CN112778500A - 得自亚甲基桥连的多(环己基-芳族)胺的酚醛胺环氧固化剂和含有其的环氧树脂组合物 - Google Patents
得自亚甲基桥连的多(环己基-芳族)胺的酚醛胺环氧固化剂和含有其的环氧树脂组合物 Download PDFInfo
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- CN112778500A CN112778500A CN202011230099.6A CN202011230099A CN112778500A CN 112778500 A CN112778500 A CN 112778500A CN 202011230099 A CN202011230099 A CN 202011230099A CN 112778500 A CN112778500 A CN 112778500A
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- phenalkamine
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- aromatic
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Classifications
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- C08G59/621—Phenols
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C215/00—Compounds containing amino and hydroxy groups bound to the same carbon skeleton
- C07C215/46—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups bound to carbon atoms of at least one six-membered aromatic ring and amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings of the same carbon skeleton
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- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B26/00—Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
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- C04B26/10—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G59/5026—Amines cycloaliphatic
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/56—Amines together with other curing agents
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract
本发明涉及一种新结构类型的酚醛胺、酚醛胺固化剂组合物、制备这样的酚醛胺的方法和制备这样的组合物的方法。本发明的酚醛胺固化剂组合物可通过使腰果酚与醛化合物和亚甲基桥连的多(脂环族‑芳族)胺混合物反应制备。这些固化剂组合物可用于固化、硬化和/或交联环氧树脂。
Description
背景技术
曼尼希反应基于醛如甲醛、酚类化合物和胺的反应。在这一反应中使用各种形式的酚类化合物、胺和醛。曼尼希碱产物特别适用于固化环氧树脂。
酚醛胺(phenalkamine)固化剂是通过使腰果酚(腰果壳液的酚类提取物)、醛化合物如甲醛和胺反应获得的一类曼尼希碱。通常,它们由1摩尔当量的腰果酚与1至2摩尔当量的脂族多亚乙基多胺和1至2摩尔当量的甲醛在80-100℃下反应制成。芳族多胺也适用于这一反应。
可获自Cardolite Inc.的市售酚醛胺NC 541和NC 540和可获自Evonik Corp.的Sunmide CX105使用乙二胺和二亚乙基三胺作为胺来源。可获自Evonik Corp.的Sunmide1151酚醛胺使用间二甲苯二胺作为胺原材料。
酚醛胺是用于室温或低温固化应用的良好环氧树脂硬化剂。此外,它们提供良好的耐化学性、优异的耐水性、良好的与环氧树脂的相容性、低毒性和良好的柔性。因此,它们用于海洋、工业维修和土木工程应用。
英国专利1,529,740描述了作为由腰果酚与多亚乙基多胺和甲醛制成的多(氨基亚烷基)取代酚(下示结构)的混合物的酚醛胺。一般而言,不可能容易地控制这些产物的分子量分布,因此它们大多是粘性液体。
R=具有15个碳原子的烃基取代基
x=1-5,n=1-3,R’=H。
美国专利6,262,148 B1描述了带有芳族或脂环族环的酚醛胺的组合物。这些组合物由腰果酚与醛和脂环族或芳族多胺制备。国际申请公开WO 2009/080209 A1描述了包含与多胺盐掺混的酚醛胺的环氧固化剂的制备。这些固化剂用于增强环氧树脂的固化速率。
发明内容
发明概述
本发明涉及采用亚甲基桥连的多(脂环族-芳族)胺(有时被称为“MPCA”)的混合物作为胺源获得的酚醛胺。因此,本公开揭示了一种新的结构类型的酚醛胺、固化剂组合物、制造这样的酚醛胺的方法和制造这样的组合物的方法。这些固化剂组合物可用于固化、硬化和/或交联环氧树脂。此外,这些本发明的酚醛胺固化剂可提供环氧涂料在环境温度(23℃)下在<8h内或在5℃下在<16h内的干固化并提供如由增强的低温表面外观和耐化学性的改进所表明的改进的涂层性能。这种性能组合允许进一步利用基于MPCA的酚醛胺作为低温罐衬里的固化剂,在低温罐衬里中需要改进的耐化学性以运输和储存油气行业中的化学品。
本发明的MPCA基酚醛胺与现有技术的酚醛胺相比具有提供更快的胺-环氧反应速率的优点。这种独特的性质提供了与衍生自亚烷基胺,如乙二胺的传统酚醛胺产品相比更低的氨基甲酸酯化倾向和更短的涂层干燥时间的优点。此外,基于本发明的MPCA酚醛胺固化剂的涂料组合物对一系列化学试剂,包括醇(乙醇、甲醇)、二甲苯、酮(甲基异丁基酮)、苛性钠和硫酸表现出非常好的耐化学性,并在这一方面优于由衍生自乙二胺的酚醛胺制成的涂料。
在MPCA混合物的制备中,使苯胺或甲苯胺与含有显著量低聚物的甲醛的缩合产物进行催化氢化法。通过蒸馏分离挥发性更高的氢化和部分氢化的产物并由此获得原始混合物的较重组分(MPCA)或塔底物。MPCA由下面的化学结构表示:
本发明涉及通过使腰果酚(根据下式III的结构)与MPCA(根据下式II的结构)和醛反应获得的酚醛胺混合物,从而获得由根据下式IV的结构表示的组合物。尽管式IV显示了醛和腰果酚与MPCA的一个氨基的组成,但MPCA的其它氨基有可能以类似方式反应以生成胺取代产物的混合物。
其中n=0、2、4或6;R互相独立地选自H和CH3;
互相独立地选自环己基和苯基;A互相独立地选自CH2和NH;B互相独立地选自H、OH和NH2;R’=H、C1-C10烷基、Ph、C5-C6脂环族基团或C5-C10芳族基团;y=0-1;z=0-1;且y和z之和为0至2。优选地,R’=H或C1烷基。
本公开还提供了包含式(IV)的酚醛胺混合物的固化剂组合物。
本公开的优选固化剂组合物具有大约50至大约500的基于100%固含量计的胺氢当量(AHEW)。本公开在另一个方面中提供了胺-环氧组合物和由其制成的经固化产物。例如,根据本公开的胺-环氧组合物包含含有新型酚醛胺组合物的固化剂组合物和含有至少一种多官能环氧树脂的环氧组合物,所述新型酚醛胺组合物包含至少一个腰果酚基团并具有至少两个活性胺氢原子。
本公开还提供了包含式(IV)的酚醛胺混合物的固化剂组合物作为环氧树脂硬化剂的用途。
由本文中公开的胺-环氧组合物制成的制品包括但不限于胶粘剂、涂料、底漆、密封剂、固化配混物、建筑产品、铺地产品和复合材料产品。此外,这样的涂料、底漆、密封剂或固化配混物可施加到金属或水泥基基底上。固化剂和环氧树脂的混合物经常不需要“熟化时间”以获得具有高光泽度和澄清度的接触产物。熟化时间或培养时间被定义为在环氧树脂与胺混合和将产物施加到目标基底上之间的时间。其也可被定义为使混合物变澄清所需的时间。
发明详述
本发明的新型酚醛胺混合物可通过使腰果酚与醛化合物和MPCA反应以产生由根据下式(IV)的结构表示的组合物而制备:
其中n=0、2、4或6;R互相独立地选自H和CH3;
互相独立地选自环己基和苯基;A互相独立地选自CH2和NH;B互相独立地选自H、OH和NH2;R’=H、C1-C10烷基、Ph、C5-C6脂环族基团、或C5-C10芳族基团;y=0-1;z=0-1;且y和z之和为0至2。优选地,R’=H或C1烷基。
在一个优选实施方案中,酚醛胺混合物由根据下式(V)的结构表示:
其中n=0、2、4或6;R互相独立地选自H和CH3;
互相独立地选自环己基和苯基;A互相独立地选自CH2和NH;B互相独立地选自H、OH和NH2;R’=H、C1-C10烷基、Ph、C5-C6脂环族基团或C5-C10芳族基团;y=0-1;z=0-1;且y和z之和为0至2。优选地,R’=H或C1烷基。
在另一优选实施方案中,酚醛胺混合物由根据下式(VI)的结构表示:
其中n=0、2、4或6;互相独立地选自环己基和苯基;A互相独立地选自CH2和NH;B互相独立地选自H、OH和NH2;R’=H、C1-C10烷基、Ph、C5-C6脂环族基团或C5-C10芳族基团;y=0-1;z=0-1;且y和z之和为0至2。优选地,R’=H或C1烷基。
优选地,酚醛胺混合物包括至少一种选自下组的酚醛胺
其中n=0、2、4或6;且R’=H、C1-C10烷基、Ph、C5-C6脂环族基团或C5-C10芳族基团。在一个优选实施方案中,酚醛胺混合物包含上组中列举的六种酚醛胺中的每一种。优选地,在包含含有选自式(VII)、(VIII)、(IX)、(X)、(XI)和(XII)的酚醛胺的六种酚醛胺的酚醛胺混合物的固化剂组合物中,酚醛胺如下存在于该混合物中:3-9重量%式(VII)的酚醛胺、3-11重量%式(VIII)的酚醛胺、30-45重量%式(IX)的酚醛胺、10-17重量%式(X)的酚醛胺、5-10重量%式(XI)的酚醛胺和15-30重量%式(XII)的酚醛胺。优选地,R’=H或C1烷基。
本公开还提供了包含式(IV)、(V)或(VI)任一种的酚醛胺混合物的固化剂组合物。在一个优选实施方案中,该固化剂组合物包含含有至少一种式(VII)、(VIII)、(IX)、(X)、(XI)或(XII)的酚醛胺的酚醛胺混合物。在另一优选实施方案中,该固化剂组合物包含含有选自式(VII)、(VIII)、(IX)、(X)、(XI)和(XII)的酚醛胺的六种酚醛胺的酚醛胺混合物。
在一个优选实施方案中,该固化剂组合物可进一步包括具有至少两个胺官能团的附加胺。本发明的酚醛胺固化剂可与附加胺固化剂(作为共固化剂)结合用于固化环氧树脂。
具有至少两个胺官能团的附加胺的优选实例包括二亚乙基三胺(DETA)、三亚乙基四胺(TETA)、四亚乙基五胺(TEPA)、五亚乙基六胺(PEHA)、六亚甲基二胺(HMDA)、1,3-戊二胺(DYTEKTM EP)、2-甲基-1,5-戊二胺(DYTEKTMA)、三氨基壬烷、N-(2-氨基乙基)-1,3-丙二胺(N3-胺)、N,N'-1,2-乙烷二基双-1,3-丙二胺(N4-胺)或二亚丙基三胺;芳基脂族胺,如间苯二甲胺(mXDA)或对苯二甲胺;脂环族胺,如1,3-双(氨基甲基)环己基胺(1,3-BAC)、异佛尔酮二胺(IPDA)、4,4'-亚甲基双环己胺、1,2-二氨基环己基胺(DCHA)、氨基丙基环己基胺(APCHA)、亚甲基桥连的多(脂环族-芳族)胺如MPCA、芳族胺,如间苯二胺、二氨基二苯甲烷(DDM)或二氨基二苯砜(DDS);杂环胺,如N-氨基乙基哌嗪(NAEP)或3,9-双(3-氨基丙基)2,4,8,10-四氧杂螺环(5,5)十一烷;聚烷氧基胺(其中烷氧基可以是氧亚乙基、氧亚丙基、氧-1,2-亚丁基、氧-1,4-亚丁基)或其共聚物,如4,7-二氧杂癸烷-1,10-二胺、1-丙胺、3,3'-(氧基双(2,1-乙烷二基氧基))双(二氨基丙基化二乙二醇)(ANCAMINE1922A)、聚(氧基(甲基-1,2-乙烷二基))、α-(2-氨基甲基乙基)ω-(2-氨基甲基乙氧基)(JEFFAMINE D 230、D-400)、三乙二醇二胺和低聚物(JEFFAMINEXTJ-504、JEFFAMINE XTJ-512)、聚(氧基(甲基-1,2-乙烷二基))、α,α'-(氧基二-2,1-乙烷二基)双(ω-(氨基甲基乙氧基))(JEFFAMINE XTJ-511)、双(3-氨基丙基)聚四氢呋喃350、双(3-氨基丙基)聚四氢呋喃750、聚(氧基(甲基-1,2-乙烷二基)),α-氢-ω-(2-氨基甲基乙氧基)醚与2-乙基-2-(羟甲基)-1,3-丙二醇(3:1)(JEFFAMINE T-403)和二氨基丙基二氨基丙基二丙二醇。
其它具有至少两个胺官能团的附加胺包括酰氨基胺和聚酰胺固化剂。聚酰胺固化剂由二聚脂肪酸(二聚体酸)和多亚乙基胺和通常一定量的有助于控制分子量和粘度的单体脂肪酸的反应产物组成。“二聚”或“二聚体”或“聚合”脂肪酸是指获自不饱和脂肪酸的聚合的酸。也用于制造聚酰胺的常见单官能不饱和C-6至C-20脂肪酸包括妥尔油脂肪酸(TOFA)或大豆脂肪酸等。
其它具有至少两个胺官能团的附加胺包括由酚类化合物与胺和甲醛形成的酚醛胺和曼尼希碱。本公开还提供了胺-环氧组合物和由其制成的固化产物。后者包含以下物质的反应产物:
(a)固化剂组合物,其包含如下所示的腰果酚的MPCA衍生的曼尼希碱(酚醛胺):
其中n=0、2、4或6;R互相独立地选自H和CH3;
互相独立地选自环己基和苯基;A互相独立地选自CH2和NH;B互相独立地选自H、OH和NH2;R’=H、C1-C10烷基、Ph、C5-C6脂环族基团或C5-C10芳族基团;y=0-1;z=0-1;且y和z之和为0至2;和
(b)环氧组合物,其包含至少一种多官能环氧树脂。
本公开还提供了包含式(IV)、(V)或(VI)任一种的酚醛胺混合物的固化剂组合物作为环氧树脂硬化剂的用途。本公开还提供了包含含有至少一种式(VII)、(VIII)、(IX)、(X)、(XI)或(XII)的酚醛胺的酚醛胺混合物的固化剂组合物作为环氧树脂硬化剂的用途。在一个优选实施方案中,该固化剂组合物包含含有选自式(VII)、(VIII)、(IX)、(X)、(XI)和(XII)的酚醛胺的至少六种酚醛胺的酚醛胺混合物。
本公开的胺-环氧组合物包含固化剂组合物和含有至少一种多官能环氧树脂的环氧组合物。本文所用的多官能环氧树脂描述每分子含有2个或更多个1,2-环氧基的化合物。该环氧树脂优选选自芳族环氧树脂、脂环族环氧树脂、脂族环氧树脂、缩水甘油酯树脂、硫代缩水甘油醚树脂、N-缩水甘油醚树脂及其组合。
适用于本公开的优选芳族环氧树脂包含多元酚的缩水甘油醚,包括二元酚的缩水甘油醚。进一步优选的是以下物质的缩水甘油醚:间苯二酚、氢醌、双-(4-羟基-3,5-二氟苯基)-甲烷、1,1-双-(4-羟苯基)-乙烷、2,2-双-(4-羟基-3-甲基苯基)-丙烷、2,2-双-(4-羟基-3,5-二氯苯基)丙烷、2,2-双-(4-羟苯基)-丙烷(在商业上称为双酚A)、双-(4-羟苯基)-甲烷(在商业上称为双酚F,其可含有变化量的2-羟苯基异构体)等,或它们的任何组合。另外,下面结构的高级二元酚也可用于本公开:
其中R’是二元酚、如上面列举的那些二元酚的二价烃基,且p是在0至大约7之间的平均值。根据该式的材料可通过使二元酚和表氯醇的混合物聚合或通过二元酚的二缩水甘油醚和二元酚的混合物升级(advancing)制备。尽管在任一给定分子中p的值是整数,但该材料始终是可通过不一定为整数的p的平均值表征的混合物。在本公开的一个方面中,可使用p的平均值在0至大约7之间的聚合物材料。
在本公开的一个方面中,所述至少一种多官能环氧树脂优选是双酚-A的二缩水甘油醚(DGEBA)、DGEBA的高级或更高分子量形式、双酚-F的二缩水甘油醚、酚醛清漆树脂的二缩水甘油醚或它们的任何组合。通过升级法制备DGEBA的更高分子量形式或衍生物,其中使过量DGEBA与双酚-A反应以产生环氧封端产物。这样的产物的环氧当量(EEW)为大约450至大约3000或更大。由于这些产物在室温下是固体,因此它们经常被称作固体环氧树脂。
在优选实施方案中,所述至少一种多官能环氧树脂是由下面结构表示的双酚-F或双酚-A的二缩水甘油醚:
其中R”=H或CH3,且p是在0至大约7之间的平均值。DGEBA由R”=CH3和p=0的上面结构表示。DGEBA或高级DGEBA树脂由于它们的低成本和高性能性质的结合而常用于涂料配制剂。具有大约174至大约250,更通常大约185至大约195的EEW的商业品级DGEBA是易得的。在这些低分子量下,环氧树脂是液体并经常被称为液体环氧树脂。本领域技术人员会理解的是,大多数品级的液体环氧树脂是轻微聚合的,因为纯DGEBA具有大约174的EEW。也通过升级法制备的具有大约250至大约450的EEW的树脂被称为半固体环氧树脂,因为它们在室温下是固体和液体的混合物。具有大约160至大约750的基于固体计的EEW的多官能树脂可用于本公开。在另一方面中,多官能环氧树脂具有大约170至大约250的EEW。
脂环族环氧化合物的实例包括但不限于具有至少一个脂环族环的多元醇的多缩水甘油醚,或通过用氧化剂将包含环己烯环或环戊烯环的化合物环氧化而得的包含环氧环己烷或环氧环戊烷的化合物。一些特定实例包括但不限于氢化双酚A二缩水甘油醚;3,4-环氧环己基羧酸3,4-环氧环己基甲酯;3,4-环氧基-1-甲基己烷羧酸3,4-环氧基-1-甲基环己基酯;6-甲基-3,4-环氧环己烷羧酸6-甲基-3,4-环氧环己基甲-酯;3,4-环氧基-3-甲基环己烷羧酸3,4-环氧基-3-甲基环己基甲-酯;3,4-环氧基-5-甲基环己烷羧酸3,4-环氧基-5-甲基环己基甲酯;己二酸双(3,4-环氧环己基甲基)酯;亚甲基-双(3,4-环氧环己烷);2,2-双(3,4-环氧环己基)丙烷;二环戊二烯二环氧化物;亚乙基-双(3,4-环氧环己烷羧酸酯);环氧六氢邻苯二甲酸二辛酯;和环氧六氢邻苯二甲酸二-2-乙基己酯。
脂族环氧化合物的实例包括但不限于脂族多元醇或其环氧烷加合物的多缩水甘油醚、脂族长链多元酸的多缩水甘油酯、通过丙烯酸缩水甘油酯或甲基丙烯酸缩水甘油酯的乙烯基聚合合成的均聚物,和通过丙烯酸缩水甘油酯或甲基丙烯酸缩水甘油酯和其它乙烯基单体的乙烯基聚合合成的共聚物。一些特定实例包括但不限于多元醇的缩水甘油醚,如1,4-丁二醇二缩水甘油醚;1,6-己二醇二缩水甘油醚;甘油的三缩水甘油醚;三羟甲基丙烷的三缩水甘油醚;山梨糖醇的四缩水甘油醚;二季戊四醇的六缩水甘油醚;聚乙二醇的二缩水甘油醚;和聚丙二醇的二缩水甘油醚;通过将一种类型、或两种或更多种类型的环氧烷加成到脂族多元醇如乙二醇、丙二醇、三羟甲基丙烷和甘油上而获得的聚醚多元醇的多缩水甘油醚。
缩水甘油酯树脂通过使在分子中具有至少两个羧酸基团的多羧酸化合物和表氯醇反应获得。这样的多羧酸的实例包括脂族、脂环族和芳族多羧酸。脂族多羧酸的实例包括草酸、琥珀酸、戊二酸、己二酸、庚二酸、癸二酸、辛二酸、壬二酸或二聚或三聚亚油酸。脂环族多羧酸包括四氢邻苯二甲酸、4-甲基四氢邻苯二甲酸、六氢邻苯二甲酸或4-甲基六氢邻苯二甲酸,且芳族多羧酸包括邻苯二甲酸、间苯二甲酸或对苯二甲酸。
硫代缩水甘油醚树脂衍生自二硫醇,例如乙烷-1,2-二硫醇或双(4-巯甲基苯基)醚。
通过表氯醇与含有至少两个胺氢原子的胺的反应产物的脱氯化氢获得N-缩水甘油基树脂。这样的胺是例如苯胺、n-丁胺、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,N-缩水甘油基树脂也包括异氰脲酸三缩水甘油酯,环亚烷基脲例如亚乙基脲或1,3-亚丙基脲的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,例如5,5-二甲基乙内酰脲。
对于一个或多个所述实施方案,所述树脂组分进一步包括反应性稀释剂。反应性稀释剂是在固化过程中参与与硬化剂组分的化学反应并结合入经固化组合物中的化合物,优选是单官能环氧化物。反应性稀释剂也可用于为各种应用而改变可固化组合物的粘度和/或固化性质。对于一些应用,反应性稀释剂可提供较低粘度以影响流动性质,延长适用期和/或改进可固化组合物的粘合性质。例如,可降低粘度以允许在仍允许容易施加的同时提高配制剂或组合物中的颜料含量,或允许使用更高分子量的环氧树脂。因此,在本公开的范围内,包含至少一种多官能环氧树脂的环氧组分可进一步包含单官能环氧化物。单环氧化物的实例包括但不限于氧化苯乙烯,环氧环己烷,和酚、甲酚、叔丁基酚、其它烷基酚、丁醇、2-乙基己醇、C4至C14醇等的缩水甘油醚,或它们的组合。多官能环氧树脂也可存在于溶液或乳液中,其中稀释剂是水、有机溶剂或其混合物。多官能环氧树脂的量可为环氧组分的按重量计大约50%至100%、大约50%至大约90%、大约60%至大约90%、大约70%至大约90%,和在一些情况下大约80%至大约90%。对于一个或多个所述实施方案,反应性稀释剂为树脂组分的总重量的小于60重量%。
特别合适的多官能环氧化合物是双酚-A和双酚-F的二缩水甘油醚,双酚-A和双酚-F的升级的二缩水甘油醚,和环氧酚醛清漆树脂。该环氧树脂可以是单一树脂,或其可以是互相相容的环氧树脂的混合物。
本公开的胺-环氧组合物优选具有1.5:1至0.7:1的环氧组合物中的环氧基与固化剂组合物中的胺氢的化学计量比。例如,这样的胺-环氧组合物可优选具有1.5:1、1.4:1、1.3:1、1.2:1、1.1:1、1:1、0.9:1、0.8:1或0.7:1的化学计量比。在另一方面中,化学计量比为1.3:1至0.7:1,或1.2:1至0.8:1,或1.1:1至0.9:1。
本公开的组合的MPCA衍生的腰果酚的曼尼希碱(酚醛胺)和胺共固化剂-环氧组合物优选具有1.5:1至0.7:1的环氧组合物中的环氧基与固化剂组合物中的胺氢的化学计量比。例如,这样的胺-环氧组合物可具有1.5:1、1.4:1、1.3:1、1.2:1、1.1:1、1:1、0.9:1、0.8:1或0.7:1的化学计量比。在另一方面中,化学计量比为1.3:1至0.7:1,或1.2:1至0.8:1,或1.1:1至0.9:1。
优选地,MPCA衍生的腰果酚的曼尼希碱(酚醛胺)和胺共固化剂的重量比为大约1:1至大约1:0.05。在另一实施方案中,MPCA衍生的腰果酚的曼尼希碱(酚醛胺)和胺共固化剂的重量比优选为大约1:0.75至大约1:0.25。
本公开还涉及一种生产式(IV)、(V)或(VI)任一种所示的酚醛胺混合物的方法,其包括使以下物质反应的步骤:
(i)下式所示的腰果酚
其中n=0、2、4或6;
(ii)下式所示的MPCA
其中R互相独立地选自H和CH3;
(iii)醛。
在该方法的一个优选实施方案中,腰果酚与MPCA的摩尔比在1:1至1:3的范围内。在另一实施方案中,腰果酚与MPCA的摩尔比优选在1:1至1:2的范围内。MPCA与醛的摩尔比优选在1:1至1:3的范围内。在另一实施方案中,MPCA与醛的摩尔比优选在1:1至1:1.2的范围内。
在该方法的一个优选实施方案中,可在一步法中通过将腰果酚与胺混合并在所需反应温度下用甲醛处理这种混合物来进行反应。或者,在该方法的另一优选实施方案中,可优选将腰果酚与醛混合,并将其在反应温度下用MPCA处理。该反应可在40℃-150℃下进行。在另一优选实施方案中,该反应可在80℃-120℃下进行。在反应完成后优选通过水的蒸馏获得产物。
在该方法的一个优选实施方案中,所用醛化合物由结构式RCOH表示,其中R=H、C1-C10烷基、Ph、C5-C6脂环族基团、C5-C10芳族基团或其混合物。优选的醛是甲醛、乙醛、丙醛、丁醛、戊醛、己醛、庚醛、辛醛、壬醛、癸醛、苯甲醛、环戊烷甲醛和环己烷甲醛。最优选的醛是甲醛和乙醛。甲醛可作为水溶液或以聚合物形式(低聚甲醛)使用。
腰果酚与MPCA和醛的摩尔比决定了MPCA中的氨基取代基的反应程度。预期为氨基取代基的混合物。假设氨基与醛的摩尔比相等,则当氨基与腰果酚的摩尔比>1.0时,腰果酚上的较高取代的(>1)胺取代基的比率提高。
本公开还涉及一种生产固化剂组合物的方法,包括合并式(IV)、(V)或(VI)任一种的酚醛胺和具有至少两个胺官能团的附加胺的步骤。
本公开的组合物可用于生产各种硬化制品。根据在制品的制造过程或制品的最终应用的要求,在配制剂和组合物中可使用各种添加剂以调节特定性质。这些添加剂包括,但不限于,溶剂(包括水)、加速剂、增塑剂、填料、纤维如玻璃或碳纤维、颜料、颜料分散剂、流变改性剂、触变胶、流动或流平助剂、表面活性剂、消泡剂、杀生物剂或它们的任何组合。要理解的是,本领域中已知的其它混合物或材料可包括在该组合物或配制剂中并在本公开的范围内。
本公开还涉及本发明的组合物用于制备硬化制品的用途。例如,制品可包含胺-环氧组合物,其包含固化剂组合物和环氧组合物。固化剂组合物可包含MPCA衍生的腰果酚的曼尼希碱(酚醛胺)。环氧组合物可包含至少一种多官能环氧树脂。任选地,在用于生产制品的组合物或配制剂中可存在各种添加剂,取决于所需性质。这些添加剂可包括,但不限于,溶剂(包括水)、加速剂、增塑剂、填料、纤维如玻璃或碳纤维、颜料、颜料分散剂、流变改性剂、触变胶、流动或流平助剂、表面活性剂、消泡剂、杀生物剂或它们的任何组合。这些添加剂的选择和量由配方设计师选定。尽管不是强制性的,但可用的代表性加速剂包括:三氟化硼胺络合物、取代酚,如2,4,6-三(二甲基氨基甲基)酚、叔胺,如苄基二甲基胺和咪唑。
根据本公开的优选制品包括,但不限于,涂料、胶粘剂、底漆、密封剂、固化配混物、建筑产品、铺地产品、复合材料产品、层压件、灌封配混物、灰浆、填料、水泥基灌浆材料或自流平铺地材料。视特定应用的需要,基于这些胺-环氧组合物的涂料可含有稀释剂,如水或有机溶剂。涂料可含有各种类型和含量的用于漆和底漆应用的颜料。胺-环氧涂料组合物包含具有40至400μm(微米),优选80至300μm,更优选100至250μm的厚度的层,以用于施加到金属基底上的保护涂层。此外,为了用于铺地产品或建筑产品,涂料组合物包含具有50至10,000μm的厚度的层,取决于产品类型和所需的最终性质。提供有限的机械和化学耐受性的涂层产品包含具有50至500μm,优选100至300μm的厚度的层;而提供高机械和化学耐受性的涂层产品,例如自流平地板,包含具有1,000至10,000μm,优选1,500至5,000μm的厚度的层。
附加组分或添加剂可与本公开的组合物一起使用以生产制品。此外,可将这样的涂料、底漆、密封剂、固化配混物或灰浆施加到金属或水泥基基底上。
为环氧组合物选择的相对于固化剂组合物的相对量可取决于例如最终用途制品、其所需性质和用于生产最终用途制品的制造方法和条件而变化。例如,在使用某些胺-环氧组合物的涂料应用中,相对于固化剂组合物的量并入更多的环氧树脂可导致涂料具有增加的干燥时间,但具有提高的硬度和改进的如通过光泽度测得的外观。
各种基底适合在如本领域普通技术人员众所周知的那样适当的表面准备的情况下施加本发明的涂料。这样的基底包括,但不限于,混凝土和各种类型的金属和合金,如钢和铝。本公开的涂料适用于涂装或涂布大的金属物体或水泥基基底,包括船舶、桥梁、工业厂房和设备,和地板。
本发明的涂料可通过任何数目的技术施加,包括喷涂、刷涂、辊涂、油漆手套(paint mitt)等。为了施加本发明的非常高固含量或100%固含量涂料,可使用多组分喷涂设备,其中在通往喷枪的线路中、在喷枪本身中混合胺和环氧组分,或在它们离开喷枪时将这两种组分混合在一起。使用这种技术可减轻在配制剂适用期方面的限制,所述适用期通常随胺反应性和固含量两者提高而降低。可使用加热的多组分设备降低组分的粘度,由此改进易施加性。
建筑和铺地应用包括包含与建筑工业中常用的混凝土或其它材料组合的本公开的胺-环氧组合物的组合物。本公开的组合物的应用包括但不限于其作为底漆、深渗透底漆、涂料、固化配混物和/或新或旧混凝土的密封剂(如参考ASTM C309-97)的用途,所述标准经此引用并入本文。作为底漆或密封剂,可在施加涂料前将本公开的胺-环氧组合物施加到表面上以改进粘合接合。当涉及混凝土和水泥基应用时,涂料是用于施加在表面上以建立保护或装饰层或涂层的试剂。也可由本文中公开的组合物制备裂纹注入和裂纹填充产品。本公开的胺-环氧组合物可与水泥基材料,如混凝土拌合料混合以形成聚合物或改性水泥、瓷砖填缝剂等。包含本文中公开的胺-环氧组合物的复合材料产品或制品的非限制性实例包括网球拍、滑雪板、自行车车架、飞机机翼、玻璃纤维增强的复合材料和其它模制品。
在本公开的固化剂组合物的特定用途中,可在低温下将涂料施加到各种基底,如混凝土和金属表面上,其具有快速固化速度和良好的涂层外观。这对需要良好美观性的面漆应用尤其重要,并为仍有待克服伴随良好涂层外观的快速低温固化的工业中长期面临的挑战提供了解决方案。在快速低温固化速度下,可缩短作业或设备停工的时间,或对于室外应用,可延长在寒冷气候中的工作季节。
快速环氧固化剂能使胺固化的环氧涂料在短时间内以高固化度固化。通过测量涂层干燥时间的薄膜凝固时间(set time)(TFST)监测涂层的固化速度,薄膜凝固时间分为4级:阶段1,指触干燥(set to touch);阶段2,表干(tack free);阶段3,实干(dry hard);和阶段4,干透(dry through)。阶段3干燥时间指示涂层多快固化和干燥。对于快速环境固化涂层,阶段3干燥时间小于6小时,或小于4小时,或优选小于4小时。低温固化通常是指在环境温度以下的固化温度、10℃或5℃,或在一些情况下0℃。对于快速低温固化,在5℃下的阶段3干燥时间小于16小时,其中阶段3干燥时间小于10小时、优选小于8小时时的值会提供显著的生产率益处。
通过固化度测量涂层固化得多好。经常使用本领域技术人员公知的DSC(差示扫描量热法)技术测定固化度。充分固化的涂层具有在7天后至少85%或至少90%或至少95%的在环境温度(25℃)下的固化度。充分固化的涂层具有在7天后至少80%或至少85%或至少90%的在5℃下的固化度。
许多快速低温环氧固化剂可快速固化环氧树脂。但是由于环氧树脂和固化剂尤其在10℃或5℃的低温下的相容性差,在树脂和固化剂之间发生相分离并且固化剂迁移到涂层表面,造成表现为粘性和浑浊涂层的差的涂层外观。环氧树脂和固化剂之间的良好相容性带来具有良好的抗氨基甲酸酯化(carbamation)和良好的涂层外观的澄清有光泽的涂层。本公开的固化剂组合物提供快速固化速度、良好相容性和高固化度的结合。
具体实施方式
实施例
提供这些实施例以例示本发明的某些方面并且不应限制在此所附权利要求书的范围。
实施例1:在腰果酚:MPCA:甲醛摩尔比(1:1:1)下合成MPCA的酚醛胺
在配有N2入口、加料漏斗和温度探针的三颈1升圆底烧瓶中装载腰果酚(298克,1.0摩尔)和MPCA(350克,1.0摩尔)。将混合物加热到80℃。加入37%甲醛溶液(81克,37重量%,30克,1.0摩尔)以保持80-90℃的反应温度。在加入后,使混合物在90-95℃下保持1小时。在120℃下蒸馏水且产物作为浅棕色液体获得。将这种产物冷却到环境温度并用2,4,6-三(二甲基氨基甲基)酚(34.7克)和苄醇(173克)处理。所得产物具有5,710mPa.s@23℃的粘度和150g/eq的理论AHEW。
实施例2:在腰果酚:MPCA:甲醛摩尔比(1:1.5:1.0)下合成MPCA的酚醛胺
在配有N2入口、加料漏斗和温度探针的三颈1升圆底烧瓶中装载腰果酚(298克,1.0摩尔)和MPCA(525克,1.50摩尔)。将混合物加热到80℃。加入37%甲醛溶液(81克,37重量%、30克,1.0摩尔)以保持80-90℃的反应温度。在加入后,使混合物在90-95℃下保持1小时。在120℃下蒸馏水且产物作为浅棕色液体获得。将这种产物冷却到环境温度并用2,4,6-三(二甲基氨基甲基)酚(43.95克)和苄醇(219.74克)处理。所得产物具有6,290mPa.s@23℃的粘度和154g/eq的理论AHEW。
实施例3:在腰果酚:MPCA:甲醛摩尔比(1:1.5:1.25)下合成MPCA的酚醛胺
在配有N2入口、加料漏斗和温度探针的三颈1升圆底烧瓶中装载腰果酚(298克,1.0摩尔)和MPCA(525克,1.50摩尔)。将混合物加热到80℃。加入37%甲醛溶液(101.35克,37重量%,37.5克,1.25摩尔)以保持80-90℃的反应温度。在加入后,使混合物在90-95℃下保持1小时。在120℃下蒸馏水且产物作为浅棕色液体获得。将这种产物冷却到环境温度并用2,4,6-三(二甲基氨基甲基)酚(44.10克)和苄醇(220.5克)处理。所得产物具有10,970mPa.s@23℃的粘度和182g/eq的理论AHEW。
实施例4:在腰果酚:MPCA:氨基丙基环己基胺:甲醛摩尔比(1:0:0.8:0.2:1.0)下合成MPCA的酚醛胺
在配有N2入口、加料漏斗和温度探针的三颈1升圆底烧瓶中装载腰果酚(298克,1.0摩尔)、MPCA(280克,0.8摩尔)和氨基丙基环己基胺(31.25克,0.2摩尔)。将混合物加热到80℃。加入37%甲醛溶液(81克,37重量%,30克,1.0摩尔)以保持80-90℃的反应温度。在加入后,使混合物在90-95℃下保持1小时。在120℃下蒸馏水且产物作为浅棕色液体获得。将这种产物冷却到环境温度并用2,4,6-三(二甲基氨基甲基)酚(32.7克)和苄醇(163.6克)处理。所得产物具有2,440mPa.s@23℃的粘度和233g/eq的理论AHEW。
实施例5:在腰果酚:MPCA:氨基丙基环己基胺:甲醛摩尔比(1:0:1.2:0.3:1.0)下合成MPCA的酚醛胺
在配有N2入口、加料漏斗和温度探针的三颈1升圆底烧瓶中装载腰果酚(298克,1.0摩尔)、MPCA(420克,1.2摩尔)和氨基丙基环己基胺(46.88克,0.3摩尔)。将混合物加热到80℃。加入37%甲醛溶液(81克,37重量%、30克,1.0摩尔)以保持80-90℃的反应温度。在加入后,使混合物在90-95℃下保持1小时。在120℃下蒸馏水且产物作为浅棕色液体获得。将这种产物冷却到环境温度并用2,4,6-三(二甲基氨基甲基)酚(40.9克)和苄醇(204.5克)处理。所得产物具有2,250mPa.s@23℃的粘度和230g/eq的理论AHEW。
实施例6:在腰果酚:MPCA:三氨基壬烷:甲醛摩尔比(1:0:0.65:0.65:1.3)下合成MPCA的酚醛胺
在配有N2入口、加料漏斗和温度探针的三颈1升圆底烧瓶中装载腰果酚(298克,1.0摩尔)、MPCA(227.5克,0.65摩尔)和三氨基壬烷(112.65克,0.65摩尔)。将混合物加热到80℃。加入37%甲醛溶液(105.4克,37重量%,39克,1.3摩尔)以保持80-90℃的反应温度。在加入后,使混合物在90-95℃下保持1小时。在120℃下蒸馏水且产物作为浅棕色液体获得。将这种产物冷却到环境温度并用2,4,6-三(二甲基氨基甲基)酚(34.41克)和苄醇(172.03克)处理。所得产物具有2,100mPa.s@23℃的粘度和136g/eq的理论AHEW。
性能测试
除非另行规定,通过混合上述实施例中给出的组分,制备固化剂混合物,其中环氧组分为(Epon 828,DER 331类型)的标准双酚-A基环氧树脂,EEW 190。所用的配方规定在表1中。然后使用1:1(胺:环氧当量)的化学计量水平混合它们。
表1.透明涂层配方筛选–MPCA酚醛胺
对如表1中规定的配方施以一系列应用试验以测定它们的性能属性。适应性修改的试验程序规定在表2中。
表2:试验方法
凝胶时间表征组合物从液体转变成凝胶的时间。用TECHNE胶凝计时器(型号FGT6)使用ASTM D2471测量胺-环氧组合物的凝胶时间。使用Beck-Koller记录仪根据ASTMD5895测定干燥时间或薄膜凝固时间(TFST)。使用Bird涂施器,在标准玻璃板上,以150μmWFT(湿膜厚度)的湿膜厚度制备胺-环氧涂层,产生±100μm的干膜厚度。该涂层在Lunaire(TPS)环境室中在23℃和5℃和60%相对湿度(RH)下固化。评估的所有体系的数据报道在表3中。
表3.MPCA酚醛胺固化剂的工艺性能
当在23℃和5℃两者固化时,基于本发明的固化剂的涂料组合物与用标准市售EDA基酚醛胺获得的那些相比表现出多种改进的性质。这些包括更快的薄膜干燥时间、硬度发展和增强的低温表面外观,当涂层在不利的低温条件下固化时最为显著。这些结果被认为是这些类型的涂料的显著工艺性能益处,因为更快的性质发展和增强的低温固化性能可在海洋和保护涂层涂料市场中提供生产率益处。形式[F]是其中将第二固化剂添加到该新型MPCA酚醛胺中以形成共混物也可增强工艺性能性质的一个实施例。在这一实施例中,5%的Ancamine 2801固化剂将实施例1所显示的初始固化剂粘度降低±40%,并另外提供低温固化发展的改进而没有不利地影响其它性质,如耐水渍性。
在23℃,所有涂层都表现出良好的光泽发展并且没有任何油腻的胺和表面缺陷。在较低应用温度下,基于MPCA的涂层保持非常高的光泽度和无油脂表面,而形式[E]中所用的参比酚醛胺表现出光泽度的降低且澄清涂层产生轻微浑浊,当这一体系在5℃下施加和固化时,这变得更显著。基于由实施例1、2和6开发的MPCA-酚醛胺的配制剂的光泽度和表面保持优于EDA基对照物,这指示基于MPCA胺的固化剂技术的改进的相容性。所得结果清楚表明含本发明的固化剂的涂料既具有快速固化又具有良好涂层外观,表明固化剂和环氧树脂之间的良好相容性。
许多胺基体系容易具有差的早期耐水渍性和发生氨基甲酸酯化。后者是存在于涂层表面上的游离胺与大气中的湿气和二氧化碳反应,结果是在涂层表面形成不溶性白色盐。为了评估这一点,使用Bird涂施器以大约75μm(湿膜厚度)的湿膜厚度将澄清涂层施加到干净的Lenata卡纸上。Lenata卡纸在使用前用乙醇清洁。该涂层在23℃和5℃和60%相对湿度(RH)下固化1天和7天。将不起毛棉片置于试验板上,确保其距板的边缘至少12mm。棉片用2-3毫升软化水弄湿并用合适的盖子(例如表面皿)覆盖。使该板静置指定时间(标准时间是24小时)。在该时间后,移除棉片并用布或纸巾擦干涂层。立即检查板的氨基甲酸酯化并评级。在Evonik使用的试验中,评级5代表无氨基甲酸酯化和优异的表面,而0代表过度白化或严重氨基甲酸酯化。对于水渍试验,在不存在不起毛布的情况下,将水滴施加到涂层上。耐水渍性的评级与氨基甲酸酯化相同。如表3中概括的数据表明用本发明的固化剂固化的涂层与参比酚醛胺相比提供改进的氨基甲酸酯化和耐水渍性,尤其是在5℃的低温下施加时。
耐化学性研究
也评估了基于胺固化剂的几种配制剂的基础耐化学性性质。在这一试验中制备具有20.00克大致重量(直径±55mm,厚度±10mm)的固化圆盘。使用借助得自实施例1的固化剂在23℃下固化7天的标准液体双酚-A基(DGEBA,EEW=190)环氧树脂进行根据ASTM D543的浸渍研究。对各试剂测试两个样品。表4显示在各种化学品中在23℃下浸渍7天和28天后的平均重量变化百分比。
表4:MPCA-酚醛胺的耐化学性-连续浸渍
这些研究表明基于本发明的MPCA酚醛胺固化剂的涂料组合物对于一系列化学试剂表现出非常好的耐化学性。与标准EDA基酚醛胺相比最显著的是对于二甲苯混合物和甲基异丁基酮(MIBK)的优异耐受性。在这一研究中,基于形式[A]的圆盘在浸渍过程中表现出非常低的重量增加水平,而EDA对照物在MIBK和二甲苯中表现出严重溶胀和浸渍28天后分别为18.9%和44.4%的重量增加。
Claims (16)
5.权利要求4的酚醛胺混合物,其包含来自权利要求4中列出的那些的六种酚醛胺。
6.一种固化剂组合物,其包含根据权利要求1-5任一项的酚醛胺混合物。
7.权利要求6的固化剂组合物,其进一步包含具有至少两个胺官能团的附加胺。
8.根据权利要求1-5任一项的酚醛胺混合物或根据权利要求6-7任一项的固化剂组合物作为环氧树脂硬化剂的用途。
10.权利要求9的方法,其中腰果酚与亚甲基桥连的多(脂环族-芳族)胺的摩尔比在1:1至1:3的范围内,且亚甲基桥连的多(脂环族-芳族)胺与醛的摩尔比在1:1至1:3的范围内。
11.权利要求9的方法,其中将腰果酚和至少一种亚甲基桥连的多(脂环族-芳族)胺在40-150℃的温度下混合,然后在40-150℃的温度下用醛处理。
12.权利要求9的方法,其中将腰果酚和醛在40-150℃的温度下混合,然后在40-150℃的温度下用至少一种亚甲基桥连的多(脂环族-芳族)胺处理。
13.权利要求9的方法,其中所述醛选自甲醛、低聚甲醛、乙醛、丙醛、丁醛、戊醛、己醛、庚醛、辛醛、壬醛、癸醛、苯甲醛、环戊烷甲醛和环己烷甲醛。
14.一种制备权利要求7的固化剂组合物的方法,包括合并式(IV)的酚醛胺混合物和具有至少两个胺官能团的附加胺。
15.根据权利要求1-5任一项的酚醛胺混合物或根据权利要求6-7任一项的固化剂组合物与至少一种环氧树脂一起用于制备硬化制品的用途。
16.权利要求15的用途,其中所述制品是涂层、胶粘剂、建筑产品、铺地产品或复合材料产品。
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