CN100586935C - 1-咪唑甲基-取代的2-萘酚及其作为低温固化促进剂的用途 - Google Patents
1-咪唑甲基-取代的2-萘酚及其作为低温固化促进剂的用途 Download PDFInfo
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- CN100586935C CN100586935C CN200480010051A CN200480010051A CN100586935C CN 100586935 C CN100586935 C CN 100586935C CN 200480010051 A CN200480010051 A CN 200480010051A CN 200480010051 A CN200480010051 A CN 200480010051A CN 100586935 C CN100586935 C CN 100586935C
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- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims abstract description 41
- 150000001875 compounds Chemical class 0.000 claims abstract description 35
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- 125000006652 (C3-C12) cycloalkyl group Chemical group 0.000 claims abstract description 8
- 238000001802 infusion Methods 0.000 claims abstract description 7
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- -1 glycidyl ester Chemical class 0.000 claims description 16
- 239000000654 additive Substances 0.000 claims description 6
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- 150000004985 diamines Chemical class 0.000 claims description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 5
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 claims description 4
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical group C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 4
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 2
- 125000002723 alicyclic group Chemical group 0.000 claims description 2
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 2
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- 125000003118 aryl group Chemical group 0.000 abstract 2
- 125000000027 (C1-C10) alkoxy group Chemical group 0.000 abstract 1
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- IYDJTTMEODZPPB-UHFFFAOYSA-N 3-chloro-2,6-diethyl-4-methylaniline Chemical compound CCC1=CC(C)=C(Cl)C(CC)=C1N IYDJTTMEODZPPB-UHFFFAOYSA-N 0.000 description 2
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- 230000007704 transition Effects 0.000 description 1
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Abstract
通式化合物(I)和(II)，其中R1，R2和R3相互独立地分别为H；C1-17烷基；C3-12环烷基，任选被C1-4烷基基团取代；C4-20环烷基-烷基，任选被C1-4烷基基团取代；C6-10芳基，任选被1-3个C1-4烷基基团，-CN，卤素，OH或C1-10烷氧基取代；C7-15苯烷基，任选被1-3个C1-4烷基基团取代；C3-12烯基；C3-12炔基；或芳族或脂肪族C3-12酰基；R4，R5，R6，R7，R8，和R9相互独立地分别为H；C1-17烷基；C3-12环烷基，任选被C1-4烷基基团取代；C4-20环烷基-烷基，任选被C1-4烷基基团取代；C6-10芳基，任选被1-3个C1-4烷基基团取代；C7-15苯烷基，任选被1-3个C1-4烷基基团取代；C3-17烯基；C3-12炔基；C1-12烷氧基；或OH；对于通式(I)，R是C1-12烷基；C3-12环烷基，任选被C1-4烷基基团取代；C4-20环烷基-烷基，任选被C1-4烷基基团取代；C6-10芳基，任选被1-3个C1-4烷基基团取代；C7-15苯烷基，任选被1-3个C1-4烷基基团取代；C3-12烯基；或C3-12炔基；同时对于通式(II)n＝2-12；在用作压塑材料，烧结粉末，封铸体系，或浇铸树脂的可固化环氧树脂组合物中用作促进剂，或使用树脂浸泡法，湿铺叠法和注射成型法生产具有优良层间剪切强度的半固化片或层压制品，或生产元部件，特别是大表面积部件。
Description
低温固化促进剂
本发明涉及新颖的曼尼希碱1-咪唑甲基-取代的2-萘酚化合物，还涉及其作为环氧树脂体系促进剂的用途，它可使层压制品有高的ILS值，特别是用树脂浸泡法、湿铺叠法和其它浸渍法生产的浸渍型树脂。另外，本发明的促进剂还适合在烧结粉末，浇铸树脂和压塑材料中应用。
化合物1-咪唑甲基-2-萘酚和与环氧树脂有关的其它咪唑催化剂以及促进剂是已知的。
然而，惯用的咪唑化合物如咪唑，1-甲基咪唑，2-甲基咪唑，2-乙基-4-甲基咪唑或2-苯基咪唑在用于预浸渍料坯配方时会产生室温下半固化片储存稳定性不足的问题。
过去人们尝试用有机酸或无机酸与咪唑化合物反应形成盐来降低其反应性以解决该问题，例如可参看US3,356,645和US5,001,212。尽管在那些情况下半固化片的储存稳定性(简称放置时间)得到了改进，但仍不能满足很多应用的要求。
另一种提高半固化片放置时间的方法是使咪唑与金属盐反应形成咪唑配合物，例如可参看US4,101,514和US4,487,914。一般来说，用这种方法来改进放置时间是以提高工艺温度为代价的。此外，存在于已固化环氧树脂体系中的金属配合物会导致介电值的劣化，同时也导致吸水性的增加。然而在很多应用中都要求吸水性基本不变，否则会造成玻璃化转变温度降低，从而导致浸渍化合物机械性能、电性能和热性能的大幅改变。
EP0761709描述了作为催化剂的1-咪唑甲基-取代的2-萘酚化合物，基本上避免了上述引证文献所描述的缺点。环氧树脂体系中所含的上述化合物是稳定的曼尼希碱，可以显著提高进整个体系在室温下的放置时间。含有该催化剂的配方在110℃到150℃的温度范围内可迅速固化。这种材料显示了良好的机械性能和相对高的玻璃化转变范围。含有这种催化剂的半固化片在室温下可毫无问题地储存16天并加工成层压制品。
生产价格看好的大表面积部件的既定方法包括树脂浸泡法和其它的浸渍方法。为了能够使用树脂浸泡法，例如RTM，所用的环氧树脂配方在23℃到60℃时的粘度应在100-1000mPa·s之间，但优选在100-500mPa·s之间。基于成本的考虑，浸渍操作应在100℃以下进行。例如，选用湿铺叠法制备大表面积部件时，同样基于经济原因，固化温度应始终远低于100℃。为了更容易操作，用该法制造的半成品(半固化片)在室温下应有相对长的储存稳定性，这就意味着半固化片必须在储存一段时间，例如4天或更多天后，能够无故障地转变成层压制品。当该法制备的层压制品用于能量发生装置，层压制品在使用过程中将承受转动运动并受到相当大的剪切力时，必须保证层压制品各层间的粘附力不能低于某一最低值。度量这种粘附力的一种方式称作层间剪切强度，也简称为ILS，可按照ASTM标准(ASTM D 2344-84)测定。因此实现该应用的目标是获得最大ILS值。
目前已发现在半固化片配方中加入1-(咪唑基-2-甲基)-2-萘酚确实可以显著提高半固化片在室温时的储存稳定性，但却不能获得很高的层间剪切强度值。不管是在60℃下固化4小时，还是在75℃下固化4小时或甚至8小时，或在140℃下固化30分钟，可获得的最大值约为22MPa。
现在令人吃惊地发现，曼尼希碱1-咪唑甲基-取代的2-萘酚化合物(其芳族羟基已被烷基化)具有一种可用作环氧树脂体系促进剂的特性，特别适用于树脂浸泡法、湿铺叠法和其它浸渍方法，因为用这些方法浸渍成的半成品除了半固化片有2-8天的储存稳定期，同时它在60℃或75℃下固化4到8小时后的ILS值最高可达50MPa。
据此，本发明首先提供了通式(I)和通式(II)化合物：
其中
R1，R2和R3相互独立地分别为H；C1-17烷基；
C3-12环烷基，任选被C1-4烷基基团取代；
C4-20环烷基-烷基，任选被C1-4烷基基团取代；
C6-10芳基，任选被1-3个C1-4烷基基团，-CN，卤素，OH或C1-10烷氧基取代；
C7-15苯烷基，任选被1-3个C1-4烷基基团取代；
C3-12烯基；C3-12炔基；或
芳族或脂肪族C3-12酰基；
R4，R5，R6，R7，R8，和R9相互独立地分别为H；C1-17烷基；
C3-12环烷基，任选被C1-4烷基基团取代；
C4-20环烷基-烷基，任选被C1-4烷基基团取代；
C6-10芳基，任选被1-3个C1-4烷基基团取代；
C7-15苯烷基，任选被1-3个C1-4烷基基团取代；
C3-17烯基；C3-12炔基；C1-12烷氧基；或OH；对于通式(I)
R是C1-12烷基；C3-12环烷基，任选被C1-4烷基基团取代；
C4-20环烷基-烷基，任选被C1-4烷基基团取代；
C6-10芳基，任选被1-3个C1-4烷基基团取代；
C7-15苯烷基，任选被1-3个C1-4烷基基团取代；
C3-12烯基；或C3-12炔基；同时对于通式(II)，n＝2-12。
就基团R1，R2和R3来说，优选的通式(I)和(II)化合物为其中的R1，R2和R3相互独立地分别为H；C1-12烷基；苯基；C7-15苯烷基，任选被1-3个C1-4烷基基团取代；特别优选的化合物为其中的R2和R3分别为H；同时R1为C1-12烷基；苯基；或C7-15苯烷基，任选被1-3个C1-4烷基基团取代。
就基团R来说，优选的通式(I)化合物为其中的R为C1-12烷基；或C3-12烯基；同时当未被取代的脂肪族桥为-(CH2)-(CH2)n-CH2-时，优选的通式(II)化合物为其中的因子n＝6-12。
就基团R4到R9来说，优选的通式(I)和(II)化合物为其中的基团R4到R9为氢原子(H)。
前述对于通式(I)和(II)化合物中基团R1，R2和R3；R4到R9；通式(I)化合物中基团R；以及通式(II)化合物中因子n所作的优选也适用于任何预期的组合。
特别优选的通式(I)和(II)化合物为其中基团R2到R9为氢原子，并且基团R1为C1-4烷基(甲基，乙基，正，异-丙基，正，异，叔-丁基)，或苯基，任选被1-3个C1-4烷基基团取代，同时R为C3-12烷基或C3-12烯基，且通式(II)中n＝8，10，或12。
进一步优选的化合物为R1＝甲基，R2-9的每一个基团都为氢原子，R＝正-丁基，正-壬基，正-十二烷基，或烯丙基，同时n＝8。
本发明的化合物可采用原有的已知方法制备。例如，为此目的，首先按照EP0761709A所描述的方法制备1-咪唑甲基-取代的2-萘酚，然后采用传统方法，优选在碱性介质中，将萘酚上的羟基基团醚化。对于每一个通式(II)中两个环状体系相同的化合物来说，两个环状体系是通过脂肪族，未被取代的烃链来桥联的。
正如开始时所提到的，本发明的化合物适合用作可固化环氧树脂体系的促进剂。
因此本发明进一步提供了可固化环氧树脂组合物，包含：
a)环氧化物含量为0.1-11，优选为0.1-2.2环氧当量/kg的环氧树脂，
b)通式(I)或(II)化合物，
c)用于环氧树脂的固化剂，以及任选的
d)环氧树脂工艺中惯用的添加剂。
原则上讲，所有的环氧树脂都适合做组分(a)。
合适的实例包括脂环族多元醇，例如2，2-双(4’-羟基环己基)丙烷的二缩水甘油醚或聚缩水甘油醚，多羟基苯酚，如间苯二酚，双(4’-羟苯基)甲烷(双酚F)，2，2-双(4’-羟苯基)丙烷(双酚A)，2，2-双(4’-羟基-3’，5’-二溴苯基)丙烷，1，1，2，2-四(4’-羟苯基)乙烷的二缩水甘油醚或聚缩水甘油醚或苯酚与甲醛的缩合产物，如苯酚酚醛树脂和甲酚酚醛树脂；另外还有上述引用的多元醇和聚苯酚的二-或聚(β-甲基缩水甘油)醚，多元羧酸如邻苯二甲酸，对苯二酸，四氢邻苯二甲酸和六氢邻苯二甲酸的聚缩水甘油醚和聚(β-甲基缩水甘油)醚；氨基酚的缩水甘油衍生物，如三缩水甘油-对-氨基酚；胺，酰胺和杂环氮碱，如N，N-二缩水甘油苯胺，N，N--二缩水甘油甲苯胺，N，N，N，N-四缩水甘油-双(4-氨基苯)甲烷，三缩水甘油异氰尿酸酯，N，N-二缩水甘油-N，N’-亚乙基脲，N，N’-二缩水甘油-5，5-二甲基乙内酰脲，N，N’-二缩水甘油-5-异丙基乙内酰脲，N，N’-二缩水甘油-5，5-二甲基-6-异丙基-5，6-二氢尿嘧啶的N-缩水甘油衍生物；多官能环氧树脂，如EP-A 205409和EP-A 204659所描述的2，6-二取代4-环氧丙苯基缩水甘油醚及其加成物；由两个缩水甘油氧基团和2，3-环氧丙基基团取代的双酚，如GB 828364中所描述的2，2-双(3’-环氧丙基-4’-环氧丙苯基)丙烷；四羟甲基取代的环己醇，环己酮、环戊醇和环戊酮的缩水甘油衍生物，如US 4,549,008中所描述的化合物；缩水甘油氧取代的二苯甲酮；以及缩水甘油氧二酮，US 4,649,181中所描述的化合物。
一般而言，也可以使用两种或两种以上环氧树脂的混合物作为本发明配方中的组分。
适合的环氧树脂优选包括缩水甘油醚如双酚A或F，缩水甘油酯，芳族或杂环化合物的N-缩水甘油衍生物和N，O-缩水甘油衍生物，以及脂环族缩水甘油化合物。优选具有官能度0.1-2.2环氧当量/kg的环氧树脂。
原则上讲，环氧树脂化学领域所惯用的所有固化剂都能用作本发明的固化剂，或组分(c)，例如胺，双氰胺，氰基胍，三聚氰胺，酚醛，例如包括甲酚-酚醛，多元醇和酸酐。
原则上讲适合的固化剂也包括二羟基芳香族化合物如已提到的双酚和二元酚。除了二元酚，也可使用三元酚或多元酚，如2，4，6-三[2’-(对-羟苯基)-2’-丙基]苯(购自Mitsui Petrochemical公司)。
优选使用的固化剂为胺和聚胺，例如Jeffamine D类和T类，及其它的胺和聚胺。可提及的具体实例包括邻-，间-，和对-，苯二胺；二氨基甲苯，如2，4-甲苯二胺，1，4-二氨基-2-甲氧基苯，2，5-二氨基二甲苯，1，3-二氨基-4-氯苯，4，4’-二氨基二苯基甲烷，4，4’-二氨基二苯基醚，4，4’-二氨基二苯基硫醚，4，4’-二氨基二苯基砜，2，2’-二氨基苯甲酮，1，8-或1，5-二氨基萘，2，6-二氨基吡啶，1，4-哌嗪，2，4-二氨基嘧啶，2，4-二氨基-s-三嗪，二-，三-，四-，六-，七-，八-，和十-亚甲基二胺，3-甲基环庚烷-1，6-二胺，3-甲氧基六亚甲基二胺，2，11-二氨基十二烷，2，2，4-和2，4，4-三甲基六亚甲基二胺，1，2-双(3-氨基丙氧基)乙烷，N，N’-二甲基乙二胺，N，N’-二甲基-1，6-二氨基己烷以及分子式为H2N(CH2)3O(CH2)2O(CH2)3-NH2和H2N(CH2)3S(CH2)3NH2的二胺，1，4-二氨基环己烷，1，4-双(2-甲基-4-氨苯基)苯，1，4-双(氨甲基)苯。
另外适用的胺有碳环-芳族二胺，特别是取代的双核二胺，如双(3，5-二异丙基-4-氨苯基)甲烷，双(2-氯-3，5-二乙基-4-氨苯基)甲烷，双(3-乙基-4-氨基-5-仲-丁苯基)甲烷，双(2-氯-3，5-二乙基-4-氨苯基)甲烷和双(3，5-二乙基-4-氨苯基)甲烷。
另外适用的胺有丙烷-1，3-二胺，间-二甲苯二胺，双(4-氨基环己基)丙烷，3-氨甲基-3，5，5-三甲基环己基胺(异佛尔酮二胺)，聚氨基酰胺，例如包含脂肪族聚胺和脂肪酸的二聚或三聚物的聚氨基酰胺；多酚，如间苯二酚，对苯二酚，双酚A和苯酚/乙醛树脂，以及聚硫醇如“Thiokols”。
优选的固化剂为二胺或聚胺，氨基封端的聚亚烷基二醇(如Jeffamine胺，氨基-多-四氢呋喃)或聚氨基酰胺，特别是丙二醇和乙二醇的二聚物或共聚物，分子量为150-5000，优选为200-600的氨基封端的聚丁二烯。
进一步优选的固化剂为氨基封端的聚醚二胺，特别是氧亚烷基重复单元数小(小于10，优选小于6)的短链聚氧亚烷基二胺，可提及的市售固化剂为
公司的D-230，一种氧亚丙基平均重复单元数为2.6的聚环氧丙烷二胺。
可选用环氧树脂工艺中惯用的添加剂作为任选组分d)。即涉及特殊应用时本领域技术人员所知道和使用的那些常用助剂和添加剂。实例包括有机或无机的填料和颜料，脱模剂，以及影响粘度的添加剂。
在制备本发明的可固化组合物时，预先将本发明的促进剂一般在高温下溶解到固化剂中：例如使用一种固化剂时，在大约80℃下溶解促进剂。然后将溶液冷却到40℃，再与环氧树脂混合。该混合物可随后直接用做RTM原料或浸渍溶液。另外也可以预先将本发明的促进剂均匀地分散在环氧树脂中，例如采用适合的搅拌方法进行分散，如采用Ultra-Turrax或三辊磨。
按总组成计，优选加入1-10份重的本发明化合物，特别优选加入5-7份重。固化剂按惯用量加入，因此可按平均每个环氧基团加入0.5-1.5，优选0.8-1.2个固化剂官能团来计算。原则上讲，助剂和添加剂的加入量范围可以很宽，只要不导致预期组合物粘度的大幅增加即可。
正如已提及的那样，本发明化合物的使用，例如用于环氧树脂/胺配方，会降低由此制得的半固化片在室温下的储存稳定性。然而含有本发明促进剂的半固化片却能使ILS值高达50Mpa。因此本发明促进剂特别适合在用作压塑材料，烧结粉末，封铸体系，或浇铸树脂的环氧树脂配方中使用，也适合采用树脂浸泡法，湿铺叠法和注射成型法生产半固化片或层压制品时使用。
实验部分
a)曼尼希碱的制备。以1-咪唑甲基-2-萘酚(二甲基亚砜中的碱性变
量)为例对萘酚醚化反应进行一般性描述。
一个带回流冷凝器、内置温度计、滴液漏斗和KPG搅拌的磺化长颈瓶(300-400ml)，瓶内装有二甲基亚砜，在搅拌下加入所选的萘酚。得到浅褐色的悬浮液。向搅拌着的溶液中加入粉末状KOH。溶液从浅褐色变成绿色，15分钟后澄清形成仍含有少量固体成分的深绿色溶液。瓶内温度约为22℃。在该温度下分别逐滴滴加卤代烷烃或二卤代烷烃。混合物15分钟内升温到30℃。然后在下一个9分钟内加入剩余的卤代烷烃或二卤代烷烃。将瓶中混合物从初始温度加热到刚刚超过50℃，然后再加热到约70℃。在此温度下将瓶中混合物搅拌2-3小时。随后将反应液倒到150克冰上。得到一种浅褐色-棕色固体和乳白色水相。从水相分离出有机相，随后用甲苯摇动萃取5次，每次用甲苯50ml。用无水硫酸钠干燥合并的有机相。静置过夜后用吸滤器除掉干燥剂，同时溶剂在旋转蒸发器上去除。用20ml异丙醇吸收粗产品，在回流下加热到约65℃。用干冰使溶液中的产品结冰析出，然后用吸滤器除掉异丙醇。最后将固体在约40℃/0.3毫巴条件下干燥约2小时。从下表1可以找到个别组分的使用量。
表1
| E<sup>1)</sup> | Comp.1<sup>2)</sup> | Comp.2<sup>2)</sup> | Comp.3<sup>2)</sup> | Solv.<sup>3)</sup> | Yld.<sup>4)</sup> | M.p.<sup>5)</sup> |
| 1 | 11.91(50) | 10.56(51) | 3.08(55) | 100 | 80-86 | 83 |
| 2 | 35.73(150) | 18.91(153) | 9.24(165) | 300 | 37 | 93 |
| 3 | 35.73(150) | 38.13(153) | 9.24(165) | 300 | 91 | 81 |
| 4 | 35.73(150) | 14.16(153) | 9.24(165) | 300 | 85 | 91 |
| 5 | 28.59(120) | 18.0(60) | 7.08(126) | 300 | 48 | 158 |
1)E＝实验；2)Comp.＝组分，单位g或mmol()，组分1＝1-咪唑甲基-2-萘酚，组分2依实验不同分别为：E1＝壬基溴，E2＝烯丙基溴，E3＝十二烷基溴，E4＝丁基氯，E5＝1，10-二溴十二烷；组分3＝KOH
3)Solv.＝溶剂，单位ml，上述实验所用的溶剂均为二甲基亚砜(DMSO)；
4)Yld.＝收率，单位％；5)M.p.＝熔点(DSC法)，单位℃。产品的其它特征用1H和13CNMR(d6-DMSO)和C，H，N，O元素分析法测定。
按所需配方的重量计，本发明化合物加入量优选为1-10份，特别优选加入5-7份。相关内容可参看表2。
b)本发明曼尼希碱的应用实施例
将上述实验a)部分得到的产物于60-80℃的温度下溶于胺固化剂中。由此得到橙色至暗棕色透明溶液。冷却到室温后，将该溶液与计算量的环氧树脂混合。详情参见下表2。
表2
1)Araldite LY556 双酚-A Harz(Vantico AG)
2)Jeffamine Jeffamine D-230(Huntsman)
3)XU3132 1-咪唑甲基-2-萘酚(Vantico AG)
4)E1/E2/E3 实验1，2和3(参见表1)
5)DY965 增韧剂DY965(Vantico AG)
6)制备 制备半固化片和层压制品的天数
7)半固化片 堆叠数＝12
8)树脂含量 层压制品被压缩后的树脂百分含量
9)储存 在室温＝20-25℃下储存
10)Fmax ASTM D 2344中的极限强度(拉断载荷)
σmax ASTM D 2344中的剪切强度
11)Nm，Ng Nm＝不可测，Ng＝未测
12)粘度 用带有盘/盘装置的流变仪Rheometrix RD2测定
令人吃惊地是，从表2配方E6，E7和对比例可以看出，在低温范围(60℃和75℃/4-8小时)，用本发明的促进剂可以获得非常好的层间剪切强度。ILS值大大高于对比体系。用本发明促进剂所得到的体系在60℃时的粘度为150mPa·s，也远远低于对比体系，60℃时的粘度为800-1000mPa·s。这是本发明促进剂用于浸渍方法时的又一关键优势，因为该方法需要体系低粘度。
Claims (14)
1.通式化合物(I)和(II)：
其中
R1，R2和R3相互独立地分别为H；C1-17烷基；
C3-12环烷基，任选被C1-4烷基基团取代；
C4-20环烷基-烷基，任选被C1-4烷基基团取代；
C6-10芳基，任选被1-3个C1-4烷基基团，-CN，卤素，OH或C1-10烷氧基取代；
C7-15苯烷基，任选被1-3个C1-4烷基基团取代；
C3-12烯基；C3-12炔基；或芳族或脂肪族C3-12酰基；
R4，R5，R6，R7，R8和R9相互独立地分别为H；C1-17烷基；
C3-12环烷基，任选被C1-4烷基基团取代；
C4-20环烷基-烷基，任选被C1-4烷基基团取代；
C6-10芳基，任选被1-3个C1-4烷基基团取代；
C7-15苯烷基，任选被1-3个C1-4烷基基团取代；
C3-17烯基；C3-12炔基；C1-12烷氧基；或OH；对于通式(I)
R是C1-12烷基；C3-12环烷基，任选被C1-4烷基基团取代；
C4-20环烷基-烷基，任选被C1-4烷基基团取代；
C6-10芳基，任选被1-3个C1-4烷基基团取代；
C7-15苯烷基，任选被1-3个C1-4烷基基团取代；
C3-12烯基；或C3-12炔基；同时对于通式(II)，n＝2-12。
2.根据权利要求1所述的化合物，其中R1，R2和R3相互独立地分别为H；C1-12烷基；苯基；或C7-15苯烷基，任选被1-3个C1-4烷基基团取代。
3.根据权利要求2所述的化合物，其中R2和R3分别为H；同时R1为C1- 12烷基；苯基；或C7-15苯烷基，任选被1-3个C1-4烷基基团取代。
4.根据权利要求1-3之一所述的化合物，其中通式(I)中的R为C1-12烷基；或C3-12烯基；同时通式(II)中n＝6-12。
5.根据权利要求1-3之一所述的化合物，其中基团R4到R9为氢原子。
6.根据权利要求4所述的化合物，其中基团R4到R9为氢原子。
7.根据权利要求1所述的化合物，其中，R1＝甲基；R2-9每一个都为氢原子；对于通式(I)，R＝正-丁基，正-壬基，正-十二烷基，或烯丙基。
8.权利要求1所述的化合物作为促进剂在环氧树脂组合物中的应用。
9.可固化组合物，包括
a)环氧化物含量为0.1-11环氧当量/kg的环氧树脂，
b)权利要求1所述的化合物，按a)到d)所构成的组合物总量计，加入1-10份重，
c)用于环氧树脂的固化剂，其加入量按每个环氧基团加入0.5-1.5个固化剂官能团来计算，以及任选的
d)环氧树脂工艺中惯用的添加剂。
10.根据权利要求9所述的组合物，其特征在于固化剂选自胺类化合物。
11.根据权利要求10所述的组合物，其特征在于固化剂是聚环氧丙烷二胺。
12.根据权利要求9所述的组合物，其特征在于环氧树脂为缩水甘油醚，缩水甘油酯，芳族或杂环化合物的N-缩水甘油或N，O-缩水甘油衍生物，或脂环族缩水甘油化合物。
13.权利要求9所述的可固化组合物作为压塑材料、烧结粉末、封铸体系或浇铸树脂的应用。
14.权利要求9所述的可固化组合物在用树脂浸泡法、湿铺叠法或注射成型法生产半固化片和层压制品中的应用。
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| CN105254618B (zh) * | 2015-11-24 | 2019-01-01 | 盐城工学院 | 一种2-甲基咪唑类固化剂及其制备方法 |
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| CH648844A5 (en) * | 1981-05-15 | 1985-04-15 | Siegfried Ag | Thenyloxy ethers of imidazolylmethylaryl compounds, their preparation and their use as fungicides and bactericides |
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| EP0761709B1 (en) * | 1995-09-12 | 2000-05-03 | Ciba SC Holding AG | 1-Imidazolylmethyl-2-naphthols as catalysts for curing epoxy resins |
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| WO2004092141A1 (en) | 2004-10-28 |
| JP2006523656A (ja) | 2006-10-19 |
| DE602004001459T2 (de) | 2007-02-01 |
| ES2263141T3 (es) | 2006-12-01 |
| KR101158270B1 (ko) | 2012-06-20 |
| JP4584913B2 (ja) | 2010-11-24 |
| CN1774424A (zh) | 2006-05-17 |
| DK1613604T3 (da) | 2006-10-30 |
| KR20060003352A (ko) | 2006-01-10 |
| TW200427723A (en) | 2004-12-16 |
| EP1613604A1 (en) | 2006-01-11 |
| ATE332292T1 (de) | 2006-07-15 |
| DE602004001459D1 (de) | 2006-08-17 |
| US7468441B2 (en) | 2008-12-23 |
| TWI349682B (en) | 2011-10-01 |
| EP1613604B1 (en) | 2006-07-05 |
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