CN110498904A - 快速固化型环氧体系 - Google Patents
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Abstract
本发明涉及快速固化型环氧体系。本发明涉及一种组合物,其包含a)至少一种环氧树脂,b)至少一种具有至少两个仲氨基的胺,这两个仲氨基是一个有机环体系的组成部分,和c)至少一种极强布朗斯台德酸的盐,其具有选自金属离子、含金属的离子、鏻离子和铵离子的反荷离子;涉及其制备方法及其用途。
Description
环氧树脂,尤其是由双酚A和表氯醇制成的那些,是制备高品质浇注树脂、涂料物料、复合材料和胶粘剂的已知原料。用多胺固化的芳族环氧树脂除了良好的耐化学品性和耐溶剂性外还对许多基底具有良好的粘附强度。
为了加速环氧-胺-涂料体系的固化,可以使用催化剂(US 3,492,269 A、US 5,470,896 A、GB 1,105,772 A)。
EP 0 083 813 A1、EP 2 957 584 A1、US 5,441,000 A、US 5,629,380 A、WO 96/09352 A1公开了用不同的胺进行环氧树脂的催化固化。
环状胺在环氧固化中表现出优点。US 8,951,619 B2和US 9,006,385 B2尤其公开了用N-取代的哌嗪进行环氧树脂的无催化剂的固化。
CN 106905816 A、CN 106833261 A、JP H08-113876 A、DE 1 954 701 A1、CA 2165 585 A1和US 3,055,901 A公开了用氨基乙基哌嗪进行环氧树脂的无催化剂的固化。
EP 0 969 030 A1公开了环氧/胺-涂料体系,其胺组分是脂族胺。该组合物可以具有催化剂。在实施例中,此外使用氨基乙基哌嗪作为固化剂。
US 4,775,734 A公开了在使用催化量的不同的胺的四氟硼酸盐或六氟磷酸盐的情况下用尤其氨基乙基哌嗪、双(氨基丙基)哌嗪或哌啶进行环氧树脂的固化。
EP 3 255 078 A1公开了包含至少一种环氧化合物、2-(2,2,6,6-四甲基哌啶-4-基)丙烷-1,3-二胺和任选催化剂的环氧树脂组合物,所述催化剂尤其可以是无机盐。
US 2012/0010330 A1公开了在至少10%的烷基酚存在下用尤其选自哌嗪或高哌嗪的环状二胺进行环氧树脂的固化。然而,使用含酚添加剂的缺点是它们的过敏性作用和它们的毒性。 所公开的组合物的固化可以在催化剂存在下进行,催化剂可以是硝酸钙。
WO 2017/074810 A1公开了包含环氧树脂、聚醚胺和另一种胺固化剂以及金属三氟甲磺酸盐-催化剂的组合物,该胺固化剂尤其可以是一种咪唑或咪唑啉。
此外,现有技术中的组合物的共同之处是,它们固化过慢或仅在高温下固化。
然而,对于许多应用而言重要的是,表面固化或完全彻底固化特别快速地进行或在低温下进行。前者可以提高生产率,或加速下一个加工步骤。后者尤其在寒冷地区中是重要的,以例如为船只或管道提供防腐蚀涂层,以使得在那里在冬季也可以进一步操作。
因此,本文的目的是提供环氧体系,其在相同的条件下比迄今已知的配制品明显更快地反应。另一个目的是提供环氧配制品,其在明显低于室温的温度下比迄今可能更快地部分固化或完全固化。如果它们尽可能不含有毒和过敏性的添加剂,则将是更理想的。
本文提出的目的通过根据本发明的组合物得以实现,所述组合物包含
a) 至少一种环氧树脂,
b) 至少一种具有至少两个仲氨基的环状胺,这两个仲氨基是有机环体系的组成部分,和
c) 至少一种极强布朗斯台德酸的盐,其具有选自金属离子、含金属的离子、鏻离子和铵离子的反荷离子。
优选地,根据本发明的组合物此外不含酚,即它们不含酚和取代的酚。取代的酚在此应理解为是指在结构上衍生自苯酚的化合物。特别地,根据本发明的组合物优选不含烷基化的酚。相应的不含酚的组合物具有低毒性和过敏性的优点。
组分a)是至少一种环氧树脂。原则上,所有环氧化合物都适用于此。
合适的环氧化合物例如描述在EP 675 185 A2中。可以考虑多种已知化合物,其每分子含有多于一个环氧基团,优选两个环氧基团。这些环氧化合物在此既可以是饱和的也可以是不饱和的,以及可以是脂族、脂环族、芳族或杂环的,并且还可以具有羟基。它们此外可以含有在混合-或反应条件下不引起干扰性副反应的那些取代基,例如烷基-或芳基取代基或醚基团。
优选的环氧化合物在此是缩水甘油醚,其衍生自多元酚,特别是双酚以及酚醛清漆,并且其基于环氧基团的数量计的摩尔质量ME(“环氧当量重量”,“EV值”)为100至1500g/val,但特别是150至250 g/val。
特别优选的环氧化合物衍生自间苯二酚,对苯二酚,2,2-双-(4-羟基苯基)-丙烷(双酚A),二羟基二苯基甲烷的异构体混合物(双酚F),4,4'-二羟基二苯基环己烷,4,4'-二羟基-3,3'-二甲基二苯基丙烷,4,4'-二羟基联苯,4,4'-二羟基二苯甲酮,双-(4-羟基苯基)-1,1-乙烷,双-(4-羟基苯基)-1,1-异丁烷,2,2-双-(4-羟基-叔丁基苯基)-丙烷,双-(2-羟基萘基)-甲烷,1,5-二羟基萘,三-(4-羟基苯基)甲烷,双-(4-羟基苯基)醚,双-(4-羟基苯基)砜,以及上述化合物的氯化-和溴化产物(例如四溴双酚A)。
非常特别优选地,使用基于双酚A和双酚F的液体二缩水甘油醚,其环氧当量重量为150至200 g/val。
优选地,也可以使用多元醇的多缩水甘油醚,例如乙二醇-1,2-二缩水甘油醚、丙二醇-1,2-二缩水甘油醚、丙二醇-1,3-二缩水甘油醚、丁二醇二缩水甘油醚、戊二醇二缩水甘油醚(也称为新戊二醇二缩水甘油醚)、己二醇二缩水甘油醚、二乙二醇二缩水甘油醚、二丙二醇二缩水甘油醚、更高级的聚氧亚烷基二醇二缩水甘油醚,例如更高级的聚氧亚乙基二醇二缩水甘油醚和二醇二缩水甘油醚、混合聚氧亚乙基-亚丙基二醇二缩水甘油醚、聚氧四亚甲基二醇二缩水甘油醚、甘油的多缩水甘油醚、1,2,6-己三醇的多缩水甘油醚、三羟甲基丙烷的多缩水甘油醚、三羟甲基乙烷的多缩水甘油醚、季戊四醇的多缩水甘油醚、山梨糖醇的多缩水甘油醚、烷氧基化多元醇(例如甘油、三羟甲基丙烷、季戊四醇等)的多缩水甘油醚、环己烷二甲醇的二缩水甘油醚、双-(4-羟基环己基)甲烷的二缩水甘油醚和2,2-双-(4-羟基环己基) 丙烷的二缩水甘油醚、蓖麻油的多缩水甘油醚、三-(2-羟基-乙基)异氰脲酸三缩水甘油酯。
此外可考虑优选作为组分A) 的是:聚-(N-缩水甘油基)化合物,其可通过表氯醇和胺的反应产物的脱卤化氢来获得,所述胺如苯胺、正丁基胺、双-(4-氨基苯基)甲烷、间-苯二甲胺或双-(4-甲基氨基苯基)甲烷。但是,聚-(N-缩水甘油基)化合物也包括异氰脲酸三缩水甘油酯、三缩水甘油基尿唑及其低聚物、环亚烷基脲的N,N’-二缩水甘油基衍生物和乙内酰脲的二缩水甘油基衍生物。
此外,也可以优选使用多羧酸的多缩水甘油酯,其通过表氯醇或类似的环氧化合物与脂族、脂环族或芳族多羧酸如草酸、琥珀酸、己二酸、戊二酸、邻苯二甲酸、对苯二甲酸、四氢邻苯二甲酸、六氢邻苯二甲酸、2,6-萘二甲酸和更高级的二羧酸二缩水甘油酯,例如二聚或三聚的亚麻酸的反应来获得。实例是己二酸二缩水甘油酯、邻苯二甲酸二缩水甘油酯和六氢邻苯二甲酸二缩水甘油酯。
此外可优选提及不饱和羧酸的缩水甘油酯和不饱和醇或不饱和羧酸的环氧化酯。除了多缩水甘油醚外,可以以基于多缩水甘油醚的质量计最多30重量%,优选10至20重量%的质量比例一起使用少量的单环氧化物例如甲基缩水甘油醚,丁基缩水甘油醚,烯丙基缩水甘油醚,乙基己基缩水甘油醚,长链脂族缩水甘油醚,例如鲸蜡基缩水甘油醚和硬脂基缩水甘油醚,更高级的异构的醇混合物的单缩水甘油醚,C12至C13醇的混合物的缩水甘油醚,苯基缩水甘油醚,甲苯基缩水甘油醚,对叔丁基苯基缩水甘油醚,对辛基苯基缩水甘油醚,对苯基-苯基缩水甘油醚,烷氧基化(oxalkylierten)月桂醇的缩水甘油醚以及单环氧化物例如环氧化单不饱和烃(氧化丁烯、-环己烯、-苯乙烯)。
合适的环氧化合物的详细列举可以在A. M. Paquin的手册"Epoxidverbindungenund Epoxidharze",Springer Verlag,Berlin,1958,第IV章中和在Lee Neville "Handbook of Epoxy Resins",1967,第2章中找到。
在此可以优选考虑缩水甘油醚和缩水甘油酯、脂族环氧化物、基于双酚A和/或双酚F的二缩水甘油醚和甲基丙烯酸缩水甘油酯作为环氧化合物。这种环氧化物的实例还有异氰脲酸三缩水甘油酯(TGIC,商品名ARALDIT 810,Huntsman)、对苯二甲酸二缩水甘油酯和偏苯三酸三缩水甘油酯的混合物(商品名ARALDIT PT 910和912,Huntsman)、叔碳酸(Versaticsäure)的缩水甘油酯(商品名CARDURA E10,Shell)、3',4'-环氧环己烷甲酸-3,4-环氧环己基甲酯(ECC)、乙基己基缩水甘油醚、丁基缩水甘油醚、季戊四醇四缩水甘油醚(商品名POLYPOX R 16,UPPC AG)以及具有游离环氧基团的其它Polypox类型。
也可以使用所提及的环氧化合物的混合物。
特别优选的环氧树脂是基于双酚A-二缩水甘油醚、双酚F-二缩水甘油醚、4,4'-亚甲基-双[N,N-双(2,3-环氧丙基)苯胺]、己二醇二缩水甘油醚、丁二醇二缩水甘油醚、三羟甲基丙烷三缩水甘油醚、1,2,3-丙三醇三缩水甘油醚、季戊四醇四缩水甘油醚和六氢邻苯二甲酸二缩水甘油酯的多环氧化物。
优选使用上述环氧化合物的混合物作为组分A)。
作为具有至少两个仲氨基(它们两个是有机环体系的组成部分)的胺b),原则上可以考虑具有至少两个仲环氨基的所有化合物。此外,胺b)还可以具有其它的伯或非环仲氨基作为NH载体。然而,在根据本发明的组合物中使用的胺优选不具有其它的伯或非环仲氨基,即它们仅具有至少两个是有机环体系的组成部分的仲氨基。然而此外,根据本发明使用的胺当然还可以具有非反应性的叔氨基。
“有机环体系”应理解为意指可具有一个、两个或至少三个(任选地与不含氮的杂环或非杂环稠合的)含氮杂环的杂环体系。在此,有机环体系也可以在含氮的环中具有不同于氮的其它杂原子,特别是氧、硫和/或磷。在此,“一个”含氮的环在本文中被理解为意指含氮的单环或与不含氮的杂环、环烷烃、环烯烃或芳烃共用环键的含氮的单环(即含氮的环,在其上任选稠合不含氮的杂环、环烷烃、环烯烃或芳烃)。
具有至少两个仲氨基的胺也可以是也相应的具有仲环氨基和任选其它的伯或非环仲氨基的化合物与对NH基团呈反应性的基团,尤其单和多环氧化物(加合物)、多异氰酸酯、聚碳二亚胺、酚(与醛和酮的曼尼希反应)和取代的酚(曼尼希碱的交换)、聚酯、多羧酸、聚丙烯酸酯和聚甲基丙烯酸酯的反应产物。
在一个优选的实施方案中,胺b)是具有至少两个仲环氨基的胺,所述仲环氨基中至少两个属于不同的环。特别优选地,胺b)是在两个至四个不同的环上具有两个至四个仲环氨基的胺。相应的具有至少两个不同环的胺优选也应理解为意指由至少两个单杂环构成的稠合杂环。
非常特别优选地,所述至少两个仲环氨基属于同一环。
还更优选的胺b)具有式(I)
其中
- 其中R1至R4表示H或有机基团,且
- X = –(Y1)m-(A1)n-(Y2)o-(A2)p-(Y3)q-(A3)r-(Y4)s, (II)
其中彼此独立地
◦ m、n、o、p、q、r和s = 0或1,
◦ A1、A2、A3 = 亚烷基或亚烯基,且
◦ Y1、Y2、Y3、Y4 = NR5、PR5、O或S,其中R5彼此独立地= H或有机基团,
◦ 其中选自R1至R5和任选存在的亚烷基和/或亚烯基A1、A2、A3的基团中的各两个有机基团也可以形成一个或多个其它环,
- 条件是,选自Y1、Y2、Y3、Y4中的至少一个存在的基团是NR5,其中R5 = H。
关于在式(I)中所示的环,该环状胺是饱和或部分不饱和的。相应的胺比不包括在该式下的芳族胺和咪唑啉更快地反应。在环状胺中任选存在的其它环不仅可以是饱和或不饱和的,而且还可以是芳族的。优选地,在环状体系中任选存在的其它环是非芳族的,即饱和或不饱和的。
关于在式(I)中所示的环,优选的环状胺是饱和的。
优选地,与环上的氨基相邻的碳原子中的至少一个= H,即基团R1、R2、R3和R4中的至少一个= H。更优选地,基团R1、R2、R3和R4中的至少两个= H。优选的是至少三个,特别优选所有基团R1、R2、R3和R4 = H。相应地,未取代的胺比其它胺更快地反应。
在基团X中,如果存在,A1、A2和A3彼此独立地是亚烷基或亚烯基。它们又可以带有有机基团。如果亚烷基和/或亚烯基本身具有一个或多个有机基团,则选自亚烷基和/或亚烯基的有机基团的各两个有机基团也可以相互或与任选存在的有机基团R1至R5形成一个或多个其它环。
选自R1至R5和任选存在的亚烷基和/或亚烯基A1、A2、A3的基团中的存在的基团可以被至少一个基团–NHR6或–NH2取代,其中R6 =有机基团。即,在式(I)中,除了至少两个环氨基之外,也还可以存在其它伯或非环仲氨基。
优选地,如果存在,A1、A2和A3各自彼此独立地具有式(III),
-(CR7R8)x-(CR9=CR10)y-(CR11R12)z- (III)
其中彼此独立地
- R7、R8、R9、R10、R11和R12 = H或有机基团,且
- 1 ≤ x + y + z ≤ 7。
指数x、y和z可以相应于它们所属的基团A1、A2和A3优选也被称为指数x1、y1和z1,x2、y2和z2和x3、y3和z3。
优选地,X具有2至15个原子的链长。因此,优选地,所有x、½•y和z以及m、o、q和s的总和是2至15的值,更优选2至8的值,还更优选2至5的值,并且非常特别优选2至4的值。换句话说,优选的是2 ≤ m + o + q + s + x1 + ½•y1 + z1 + x2 + ½•y2 + z2 + x3 + ½•y3 +z3 ≤ 15。更优选的是2 ≤ m + o + q + s + x1 + ½•y1 + z1 + x2 + ½•y2 + z2 + x3 +½•y3 + z3 ≤ 8,更优选2 ≤ m + o + q + s + x1 + ½•y1 + z1 + x2 + ½•y2 + z2 + x3 +½•y3 + z3 ≤ 5,非常特别优选2 ≤ m + o + q + s + x1 + ½•y1 + z1 + x2 + ½•y2 + z2+ x3 + ½•y3 + z3 ≤ 4。
式(I)的胺是(任选双-/多)环状化合物,因为与氨基相邻的两个碳原子在两侧与式(II)的取代的(杂)亚烷基连接。
更优选地,式(I)除了环上的NH基团的氮原子而外在环中具有最多一个另外的杂原子,即X优选具有式(IIa)
X = –(CR7R8)x-(Y)o-(CR11R12)z– (IIa)
其中
- x和z = 0、1、2、3、4、5、6或7,
- o = 0,
- 2 ≤ x + o + z ≤ 15
- R7、R8、R11、R12 = H或有机基团,且
- Y = NH。
非常特别优选地,在式(IIa)中x = z = 1。
此时相应适用的是,在式(I)中选自R1至R8、R11和R12的各两个有机基团也可以形成一个或多个其它环。
基团R1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11和R12可以是有机基团。优选的有机基团是烷基、烯基、炔基、芳基或芳烷基。它们可以在其链内是杂原子取代的和/或带有取代基。优选的有机基团是烷基、烯基、炔基、芳基或芳烷基,其在链内可以带有一个或多个醚基、羧基、氨基、酰氨基、脲基、氨基甲酸酯基、碳酸酯基、脒基或胍基。此外, 优选的有机基团可以带有一个或多个选自有机基团的取代基,任选具有醚基、羧基、氨基、酰氨基、脲基、氨基甲酸酯基、碳酸酯基、脒基或胍基,其任选地也可以被羟基、腈基或卤素基团取代或本身是羟基、腈基或卤素基团。
特别优选的胺b)选自3,7-二氮杂双环[4.3.0]壬烷、2,8-二氮杂双环[4.3.0]壬烷、2-苯基-2-咪唑啉、3,8-二氮杂双环[3.2.1]辛烷、2,2'-二联咪唑烷、1H-八氢-咪唑并[4,5-c]吡啶、1,4,8-三氮杂螺[4.5]癸烷、1,4-二氮杂螺[4.5]癸烷、吡唑烷、2,2-二甲基咪唑烷、1,4,7-三氮杂环壬烷、十氢-2,6-二甲基吡嗪并[2,3-b]吡嗪、六氢哒嗪、十氢-4a,8a-二甲基吡嗪并[2,3-b]吡嗪、4,4'-亚甲基双[哌啶]、2,2'-亚甲基双[哌啶]、十四氢-4,7-菲咯啉、2,2'-二联哌啶、4,4'-二联哌啶、十四氢吩嗪、十氢喹喔啉、1,5-十氢二氮杂萘、八氢-1H-环戊并吡嗪、2,2'-二联吡咯烷、哌嗪、2-甲基哌嗪、2,2-二甲基哌嗪、2,3-二甲基哌嗪、2-乙基哌嗪、2,5-二甲基哌嗪、2,6-二甲基哌嗪、2,6-二氮杂双环[3.3.0]辛烷、3,7-二氮杂双环[3.3.0]辛烷、2,3,5,6-四甲基哌嗪、2,3,5-三甲基哌嗪、2,2'-二联哌啶、2-(2-哌啶基)-哌嗪、2,2'-二联吗啉、十氢-2,6-二氮杂萘、十氢-2,7-二氮杂萘、高哌嗪、2-甲基高哌嗪、6-甲基-1,4-二氮杂环庚烷、双[2-(哌嗪-1-基)乙基]胺和1,2-二哌嗪基乙烷。
式(I)的化合物也可以以混合物形式来使用。
根据本发明的组合物此外包含至少一种极强布朗斯台德酸的盐,其具有选自金属离子、含金属的离子、鏻离子和铵离子的反荷离子。相应的盐用作催化剂。在此,应将这种极强酸理解为是指其pKa值(或在多质子酸的情况下,其第一质子转移阶段的pKa值)小于或等于-9.01的酸。优选地,所述极强酸的pKa值为-9.5至-25,特别优选-9.9至-21。
pKa被定义为平衡常数Ka的负十进制对数,并且被认为是酸的强度的量度。pKa值越小,酸就越强。pKa值如F.G. Bordwell, “Equilibrium Acidities inDimethylsulfoxide Solution“, Acc. Chem. Res. 1988, 21, 456-463中公开的那样来确定。
优选的盐是在下表1中在第一栏中总结的极强酸的相应盐:
表1:
酸 | pKa值 | 文献位置,如果没有在Bordwell中公开 |
高氯酸 | -10 | 1 |
三氟甲磺酸 | -14 | |
碘化氢 | -9.5 | 2 |
六氟磷酸 | -10 | 3 |
六氟锑酸 | -17 | 3 |
1)Hollemann Wiberg, Lehrbuch der anorganischen Chemie, 第91-100版, Walterder Gruyter Verlag, Berlin, New York, 1985, 第428页。
2)Journal of Physical Chemistry A, Volume 120, Issue 20, 第3663-3669页。
3)http://www.periodensystem-online.de/index.phpsel=wertdesc&prop=pKs-Werte&show=list&id=acid。
这些极强酸的反荷离子选自金属离子、含金属的离子、鏻离子和铵离子。优选的金属离子是碱土金属阳离子,特别是铍-、镁-、钙-、锶-和钡-离子,以及锂-、铝-、铋-、锌-和铕离子。
含金属的离子是含有至少一种金属但不是纯金属离子的离子。它们优选是金属化合物离子,例如四苯基锑离子。
所述反荷离子也可以是铵离子(NH4 +)或任选烷基化和/或芳基化的鏻离子。非常特别优选的是铵离子。
优选的极强酸的盐是三氟甲磺酸钙、三氟甲磺酸铕、三氟甲磺酸钡、三氟甲磺酸铝、三氟甲磺酸铋、三氟甲磺酸锂、高氯酸锂、高氯酸钡、六氟磷酸锂和高氯酸锌。 非常特别优选的是三氟甲磺酸钙、三氟甲磺酸铕、六氟磷酸锂和高氯酸锂。
优选的是在有机介质(例如苄醇)中良好溶解的盐,即在20℃下在苄醇中溶解度为至少10 g/l的盐。
优选地,根据本发明的组合物此外可以具有d)不具有作为有机环体系的组成部分的至少两个仲氨基的胺和/或e)其它助剂或添加剂。
这样的胺d)优选是二胺或多胺。它们可以是单体的、低聚的和/或聚合的化合物。优选的单体的和低聚的化合物选自二胺、三胺和四胺。二胺或多胺d)的胺基可以与伯、仲或叔碳原子连接,优选与伯或仲碳原子连接。也可以使用二胺和/或多胺的混合物作为组分d)。
作为组分d),优选可以单独或以混合物形式使用下列胺:
• 脂族胺,特别是多亚烷基多胺,其优选选自1,2-乙二胺、1,2-丙二胺、1,3-丙二胺、1,2-丁二胺、1,3-丁二胺、1,4-丁二胺、2-(乙基氨基)乙胺、3-(甲基氨基)丙胺、二亚乙基三胺、三亚乙基四胺、五亚乙基六胺、三甲基六亚甲基二胺、2,2,4-三甲基六亚甲基二胺、2,4,4-三甲基六亚甲基二胺、2-甲基-戊二胺、六亚甲基二胺、N-(2-氨基乙基)-1,2-乙二胺、N-(3-氨基丙基)-1,3-丙二胺、N,N"-1,2-乙二基双-(1,3-丙二胺)、二亚丙基三胺、己二酸二酰肼和肼;
• 氧化烯多胺,其优选选自聚氧亚丙基二胺和聚氧亚丙基三胺(例如Jeffamine® D-230、Jeffamine® D-400、Jeffamine® T-403、Jeffamine® T-5000)、1,13-二氨基-4,7,10-三氧杂十三烷、4,7-二氧杂癸烷-1,10-二胺;
• 脂环族胺,其优选选自异佛尔酮二胺(3,5,5-三甲基-3-氨基甲基-环己胺),单独或以异构体混合物形式的4,4'-二氨基二环己基甲烷、2,4'-二氨基二环己基甲烷和2,2'-二氨基二环己基甲烷,3,3'-二甲基-4,4'-二氨基-二环己基甲烷、N-环己基-1.3-丙二胺、1,2-二氨基环己烷、3-(环己基氨基)丙胺、TCD-二胺(3(4), 8(9)-双(氨基甲基)三环[5.2.1.02,6]癸烷)、4-甲基环己烷-1,3-二胺,
• 具有环氨基和至少一个非环伯或仲氨基的胺,优选1-(3-氨基乙基)哌嗪(AEP)、1-(3-氨基丙基)哌嗪;
• 芳脂族胺,优选苯二甲胺;
• 芳族胺,优选苯二胺,特别是1,3-苯二胺和1,4-苯二胺,和任选地单独或以异构体混合物形式的4,4'-二氨基二苯基甲烷、2,4'-二氨基二苯基甲烷、2,2'-二氨基二苯基甲烷;
•加成固化剂,特别是环氧化合物,特别是双酚A和F的缩水甘油醚与过量胺的反应产物;
• 聚酰胺基胺固化剂,特别是通过单-和多羧酸与多胺的缩合获得的聚酰胺基胺固化剂,非常特别是通过二聚脂肪酸与多亚烷基多胺的缩合;
• 曼尼希碱固化剂,特别是通过一元或多元酚与醛,特别是甲醛,和多胺的反应,曼尼希碱固化剂;和
• 曼尼希碱,特别是基于苯酚和/或间苯二酚,甲醛和间苯二甲胺以及N-氨基乙基哌嗪和下述的共混物:N-氨基乙基哌嗪与壬基苯酚和/或苄醇,腰果壳油酚醛胺(Phenalkamine),其由腰果酚、醛和胺在曼尼希反应中获得。
也可以使用上述二胺或多胺的混合物作为组分d)。
优选的其它助剂和添加剂e)可以是环氧化学中常用的化合物。优选的助剂和添加剂e)是颜料、溶剂、流平剂、改性剂,例如苄醇或壬基苯酚,脱气剂、消光剂、反应性稀释剂,以及常规催化剂,如水杨酸。
在一个优选的实施方案中,不使用胺d)。在一个优选的实施方案中,不使用其它常规催化剂,即可能的助剂和添加剂限于颜料、溶剂、流平剂、改性剂、脱气剂、消光剂和反应性稀释剂。
在根据本发明的组合物中的组分a)至e)的组成优选为下列重量百分比例,基于组合物的总质量计:
a) 环氧树脂 30 – 95 %
b) 环状胺 1 – 50 %
c) 极强布朗斯台德酸的盐 0.001 – 5 %,
优选0.1 – 3 %,
d) 其它胺 0 – 48 %和
e) 其它助剂或添加剂0 – 48 %。
此外优选地,胺b)的重量百分比例基于胺b)和d)的总质量计为至少10重量%,特别优选至少30%,非常特别优选至少50%,还更优选至少70%。
此外,本发明的主题是制备根据本发明的组合物的方法,其中将至少一种环氧树脂a)、至少一种环状胺b)和至少一种极强酸的盐c)相互混合。
此外,本发明的主题是根据本发明的组合物作为浇铸树脂、涂料物料、复合材料或胶粘剂或作为它们的组成部分的用途。
实验部分:
实施例1)
为了证明所要求保护的催化剂的特别的反应性,首先将模型实验相互比较。为此,各自将0.025摩尔(3.75g)1,2-环氧-3-苯氧基丙烷加入到22.68g甲苯(溶剂)和2.08g 十四烷(内标)的混合物中。此外,加入0.025摩尔(2.13g)的哌啶和0.06g各自的催化剂。在混合之后立即进行GC并且将1,2-环氧-3-苯氧基丙烷的含量与十四烷的含量比较。在室温下4小时后,借助于GC检测测定1,2-环氧-3-苯氧基丙烷(EP)的残余含量(通过内标十四烷校准)。由此产生以下结果:
催化剂的比较
催化剂 | 0-样品中的% EP | 在室温下4小时后的% EP | |
1* | 无催化剂 | 97 | 93 |
2* | 二月桂酸二丁基锡 | 99 | 93 |
3* | 二氮杂双环壬烷 (DBN) | 97 | 95 |
4* | 二氮杂双环十一烷 (DBU) | 96 | 93 |
5* | 二氮杂双环辛烷 (DABCO) | 94 | 93 |
6* | 乙酰丙酮锌 | 94 | 90 |
7* | 三溴化四丁基铵 | 91 | 87 |
8* | 新癸酸铋 | 91 | 88 |
9* | 四丁醇钛 | 95 | 94 |
10* | 水杨酸 | 93 | 90 |
11* | 苯酚 | 97 | 85 |
12 | 三氟甲磺酸钙 | 90 | 0 |
13 | 三氟甲磺酸铋 | 90 | 57 |
14 | 三氟甲磺酸钠 | 96 | 52 |
15 | 三氟甲磺酸铕 | 85 | 16 |
16 | 三氟甲磺酸钡 | 96 | 37 |
17 | 三氟甲磺酸铝 | 98 | 53 |
18 | 三氟甲磺酸锂 | 90 | 28 |
19 | 高氯酸锂 | 73 | 9 |
20 | 高氯酸钡 | 85 | 26 |
21 | 高氯酸锌 | 96 | 46 |
22 | 六氟磷酸铵 | 86 | 43 |
23 | 高氯酸钙 | 98 | 49 |
24 | 碘化钐 | 98 | 37 |
25 | 六氟磷酸钾 | 97 | 36 |
26 | 六氟磷酸锂 | 78 | 9 |
27 | 三氟甲磺酸锌 | 98 | 44 |
28 | 三氟甲磺酸铜 | 93 | 48 |
29 | 三氟甲磺酸钐 | 84 | 32 |
30 | 三氟甲磺酸镁 | 94 | 41 |
31 | 三氟甲磺酸铟 | 89 | 39 |
32 | 三氟甲磺酸镍 | 100 | 56 |
33 | 三氟甲磺酸铁 | 93 | 39 |
34 | 三氟甲磺酸锰 | 93 | 44 |
35 | 三氟甲磺酸锡 | 96 | 42 |
36 | 三氟甲磺酸铽 | 90 | 41 |
37 | 高氯酸镉 | 98 | 64 |
38 | 高氯酸铁 | 97 | 52 |
39 | 高氯酸锰 | 98 | 59 |
40 | 高氯酸铟 | 99 | 59 |
* 非根据本发明的对比实验。
实施例2)
为了证明所要求保护的胺的特别的反应性,首先将模型实验相互比较。为此,各自将0.025摩尔(3.75g)1,2-环氧-3-苯氧基丙烷加入到22.68g甲苯(溶剂)和2.08g 十四烷(内标)的混合物中。此外,加入0.025NH当量的胺和0.06g三氟甲磺酸钙。在混合之后立即进行GC并且将1,2-环氧-3-苯氧基丙烷的含量与十四烷的含量比较。在室温下4小时后,借助于GC检测测定1,2-环氧-3-苯氧基丙烷(EP)的残余含量(通过内标十四烷校准)。由此产生以下结果:
胺 | 0-样品中的% EP | 在室温下4小时后的% EP | 在5℃下4小时后的% EP | |
1* | 丁胺 | 92 | 52 | 73 |
2* | 甲基丙基胺 | 92 | 46 | 91 |
3* | 乙醇胺 | 91 | 63 | 80 |
4 | 哌啶 | 93 | 0 | 32 |
* 非根据本发明的对比实验。
从模型实验可以清楚地看出,所要求保护的组合物比常规体系显著更具反应性。
实施例3a)*
将100份高哌嗪(Aldrich)与66份苄醇和380份Epikote 828(环氧当量190,Hexion)紧密混合,并然后立即进行DSC。
实施例3b)
在100份高哌嗪(Aldrich)和66份苄醇中溶解0.5份三氟甲磺酸钙(Aldrich),并将该混合物与380份Epikote 828(环氧当量190,Hexion)紧密混合,并且然后立即进行DSC。
实施例3c)*
在100份异佛尔酮二胺(Evonik Industries)和66份苄醇中溶解0.5份硝酸钙(Aldrich),并将该混合物与445份Epikote 828(环氧当量190,Hexion)紧密混合,并且然后立即进行DSC。
* 非根据本发明的对比实验。
在根据本发明的实验中,放热峰以及该放热峰值的开始均较低。因此,根据本发明的反应性组合物比没有催化剂或没有具有两个环NH基团的胺更具反应性。
Claims (16)
1.组合物,其包含
a) 至少一种环氧树脂,
b) 至少一种具有至少两个仲氨基的胺,这两个仲氨基是有机环体系的组成部分,和
c) 至少一种极强布朗斯台德酸的盐,其具有选自金属离子、含金属的离子、鏻离子和铵离子的反荷离子。
2.根据权利要求1的组合物,
其特征在于,
所述至少一种环氧树脂是基于双酚A-二缩水甘油醚、双酚F-二缩水甘油醚、4,4'-亚甲基-双[N,N-双(2,3-环氧丙基)苯胺]、己二醇二缩水甘油醚、丁二醇二缩水甘油醚、三羟甲基丙烷三缩水甘油醚、1,2,3-丙三醇三缩水甘油醚、季戊四醇四缩水甘油醚和六氢邻苯二甲酸二缩水甘油酯的多环氧化物。
3.根据权利要求1或2的组合物,
其特征在于,
仲环氨基中的至少两个属于不同的环。
4.根据权利要求1或2的组合物,
其特征在于,
所有仲环氨基属于同一环。
5.根据权利要求4的组合物,
其特征在于,
所述胺具有式(I)
其中
- 其中R1至R4表示H或有机基团,且
- X = –(Y1)m-(A1)n-(Y2)o-(A2)p-(Y3)q-(A3)r-(Y4)s (II)
其中彼此独立地
◦ m、n、o、p、q、r和s = 0或1,
◦ A1、A2、A3 = 亚烷基或亚烯基,且
◦ Y1、Y2、Y3、Y4 = NR5、PR5、O或S,其中R5彼此独立地= H或有机基团,
◦ 其中选自R1至R5和任选存在的亚烷基和/或亚烯基A1、A2、A3的基团中的各两个有机基团也可以形成一个或多个其它环,
- 条件是,选自Y1、Y2、Y3、Y4中的至少一个存在的基团是NR5,其中R5 = H。
6.根据权利要求5的组合物,
其特征在于,
A1、A2和A3彼此独立地具有式(III)
-(CR7R8)x-(CR9=CR10)y-(CR11R12)z- (III)
其中彼此独立地
- R7、R8、R9、R10、R11和R12 = H或有机基团,且
- 1 ≤ x + y + z ≤ 7。
7.根据权利要求5或6的组合物,
其特征在于,
式(II)中的X具有2至15个原子的链长。
8.根据权利要求5至7任一项的组合物,
其特征在于,
X具有式(IIa)
X = –(CR7R8)x-(Y)o-(CR11R12)z– (IIa)
其中
- x和z = 0、1、2、3、4、5、6或7,
- o = 1,
- 2 ≤ x + o + z ≤ 15
- R7、R8、R11、R12 = H或有机基团,且
- Y = NH。
9.根据前述权利要求任一项的组合物,
其特征在于,
胺b)选自3,7-二氮杂双环[4.3.0]壬烷、2,8-二氮杂双环[4.3.0]壬烷、2-苯基-2-咪唑啉、3,8-二氮杂双环[3.2.1]辛烷、2,2'-二联咪唑烷、1H-八氢-咪唑并[4,5-c]吡啶、1,4,8-三氮杂螺[4.5]癸烷、1,4-二氮杂螺[4.5]癸烷、吡唑烷、2,2-二甲基咪唑烷、1,4,7-三氮杂环壬烷、十氢-2,6-二甲基吡嗪并[2,3-b]吡嗪、六氢哒嗪、十氢-4a,8a-二甲基吡嗪并[2,3-b]吡嗪、4,4'-亚甲基双[哌啶]、2,2'-亚甲基双[哌啶]、十四氢-4,7-菲咯啉、2,2'-二联哌啶、4,4'-二联哌啶、十四氢吩嗪、十氢喹喔啉、1,5-十氢二氮杂萘、八氢-1H-环戊并吡嗪、2,2'-二联吡咯烷、哌嗪、2-甲基哌嗪、2,2-二甲基哌嗪、2,3-二甲基哌嗪、2-乙基哌嗪、2,5-二甲基哌嗪、2,6-二甲基哌嗪、2,6-二氮杂双环[3.3.0]辛烷、3,7-二氮杂双环[3.3.0]辛烷、2,3,5,6-四甲基哌嗪、2,3,5-三甲基哌嗪、2,2'-二联哌啶、2-(2-哌啶基)-哌嗪、2,2'-二联吗啉、十氢-2,6-二氮杂萘、十氢-2,7-二氮杂萘、高哌嗪、2-甲基高哌嗪、6-甲基-1,4-二氮杂环庚烷、双[2-(哌嗪-1-基)乙基]胺和1,2-二哌嗪基乙烷。
10.根据前述权利要求任一项的组合物,
其特征在于,
所述极强布朗斯台德酸的盐是碱土金属盐、锂盐、铝盐、铋盐、锌盐、铕盐、四苯基锑盐、鏻盐或铵盐。
11.根据前述权利要求任一项的组合物,
其特征在于,其此外具有
d) 胺,其不具有作为有机环体系的组成部分的至少两个仲氨基,和/或
e) 其它助剂或添加剂。
12.根据权利要求11的组合物,
其特征在于,
胺d)选自
- 脂族胺,
- 氧化烯多胺,
- 脂环族胺,
- 具有环氨基和至少一个非环伯或仲氨基的胺,
- 芳脂族胺,
- 芳族胺,
- 加成固化剂,
- 聚酰胺基胺固化剂
- 曼尼希碱固化剂,和
- 曼尼希碱。
13.根据前述权利要求任一项的组合物,
其特征在于,
所述组合物以下列重量百分比例具有组分a)至e),基于所述组合物的总质量计:
a) 环氧树脂30 – 95 %
b) 环状胺1 – 50 %
c) 极强酸的盐0.001 – 5 %
d) 其它胺0 – 48 %,和
e) 其它助剂或添加剂0 – 48 %。
14.根据权利要求11-13任一项的组合物,
其特征在于,
胺b)的重量百分比例为至少10重量%,基于胺b)和d)的总质量计。
15.制备根据前述权利要求1-14任一项的组合物的方法,
其特征在于,
将至少一种环氧树脂 a)、至少一种环状胺 b)和至少一种极强布朗斯台德酸的盐c)相互混合。
16.根据权利要求1-14任一项的组合物作为浇注树脂、涂料物料、复合材料或胶粘剂或作为它们的组成部分的用途。
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- 2019-05-16 KR KR1020190057278A patent/KR20190132250A/ko not_active Application Discontinuation
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Also Published As
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US20190352452A1 (en) | 2019-11-21 |
US11370877B2 (en) | 2022-06-28 |
EP3569630B1 (de) | 2022-08-03 |
JP2019199611A (ja) | 2019-11-21 |
EP3569630A1 (de) | 2019-11-20 |
KR20190132250A (ko) | 2019-11-27 |
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