。在一些实施方式中,酸酐硬化剂上的酸酐基团与环氧树脂上的环氧基团的摩尔比为0.3:1至0.8:1,特别是0.4:1至0.75:1。
该方法还包括固化第二产物以形成固化的环氧材料。如下面的工作实施例所示,固化通常在一系列升高的温度下进行。在一些实施方式中,在170至240℃的最高温度下进行固化可固化组合物,特别是190至230℃,更特别是200至230℃。
固化可以任选地在固化促进剂存在下进行。当存在时,固化促进剂可以在亚苯基醚低聚物与酸酐硬化剂反应之前或期间加入,或者在向第一产物中加入环氧树脂之前、期间或之后添加。合适的固化促进剂的实例包括异佛尔酮二胺、三亚乙基四胺、二亚乙基三胺、氨基乙基哌嗪、1,2-和1,3-二氨基丙烷、2,2-二甲基丙二胺、1,4-二氨基丁烷、1,6-二氨基己烷、1,7-二氨基庚烷、1,8-二氨基辛烷、1,9-二氨基任烷、1,12-二氨基十二烷、4-氮杂七亚甲基二胺、N,N’-双(3-氨丙基)丁烷-1,4-二胺、环己烷二胺、二氰二胺、二酰胺二苯甲烷、二酰胺二苯基磺酸(胺加合物)、4,4’-亚甲基二苯胺、二乙基甲苯二胺、间-亚苯基二胺、三聚氰胺甲醛、四亚乙基五胺、3-二乙基氨丙基胺、3,3’-亚氨基二丙胺、2,4-双(对氨基苄基)苯胺、四亚乙基五胺、3-二乙基氨丙基胺、2,2,4-和2,4,4-三甲基六亚甲基二胺、1,2-和1,3-二氨基环己烷、1,4-二氨基-3,6-二乙基环己烷、1,2-二氨基-4-乙基环己烷、1,4-二氨基-3,6-二乙基环己烷、1-环己基-3,4-二氨基环己烷、4,4’-二氨基二环己基甲烷、4,4’-二氨基二环己基丙烷、2,2-双(4-氨基环己基)丙烷、3,3’-二甲基-4,4’-二氨基二环己基甲烷、3-氨基-1-环己烷氨基丙烷、1,3-和1,4-双(氨基甲基)环己烷、间二甲苯二胺和对二甲苯二胺、二乙基甲苯二胺、三乙胺、三丁胺、二甲基苯胺、二乙基苯胺、α-甲基苄基二甲胺、N,N-二甲氨基乙醇、N,N-二甲氨基甲酚、三(N,N-二甲氨基甲基)苯酚、2-甲基咪唑、2-乙基咪唑、2-月桂基咪唑、2-十七烷基咪唑、2-苯基咪唑、4-甲基咪唑、4-乙基咪唑、4-月桂基咪唑、4-十七烷基咪唑、2-苯基-4-甲基咪唑、2-苯基-4-羟甲基咪唑、2-乙基-4-甲基咪唑、2-乙基-4-羟甲基咪唑、1-氰乙基-4-甲基咪唑、2-苯基-4,5-二羟甲基咪唑及它们的组合。当存在时,每100重量份环氧树脂,固化促进剂的用量可以为0.02至2重量份,特别是0.04至0.4重量份。
除了亚苯基醚低聚物、酸酐硬化剂和环氧树脂之外,用于形成固化的环氧材料的组分可以包括填料、增强剂、添加剂或其组合。
合适的填料和增强剂可以是纳米颗粒的形式,即,如使用光散射方法所确定的中值粒度(D50)小于100纳米的颗粒。有用的填料或增强剂包括例如硅酸盐和硅石粉末,诸如硅酸铝(莫来石)、合成硅酸钙、硅酸锆、熔融石英、结晶二氧化硅、石墨和天然硅砂;硼粉末诸如氮化硼粉末和硼硅酸盐粉末;氧化物,诸如TiO2、氧化铝和氧化镁;硫酸钙(作为其无水物、二水合物或三水合物);碳酸钙如白垩、石灰石、大理石和合成的沉淀碳酸钙;滑石,包括纤维状、模块式、针状和层状滑石;硅灰石;表面处理硅灰石;玻璃球,诸如空心和实心玻璃球、硅酸盐球、空心微珠和硅铝酸盐球(armosphere);高岭土,包括硬质高岭土、软质高岭土、煅烧高岭土、和包含本领域已知的各种涂层以促进与聚合物基体树脂相容性的高岭土;单晶纤维或“晶须”,诸如碳化硅、氧化铝、碳化硼、铁、镍和铜晶须;纤维(包括连续和切碎的纤维),诸如碳纤维(包括碳纳米纤维)、玻璃纤维(诸如E、A、C、ECR、R、S、D和NE玻璃纤维)、玄武岩纤维、陶瓷纤维、芳香族聚酰胺纤维(包括聚(对苯二甲酰对苯二胺)纤维)、硼纤维、液晶纤维和聚乙烯纤维;硫化物,诸如硫化钼和硫化锌;钡化合物,诸如钛酸钡、钡铁氧体、硫酸钡和重晶石;金属和金属氧化物,诸如颗粒状和纤维状铝、青铜、锌、铜和镍;片状填料如玻璃薄片、片状碳化硅、二硼化铝、铝薄片和钢片;无机纤维填料,例如短无机纤维,诸如衍生自包含硅酸铝、氧化铝、氧化镁和硫酸钙半水合物中的至少一种的共混物的那些;天然填料和增强材料,诸如粉碎木材得到的木粉,纤维产品诸如纤维素、棉花、剑麻、黄麻、淀粉、软木粉、木质素、花生壳、玉米和稻谷壳;有机填料,诸如聚四氟乙烯;由能够形成纤维的有机聚合物形成的增强有机纤维填料,诸如聚(醚酮)、聚酰亚胺、聚苯并恶唑、聚(苯硫醚)、聚酯、聚乙烯、芳香族聚酰胺、芳香族聚酰亚胺、聚醚酰亚胺、聚四氟乙烯、丙烯酸树脂和聚(乙烯醇);以及其它填料和增强剂,诸如云母、粘土、长石、烟尘、铝硅酸镁盐、石英、石英岩、珍珠岩、风化硅石、硅藻土和炭黑;以及前述填料和增强剂的组合。当存在时,基于固化的环氧材料的总重量,填料和增强剂的通常以5至90重量%的量存在。在此范围内,填料和增强剂的含量可以是10至80重量%,特别是20至80重量%,更特别是40至80重量%,甚至更特别是50至80重量%。
合适的添加剂包括着色剂(包括染料和颜料)、抗氧化剂、热稳定剂、光稳定剂、增塑剂、润滑剂、流动改性剂、防滴剂、阻燃剂、抗静电剂、流动促进剂、加工助剂、基底粘合剂、脱模剂、增韧剂、低轮廓添加剂、应力消除添加剂及它们的组合。当存在时,基于固化的环氧材料的总重量,添加剂通常以0.5至10重量%,特别是1至5重量%的量使用。
本方法的一个重要优点是,其生产的固化的环氧材料的具有高于未使亚苯基醚低聚物与酸酐硬化剂预反应而生产的相应材料的耐热性。例如,改善的耐热性可以表现为增加的玻璃化转变温度。因此,在一些实施方式中,固化的环氧材料表现出通过差示扫描量热法测量的150至250℃,特别是170至230℃,更特别是180至225℃的玻璃化转变温度。固化的环氧材料还表现出良好的延展性,这是包含亚苯基醚低聚物的环氧组合物的特征,并且如下面在工作实施例中所示,其相对独立于其制备方法。良好的延展性可以表现为,根据ASTMD 4812-11在23℃下测量的在23℃下的80至200焦耳/米,特别是100至200焦耳/米的无缺口悬臂梁冲击强度。总之,与含有亚苯基醚低聚物并通过其它方法制备的固化环氧树脂组合物相比,通过本发明方法制备的固化环氧树脂组合物表现出改进的耐热性和相当的冲击强度。并且与缺乏亚苯基醚低聚物的固化环氧组合物相比,通过本发明方法制备的固化环氧组合物表现出相当的耐热性和改善的冲击强度。
在该方法的一个非常具体的实施方式中,亚苯基醚低聚物与酸酐硬化剂的反应在60至120℃的温度下进行;亚苯基醚低聚物具有在25℃在氯仿中测量的0.03至0.2分升/克的特性粘度为,以及平均1.5至2.5羟基基团/分子;酸酐硬化剂包含具有98至200克/摩尔的分子量的单酸酐;所述亚苯基醚低聚物与酸酐硬化剂的反应在溶剂存在下进行,并且该方法还包括从第一产物、第二产物或两者中去除溶剂;以5至40重量份的量使用亚苯基醚低聚物,以20至40重量份的量使用酸酐硬化剂,并且以35至65重量份的量使用环氧树脂,全部基于亚苯基醚低聚物、酸酐硬化剂和环氧树脂的总计100重量份;使第二产物固化在180至250℃的最高温度下进行;并且固化的环氧材料表现出通过差示扫描量热法测量的150至250℃的玻璃化转变温度,在23℃下根据ASTM D 4812-11测量的在23℃下的80至200焦耳/米,特别是100至200焦耳/米的无缺口悬臂梁冲击强度。
另一实施方式是通过任何上述变型中的方法形成的固化的环氧材料,其表现出用过差示扫描量热法测得的150至250℃的玻璃化转变温度,以及在23℃下根据ASTM D 481211测量的在23℃下的80至200焦耳/米,特别是100至200焦耳/米的无缺口悬臂梁冲击强度。
另一实施方式是一种用于铝导体复合材料核增强电缆的复合材料核,该复合材料核包含:选自由碳纤维(包括碳纳米纤维)、玄武岩纤维、玻璃纤维、陶瓷纤维、芳香族聚酰胺纤维(包括聚(对苯二甲酰对苯二胺)纤维)、硼纤维、液晶纤维和聚乙烯纤维(包括高性能聚乙烯纤维)组成的组的两种以上类型的纵向取向且基本上连续的增强纤维;和围绕增强纤维的固化的环氧材料,其中固化的环氧材料是包含亚苯基醚低聚物、环氧树脂和固化促进剂的反应组分的产物;其中所述复合材料核具有至少50体积%的纤维。复合材料核的一个优点是耐高温。例如,在一些实施方式中,复合材料核具有90至230℃的可操作范围。
在一些实施方式中,两种以上类型纵向取向且基本上连续的增强纤维选自由碳纤维、玻璃纤维和陶瓷纤维组成的组。
铝导体复合材料核增强电缆通常是已知的。参见例如D.M.Wilson等的美国专利申请公布No.US 2013/0167502 A1和C.Hiel等的美国专利申请公布No.US 2010/0163275 A1。本发明的复合材料与现有技术复合材料核的不同之处至少在于其并入有亚苯基醚低聚物。
固化的环氧材料是包含亚苯基醚低聚物、环氧树脂和固化促进剂的反应组分的产物。前文描述了用于环氧树脂的固化促进剂。
在一些实施方式中,固化促进剂包含酸酐硬化剂,并且使亚苯基醚低聚物、环氧树脂和固化促进剂反应包括使亚苯基醚低聚物与酸酐硬化剂反应以形成第一产物;向第一产物中加入环氧树脂和纤维以形成第二产物;和使第二产物固化以形成围绕纤维的固化的环氧材料。
在其它实施方式中,亚苯基醚低聚物与环氧树脂反应,并且使得到的产物与固化促进剂反应。在又一些实施方式中,使亚苯基醚低聚物、环氧树脂和固化促进剂同时反应。
在任意这些实施方式中,可使用拉挤成型工艺将纤维掺入未固化的环氧材料中,并固化纤维周围的环氧材料。
以上在形成固化的环氧材料的方法的上下文中描述的所有变化也适用于复合材料核。
复合材料核具有至少50体积%的纤维。在这一限制下,纤维体积百分数可以为50至90,特别是50至80,更特别是60至80。
图5为用于铝导体复合材料核增强电缆的复合材料核(1)的示意性横截面图;玻璃纤维(2)和碳纤维(3)散布在固化的环氧材料(4)中。
图6为用于铝导体复合材料核增强电缆的复合材料核(1)的示意性横截面图;核包含处于固化的环氧材料(4)中的碳纤维(3)中心区域以及处于固化的环氧材料(4)中的玻璃纤维(2)外周区域。
本发明包括至少下列实施方式。
实施方式1:一种形成固化的环氧材料的方法,该方法包含:使亚苯基醚低聚物与酸酐硬化剂反应以形成第一产物;将环氧树脂加入到第一产物以形成第二产物;以及将第二产物固化以形成固化的环氧材料。
实施方式2:实施方式1的方法,其中所述亚苯基醚低聚物与酸酐硬化剂的反应在50至160℃的温度下进行。
实施方式3:实施方式2的方法,其中所述亚苯基醚低聚物与酸酐硬化剂的反应在选自由C3-C8酮、C6-C8醚、C3-C6 N,N-二烷基酰胺、C6-C10芳香族烃、C1-C3氯代烃、C3-C6烷基烷酸酯、C2-C6烷基氰化物、C2-C4二烷基亚砜及它们的组合组成的组中的溶剂的存在下进行。
实施方式4:实施方式1-3中任一项的方法,其中第一产物是均相溶液,其中亚苯基醚低聚物上的至少75摩尔%的酚羟基基团已与酸酐硬化剂反应。
实施方式5:实施方式1-4中任一项的方法,其中所述将环氧树脂加入到第一产物在60至120℃的温度下进行。
实施方式6:实施方式1-5中任一项的方法,其中第二产物是均相溶剂,其中亚苯基醚低聚物上的至少75摩尔%的酚羟基基团已与酸酐硬化剂反应。
实施方式7:实施方式1-6中任一项的方法,其中所述将第二产物固化在170至220℃的最高温度下进行。
实施方式8:实施方式1-7中任一项的方法,其中以5至40重量份的量使用亚苯基醚低聚物,以20至40重量份的量使用酸酐硬化剂,并且以35至65重量份的量使用环氧树脂,全部基于100重量份的亚苯基醚低聚物、酸酐硬化剂和环氧树脂的总量。
实施方式9:实施方式1-8中任一项的方法,其中亚苯基醚低聚物具有在25℃在氯仿中测量的0.03至0.2分升/克的特性粘度。
实施方式10:实施方式1-9中任一项的方法,其中亚苯基醚低聚物具有平均1.5至3个羟基基团/分子。
实施方式11:实施方式1-10中任一项的方法,其中酸酐硬化剂包含具有98至400克/摩尔的分子量的单酸酐。
实施方式12:实施方式1-11中任一项的方法,其中酸酐硬化剂选自由马来酸酐、琥珀酸酐、十二碳烯基琥珀酸酐、环己烷-1,2-二羧酸酐、顺-4-环己烯-1,2-二羧酸酐、4-甲基-4-环己烯-1,2-二羧酸酐、邻苯二甲酸酐、六氢化邻苯二甲酸酐、四氢邻苯二甲酸酐、甲基四氢邻苯二甲酸酐、偏苯三酸酐、二苯甲酮四羧酸二酐、乙二醇双(偏苯三酸酐)、甘油三(偏苯三酸酐)、5-降冰片烯-2,3-二羧酸酐、甲基-5-降冰片烯-2,3-二羧酸酐及它们的组合组成的组。
实施方式13:实施方式1-12中任一项的方法,其中环氧树脂具有1.5至10个环氧基团/分子的平均环氧官能度,以及90至500克/当量的环氧当量重量。
实施方式14:实施方式1-13中任一项的方法,其中环氧树脂选自由N-缩水甘油邻苯二甲酰亚胺、N-缩水甘油四氢邻苯二甲酰亚胺、苯基缩水甘油醚、对丁基苯基缩水甘油醚、苯乙烯氧化物、新己烯氧化物、乙二醇二缩水甘油醚、聚乙二醇二缩水甘油醚、丙二醇二缩水甘油醚、聚丙二醇二缩水甘油醚、四亚甲基二醇二缩水甘油醚、聚四亚甲基二醇二缩水甘油醚、己二酸二缩水甘油酯、癸二酸二缩水甘油酯、邻苯二甲酸二缩水甘油酯、双酚A二缩水甘油醚、双酚F二缩水甘油醚、双酚S二缩水甘油醚、间苯二酚二缩水甘油醚、四缩水甘油基二氨基二苯基甲烷、前述化合物的低聚物、苯酚-甲醛酚醛清漆的缩水甘油醚、甲酚-甲醛酚醛清漆的缩水甘油醚、叔丁基苯酚-甲醛酚醛清漆的缩水甘油醚、仲丁基苯酚-甲醛酚醛清漆的缩水甘油醚、叔辛基苯酚-甲醛酚醛清漆的缩水甘油醚、枯基苯酚-甲醛酚醛清漆的缩水甘油醚、癸基苯酚-甲醛酚醛清漆的缩水甘油醚、溴苯酚-甲醛酚醛清漆的缩水甘油醚、氯苯酚-甲醛酚醛清漆的缩水甘油醚、苯酚-双(羟甲基)苯酚醛清漆的缩水甘油醚、苯酚-双(羟甲基联苯)酚醛清漆的缩水甘油醚、苯酚-羟基苯甲醛酚醛清漆的缩水甘油醚、苯酚-二环戊二烯酚醛清漆的缩水甘油醚、萘酚-甲醛酚醛清漆的缩水甘油醚、萘酚-双(羟甲基)苯酚醛清漆的缩水甘油醚、萘酚-双(羟甲基联苯)酚醛清漆的缩水甘油醚、萘酚-羟基苯甲醛酚醛清漆的缩水甘油醚、萘酚-二环戊二烯酚醛清漆的缩水甘油醚、对氨基苯酚的三缩水甘油醚、甲酚-甲醛酚醛清漆的缩水甘油醚、BPA酚醛清漆环氧树脂、1,4-丁二醇的二缩水甘油醚、环氧化大豆油、环氧化蓖麻油、新戊二醇的二缩水甘油醚、2-乙基己基缩水甘油醚、丁基缩水甘油醚、苯基缩水甘油醚、叔丁基缩水甘油醚、邻甲苯基缩水甘油醚、壬基苯酚缩水甘油醚、环己烷二甲醇二缩水甘油醚、三羟甲基乙烷三缩水甘油醚、三羟甲基丙烷三缩水甘油醚、间二甲苯二胺的四缩水甘油醚、四苯酚乙烷的四缩水甘油醚、二环戊二烯二氧化物、3,4-环氧环己基甲基-3,4-环氧环己基羧酸酯、二羟基萘的二缩水甘油醚以及它们的组合组成的组。
实施方式15:实施方式1-14中任一项的方法,其中固化的环氧材料显示出通过差示扫描量热法测量的150至250℃的玻璃化转变温度,以及在23℃下根据ASTM D 4812-11确定的在23℃下的80至200焦耳/米,特别是100至200焦耳/米的无缺口悬臂梁冲击强度。
实施方式16:实施方式1的方法,其中所述亚苯基醚低聚物与酸酐硬化剂的反应在60至120℃的温度下进行;其中亚苯基醚低聚物具有在25℃在氯仿中测量的0.03至0.2分升/克的特性粘度,以及平均1.5至2.5个羟基基团/分子;其中酸酐硬化剂包含具有98至200克/摩尔的分子量的单酸酐;其中所述亚苯基醚低聚物与酸酐硬化剂的反应在溶剂存在下进行;并且其中方法进一步包含从第一产物、第二产物或两者中去除溶剂;其中以5至40重量份的量使用亚苯基醚低聚物,以20至40重量份的量使用酸酐硬化剂并且以35至65重量份的量使用环氧树脂,全部基于100重量份的亚苯基醚低聚物、酸酐硬化剂和环氧树脂的总量;其中所述将第二产物固化在180至250℃的最高温度下进行;并且其中固化的环氧材料表现出通过差示扫描量热法测得的150至250℃的玻璃化转变温为,以及在23℃下根据ASTMD 4812-11测量的在23℃下的80至200焦耳/米,特别为100至200焦耳/米的无缺口悬臂梁冲击强度。
实施方式17:一种通过实施方式1-16中任一项的方法形成的固化的环氧材料,其表现出通过差示扫描量热法测量的150至250℃的玻璃化转变温度,以及在23℃下根据ASTMD 4812-11确定的在23℃下的80至200焦耳/米,特别是100至200焦耳/米的无缺口悬臂梁冲击强度。
实施方式18:一种亚苯基醚低聚物与单酸酐反应的产物,其中亚苯基醚低聚物具有平均1.5至3个羟基基团/分子,其中亚苯基醚低聚物与单酸酐以有效于提供0.04:1至0.26:1的羟基基团与酸酐基团的初始摩尔比的量进行反应,并且其中在产物中,亚苯基醚低聚物上的至少75摩尔%的羟基基团已与单酸酐反应。
实施方式19:一种用于铝导体复合材料核增强电缆的复合材料核,复合材料核包含:选自由碳纤维、玄武岩纤维、玻璃纤维、陶瓷纤维、芳香族聚酰胺纤维、硼纤维、液晶纤维和聚乙烯纤维组成的组中选择的两种以上类型的纵向取向且基本上连续的增强纤维;和围绕增强纤维的固化的环氧材料,其中固化的环氧材料是包含亚苯基醚低聚物、环氧树脂和固化促进剂的反应组分的产物;其中复合材料核具有至少50体积%的纤维。
实施方式20:实施方式19的复合材料核,其中固化促进剂包含酸酐硬化剂,并且其中使亚苯基醚低聚物、环氧树脂和固化促进剂反应包括使亚苯基醚低聚物与酸酐硬化剂反应以形成第一产物;向第一产物加入环氧树脂和纤维以形成第二产物;和使第二产物固化以形成围绕纤维的固化的环氧材料;或其中使亚苯基醚低聚物、环氧树脂和固化促进剂反应包含使亚苯基醚低聚物与环氧树脂反应以形成第一产物;向第一产物加入固化促进剂和纤维以形成第二产物;和使第二产物固化以形成围绕纤维的固化的环氧材料。
本文公开的所有范围都包括端点,并且端点可以相互独立地组合。本文公开的每个范围构成了所公开范围内的任何点或子范围的公开。
通过以下非限制性实施例进一步说明本发明。
实施例1-3、比较例1-6
表1中描述了实施例中使用的组分。
表1
如表2中总结的配方,其中组分量以每100重量份树脂的重量份数表示,其中“树脂”定义为环氧树脂(TGDDM)、酸酐硬化剂(Me-NADIC)和亚苯基醚低聚物(PPE-2OH 0.09)的总和。
表2
PPE-2OH 0.09 | TGDDM | Me-NADIC | 1-MI | |
比较例1 | 10.12 | 55.64 | 34.25 | 0.13 |
比较例2 | 20.02 | 50.05 | 29.93 | 0.13 |
比较例3 | 29.73 | 44.60 | 25.67 | 0.13 |
比较例4 | 10.12 | 55.64 | 34.25 | 0.13 |
比较例5 | 20.02 | 50.05 | 29.93 | 0.13 |
比较例6 | 29.73 | 44.60 | 25.67 | 0.13 |
实施例1 | 10.12 | 55.64 | 34.25 | 0.13 |
实施例2 | 20.02 | 50.05 | 29.93 | 0.13 |
实施例3 | 29.73 | 44.60 | 25.67 | 0.13 |
对于比较例1-3,混合所有组分并且将所得混合物固化。在80℃将TGDDM、PPE-2OH0.09、Me-NADIC和1-MI溶解于甲基乙基酮(MEK)中。从均相溶液中除去MEK。将树脂转移到预热到100℃的模具中。将填充好的模具放入设定在100℃的烘箱中并且将固化温度如下程序升温至220℃:
·在100℃下60分钟后,将温度升高到120℃;
·在120℃下60分钟后,将温度升高到140℃;
·在140℃下60分钟后,将温度升高到150℃;
·在150℃下60分钟后,将温度升高到160℃;
·在160℃下60分钟后,将温度升高到175℃;
·在175℃下60分钟后,将温度升高到200℃;
·在200℃下60分钟后,将温度升高到220℃;
·将温度在220℃下保持60分钟。
对于比较例4-6,在加入Me-NADIC并且将所得的混合物固化之前,使用TGDDM对PPE-2OH 0.09进行预处理。在80℃将TGDDM、PPE-2OH0.09和1-MI溶解于MEK中。将溶液在80℃下保持60分钟。然后加入Me-NADIC并溶解。从均相溶液中除去MEK。将树脂转移到预热到100℃的模具中。将填充好的模具放入设定在100℃的烘箱中,并且将固化温度如下程序升温至220℃:
·在100℃下60分钟后,将温度升高到120℃;
·在120℃下60分钟后,将温度升高到140℃;
·在140℃下60分钟后,将温度升高到150℃;
·在150℃下60分钟后,将温度升高到160℃;
·在160℃下60分钟后,将温度升高到175℃;
·在175℃下60分钟后,将温度升高到200℃;
·在200℃下60分钟后,将温度升高到220℃;
·将温度在220℃下保持60分钟。
对于实施例1-3,在加入TGDDM并且将所得的混合物固化之前,使用Me-NADIC预处理PPE-2OH。在80℃下将PPE-2OH、Me-NADIC和1-MI溶解于MEK中。将溶液在80℃下保持60分钟。然后加入TGDDM并且溶解。从均相溶液中除去MEK。将树脂转移到预热到100℃的模具中。将填充好的模具放入设定在100℃的烘箱中,并且使固化温度如下程序升温至220℃:
·在100℃下60分钟后,将温度升高到120℃;
·在120℃下60分钟后,将温度升高到140℃;
·在140℃下60分钟后,将温度升高到150℃;
·在150℃下60分钟后,将温度升高到160℃;
·在160℃下60分钟后,将温度升高到175℃;
·在175℃下60分钟后,将温度升高到200℃;
·在200℃下60分钟后,将温度升高到220℃;
·将温度在220℃下保持60分钟。
通过差示扫描量热法(DSC)确定玻璃化转变温度并且汇总于表3中。明显地,与通过包括同时混合所有组分的方法(比较例1-3)或通过包括使亚苯基醚低聚物与环氧树脂预反应的方法(比较例4-6)制得的固化材料相比,通过包括使亚苯基醚低聚物与酸酐预反应的方法(实施例1-3)制得的固化材料具有显著更高的玻璃化转变温度值。
表3
T<sub>g</sub>(℃) | |
比较例1 | 176.4 |
比较例2 | 181.7 |
比较例3 | 195.9 |
比较例4 | 188.2 |
比较例5 | 188.7 |
比较例6 | 199.3 |
实施例1 | 221.3 |
实施例2 | 220.6 |
实施例3 | 220.5 |
比较例7
本实施例示出了没有亚苯基醚低聚物的固化的环氧材料的制备和性能。将TGDDM、Me-NADIC和1-MI混合在一起以形成均相溶液。如表4中总结的配方。将树脂转移到预热到100℃的模具中。将填充好的模具放入设定在100℃的烘箱中,并且如下使固化温度程序升温至220℃:
·在100℃下60分钟后,将温度升高到120℃;
·在120℃下60分钟后,将温度升高到140℃;
·在140℃下60分钟后,将温度升高到150℃;
·在150℃下60分钟后,将温度升高到160℃;
·在160℃下60分钟后,将温度升高到175℃;
·在175℃下60分钟后,将温度升高到200℃;
·在200℃下60分钟后,将温度升高到220℃;
·将温度在220℃下保持60分钟。
表4
PPE-2OH 0.09 | TGDDM | Me-NADIC | 1-MI | |
比较例7 | 0.00 | 61.32 | 38.68 | 0.13 |
表5将含有亚苯基醚低聚物的实施例1、2和3的性质与不含亚苯基醚低聚物的比较例7的性质进行比较。通过DSC确定玻璃化转变温度值,单位为摄氏度。在23℃下根据ASTM D4812-11,使用横截面尺寸为3.2×12.7毫米的测试棒确定无缺口悬臂梁冲击强度值,以焦耳/米为单位表示。根据ASTM D 792-08在23℃下确定密度值,以克/立方厘米为单位表示。在23℃下根据IPC-TM-650-2.5.5.9和1千兆赫下确定介电常数(Dk)和损耗正切(Df)值,无单位。在固化的铸件上确定收缩值,以百分数为单位表示。在将模具和铸件冷却至室温后,在三个位置测量模具的宽度,并且在相同的三个位置测量固化环氧树脂的宽度。确定模具和铸件测量的平均值。由以下等式确定收缩百分比:
收缩百分比=100×[(模具宽度-铸件宽度)/(模具宽度)]
如之前观察的,与在固化之前通过混合所有组分制备的比较例1、2和3的固化材料相比,通过使亚苯基醚低聚物与酸酐硬化剂预反应制备的实施例1、2和3的固化材料表现出大幅提高的Tg值。
相比于未使用亚苯基醚低聚物制备的比较例7的固化材料,实施例1、2和3的固化材料表现出相当的Tg值,但冲击强度值明显较高,且密度、介电常数(Dk)和损耗正切(Df)值较低。事实上,在所研究的范围内,冲击强度增加超过180%。另外,固化过程中收缩率大幅下降。收缩会对复合材料的性能产生负面影响。收缩导致形成残余应力,这会通过界面脱粘和基体微裂纹对机械性能产生不利影响。
表5
低吸湿性在复合材料中很重要。吸收的湿气会对性能产生不利影响。除了增加复合材料的重量之外,吸收的水将起增塑剂的作用并降低性能。此外,吸收的水可以通过差异溶胀导致吸湿应力,降低界面粘附并引起腐蚀。在80℃下将样品进行浸泡于水中,并且测量吸水量及重量和长度随浸泡时间的变化。图1是吸水量与浸泡时间的关系曲线。增加PPE-2OH含量与降低吸水量有关。图2是样品长度与浸泡时间的关系曲线。浸入水中后,增加PPE-2OH含量与增加尺寸稳定性有关。
实施例4-6、比较例8-14
这些实施例进一步说明了使亚苯基醚低聚物与酸酐硬化剂预反应的效果。在这些实验中,环氧树脂为DGEBPA且酸酐硬化剂为NADIC。表6中总结了配方,其中组分量以每100份树脂的重量份数为单位表示,其中“树脂”定义为环氧树脂(DGEBPA)、酸酐硬化剂(NADIC)和亚苯基醚低聚物(PPE-2OH 0.09)的总和。所有实例均配制有约10-12%的过量环氧当量。
表6
PPE-2OH 0.09 | DGEBPA | NADIC | 1-MI | |
比较例8 | 10.14 | 64.23 | 25.63 | 0.16 |
比较例9 | 20.08 | 58.00 | 21.92 | 0.16 |
比较例10 | 30.08 | 51.52 | 18.40 | 0.16 |
比较例11 | 10.40 | 64.92 | 24.68 | 0.16 |
比较例12 | 20.48 | 58.48 | 21.04 | 0.16 |
比较例13 | 30.57 | 51.82 | 17.61 | 0.16 |
比较例14 | 0.00 | 70.43 | 29.57 | 0.16 |
实施例4 | 10.14 | 64.23 | 25.63 | 0.16 |
实施例5 | 20.08 | 58.00 | 21.92 | 0.16 |
实施例6 | 30.08 | 51.52 | 18.40 | 0.16 |
对于比较例8-10,在加入NADIC并且将所得的混合物固化之前,使PPE-2OH 0.09与DGEBPA预反应。在80℃下将PPE-2OH 0.09溶解于甲基乙基酮(MEK)中。然后加入DGEBPA和1-MI。将溶液在80℃下保持搅拌60分钟。然后加入NADIC并溶解。从均相溶液中除去MEK。将树脂转移到预热到100℃的模具中。将填充好的模具置于设定在100℃的烘箱中,并且如下使固化温度程序升温至220℃:
·在100℃下60分钟后,将温度升高到120℃;
·在120℃下60分钟后,将温度升高到140℃;
·在140℃下60分钟后,将温度升高到150℃;
·在150℃下60分钟后,将温度升高到160℃;
·在160℃下60分钟后,将温度升高到175℃;
·在175℃下60分钟后,将温度升高到200℃;
·在200℃下60分钟后,将温度升高到220℃;
·将温度在220℃下保持60分钟。
对于比较例11-13,在加入PPE-2OH 0.09并将所得混合物固化之前,使NADIC与DGEBPA预反应。在80℃下将DGEBPA、NADIC和1-MI溶解于MEK中。该溶液在80℃保持60分钟。然后加入PPE-2OH 0.09并溶解。从均相溶液中除去MEK。将树脂转移到预热到100℃的模具中。将填充好的模具置于设定在100℃的烘箱中,并且如下使固化温度程序升温至220℃:
·在100℃下60分钟后,将温度升高到120℃;
·在120℃下60分钟后,将温度升高到140℃;
·在140℃下60分钟后,将温度升高到150℃;
·在150℃下60分钟后,将温度升高到160℃;
·在160℃下60分钟后,将温度升高到175℃;
·在175℃下60分钟后,将温度升高到200℃;
·在200℃60分钟后,将温度升高到220℃;
·将温度在220℃下保持60分钟。
对于比较例14,将NADIC、DGEBPA和1-MI溶解于MEK中。然后,从均相溶液中除去MEK。将树脂转移到预热到100℃的模具中。将填充好的模具置于设定在100℃的烘箱中并且如下将固化温度程序升温至220℃:
·在100℃下60分钟后,将温度升高到120℃;
·在120℃下60分钟后,将温度升高到140℃;
·在140℃下60分钟后,将温度升高到150℃;
·在150℃下60分钟后,将温度升高到160℃;
·在160℃下60分钟后,将温度升高到175℃;
·在175℃下60分钟后,将温度升高到200℃;
·在200℃下60分钟后,将温度升高到220℃;
·将温度在220℃下保持60分钟。
对于实施例4-6,在加入DGEBPA并将所得混合物固化之前,使PPE-2OH 0.09与NADIC预反应。在80℃下将PPE 2OH 0.09、NADIC和1-MI溶解在MEK中。将溶液在80℃保持60分钟。然后加入DGEBPA并且溶解。从均相溶液中除去MEK。将树脂转移到预热到100℃的模具中。将填充好的模具置于设定在100℃的烘箱中并且如下将固化温度程序升温至220℃:
·在100℃下60分钟后,将温度升高到120℃;
·在120℃下60分钟后,将温度升高到140℃;
·在140℃下60分钟后,将温度升高到150℃;
·在150℃下60分钟后,将温度升高到160℃;
·在160℃下60分钟后,将温度升高到175℃;
·在175℃下60分钟后,将温度升高到200℃;
·在200℃下60分钟后,将温度升高到220℃;
·将温度在220℃下保持60分钟。
表7中总结了由DSC确定的玻璃化转变温度值。明显地,与通过包括同时混合所有组分的方法制备的相应比较例以及通过包括使亚苯基醚低聚物与环氧树脂预反应的方法制备的比较例相比,通过包括使亚苯基醚低聚物与酸酐硬化剂预反应的方法制备的本发明实施例表现出更高的Tg值。对于在约10重量份亚苯基醚低聚物下进行比较,参见比较例8(138.9℃)、比较例11(139.5℃)及实施例4(144.3℃)之间的比较。对于在约20重量份亚苯基醚低聚物下进行比较,参见比较例9(143.6℃)、比较例12(144.2℃)与实施例5(152.8℃)之间的比较。对于在约30重量份亚苯基醚低聚物下进行比较,参见比较例10(151.6℃)、比较例13(150.3℃)与实施例6(165.1℃)之间的比较。
表7
T<sub>g</sub>(℃) | |
比较例8 | 138.9 |
比较例9 | 143.6 |
比较例10 | 151.6 |
比较例11 | 139.5 |
比较例12 | 144.2 |
比较例13 | 150.3 |
比较例14 | 136.3 |
实施例4 | 144.3 |
实施例5 | 152.8 |
实施例6 | 165.1 |
实施例7和8、比较例15和16
这些实施例示出了较高和较低分子量亚苯基醚低聚物的使用。所有的例子均含有约20重量份亚苯基醚低聚物和约10-12%过量的环氧当量。表8中总结了配方,其中各组分的量以每100份树脂的重量份为单位进行表示,其中“树脂”定义为环氧树脂、酸酐硬化剂和亚苯基醚低聚物的总和。
表8
PPE-2OH 0.06 | PPE-2OH 0.12 | DGEBPA | NADIC | 1-MI | |
比较例15 | 20.08 | 0.00 | 58.00 | 21.92 | 0.16 |
比较例16 | 0.00 | 19.91 | 57.49 | 22.61 | 0.16 |
实施例7 | 20.08 | 0.00 | 58.00 | 21.92 | 0.16 |
实施例8 | 0.00 | 19.91 | 57.49 | 22.61 | 0.16 |
对于比较例15和16,在80℃下在MEK中混合PPE-2OH 0.06或PPE-2OH 0.12、DGEBPA、NADIC和1-MI。从均相溶液中除去MEK。将树脂转移到预热到100℃的模具中。将填充好的模具放入设定在100℃的烘箱中并且如下将固化温度程序升温至220℃:
·在100℃下60分钟后,将温度升高到120℃;
·在120℃下60分钟后,将温度升高到140℃;
·在140℃下60分钟后,将温度升高到150℃;
·在150℃下60分钟后,将温度升高到160℃;
·在160℃下60分钟后,将温度升高到175℃;
·在175℃下60分钟后,将温度升高到200℃;
·在200℃下60分钟后,将温度升高到220℃;
·将温度在220℃下保持60分钟。
对于实施例7和8,加入DGEBPA并且将所得的混合物固化之前,使PPE-2OH 0.06或PPE-2OH 0.12与NADIC预反应。在80℃下将PPE-2OH0.06或PPE-2OH 0.12、NADIC和1-MI加入到MEK中。将溶液在80℃保持60分钟。然后加入DGEBPA并且溶液。从均相溶液中除去MEK。将树脂转移到预热到100℃的模具中。将填充好的模具置于设定在100℃的烘箱中并且如下使固化温度程序升温至220℃:
·在100℃下60分钟后,将温度升高到120℃;
·在120℃下60分钟后,将温度升高到140℃;
·在140℃下60分钟后,将温度升高到150℃;
·在150℃下60分钟后,将温度升高到160℃;
·在160℃下60分钟后,将温度升高到175℃;
·在175℃下60分钟后,将温度升高到200℃;
·在200℃下60分钟后,将温度升高到220℃;
·将温度在220℃下保持60分钟。
通过DSC确定的玻璃化转变温度值总结于表9中。明显地,无论亚苯基醚低聚物的特性粘度为0.06分升/克(比较例15为141.4℃,实施例7为151.7℃)或0.12分升/克(比较例16为145.2℃,实施例8为156.8℃)使亚苯基醚低聚物与酸酐硬化剂预反应均产生了显著更高的玻璃化转变温度值。
表9
T<sub>g</sub>(℃) | |
比较例15 | 141.4 |
比较例16 | 145.2 |
实施例7 | 151.7 |
实施例8 | 156.8 |
实施例9和10、比较例17和18
亚苯基醚低聚物的加入增加了环氧固化机理的复杂性。亚苯基醚低聚物上酚端基的反应引入了两个额外的反应途径-通过酚基和环氧基团的反应的醚化以及通过酚和酸酐基团的反应的酯化。通过1H NMR确定这些反应的相对比率。通过一次查看两种组分的相对比率来研究反应。反应物是PPE-2OH、HHPA和DGEBPA。将DMAP用作催化剂。PPE-2OH和HHPA之间的反应使用苯甲醚作为溶剂。表10总结了反应的配方和类型,其中除苯甲醚以外的所有组分的量以每100份树脂的重量份为单位表示,其中“树脂”定义为环氧树脂、酸酐硬化剂和亚苯基醚低聚物的总和。苯甲醚的量以毫升为单位表示。
表10
PPE-2OH 0.09 | DGEBPA | HHPA | 苯甲醚 | DMAP | 反应类型 | |
比较例17 | 20.00 | 80.00 | 0.00 | 0.00 | 0.20 | 醚化 |
比较例18 | 0.00 | 74.10 | 25.90 | 0.00 | 0.19 | 酯化 |
实施例9 | 66.67 | 0.00 | 33.33 | 100.00 | 0.17 | 酯化 |
对于比较例17的亚苯基醚低聚物与环氧树脂的反应,通过在80℃下将亚苯基醚低聚物溶解于环氧树脂中然后加入DMAP来测量反应。
对于比较例18的环氧树脂与酸酐硬化剂的反应,通过混合环氧树脂和酸酐硬化剂、加热到80℃、然后加入DMAP来测量反应。
对于实施例9的亚苯基醚低聚物与酸酐硬化剂的反应,通过在80℃下将亚苯基醚低聚物溶解于苯甲醚中、加入酸酐硬化剂、然后添加DMAP来测量反应。由于亚苯基醚低聚物的浓度高,所以使用溶剂苯甲醚。
对于每个反应,作为时间的函数取出样品并且使用1H NMR进行分析。图4绘出了三个反应的反应程度对时间的曲线。速率数据显示,在该项研究的条件下,每个反应在80℃下都相当快,并且速率没有重大差异。这表明,当将亚苯基醚低聚物、环氧树脂和酸酐硬化剂混合在一起并且固化时,它们几乎随机地并入到热固性基质中。
实施例10示出了在不含溶剂的条件下亚苯基醚低聚物和酸酐硬化剂之间的反应速率。反应的配方和类型见表11。将酸酐硬化剂加热到80℃并且加入亚苯基醚低聚物并溶解。当亚苯基醚低聚物完全溶解时,加入DMAP。随着时间的推移采样并且通过1H NMR进行分析。在图3中相对于时间绘制反应程度的曲线。速率数据显示,在该研究条件下,亚苯基醚低聚物与酸酐快速反应。
表11
PPE-2OH 0.09 | HHPA | DMAP | 反应类型 | |
实施例10 | 20.00 | 80.00 | 0.20 | 醚化 |
。
Claims (18)
1.一种形成固化的环氧材料的方法,所述方法包括:
使亚苯基醚低聚物与酸酐硬化剂反应以形成第一产物,其中所述第一产物是均相溶液,其中所述亚苯基醚低聚物上的至少75摩尔%的酚羟基基团已与所述酸酐硬化剂反应;
将环氧树脂加入到所述第一产物以形成第二产物;以及
将所述第二产物固化以形成固化的环氧材料,
其中以5至40重量份的量使用所述亚苯基醚低聚物,以20至40重量份的量使用所述酸酐硬化剂,并且以35至65重量份的量使用所述环氧树脂,全部基于100重量份的所述亚苯基醚低聚物、所述酸酐硬化剂和所述环氧树脂的总量。
2.根据权利要求1所述的方法,其中在50至160℃的温度下进行所述使亚苯基醚低聚物与酸酐硬化剂反应。
3.根据权利要求2所述的方法,其中在选自由C3-C8酮、C6-C8醚、C3-C6N,N-二烷基酰胺、C6-C10芳香族烃、C1-C3氯代烃、C3-C6烷基烷酸酯、C2-C6烷基氰化物、C2-C4二烷基亚砜和它们的组合组成的组的溶剂存在下进行所述使亚苯基醚低聚物与酸酐硬化剂反应。
4.根据权利要求1至3中任一项所述的方法,其中所述第一产物是均相溶液,其中所述亚苯基醚低聚物上的至少85摩尔%的酚羟基基团已与所述酸酐硬化剂反应。
5.根据权利要求1至3中任一项所述的方法,其中在60至120℃的温度下进行所述将环氧树脂加入到所述第一产物。
6.根据权利要求1至3中任一项所述的方法,其中所述第二产物是均相溶液,其中所述亚苯基醚低聚物上的至少75摩尔%的酚羟基基团已与所述酸酐硬化剂反应。
7.根据权利要求1至3中任一项所述的方法,其中在170至220℃的最大温度下进行所述将所述第二产物固化。
8.根据权利要求1至3中任一项所述的方法,其中所述亚苯基醚低聚物具有在25℃下在氯仿中测量的0.03至0.2分升/克的特性粘度。
9.根据权利要求1至3中任一项所述的方法,其中所述亚苯基醚低聚物具有平均1.5至3个羟基基团/分子。
10.根据权利要求1至3中任一项所述的方法,其中所述酸酐硬化剂包含具有98至400克/摩尔的分子量的单酸酐。
11.根据权利要求1至3中任一项所述的方法,其中所述酸酐硬化剂选自由马来酸酐、琥珀酸酐、十二碳烯基琥珀酸酐、环己烷-1,2-二羧酸酐、顺-4-环己烯-1,2-二羧酸酸酐、4-甲基-4-环己烯-1,2-二羧酸酸酐、邻苯二甲酸酐、六氢邻苯二甲酸酐、四氢邻苯二甲酸酐、甲基四氢邻苯二甲酸酐、偏苯三酸酐、二苯甲酮四羧酸二酐、乙二醇双(偏苯三酸酐)、甘油三(偏苯三酸酐)、5-降冰片烯-2,3-二羧酸酐、甲基-5-降冰片烯-2,3-二羧酸酐及它们的组合组成的组。
12.根据权利要求1至3中任一项所述的方法,其中所述环氧树脂具有1.5至10个环氧基团/分子的平均环氧官能度,以及90至500克/当量的环氧当量重量。
13.根据权利要求1至3中任一项所述的方法,其中所述环氧树脂选自由N-缩水甘油邻苯二甲酰亚胺、N-缩水甘油四氢邻苯二甲酰亚胺、苯基缩水甘油醚、对丁基苯基缩水甘油醚、苯乙烯氧化物、新己烯氧化物、乙二醇二缩水甘油醚、聚乙二醇二缩水甘油醚、丙二醇二缩水甘油醚、聚丙二醇二缩水甘油醚、四亚甲基二醇二缩水甘油醚、聚四亚甲基二醇二缩水甘油醚、己二酸二缩水甘油酯、癸二酸二缩水甘油酯、邻苯二甲酸二缩水甘油酯、双酚A二缩水甘油醚、双酚F二缩水甘油醚、双酚S二缩水甘油醚、间苯二酚二缩水甘油醚、四缩水甘油基二氨基二苯基甲烷、前述化合物的低聚物、苯酚-甲醛酚醛清漆的缩水甘油醚、甲酚-甲醛酚醛清漆的缩水甘油醚、叔丁基苯酚-甲醛酚醛清漆的缩水甘油醚、仲丁基苯酚-甲醛酚醛清漆的缩水甘油醚、叔辛基苯酚-甲醛酚醛清漆的缩水甘油醚、枯基苯酚-甲醛酚醛清漆的缩水甘油醚、癸基苯酚-甲醛酚醛清漆的缩水甘油醚、溴苯酚-甲醛酚醛清漆的缩水甘油醚、氯苯酚-甲醛酚醛清漆的缩水甘油醚、苯酚-双(羟甲基)苯酚醛清漆的缩水甘油醚、苯酚-双(羟甲基联苯)酚醛清漆的缩水甘油醚、苯酚-羟基苯甲醛酚醛清漆的缩水甘油醚、苯酚-二环戊二烯酚醛清漆的缩水甘油醚、萘酚-甲醛酚醛清漆的缩水甘油醚、萘酚-双(羟甲基)苯酚醛清漆的缩水甘油醚、萘酚-双(羟甲基联苯)酚醛清漆的缩水甘油醚、萘酚-羟基苯甲醛酚醛清漆的缩水甘油醚、萘酚-二环戊二烯酚醛清漆的缩水甘油醚、对氨基苯酚的三缩水甘油醚、甲酚-甲醛酚醛清漆的缩水甘油醚、BPA酚醛清漆环氧树脂、1,4-丁二醇的二缩水甘油醚、环氧化大豆油、环氧化蓖麻油、新戊二醇的二缩水甘油醚、2-乙基己基缩水甘油醚、丁基缩水甘油醚、苯基缩水甘油醚、叔丁基缩水甘油醚、邻甲苯基缩水甘油醚、壬基苯酚缩水甘油醚、环己烷二甲醇二缩水甘油醚、三羟甲基乙烷三缩水甘油醚、三羟甲基丙烷三缩水甘油醚、间二甲苯二胺的四缩水甘油醚、四苯酚乙烷的四缩水甘油醚、二环戊二烯二氧化物、3,4-环氧-环己基-甲基-3,4-环氧-环己基羧酸酯、二羟基萘的二缩水甘油醚以及它们的组合组成的组。
14.根据权利要求1至3中任一项所述的方法,其中所述固化的环氧材料表现出
通过差示扫描量热法测量的150至250℃的玻璃化转变温度,和
在23℃下根据ASTM D 4812-11确定的在23℃下的80至200焦耳/米的无缺口悬臂梁冲击强度。
15.根据权利要求1所述的方法,
其中,在60至120℃的温度下进行所述使亚苯基醚低聚物与酸酐硬化剂反应;
其中,所述亚苯基醚低聚物具有在25℃下在氯仿中测量的0.03至0.2分升/克的特性粘度,以及平均1.5至2.5个羟基基团/分子;
其中所述酸酐硬化剂包含具有98至200克/摩尔的分子量的单酸酐;
其中在溶剂存在下进行所述使亚苯基醚低聚物与酸酐硬化剂反应;并且其中所述方法进一步包括从所述第一产物、所述第二产物或两者中除去溶剂;
其中以5至40重量份的量使用所述亚苯基醚低聚物,以20至40重量份的量使用所述酸酐硬化剂,并且以35至65重量份的量使用所述环氧树脂,全部基于100重量份的所述亚苯基醚低聚物、所述酸酐硬化剂和所述环氧树脂的总量;
其中在180至250℃的最大温度下进行所述将所述第二产物固化;并且
其中所述固化的环氧材料表现出通过差示扫描量热法测量的150至250℃的玻璃化转变温度,以及在23℃下根据ASTM D 4812-11确定的在23℃下的80至200焦耳/米的无缺口悬臂梁冲击强度。
16.一种通过权利要求1至15中任一项所述的方法形成的固化的环氧材料,并且所述固化的环氧材料表现出:
通过差示扫描量热法测量的150至250℃的玻璃化转变温度;以及
在23℃下根据ASTM D 4812-11确定的在23℃下的80至200焦耳/米的无缺口悬臂梁冲击强度。
17.一种亚苯基醚低聚物与单酸酐反应的产物,其中所述亚苯基醚低聚物具有平均1.5至3个羟基基团/分子,其中所述亚苯基醚低聚物与所述单酸酐以有效提供0.04:1至0.26:1的羟基基团与酸酐基团的初始摩尔比的量反应,并且其中在所述产物中,所述亚苯基醚低聚物上的至少75摩尔%的羟基基团已与所述单酸酐反应。
18.一种用于铝导体复合材料核增强电缆的复合材料核,所述复合材料核包含:
选自由碳纤维、玄武岩纤维、玻璃纤维、陶瓷纤维、芳香族聚酰胺纤维、硼纤维、液晶纤维和聚乙烯纤维组成的组的两种以上类型的纵向取向且基本上连续的增强纤维;以及
围绕所述增强纤维的固化的环氧材料,其中所述固化的环氧材料是使包含亚苯基醚低聚物、环氧树脂和固化促进剂的组分反应的产物,其中所述固化促进剂包含酸酐硬化剂,并且其中使所述亚苯基醚低聚物、所述环氧树脂和所述固化促进剂反应包括使所述亚苯基醚低聚物与所述酸酐硬化剂反应以形成第一产物,其中所述第一产物是均相溶液,其中所述亚苯基醚低聚物上的至少75摩尔%的酚羟基基团已与所述酸酐硬化剂反应;将所述环氧树脂和所述纤维加入到所述第一产物以形成第二产物;以及将所述第二产物固化以形成围绕所述纤维的固化的环氧材料;
其中所述复合材料核具有至少50体积%的纤维。
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