CN107474481B - 包含基于环氧化合物的聚合物的组合物 - Google Patents
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Abstract
本发明涉及包含以下组分a)、b)和c)的组合物,其制备方法及其用途。为了改进固化的环氧树脂的断裂韧性,提出了包含以下组分a)、b)和c)的组合物:a)‑75至99.5重量%的基于环氧化合物的聚合物,‑0.5至25重量%的至少一种多元醇,和‑任选的添加剂b)‑80至99重量%的固化剂,其适合于使基于环氧化合物的聚合物固化,‑1至20重量%的聚己内酯‑聚硅氧烷‑嵌段共聚物,‑任选的促进剂,和‑任选的添加剂,和c)‑任选的促进剂。
Description
技术领域
本发明涉及包含基于环氧化合物的聚合物的组合物,其制备方法及其用途。
背景技术
基于环氧化合物的聚合物主要是多官能羟基化合物与表氯醇的反应产物。聚合物基质的交联通过加聚经由环氧化物基团采用相应的固化剂进行。将它们用于不同类型的应用。将它们加工为铸塑树脂(反应树脂)、模塑料(反应树脂物料)或加工为预浸料。
作为铸塑树脂,它们在电工学方面具有广泛应用,例如用于制备用于电动机、高压套管、绝缘体或电容器的构件或者还在建筑业中作为用于表面保护的漆和涂层、混凝土结构元件的粘合或作为高强度的耐化学品的面层。而基于环氧树脂的铸塑树脂还作为粘合剂使用或用于工具制造中。
由环氧树脂组成的模塑料尤其在电工学方面例如用于包覆敏感的电工学或电子学构件如电容器、集电器或电阻器。
基于环氧树脂的层合体尤其用于飞行器的蒙皮和结构元件、风力设备的动叶片、船体、用作用于印刷电路和电路板的基础材料。它们还在运动领域和休闲领域中例如用作滑雪板、曲棍球棍、网球拍、钓竿或跳高杆。
固化的环氧树脂的宽的应用范围基于其优异的性质,例如在其良好的电绝缘性质、高强度、低收缩、良好的耐化学性及其难燃性方面。
因为对产品在各应用领域中的要求持续增长,所以还始终对起始原料,即对固化的环氧树脂提出更高的要求。
因此EP 2352793 B1描述了可分散的聚有机硅氧烷液滴和含硅氧烷的嵌段共聚物用于尤其还改性环氧树脂以提高抗冲强度和冲击韧性的用途。然而已发现,采用这样的组合物不能将断裂韧性提高至期望的水平。类似的组合物描述于US 4,663,413和US 5,037,898中。
发明内容
现在本发明的任务在于,改进固化的环氧树脂的断裂韧性,从而可以满足当前对环氧树脂材料的要求。
该任务根据本发明通过包含以下组分a)、b)和c)的组合物得以解决:
a)
-75至99.5重量%的基于环氧化合物的聚合物,
-0.5至25重量%的至少一种多元醇,和
-任选的添加剂
b)
-80至99重量%的固化剂,其适合于使基于环氧化合物的聚合物固化,
-1至20重量%的聚己内酯-聚硅氧烷-嵌段共聚物,
-任选的促进剂,和
-任选的添加剂,和
c)
-任选的促进剂。
基于环氧化合物的聚合物可以选自基于脂环族或脂族化合物的聚环氧化物、基于双酚A和/或F和由此制备的高阶树脂的聚环氧化物、基于四缩水甘油基亚甲基二苯胺(TGMDA)的聚环氧化物、基于环氧化的卤化的双酚和/或环氧化的酚醛清漆的聚环氧化物,和/或基于邻苯二甲酸、六氢邻苯二甲酸或基于对苯二甲酸、环氧化的邻氨基酚或对氨基酚、二环戊二烯和酚的环氧化的加聚产物、基于环氧化的芴酮双酚的聚环氧化物酯。
因此作为基于环氧化合物的聚合物,可以使用环氧化的苯酚酚醛清漆(苯酚和例如甲醛和/或乙二醛的缩合产物)、环氧化的甲酚酚醛清漆、基于双酚A的聚环氧化物(例如还有双酚A和四缩水甘油基亚甲基二苯胺的产物)、环氧化的卤化的双酚(例如基于四溴双酚A的聚环氧化物)和/或基于的双酚F的聚环氧化物和/或环氧化的酚醛清漆和/或基于三缩水甘油基异氰脲酸酯的环氧树脂。这尤其包括:
1001、1004、1007、1009:基于双酚A的聚环氧化物SU8(环氧化的双酚A酚醛清漆)、1031(环氧化的乙二醛-苯酚酚醛清漆)、1163(基于四溴双酚A的聚环氧化物)、03243/LV(基于3,4-环氧基环己基甲酸(3,4-环氧基环己基)甲酯和双酚A的聚环氧化物)、164(环氧化的邻甲酚酚醛清漆)-全部产品可获自Hexion Inc.。
在组分a)中基于组分a)的全部成分计,包含75至99.5重量%的基于环氧化合物的聚合物。特别优选的是95至99.5重量%的量,因为更少的量导致玻璃化转变温度的通常更不期望的降低。作为组分a)的另外的成分,基于组分a)的全部成分计,包含0.5至25重量%的至少一种多元醇。有利的是,多元醇以0.5至3重量%的量存在于组分a)中,因为在该浓度范围内,实现了断裂韧性的改进与可接受的玻璃化转变温度之间的平衡关系。优选的是甘醇(二元醇(二醇)),其可以来源于乙二醇,例如乙二醇、丙二醇、甲基乙二醇、三亚甲基二醇、新戊二醇、二亚乙基二醇、三亚乙基二醇、聚亚乙基二醇和/或聚亚丙基二醇。特别优选使用聚亚丙基二醇,因为该化合物是市场上常见的并且因此容易获得。
但此外也可以使用三元或更多元的醇,例如甘油、三羟甲基丙烷、葡萄糖和/或其它糖化合物。
此外,组分a)可以包含任选的添加剂,如加工助剂(消泡剂、脱气剂)、颜料和/或UV稳定剂,它们是商购可得的。
组分b)的主要成分是浓度为80至99重量%的固化剂(基于组分b)的全部成分计),其适合于使基于环氧化合物的聚合物固化。特别优选的是90-99重量%的量,因为由此最佳地影响组分b)的粘度。
混合物中的固化剂组分的量通常按照所使用的环氧树脂和所使用的固化剂的环氧当量(以克计的树脂量,包含1摩尔环氧基团)来调整。
作为用于环氧树脂的固化剂,例如考虑酚、咪唑、硫醇、咪唑络合物、羧酸、三卤化硼、酚醛清漆、三聚氰胺-甲醛树脂。特别优选的是酸酐固化剂,优选二羧酸酐和四羧酸酐或其改性物。作为实例,在这一点上提及以下酸酐:四氢邻苯二甲酸酐(THPA)、六氢邻苯二甲酸酐(HHPA)、甲基四氢邻苯二甲酸酐(MTHPA)、甲基六氢邻苯二甲酸酐(MHHPA)、甲基纳迪克酸酐(MNA)、十二碳烯基琥珀酸酐(DBA)或其混合物。作为改性的二羧酸酐,考虑酸酯(上述酸酐或其混合物与二醇或多元醇,例如:新戊二醇(NPG)、聚丙二醇(PPG,优选分子量200至1000)的反应产物)。
此外优选的是选自胺固化剂的固化剂,所述胺固化剂又选自多胺(脂族、脂环族或芳族)、聚酰胺、曼尼希碱、聚氨基咪唑啉、聚醚胺及其混合物。在这一点上示例性提及聚醚胺,例如Jeffamine D230、D400(Huntsman Advance Materials LLC.公司),它的使用的出众之处在于通过低的放热固化。多胺,例如异佛尔酮二胺赋予组合物高的TG值,和曼尼希碱,例如Epikure 110(Hexion Inc.)的出众之处在于低的氨基甲酸酯形成和高反应性。
此外,根据本发明的组合物的组分b)包含基于组分b)的全部成分计为1至20重量%的聚己内酯-聚硅氧烷-嵌段共聚物,其中1至10重量%的量是特别有利的,从而在合适的粘度下达到混合物的期望的有效性。大于20重量%的浓度导致加工粘度的明显升高。该嵌段共聚物是由现有技术已知的。因此尤其在US 4,663,413或EP 2 352 793B1中描述了相应的嵌段共聚物。待使用的嵌段共聚物A"-B-A'具有以下结构:
线性嵌段共聚物A”-B-A'由有机硅氧烷嵌段B和聚内酯嵌段A"或者A'组成。
n:1-200之间的整数
R2、R3、R4、R5:相同或彼此独立地选自具有至多6个碳原子的直链的或支链的烷基、烯基、卤代烷基、卤代烯基;具有5-7个碳原子的芳基或具有6-8个碳原子的芳烷基,
R1'、R1:相同或彼此独立地选自具有至多7个碳原子的烷基胺或烷基醚,
A"和A':相同或彼此独立地具有
其中
p:1-6的整数,
m:1-25的整数,
R6:氢或者具有至多6个碳原子的直链的或支链的烷基。
在这一点上示例性地提及以下化合物,其中n≥1和y>3:
作为组分b)的另一成分,其可以任选地包含通常的量(例如,1-2重量%)的促进剂,其中原则上适合的是可以用于相应的环氧树脂的由现有技术已知的全部促进剂。
在此示例性地使用例如咪唑、取代的咪唑、咪唑加合物、咪唑络合物(例如Ni-咪唑络合物)、叔胺、季铵化合物和/或季鏻化合物、氯化锡(IV)、双氰胺、水杨酸、脲、脲衍生物、三氟化硼络合物、三氯化硼络合物、环氧加成反应产物、四亚苯基硼络合物、胺硼酸盐、胺钛酸盐、金属乙酰丙酮化物、环烷酸金属盐、辛酸金属盐、辛酸锡(Zinnoctoate)、另外的金属盐和/或金属螯合物。此外可以例如是低聚的聚乙烯哌嗪、二甲氨基丙基二丙醇胺、双(二甲氨基丙基)-氨基-2-丙醇、N,N'-双(3-二甲氨基丙基)脲、N-(2-羟丙基)咪唑的混合物、二甲基-2-(2-氨基乙氧基)乙醇及其混合物、双(2-二甲氨基乙基)醚、五甲基二亚乙基三胺、二吗啉代二乙基醚、1,8-二氮杂双环[5.4.0]十一烯-7、N-甲基咪唑、1,2-二甲基咪唑、三亚乙基二胺和/或1,1,3,3-四甲基胍。
所述促进剂可以被添加至组分b)和/或单独地作为组分c)添加。但也可以完全省略添加。
作为组分b)的成分,同样又可以添加任选的添加剂,如加工助剂、颜料和/或UV稳定剂,其是商购可得的。
通过将各个成分分配至组分中,尤其分配至组分a)和b)中,利用了嵌段共聚物在固化剂中的溶解性,由此提高了组合物的储存稳定性。如果将嵌段共聚物分散至环氧树脂中,则储存稳定性更低并且观察到结晶倾向。
组分a)和b)的比例取决于树脂的环氧当量和所使用的固化剂的当量质量来确定。因此例如在使用酸酐固化剂的情况下优选每100份组分a)混入70至100份组分b)。如果使用胺固化剂,则将比例改变成每100份组分a)优选为10至30份组分b)。
固化的根据本发明的组合物的制备按照包括以下步骤的方法进行:
-制备组分a)和b)
-在最高120℃混合组分a)和b)和任选的c)
-任选地使制备的混合物成型,和
-在最高180℃的温度固化所述混合物。
组分a)和b)的制备在常规的混合设备如内混合机(Innenmischer)或挤出机中通常在室温进行。组分a)和b)是储存稳定的并且可以按需要使用。组分a)和b)的混合同样在常规设备中进行,其中优选的是,在制备组分a)和b)之后,将它们彼此在已经用于制备组分a)或b)的混合设备中混合,其中顺序并没有关系。所述混合可以在室温至120℃的温度范围内任选在真空下进行。组分a)和b)的比例再次通常由树脂和所使用的固化剂的环氧当量确定。因此例如在使用酸酐固化剂的情况下优选每100份组分a)混入70至100份组分b)。如果使用胺固化剂,则将比例改变成每100份组分a)优选为10至30份组分b)。取决于根据本发明的组合物将要用于何种应用,可以进行所制备的混合物的相应的成型。随后在又取决于所使用的固化剂的可以为介于室温(例如胺)和90-180℃(例如酸酐)之间的温度进行固化。
根据本发明的组合物在固化的状态下优选用于制备铸塑树脂、复合材料组合物、涂层、粘合剂和模塑料。
具体实施方式
借助于以下实施例将更详细地阐释本发明。
表1
根据本发明的组合物(2)的组分a)的制备:
根据本发明的组合物(2)的组分b)的制备:
将组分a)和b)在室温彼此混合并且在160℃固化。由该固化的组合物切割用于测定断裂韧性的测试样品(表2)。
在一个步骤中在室温进行来自表1的对比组合物(1)和(3)的制备并且在160℃进行固化。由固化的组合物切割用于测定断裂韧性的试样(表2)。
表2
断裂韧性的测定根据DIN 51221采用第1类拉压机进行。在这种情况下,记录在测试过程中由测试样品在负荷期间产生的阻力。使用配备有V形凹痕(60℃锥化至一个点,凹槽半径最大0.05mm)的平板(80mm x34mm x 4mm)作为测试样品。将测试样品如此放置在测试装置上,使得凹槽向下朝向支承侧。经过两个定位球塞以0.05mm/min的速度均匀地在凹痕两侧进行力的力量引入。在标准气候DIN 50-014-23/50-2下进行三重测定。在测试样品断成两段时或当负荷降低为最大负荷的99%时,终止测试。相应地计算断裂韧性。
这可以表明,单独使用聚己内酯-聚硅氧烷嵌段共聚物(I)并不导致断裂韧性的充分提高。尽管通过使用额外的硅氧烷化合物(III)相比于现有技术(1)改进了断裂韧性,但是还没有增加至期望的程度。然而,根据本发明,通过巧妙地分配成组分a)和b)和通过与嵌段共聚物组合使用少量聚丙二醇,可以使断裂韧性达到期望的更高的水平而不发生TG方面的劣化。
Claims (12)
1.组合物,其包含以下组分a)、b)和c):
a)
-75至99.5重量%的基于环氧化合物的聚合物,
-0.5至25重量%的聚丙二醇,和
-任选的添加剂,
b)
-80至99重量%的固化剂,其适合于使基于环氧化合物的聚合物固化,
-1至20重量%的聚己内酯-聚硅氧烷-嵌段共聚物,
-任选的促进剂,和
-任选的添加剂,和
c)
-任选的促进剂。
2.根据权利要求1所述的组合物,其特征在于,组分a)和b)的比例取决于树脂的环氧当量和所使用的固化剂的当量质量确定。
3.根据权利要求1所述的组合物,其特征在于,所述基于环氧化合物的聚合物为基于脂环族或脂族化合物的聚环氧化物。
4.根据权利要求3所述的组合物,其特征在于,所述基于脂环族或脂族化合物的聚环氧化物选自基于双酚A和/或F的聚环氧化物、基于四缩水甘油基亚甲基二苯胺(TGMDA)的聚环氧化物、基于环氧化的卤化的双酚和/或环氧化的酚醛清漆的聚环氧化物,和/或基于邻苯二甲酸、六氢邻苯二甲酸或基于对苯二甲酸、环氧化的邻氨基酚或对氨基酚、二环戊二烯和酚的环氧化的加聚产物、基于环氧化的芴酮双酚的聚环氧化物酯。
5.根据权利要求1所述的组合物,其特征在于,所述固化剂为酸酐。
6.根据权利要求5所述的组合物,其特征在于,所述酸酐为四氢邻苯二甲酸酐(THPA)、六氢邻苯二甲酸酐(HHPA)、甲基四氢邻苯二甲酸酐(MTHPA)、甲基六氢邻苯二甲酸酐(MHHPA)、甲基纳迪克酸酐(MNA)、十二碳烯基琥珀酸酐(DBA)或其混合物。
7.根据权利要求1所述的组合物,其特征在于,所述固化剂为胺。
8.根据权利要求7所述的组合物,其特征在于,所述胺为多胺、聚酰胺、曼尼希碱、聚氨基咪唑啉、聚醚胺及其混合物。
11.用于制备固化的组合物的方法,包括以下步骤:
-制备根据权利要求1所述的组分a)和b),
-在最高120℃的温度混合根据权利要求1所述的组分a)和b)和任选的c),
-任选地使制备的混合物成型,和
-在最高180℃的温度固化所述混合物。
12.固化的组合物,其包含根据权利要求1所述的组分,用于制备铸塑树脂、复合材料组合物、涂层、粘合剂和模塑料。
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Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5284938A (en) * | 1990-02-27 | 1994-02-08 | Shell Oil Company | Polysiloxane modified thermoset compositions |
CN1441830A (zh) * | 2000-05-31 | 2003-09-10 | 阿托菲纳公司 | 改进抗冲击性的热固性材料 |
CN102227471A (zh) * | 2008-11-28 | 2011-10-26 | 瓦克化学股份公司 | 包含硅氧烷混合物的环氧树脂及其制备方法和应用 |
CN102884100A (zh) * | 2010-03-24 | 2013-01-16 | 陶氏环球技术有限责任公司 | 包括作为增韧剂的聚(环氧丙烷)多元醇的环氧树脂组合物 |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4663413A (en) | 1985-01-04 | 1987-05-05 | Thoratec Laboratories Corp. | Polysiloxane-polylactone block copolymers |
US4855340A (en) * | 1988-02-19 | 1989-08-08 | Shell Oil Company | Stabilized epoxy resin compositions |
US4923908A (en) * | 1988-10-14 | 1990-05-08 | Zenith Electronics Corporation | Epoxy compositions, and method of making same |
US5037898A (en) | 1990-02-27 | 1991-08-06 | Shell Oil Company | Polysiloxane-polylactone block copolymer modified thermostat compositions |
KR20070041670A (ko) * | 2004-03-15 | 2007-04-19 | 디에스엠 아이피 어셋츠 비.브이. | 경화성 액체 수지 조성물 |
JP2008163116A (ja) * | 2006-12-27 | 2008-07-17 | Wacker Asahikasei Silicone Co Ltd | 半導体封止用樹脂組成物および半導体装置 |
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Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5284938A (en) * | 1990-02-27 | 1994-02-08 | Shell Oil Company | Polysiloxane modified thermoset compositions |
CN1441830A (zh) * | 2000-05-31 | 2003-09-10 | 阿托菲纳公司 | 改进抗冲击性的热固性材料 |
CN102227471A (zh) * | 2008-11-28 | 2011-10-26 | 瓦克化学股份公司 | 包含硅氧烷混合物的环氧树脂及其制备方法和应用 |
CN102884100A (zh) * | 2010-03-24 | 2013-01-16 | 陶氏环球技术有限责任公司 | 包括作为增韧剂的聚(环氧丙烷)多元醇的环氧树脂组合物 |
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