CN105102551A - 腐蚀抑制性微凝胶和内含所述微凝胶的非铬酸化底涂剂组合物 - Google Patents
腐蚀抑制性微凝胶和内含所述微凝胶的非铬酸化底涂剂组合物 Download PDFInfo
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- CN105102551A CN105102551A CN201380062932.2A CN201380062932A CN105102551A CN 105102551 A CN105102551 A CN 105102551A CN 201380062932 A CN201380062932 A CN 201380062932A CN 105102551 A CN105102551 A CN 105102551A
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- AYGUCHAPOTYFRT-UHFFFAOYSA-H zinc molybdenum(4+) diphosphate Chemical compound [Zn+2].[Mo+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O AYGUCHAPOTYFRT-UHFFFAOYSA-H 0.000 description 1
- 235000019352 zinc silicate Nutrition 0.000 description 1
- NDKWCCLKSWNDBG-UHFFFAOYSA-N zinc;dioxido(dioxo)chromium Chemical compound [Zn+2].[O-][Cr]([O-])(=O)=O NDKWCCLKSWNDBG-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
- C09D5/082—Anti-corrosive paints characterised by the anti-corrosive pigment
- C09D5/086—Organic or non-macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D235/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings
- C07D235/02—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings condensed with carbocyclic rings or ring systems
- C07D235/04—Benzimidazoles; Hydrogenated benzimidazoles
- C07D235/24—Benzimidazoles; Hydrogenated benzimidazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 2
- C07D235/28—Sulfur atoms
-
- C—CHEMISTRY; METALLURGY
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Abstract
本发明涉及适合用于非铬酸化底涂剂组合物中的腐蚀抑制性微凝胶。各离散微凝胶是由交联聚合物网络和陷留或固定在所述聚合物网络中的有机腐蚀抑制性化合物所组成。
Description
背景技术
在复合结构的制造中,可方便地使用结构粘着剂将金属结构与另一个金属结构或由树脂浸渍增强纤维所组成的复合结构结合。一般来说,为确保最高级别的粘着强度,紧接于结合之前对金属表面完全清洁灰尘、脏污、油脂和金属氧化产物。可惜,在大多数时候一般无法使用这一程序,这是因为清洁和结合操作通常间隔长的时段。在这些时段中,金属表面可能被水解,从而降低结合的粘着强度。克服此困难处的一种替代方法是在清洁金属表面上使用底涂剂。
历史上已使用铬酸化底涂剂(即,含有铬离子的溶液)以保护金属免受腐蚀影响。然而,归因于环境规定,特定来说尤其在航天工业中,铬酸盐的使用受到限制。若干种非铬酸化腐蚀抑制剂,如磷硅酸锌、磷酸钼锌、硼硅酸钙、钒酸钠、磷酸锶等等已在评估中。这些抑制剂中大多数为被动(不可类似铬酸盐般浸出)和通过牺牲性氧化方法提供腐蚀保护。因此,这些被动抑制剂不提供暴露于苛刻环境条件时需要的所欲耐久性或性能。
某些常规的有机腐蚀抑制剂仰赖于如下机制:有机物质通过与金属衬底、氧化膜或腐蚀产物反应形成粘附膜以防止进一步腐蚀来防止腐蚀。这些有机腐蚀抑制剂的一个主要缺点涉及用于形成金属衬底上强粘着结合的官能团与底涂剂调配物之间的相互作用。归因于这种相互作用,底涂剂的存放期和固化动力学会受到影响,此限制腐蚀抑制剂从在涂料中输送到达腐蚀部位。许多有机腐蚀抑制剂的另一缺点是当与基于环氧化物的腐蚀抑制性底涂剂调配物一起用于防止对如铝和铝合金的重度腐蚀材料腐蚀时其腐蚀性能无法预期。
因此,仍需要针对特定来说在如航天和汽车的工业中的结构结合应用可类似铬酸盐腐蚀抑制剂地表现的非铬酸化底涂剂调配物。
发明内容
本文中公开一种用于水基非铬酸化(也就是说,无铬酸盐)底涂剂组合物的微凝胶腐蚀抑制性材料。这种非铬酸化底涂剂组合物特别适合结构结合应用并可满足限制铬酸盐使用的环境规定。
附图说明
图1示意性地说明一种根据一个实施例制备腐蚀抑制性微凝胶的方法。
具体实施方式
本发明的腐蚀抑制性微凝胶是纳米或次微米大小的离散交联聚合物颗粒。各离散微凝胶是由具有腐蚀抑制剂化合物陷留或固定在聚合物网络中的交联聚合物网络(network)所组成。所述腐蚀抑制剂化合物在暴露于如pH改变、湿气暴露(moistureexposure)和温度提高的腐蚀触发条件后可从交联聚合物网络释放。
本文中所公开的腐蚀抑制性微凝胶可依下述方法制得:
a)通过使在液体介质中的单体乳液聚合来形成离散微凝胶;
b)将有机腐蚀抑制剂溶解在含有有机溶剂和水的水性介质中;
c)将所述微凝胶与所述水性介质混合,导致所述微凝胶膨胀和所述有机腐蚀抑制剂化合物变为陷留或固定在聚合物网络中;和
d)汽提除去所述溶剂以得到具有较小粒度微凝胶和增加的固体含量的乳胶乳液。
图1示意性地说明形成负载有腐蚀抑制性化合物的微凝胶颗粒的方法。参照图1,将离散未经处理的微凝胶颗粒10暴露于含有腐蚀抑制剂、溶剂和水的水性介质,得到负载有腐蚀抑制性化合物“I”的膨胀微凝胶10',并且在移除溶剂之后,得到收缩的腐蚀抑制性微凝胶颗粒10"。
微凝胶是具有微米、次微米或纳米大小的离散球形聚合物颗粒,并且是由交联聚合物网络所组成。微凝胶还可称作纳米海绵,这是因为其在外部条件下膨胀和收缩(也就是说,反膨胀(de-swell))而能够以可控方式实现封装物质和释放所述物质。微凝胶是通过使在特定液体介质中的单体聚合制得。通常,利用油包水型或水包油型中任一类型的乳液聚合来制备呈乳胶形式的微凝胶颗粒。在此处,用于形成微凝胶的乳液聚合包括若干子类别类型,如微乳液、迷你乳液(mini-emulsion)、无乳化剂、接种乳液聚合等等。一般来说,如分散液聚合和悬浮液聚合的在液体介质中的其它聚合法也可用于制造具有纳米到毫米大小的微凝胶颗粒。在添加乳化剂或表面活性剂下,使块状聚合物或聚合物溶液后乳化也可制得微凝胶。
用于制造微凝胶的聚合中的单体包括单官能丙烯酸和甲基丙烯酸单体,如丙烯酸乙酯(EA)、甲基丙烯酸甲酯(MMA)、丙烯酸苄酯、甲基丙烯酸苄酯、丙烯酸丁酯、甲基丙烯酸丁酯、丙烯酸丙酯、甲基丙烯酸丙酯、丙烯酸环己酯、甲基丙烯酸环己酯、丙烯酸癸酯、甲基丙烯酸癸酯、丙烯酸十二烷酯、甲基丙烯酸十二烷酯、甲基丙烯酸辛酯、丙烯酸甲氧基乙酯、甲基丙烯酸甲氧基乙酯等等;双官能丙烯酸和甲基丙烯酸单体,如甲基甲基丙烯酸(MAA)、丙烯酸(AA)、含有羟基的丙烯酸酯和甲基丙烯酸酯(如甲基丙烯酸羟基乙酯和丙烯酸羟基乙酯)、含有伯/仲/叔氨基的丙烯酸酯和甲基丙烯酸酯、丙烯酰胺和其衍生物、甲基丙烯酰胺和其衍生物等等;单官能乙烯基单体,如苯乙烯和其衍生物、乙酸乙烯酯和其衍生物等等。
用于制造微凝胶的聚合中的单体还包括选自但不限于以下的多官能交联单体:二丙烯酸酯和二甲基丙烯酸酯,如乙二醇二丙烯酸酯、二乙二醇二甲基丙烯酸酯(EGDMA)、四乙二醇二甲基丙烯酸酯等等;三丙烯酸酯和三甲基丙烯酸酯,如三羟甲基丙烷三甲基丙烯酸酯(TMPTMA)、季戊四醇三丙烯酸酯等等;二季戊四醇五丙烯酸酯、季戊四醇四丙烯酸酯;其它双官能交联单体,如二乙烯苯(DVB)、亚甲基双丙烯酰胺的衍生物等等。
制造微凝胶的聚合可包括并入用于自由基聚合的引发剂。适用引发剂包括热引发剂、氧化还原引发剂和紫外光(UV)引发剂。过氧化物和脂族偶氮化合物可作为热引发剂使用,并且包括过硫酸钠、过硫酸钾、过硫酸铵、过氧化苯甲酰(BPO)、2,2-偶氮双异丁腈(AIBN)等等。氧化还原抑制剂可由以下所组成:氧化剂,如过硫酸盐或氢过氧化物,和还原剂,如抗坏血酸、甲醛化次硫酸盐(SFS)、四甲基乙二胺(TMEDA)、2-羟基-2-亚磺酸基乙酸的二钠盐、2-羟基-2-磺酸基乙酸的二钠盐和亚硫酸氢钠的混合物(布吕格曼(Bruggolit)FF6和FF7)和偏亚硫酸氢钠等等。适用氧化还原引发剂的实例是过硫酸铵(APS)/TMEDA、氢过氧化叔丁基(TBHP)/FF7、H2O2/FF7等等。
制造微凝胶的聚合可进一步包括并入乳化剂,所述乳化剂包括阴离子、非离子和阳离子表面活性剂以及其混合物。阴离子表面活性剂包括磺酸盐、硫酸盐、醚硫酸盐、磷酸酯。典型的硫酸盐包括月桂基硫酸铵、月桂基硫酸钠(SDS,十二烷基硫酸钠)、乙氧基化(ethoxylated)和硫酸化的直链醇(艾贝斯(Abex)8018)等等。阳离子表面活性剂可含有伯、仲、或叔胺,其包括溴化十二烷基三甲基铵(DTAB)、溴化鲸蜡基三甲基铵(CTAB)等等。短或长链脂肪醇或烷烃还可作为共乳化剂使用。非离子表面活性剂包括聚氧乙烯,如壬基苯酚聚乙氧基醚(NP-4、NP-9、NP-15、NP-30、NP-40、NP-70等等)、聚氧乙二醇、聚氧丙二醇、聚氧乙二醇山梨糖醇烷基酯(聚山梨醇酯)、山梨糖醇烷基酯等等。如聚乙烯醇和羟乙基纤维素的非表面活性剂稳定剂还可作为界面稳定剂使用。上述表面活性剂的混合物可用于微凝胶乳胶乳液中以确保所欲胶态稳定性。
用于步骤(b)中的水性介质的有机溶剂选择是取决于欲陷留/固定在微凝胶中的腐蚀抑制剂的化学结构。就如苯并噻唑和苯并三唑类化合物的某些腐蚀抑制剂来说,适合的溶剂应提供良好溶解性并且其沸点应低于100℃(水的沸点)以供后续的溶剂汽提。在一个实施例中,用于溶解如苯并噻唑和苯并三唑类的有机腐蚀抑制剂的水性介质是异丙醇(IPA)和水的混合物。然而,如乙醇、甲醇或正丙醇的其它类似溶剂也可以是可能的选择。就陷留化学结构不同于苯并三唑类化合物的其它腐蚀抑制剂来说,可使用具有低于100℃沸点的其它常见溶剂,如甲基乙基酮(MEK)、丙酮、乙酸乙酯等等,此取决于抑制剂的溶解性。
由于上述步骤(c)的结果,一些腐蚀抑制剂化合物被固定或陷留在微凝胶颗粒的交联聚合物网络中。一些抑制剂化合物是通过共价键结附着到交联聚合物网络,而其它抑制剂化合物是物理地陷留或固定在交联聚合物网络中。微凝胶颗粒的核相对为疏水性而微凝胶颗粒的外表面相对为亲水性。从步骤(c)制得的微凝胶颗粒将在本发明中称作“腐蚀抑制性微凝胶”。
在步骤(a)中制得的初始微凝胶优选地具有在50nm到130nm范围内的平均粒度。在步骤(c)中制得的膨胀微凝胶可具有在160nm到220nm范围内的平均粒度,并且接着在溶剂汽提后,其收缩到如130nm到200nm的较小粒度。
上述平均粒度是通过光散射方法测得并且以平均体积计。如马尔文ζ粒度仪(MalvernZetasizer)ZS90或布鲁克海文纳米DLS(BrookhavenNanoDLS)的动态光散射仪器通常是用于纳米到微米大小的粒度分析。如日本掘场(Horiba)910、马尔文万能粒度仪(MalvernMastersizer)2000、贝克曼库尔特(BeckmanCoulter)LS13320的光散射或激光衍射粒度分析仪是应用于次微米到微米大小的粒度分析。
优选地,从步骤(c)制得的乳胶乳液具有15重量%到20重量%的固体含量,并且在步骤(d)中的溶剂汽提后,固体含量增加到20重量%到30重量%。可通过在真空下在如60℃的低温下加热进行溶剂汽提。
从步骤(d)得到的腐蚀抑制性微凝胶是呈乳胶乳液形式,其可呈这一形式并入到底涂剂调配物中。或者,从步骤(d)制得的乳胶乳液可经干燥以制得呈粉末形式的腐蚀抑制性微凝胶颗粒。可接着将所得粉末添加到所述底涂剂调配物。呈粉末形式的所述微凝胶颗粒可具有在100nm到10μm范围内的粒度。举例来说,用于从乳胶乳液得到干燥微凝胶颗粒的方法可包括:(a)使用如甲醇的沉淀剂以使乳胶不稳定,(b)收集沉淀固体,(c)洗涤除去表面活性剂,接着(d)在低温度下干燥以得到干燥粉末。作为另一个实例,干燥方法可包括:直接喷雾干燥所制得的乳胶乳液以得到干燥粉末(也就是说,使用喷嘴以高速度喷射出干燥颗粒)。
通过以本文所公开方法形成负载有腐蚀抑制剂的微凝胶颗粒,各颗粒中可并有如50%到60%的高含量腐蚀抑制剂。这一高负载量的优点在于,在减少的加料量下具高效率的抗腐蚀性能,而不会影响添加所述腐蚀抑制剂的底涂剂调配物的其它重要性质。
响应于腐蚀事件,例如,pH和/或温度改变和/或湿气暴露,释放出陷留/固定在微凝胶颗粒中的腐蚀抑制剂。当湿气或水分渗透穿过底涂剂膜并且接触微凝胶颗粒时,聚合网络的亲水部分将水合化并且膨胀体积以允许抑制剂缓慢扩散而释放到周围区域中。提高温度和pH可有利于这种膨胀并且加速固定抑制剂的扩散式释放。此外,某些特定的腐蚀抑制剂还可经由包括酯或酰胺键联的不稳定化学键锚定到微凝胶网络。由腐蚀事件所产生的碱性氢氧化物(pH提高)使所述化学键联断裂并且因而触发将锚定的抑制剂释放到底涂剂膜中以实现腐蚀保护。一旦释放,则活性腐蚀抑制剂浸出到腐蚀部位并且防止金属衬底发生腐蚀。
腐蚀抑制剂
用于制备腐蚀抑制性微凝胶颗粒中的适用有机腐蚀抑制剂可选自下述化合物:
a)基于氨基苯并噻唑的化合物,它具有结构式:
其中R3是选自H、CnH2n+1和OCnH2n+1;
b)基于苯并三唑的化合物,它具有结构式:
其中R1是选自H、CnH2n+1、COOH和OH;
其中R2是选自H和CnH2n+1;
c)基于苯基马来酰亚胺的化合物,它具有结构式:
其中各R4独立地选自:S、NH和O;和
d)基于巯基苯并咪唑的化合物,它具有结构式:
其中R5是选自:H、CnH2n+1、COOH和OH;和
其中n是整数。
如本文中所使用,术语“基于氨基苯并噻唑的化合物”是指具有核结构为稠合氨基噻唑环的苯环的化合物,如
类似地,如本文中所使用,术语“基于苯并三唑的化合物”是指具有核结构为稠合三唑环的苯环的化合物,如
基于上述基础上,“基于羧基苯并三唑的化合物”的一个实例因此将为如上所说明以羧基作为苯环上的取代基的化合物。
适合本文所述组合物和方法中的有机腐蚀抑制剂的实例包括(但不限于)氨基甲基苯并噻唑、硫醇化4-羧基苯基马来酰亚胺、4-和/或5-羧基苯并三唑(CBT)和巯基苯并咪唑(MBI)。
在一个实施例中,苯并三唑化合物是具有以下结构式的羧基苯并三唑:
腐蚀抑制剂的另一个实例是基于氨基苯并噻唑的化合物,它具有结构式:
其中R3是H、CnH2n+1或OCnH2n+1;和
其中n=1到10。
CnH2n+1的实例包括(但不限于)CH3、C2H5或C3H7等等。OCnH2n+1的实例包括(但不限于)OCH3、OC2H5或OC3H7等等。
在一个实施例中,基于氨基苯并噻唑的化合物是2-氨基-6-甲基苯并噻唑,其具有以下式:
腐蚀抑制剂的另一个实例是基于苯基马来酰亚胺的化合物,如
其中R4独立地为S、NH或O。在一个实施例中,各R4为S,且因此可称作硫醇化苯基马来酰亚胺。
非铬酸化底涂剂组合物
如上所述的腐蚀抑制性微凝胶颗粒适于并入到欲用于结构结合的底涂剂组合物中。更特定来说,非铬酸化底涂剂组合物适合在金属-到-金属结合或金属-到-复合材料结合之前处理金属表面。本文所公开的非铬酸化底涂剂组合物能够实现与常规上用于改良重度腐蚀衬底(如金属和金属合金)的耐腐蚀性的含有铬酸盐的溶液相当的耐腐蚀性。
如本文中所述,腐蚀抑制性微凝胶的组合、固化剂的类型和底涂剂组合物的pH是已发现可影响腐蚀性能的因素,使得可实现与含有铬酸盐的组合物相当的腐蚀性能。
本文所公开的非铬酸化底涂剂组合物是含有以下的水性调配物:环氧树脂;能够在大于200°F(例如250°F到350°F)的温度下固化的固化剂;包含可水解基团的有机硅烷;和本文所公开的腐蚀抑制性微凝胶。
本文所公开的非铬酸化(也就是说,无铬酸盐)底涂剂组合物提供优异的机械和耐久性质,其中基于环氧化物的粘着剂中大多数可在250°F和350°F下固化。因为无铬酸盐底涂剂组合物不含溶剂或具有极少量溶剂,所以它符合特定政府安全性和健康要求。另外,这类底涂剂组合物与如磷酸阳极氧化和溶胶-凝胶表面处理的各种表面处理兼容。
根据一个实施例,非铬酸化底涂剂调配物可包含如ECN1400(购自亨斯迈(Huntsman))的环氧树脂或包括如伊普瑞斯(Epirez)5003(购自亨斯迈)的酚醛环氧树脂、如XU3903(购自锐意卓越产品(ResolutionPerformanceproducts))和DER669(购自陶氏(Dow))的双酚A环氧树脂的环氧树脂组合;固化剂,如双(3-氨基丙基)-哌嗪(“BAPP”)(购自BASF);具有可水解基团的有机硅烷,如Z-6040(γ-缩水甘油氧基丙基三甲氧基硅烷,购自道康宁(DowCorning),密歇根州密德兰);和本文所公开的腐蚀抑制性微凝胶颗粒。
如本文中所用,术语“铬酸盐”是指铬酸盐腐蚀抑制剂,如铬酸锶、铬酸钡、铬酸锌、或铬酸钙。铬酸盐腐蚀抑制剂释放六价铬(Cr6+)(人类致癌物),因此,不期望使用它。
如本文中所用,术语“底涂剂组合物”是指欲用于提供金属衬底与结构粘着剂间充分粘着的结构结合的组合物。其还使金属衬底上的金属氧化物层稳定并且保护金属免受如因热和/或湿以及咸的环境所引起腐蚀的影响。
适于与本文所述非铬酸化腐蚀抑制性底涂剂组合物一起使用的金属衬底的实例包括钛、铝和其合金,如Al-2024、Al-6061、Al-7075、或铝-锂合金。
环氧树脂
用于非铬酸化底涂剂组合物的适用环氧树脂包括常规的具有至少约1.8官能度、或至少约2官能度并且实质上不含有离子基或酯基的固态环氧树脂。所述环氧树脂是酚类(如间苯二酚和双酚,举例来说,双酚A、双酚F等等)的任选地经链增长的固态缩水甘油醚。还适用的是芳族胺和氨基酚的固态缩水甘油衍生物,如N,N,N’,N’-四缩水甘油基-4,4’-二氨基二苯基甲烷。在其它方面中,环氧树脂是固态酚醛环氧树脂和固态双酚A的二缩水甘油醚(“DGEBA”)树脂。在某些实施例中,环氧树脂呈固体形式,或当与其它的环氧化物混合时得到固体组合物。在其它实施例中,环氧树脂具有约145到5000的环氧当量(EEW),以约300到750的当量为优选,且325的当量为最优。实例包括酚醛环氧树脂(如伊普瑞斯5003,购自亨斯迈)和双酚A环氧树脂(如XU-3903)、或固态双酚A环氧树脂(如DER669)(购自陶氏)。
适用市售环氧树脂的实例是SU-8(购自壳牌化学品公司(ShellChemicalCo.)),它是从壳牌化学品公司得到的平均官能度为约8、熔点(达兰(Durran’s))为82℃和环氧当量(EEW)为215的聚合环氧树脂;DER669(购自陶氏),它是从陶氏化学品公司(DowChemicalCompany)得到的达兰软化点为135℃到155℃和环氧当量为3500到5500的高分子量固态环氧树脂;522-C,它是从壳牌化学品公司得到的环氧当量为550到650和达兰熔点为75℃到85℃的固态DGEBA环氧树脂;和从汽巴-嘉基(Ciba-Geigy)得到的环氧官能度为3.8到5.4、环氧当量为225到235和熔点为73℃到99℃的ECN1273、1280和1299酚醛环氧树脂。这些树脂一般以固体形式供应并且研磨达到特定粒度,或以水性分散液供应。例如,ECN-1299呈水性分散液以ECN-1440从汽巴-嘉基得到,并且522C呈35201环氧树脂分散液从壳牌化学品公司得到。环氧树脂通常以占底涂剂组合物总重量约20到60重量%含量存在。
适用的环氧共聚单体树脂也可并入到底涂剂组合物中。所述树脂的实例是双酚(特别是双酚A、双酚F和双酚S)的二缩水甘油醚。还适用的是各种酚系和甲酚系酚醛型树脂、以及各种缩水甘油醚氧基胺和氨基苯酚,特别是N,N,N’,N’-四(缩水甘油基)-4,4-二氨基二苯基甲烷和N,N,O-三(缩水甘油基)-4-氨基苯酚。基于各种二羟基萘和酚化二环戊二烯的缩水甘油醚的环氧树脂也适用。
酚系树脂可包括其中邻亚甲基相对对亚甲基键比小于1.0的酚醛型酚系树脂(所谓的无规酚醛型酚系树脂)和/或可溶酚醛树脂(resole)型酚系树脂(羟甲基类型、或二亚甲基醚类型)。还可使用常见酚醛型酚系树脂和/或可溶酚醛树脂型酚系树脂的混合物。
乳化环氧树脂可用作用于底涂剂组合物中的共反应物或改性剂。这些乳液可以1%到10%的含量添加到底涂剂组合物中。适用的乳化环氧树脂可从壳牌化学品公司、汽巴-嘉基和维诺华(Vianova)购得。一些实例包括来自壳牌化学品公司的ER3510-W-60和ER3515-W-60或来自汽巴-嘉基的PY323。
在一些实施例中,分散相中环氧树脂含量占底涂剂组合物40重量%到约10重量%,而水性连续相中环氧树脂含量占底涂剂组合物60重量%到约90重量%。在分散相中的环氧树脂可是多于一种环氧树脂呈不同颗粒混合物形式的分散液,或可由仅一种类型颗粒(每颗粒含有多于一种环氧树脂)所组成。因此,可将增韧环氧树脂(如较高分子量的双酚A或双酚F环氧树脂)与高耐热性环氧树脂(如TGMDA)掺合,接着使所述混合物冷却,研磨,或以其它方式分散到必要尺寸的固态颗粒中。这些相同环氧树脂可有利地在不进行掺合下分开地分散。
环氧树脂的混合物也适用。在一个实施例中,树脂混合物含有官能度为约5.5或更小的固态环氧树脂和官能度为约6或更大的固态环氧树脂。适合地,以少量(举例来说,占组合物中所有环氧树脂重量总和40重量%以下)使用较高官能度环氧树脂(即,官能度为5或更大的环氧树脂)。已出人意料地发现以所述少量使用这类较高官能度环氧树脂可增强固化底涂剂组合物的抗溶剂性而不会实质上减低粘着性质。一种优选的高官能度环氧树脂是SU-8,它是平均官能度为8的聚合固态环氧树脂。
在一个实施例中,非铬酸化底涂剂组合物包括下述环氧树脂的混合物:
1)30到70重量%的官能度为约1.8到约4和环氧当量为约400到约800的环氧树脂;
2)5到20重量%的官能度为约1.8到约4和环氧当量为约2000到约8000的环氧树脂;和
3)10到40重量%的官能度为约5或更大并且环氧当量为约100到约400的环氧树脂,所述重量百分比总和以环氧树脂混合物总重量计为100%。
有机硅烷
如本文中所用,术语“具有可水解基团的有机硅烷”是指具有可水解基团的那些有机硅烷。
在一个实施例中,用于非铬酸化腐蚀抑制性底涂剂调配物中的有机硅烷化合物具有可与欲与金属表面结合的材料起反应或可与所述材料结合的硅烷官能团。在某些实施例中,有机硅烷具有以下结构式:
其中n大于或等于0;其中各X是OH、OCH3和OCH2H5;其中R1是CH=CH2、
或CH2-CH2-CH2-Y,其中Y是NH2、SH、OH、NCO、NH-CO-NH2、NH-(CH2)3NH2、NH-芳基、
或
和其中各R2是烷基、烷氧基、芳基、经取代的芳基、或R1。
适用的市售有机硅烷化合物(购自特种有机硅有限公司(OSiSpecialtiesInc.),康涅狄格州丹伯里)的实例包括(但不限于)A-186,它是β-(3,4-环氧基环己基)乙基三甲氧基硅烷;A-187,它是γ-缩水甘油氧基丙基三甲氧基硅烷;A-189,它是γ-巯基丙基三甲氧基硅烷;A-1100,它是γ-氨基丙基三乙氧基硅烷;A-1106,它是氨基烷基硅酮溶液;A-1170,它是双(γ-三甲氧基硅基丙基)胺;Y-9669,它是N-苯基-γ-氨基丙基-三甲氧基硅烷;Y-11777,它是氨基烷基硅酮/水溶液;和Y-11870,它是环氧官能团硅烷溶液。其它适用的市售有机硅烷包括(但不限于)Z-6040(γ-缩水甘油氧基丙基三甲氧基硅烷,来自道康宁,密歇根州米德兰)和HS2759(水性环氧官能团硅烷);HS2775(水性氨基硅烷溶液);和HS2781(具有氨基和乙烯基的水性低聚硅烷溶液),它们均由豪尔斯美国有限公司(HulsAmericaInc.),新泽西州桑默瑟(Somerset,N.J)销售。另一个实例是以商标Z-6040销售的3-缩水甘油氧基丙基甲氧基硅烷。
一般来说,有机硅烷以范围从约0.01到75份/100份环氧树脂、优选地从约0.01到30份/100份环氧树脂,更优约0.01到10份/100份环氧树脂和最优约1到7份/100份环氧树脂的量存在于腐蚀抑制性底涂剂组合物中。
在一些实施例中,将呈液体形式的有机硅烷直接添加到水性底涂剂组合物中。接着利用常规方法将有机硅烷分散于水中。举例来说,一种使有机硅烷分散在水中的方法包括在强力搅拌下将有机硅烷滴落到热固性树脂水溶液中。还可首先将有机硅烷溶解或悬浮在可与水混溶的溶剂中。在后项情况中,有机硅烷溶液在无过度搅拌或混合下简单地添加到水中。接着将所述有机硅烷水溶液与水性热固性组合物混合。
固化剂
结构结合期间的固化温度会影响底涂剂调配物在底涂剂组合物被用于腐蚀衬底(如铝和铝合金上)时得到底涂剂组合物腐蚀抑制性能的能力。因此,在一个优选的实施例中,底涂剂调配物含有在大于200°F(93℃)的温度(例如250°F到350°F(121到177℃))下固化的固化剂。在一些实施例中,可使用可在300°F(148℃)或更大温度下固化的固化剂。
如本文中所使用,用于使环氧树脂固化的“固化剂”包括在室温下是固态的实质上非水溶性固化剂。这类固化剂的实例是芳族胺固化剂,如4,4’-二氨基二苯基甲烷、2,2-双(4-[4-氨基苯氧基]苯基)丙烷和3,3’-和4,4’-二氨基二苯基砜。其它适用的固化剂是3,3’-和4,4’-二氨基二苯基氧化物、3,3-和4,4’-二氨基二苯基氧化物、3,3’-和4,4’-二氨基二苯基硫醚和3,3’-和4,4’-二氨基二苯基酮。在一些实施例中,固化剂是4,4’-[1,4-亚苯基(1-甲基亚乙基)]-双(苯胺)。还适用的是氨基和羟基封端的聚亚芳基低聚物,其中重复苯基由醚基、硫化物基、羰基、砜基、碳酸酯基、或类似基团间隔。这类固化剂的实例是氨基-和羟基-封端的聚亚芳基砜、聚亚芳基醚砜、聚醚酮、聚醚醚酮和类似变型。
还适用的是氨基和羟基封端的聚亚芳基低聚物,其中重复苯基由醚基、硫化物基、羰基、砜基、碳酸酯基、或类似基团间隔。所述固化剂的实例是氨基-和羟基封端的聚亚芳基砜、聚亚芳基醚砜、聚醚酮、聚醚醚酮和类似变型。固化剂通常以约2到约30份/100份所述热固性树脂的量存在。
“环氧固化剂”的其它实例包括经取代的氨基三嗪,如以商标CUREZOL2-Mz-吖嗪销售的2-β-(2’-甲基咪唑基-1’1-乙基-4,5-二氨基-s-三嗪;以商标胺卡胺(Ancamine)销售的改性聚胺;双氰胺(dicyanadiamide)(DICY);咪唑类;基于双脲的固化剂(如优美科(Omicure)24)或甲苯-2,4-双(N,N’-二甲基脲)(如来自CVC化学品(CVCchemicals)的优美科U-24);胺-环氧加成物和/或芳族胺,如双(3-氨基丙基)-哌嗪(BAPP)(购自巴斯夫(BASF))。
适于与本发明非铬酸化腐蚀抑制性底涂剂调配物一起使用的其它适用的固态二胺固化剂包括2,4-甲苯二胺、1,4-苯二胺、2,2-双(4-氨基苯基)六氟丙烷、2,2-双(3-氨基-4-羟基苯基)六氟丙烷、3,4’-二氨基二苯基氧化物、9,9-双(4-氨基苯基)芴、邻-甲苯胺砜和4,4’-二氨基苯甲酰苯胺。尤其优选的是9,10-双(4-氨基苯基)蒽、2,2-双(4-[3-氨基苯氧基]苯基)砜、2,2-双(4-[4-氨基苯氧基]苯基)砜、1,4-双(4-氨基苯氧基)联苯、双(4-[4-氨基苯氧基)苯基)醚和2,2-双([4-(4-氨基-2-三氟苯氧基)]苯基)六氟丙烷。还包括XU95101,它是商业上从汽巴-嘉基得到的固化剂。固化剂的一个实施例是4,4’-[1,4-亚苯基(1-甲基亚乙基)]-双(苯胺)。
在一些实施例中,使用具有低于240℃、或低于175℃熔点的固态胺固化剂。在其它实施例中,使用那些具有低于300°F、或低于220°F熔点的固态胺固化剂。当使用低于300°F的固化剂时,本文所述的底涂剂调配物中需要至少两种腐蚀抑制剂。在其它实施例中,使用具有300°F或更大,例如300°F到400°F、325°F到375°F、或如约350°F固化温度的固化剂,如BAPP(购自巴斯夫)。固化剂可以底涂剂调配物总重量约1%到10%,如约2%到5%的量使用。
如本文中所用,术语“腐蚀性能”具有它为所属领域的技术人员已知的通常含义并且举例来说使用图像执行软件测量环境暴露后经腐蚀金属的程度。ASTMB117是针对于盐雾暴露的规范,即,试件必须暴露以测量腐蚀性能的条件。暴露于ASTMB117盐雾下的试件可用于通过观察或通过利用将根据样本图像量化出现腐蚀的区域的图像概况分析软件(imageprofilingsoftware)来测量腐蚀。举例来说,腐蚀性能可测量为盐雾暴露42天后的腐蚀百分比。与铬酸盐相当的腐蚀性能意味着近似至少90%(如至少95%或97%)的试件在暴露后未被腐蚀。因此,与铬酸盐相当的腐蚀性能可意味着约小于10%腐蚀,并且在其它实施例中,是5%、4%、3%、2%或更小的腐蚀,如1%到2%。可利用ASTMD1002(为制造进行腐蚀性能试验的样本的规范)制造试件。ASTMD1002测量腐蚀性能和具体来说为搭接剪切接头(lapshearjoint)试验和测量粘着接头的剪切强度。
在一些实施例中,非铬酸化腐蚀抑制性底涂剂组合物具有如6到8或7到8的中性pH。并入微凝胶颗粒中的可释放腐蚀抑制剂有助于维持底涂剂组合物中的中性pH(如6到8或7到8的pH),从而使得底涂剂组合物与各种表面处理兼容。
如本文中所用,术语“近似”、“约”和“实质上”表示接近所述量的仍执行所欲功能或实现所欲结果的量。例如,术语“近似”、“约”和“实质上”可指在小于所述量10%内、在小于所述量5%内、在小于所述量1%内、在小于所述量0.1%内和在小于所述量0.01%内的量。
如本文中所用,术语“…的至少一部分”表示一定量的整体,它包含可包括所述整体的一定量的所述整体,它。举例来说,术语“…的一部分”可指大于0.01%整体、大于0.1%整体、大于1%整体、大于10%整体、大于20%整体、大于30%整体、大于40%整体、大于50%整体、大于60%整体、大于70%整体、大于80%整体、大于90%整体、大于95%整体、大于99%整体和100%整体的量。
实例
提供以下实例以帮助所属领域的技术人员进一步理解本发明的实施例。这些实例计划实现说明目的而不应被理解为限制本发明的实施例或随附本发明的权利要求书的范围。
实例1
制备微凝胶腐蚀抑制剂1
在70℃下于氮气氛围下,使用75g丙烯酸乙酯(EA)、60g甲基丙烯酸甲酯(MMA)、105g甲基甲基丙烯酸、30g二乙二醇二甲基丙烯酸酯(EGDMA)和30g三羟甲基丙烷三甲基丙烯酸酯(TMPTMA)的单体掺合物、0.12g过硫酸钠作为引发剂和30g艾贝斯8018作为乳化剂,通过乳液聚合制得微凝胶乳胶。所得微凝胶乳胶具有15%到20%固体(以重量计)的固体含量并且含有具有50nm到80nm平均粒度的微凝胶颗粒。
在50℃下,将181g有机抑制剂2-氨基6-甲基苯并噻唑溶解在异丙醇和水(80/20比)的水性混合物中。接着,将这一混合物添加到微凝胶乳胶中并且搅拌1小时。结果,所述微凝胶颗粒膨胀为160nm到200nm大小。在通过于真空下60℃汽提除去异丙醇使颗粒反膨胀后得到具有20到30%固体(以重量计)的固体含量的微凝胶抑制剂乳胶。所得微凝胶抑制性微凝胶颗粒在本文中称作“微凝胶腐蚀抑制剂1”。
根据表1中所公开的调配物制得水基非铬酸化(无铬酸盐)底涂剂调配物(F1)。“重量%”是指以重量计的百分比。
表1-无铬酸盐底涂剂调配物F1
组分 | 用量 |
固态双酚A环氧树脂在水中的非离子分散液 | 133g |
平均环氧官能度为3的环氧化双酚A酚醛树脂的水性分散液 | 72g |
表氯醇和双酚A的固体反应产物 | 9g |
脂族胺和酚系树脂的混合物 | 11g |
咪唑固化剂 | 4g |
非晶型二氧化硅 | 0.3g |
氰基胍(DICY) | 3g |
葩丽特(Paliotol)黄颜料 | 1.8g |
微凝胶腐蚀抑制剂1 | 110g |
缩水甘油氧基丙基三甲氧基硅烷(有机硅烷) | 总水含量的1重量% |
苯并异噻唑啉酮(BIT)的水溶液 | 总调配物的0.1重量% |
去离子(DI)水 | 以提供25重量%固体 |
将非铬酸化底涂剂调配物F1喷到经FPL蚀刻的铝合金(Al-2024)表面上以进行划线腐蚀试验(scribecorrosiontest)。FPL是指根据ASTMD2651的用于处理金属的表面蚀刻处理。为进行比较,还将购自氰特工业有限公司(CytecIndustriesInc.)的基于铬酸盐的底涂剂调配物BR6747-1(作为对照组)和购自氰特工业有限公司的无铬酸盐底涂剂调配物BR6700-1(作为参照组)喷到经FPL蚀刻的铝合金(Al-2024)表面上以进行相同划线腐蚀试验。BR6700-1含有市售无机海洛斯腐蚀抑制剂(基于磷酸锌的化合物)。对于机械试验,在FPL蚀刻之后进行根据ASTMD3933的磷酸阳极氧化(PAA)。在250°F下使底涂剂调配物固化1小时并且在盐雾暴露(ASTMB117)1000小时(42天)后接受三种腐蚀试验:a)划线腐蚀试验(ASTMD1654)和b)利用来自氰特工业有限公司的基于环氧化物的粘着剂FM73的单搭接剪切试验(ASTMD1002),和c)利用FM73粘着剂的粘合层剥离。
水基非铬酸化底涂剂调配物F1在1000小时划线试验之后提供与铬酸化底涂剂BR6747-1相当的腐蚀性能,且未观察到明显腐蚀部位,然而,使用无机抑制剂的非铬酸化底涂剂调配物BR6700-1显示接近两条划线的若干腐蚀部位。
表2显示水基非铬酸化底涂剂调配物F1提供与铬酸化底涂剂BR6747-1(对照组)相当的而且实质上高于使用无机抑制剂的非铬酸化底涂剂BR6700-1的在盐暴露之前和之后的搭接剪切强度。表2还指明水基底涂剂调配物F1得到与铬酸化底涂剂BR6747-1(对照组)相当并且比非铬酸化底涂剂BR6700-1更优的在1000小时盐暴露之前和之后的粘合层剥离强度。
表2
实例2
根据表3中所公开的调配物制得水基非铬酸化底涂剂调配物F2。“重量%”是指以重量计的百分比。
表3-无铬酸盐底涂剂调配物F2
组分 | 用量 |
固态双酚A环氧树脂在水中的非离子分散液 | 43g |
平均环氧官能度为3的环氧化双酚A酚醛树脂的水性分散液 | 23g |
表氯醇和双酚A的固体反应产物 | 5g |
2,2-双-4-(4-氨基苯氧基)苯基丙烷 | 10g |
甲苯-2,4-双(N,N’-二甲基脲) | 4g |
葩丽特黄 | 1g |
微凝胶腐蚀抑制剂1 | 65g |
非晶型二氧化硅(卡博特(Cabosil)) | 0.2g |
缩水甘油氧基丙基三甲氧基硅烷(有机硅烷) | 总水含量的1重量% |
苯并异噻唑啉酮(BIT)水溶液 | 总调配物的0.1重量% |
DI水 | 以提供20重量%固体 |
将上述调配物F2和铬酸化底涂剂调配物BR6747-1(对照组)喷到经FPL蚀刻的Al-2024铝合金表面上以进行划线腐蚀试验。对于机械试验,在FPL蚀刻之后进行磷酸阳极氧化。在250°F下使所述底涂剂调配物固化1小时并且在盐雾暴露(ASTMB117)1000小时(42天)后接受三种腐蚀试验:a)划线腐蚀试验(ASTMD1654)和b)利用FM73粘着剂的粘合层剥离。使用微凝胶抑制剂的非铬酸化底涂剂调配物F2得到与铬酸化底涂剂BR6747-1相当的1000小时划线腐蚀性能。
实例3
制备微凝胶腐蚀抑制剂2
在70℃下于氮气氛围下,使用75g丙烯酸乙酯(EA)、60g甲基丙烯酸甲酯(MMA)、105g甲基甲基丙烯酸、30g二乙二醇二甲基丙烯酸酯(EGDMA)和30g三羟甲基丙烷三甲基丙烯酸酯(TMPTMA)的单体掺合物、0.12g过硫酸钠作为引发剂和30g艾贝斯8018作为乳化剂,通过乳液聚合制得微凝胶乳胶。所得微凝胶乳胶具有15到20%固体的固体含量和具有50nm到80nm平均粒度的微凝胶颗粒。
在50℃下,将180g有机抑制剂羧基苯并三唑溶解于80/20比的异丙醇和水混合物中。接着将此混合物添加到微凝胶纳米乳胶中并且搅拌1小时。乳胶颗粒膨胀为160nm到200nm大小。在通过真空下在60℃汽提除去异丙醇使所述颗粒反膨胀后得到具有20到30重量%固体的微凝胶抑制剂乳胶。所得微凝胶抑制性微凝胶颗粒在本文中称作“微凝胶腐蚀抑制剂2”。
根据表4中所公开的调配物制得水基非铬酸化底涂剂调配物F3。“重量%”是指以重量计的百分比。
表4-非铬酸化调配物F3
组分 | 用量 |
固态双酚A环氧树脂在水中的非离子分散液 | 133g |
平均环氧官能度为3的环氧化双酚A酚醛树脂的水性分散液 | 72g |
表氯醇和双酚A的固体反应产物 | 9g |
胺固化剂(脂族胺和酚系树脂的混合物) | 11g |
咪唑固化剂 | 4g |
非晶型二氧化硅 | 0.3g |
氰基胍(DICY) | 3g |
葩丽特黄颜料 | 1.8g |
微凝胶腐蚀抑制剂2 | 110g |
缩水甘油氧基丙基三甲基硅烷(有机硅烷) | 总水含量的1重量% |
苯并异噻唑啉酮(BIT)水溶液 | 总调配物的0.1重量% |
DI水 | 以提供25重量%固体 |
将以上所显示的调配物和铬酸化底涂剂BR6747-1对照组喷到经FPL蚀刻的Al-2024合金上以进行划线腐蚀试验。对于机械试验,在FPL蚀刻之后进行磷酸阳极氧化。在250°F下使所述底涂剂固化1小时并且在盐雾暴露(ASTMB117)1000小时(42天)后接受三种腐蚀试验:a)划线腐蚀试验(ASTMD1654)和b)利用FM73粘着剂的粘合层剥离。使用微凝胶腐蚀抑制剂2的新颖非铬酸化底涂剂调配物F3显示与铬酸化底涂剂BR6747-1相当的1000小时划线腐蚀性能。
实例4
根据表5中所公开的调配物制得水基非铬酸化底涂剂调配物F4。“重量%”是指以重量计的百分比。
表5-非铬酸化底涂剂调配物F4
组分 | 用量 |
环氧甲酚酚醛树脂 | 50g |
2,2-双-4-(4-氨基苯氧基)苯基丙烷 | 19g |
葩丽特黄颜料 | 0.45g |
非晶型二氧化硅 | 0.2g |
微凝胶腐蚀抑制剂1 | 125g |
缩水甘油氧基丙基三甲氧基硅烷(有机硅烷) | 总水含量的0.25重量% |
苯并异噻唑啉酮(BIT)水溶液 | 总调配物的0.1重量% |
DI水 | 以提供20重量%固体 |
将上述底涂剂调配物F4和购自氰特工业有限公司的基于铬酸盐的底涂剂调配物BR6750(作为对照组)喷到经FPL蚀刻的Al-2024铝合金表面上以进行划线腐蚀试验。对于机械试验,在FPL蚀刻之后进行磷酸阳极氧化。在350°F下使所述底涂剂调配物固化1小时并且在盐雾暴露(ASTMB117)1000小时(42天)后接受三种腐蚀试验:a)划线腐蚀试验(ASTMD1654)和b)利用FM350NA粘着剂的粘合层剥离。使用微凝胶腐蚀抑制剂1的新颖非铬酸化底涂剂调配物F4显示与基于铬酸盐的底涂剂调配物BR6750相当的1000小时划线腐蚀性能。
实例5
具有纯苯并噻唑的对照底涂剂调配物
为进行比较,根据表6中所公开的调配物P1制得底涂剂调配物。“重量%”是指以重量计的百分比。
表6-调配物P1
组分 | 用量 |
固态双酚A环氧树脂在水中的非离子分散液 | 738g |
环氧树脂和双酚A的聚合物 | 95.6g |
表氯醇和双酚A的高分子量固体反应产物 | 121.7g |
BAPP | 92g |
胺固化剂(优美尼科(Omnicure)24) | 27g |
葩丽特黄颜料 | 7.3g |
非晶型二氧化硅 | 16g |
DI水 | 以提供57重量%固体 |
随后,将150g底涂剂调配物P1与12.6g海洛斯Z-普莱克斯(PLEX)111(基于磷酸锌的腐蚀抑制剂)、25.2g纯2-氨基6-甲基苯并噻唑(不进行微凝胶封装)和414gDI水组合以形成腐蚀抑制性底涂剂调配物。
在环境条件下贮藏过夜之后,观察到大块的固体块团形成于所制得底涂剂调配物中并且不可再分散,此表明直接添加纯2-氨基6-甲基苯并噻唑导致所述调配物损失其稳定性。相反地,含有微凝胶腐蚀抑制剂1和2的调配物(调配物F1到F4)在环境条件下超过一个月的长期贮藏后维持它的胶态稳定性。
Claims (19)
1.一种离散腐蚀抑制性微凝胶,其包含:
交联聚合物网络;和
陷留或固定在所述聚合物网络中的有机腐蚀抑制性化合物。
2.根据权利要求1所述的微凝胶,其中所述腐蚀抑制性化合物是选自下列:
(a)基于氨基苯并噻唑的化合物,其具有以下式:
其中R3是选自H、CnH2n+1和OCnH2n+1;
(b)基于苯并三唑的化合物,其具有以下式:
其中R1是选自H、CnH2n+1、COOH和OH;
其中R2是选自H和CnH2n+1;
(c)基于苯基马来酰亚胺的化合物,其具有以下式:
其中各R4独立地选自:S、NH和O;和
(d)基于巯基苯并咪唑的化合物,其具有以下式:
其中R5是选自:H、CnH2n+1、COOH和OH;和n是整数。
3.根据权利要求1所述的微凝胶,其中所述腐蚀抑制性化合物在暴露于选自pH改变、湿气暴露、温度提高和其组合的腐蚀触发条件后可从所述聚合物网络释放。
4.根据权利要求1到3中任一权利要求所述的微凝胶,其中所述交联聚合物网络是通过使选自以下的单体聚合而建立:单官能或双官能丙烯酸单体;单官能或双官能甲基丙烯酸单体;单官能乙烯基单体和其组合。
5.根据权利要求1到4中任一权利要求所述的微凝胶,其中一些腐蚀抑制性化合物是共价键结到所述交联聚合物网络,而一些腐蚀抑制性化合物是物理地陷留或固定在所述网络中。
6.一种可在大于200°F(93℃)的温度下固化的无铬酸盐腐蚀抑制性底涂剂组合物,所述底涂剂组合物包含:
至少一种环氧树脂;
在大于200°F(93℃)的温度下固化的固化剂;
包含可水解基团的有机硅烷;和
腐蚀抑制性微凝胶,其中各微凝胶是由交联聚合物网络和陷留在所述聚合物网络中的有机腐蚀抑制性化合物所组成。
7.根据权利要求6所述的底涂剂组合物,其中陷留在所述微凝胶中的所述腐蚀抑制性化合物是选自下列:
(a)基于氨基苯并噻唑的化合物,其具有以下式:
其中R3是选自H、CnH2n+1和OCnH2n+1;
(b)基于苯并三唑的化合物,其具有以下式:
其中R1是选自H、CnH2n+1、COOH和OH;
其中R2是选自H和CnH2n+1;
(c)基于苯基马来酰亚胺的化合物,其具有以下式:
其中各R4独立地选自:S、NH和O;和
(d)基于巯基苯并咪唑的化合物,其具有以下式:
其中R5是选自:H、CnH2n+1、COOH和OH;和n是整数。
8.根据权利要求6或7所述的底涂剂组合物,其中所述腐蚀抑制性化合物在暴露于选自pH改变、湿气暴露、温度提高和其组合的腐蚀触发条件后可从所述聚合物网络释放。
9.根据权利要求6到8中任一权利要求所述的底涂剂组合物,其中所述固化剂是选自以下的胺化合物:芳族胺;经取代的氨基三嗪;改性聚胺;双氰胺(DICY);基于双脲的固化剂;胺-环氧加成物;二胺;咪唑;和其组合。
10.根据权利要求9所述的底涂剂组合物,其中所述胺固化剂是选自以下的芳族胺:双(3-氨基丙基)-哌嗪(BAPP);4,4’-二氨基二苯基甲烷;2,2-双(4-[4-氨基苯氧基]苯基)丙烷;3,3’-和4,4’-二氨基二苯砜;氨基和羟基封端的聚亚芳基低聚物,其中重复苯基由醚基、硫化物基、羰基、砜基和碳酸酯基中的一者间隔。
11.根据权利要求9所述的底涂剂组合物,其中所述胺固化剂是选自:9,10-双(4-氨基苯基)蒽;2,2-双(4-[3-氨基苯氧基]苯基)砜;2,2-双(4-[4-氨基苯氧基]苯基)砜;1,4-双(4-氨基苯氧基)联苯;双(4-[4-氨基苯氧基)苯基)醚;2,2-双([4-(4-氨基-2-三氟苯氧基)]苯基)六氟丙烷;4,4’-[1,4-亚苯基(1-甲基亚乙基)]-双(苯胺)。
12.一种形成腐蚀抑制性微凝胶的方法,所述方法包括:
a)通过使单体在液体介质中乳液聚合来形成离散微凝胶;
b)将有机腐蚀抑制剂溶解在含有有机溶剂和水的水性介质中;
c)将所述微凝胶与所述水性介质混合,导致所述微凝胶膨胀和所述有机腐蚀抑制剂化合物变成陷留或固定在所述聚合物网络中;和
d)汽提除去所述溶剂以得到具有较小粒度的微凝胶的乳胶乳液。
13.根据权利要求12所述的方法,其中形成离散微凝胶的所述乳液聚合包括使选自以下的单体聚合:单官能或双官能丙烯酸单体;单官能或双官能甲基丙烯酸单体;单官能乙烯基单体和其组合。
14.根据权利要求13所述的方法,其中形成离散微凝胶的所述乳液聚合进一步包括使用选自以下的多官能交联单体:二丙烯酸酯;二甲基丙烯酸酯;三丙烯酸酯;三甲基丙烯酸酯;二季戊四醇五丙烯酸酯;季戊四醇四丙烯酸酯;二乙烯苯(DVB)、亚甲基双丙烯酰胺的衍生物;和其组合。
15.根据权利要求12到14中任一权利要求所述的方法,其中用于步骤(b)中的所述有机腐蚀抑制剂是选自下列:
(i)基于氨基苯并噻唑的化合物,其具有以下式:
其中R3是选自H、CnH2n+1和OCnH2n+1;
(ii)基于苯并三唑的化合物,其具有以下式:
其中R1是选自H、CnH2n+1、COOH和OH;
其中R2是选自H和CnH2n+1;
(iii)基于苯基马来酰亚胺的化合物,其具有以下式:
其中各R4独立地选自:S、NH和O;和
(iv)基于巯基苯并咪唑的化合物,其具有以下式:
其中R5是选自:H、CnH2n+1、COOH和OH;和n是整数。
16.根据权利要求12到15中任一权利要求所述的方法,所述方法进一步包含喷雾干燥从步骤(d)得到的所述乳胶乳液以得到呈粉末形式的微凝胶颗粒。
17.根据权利要求12到15中任一权利要求所述的方法,所述方法进一步包含使从步骤(d)得到的所述乳胶乳液不稳定并干燥以得到呈粉末形式的微凝胶颗粒。
18.一种依根据权利要求12到15中任一权利要求所述的方法制得的腐蚀抑制性微凝胶。
19.一种依根据权利要求16或17所述的方法制得的呈粉末形式的腐蚀抑制性颗粒。
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US10508203B2 (en) | 2014-09-26 | 2019-12-17 | The Boeing Company | Compositions and coatings with non-chrome corrosion inhibitor particles |
US9970122B2 (en) * | 2015-02-27 | 2018-05-15 | The Boeing Company | Use of a disulfide/dithiol compound in a seal for anodized aluminum |
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Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5574377A (en) * | 1994-08-10 | 1996-11-12 | Marquez-Lucero; Alfredo | Device for the detection and localization of organic solvent leakages and fabrication process |
CN1269710A (zh) * | 1997-07-25 | 2000-10-11 | 普罗克特和甘保尔公司 | 具有涂敷有液体可溶胀材料的透气底片的吸湿用品 |
US20080254133A1 (en) * | 2005-11-25 | 2008-10-16 | The University Of Manchester | Microgel Particle |
CN102365337A (zh) * | 2009-03-31 | 2012-02-29 | 塞特克技术公司 | 用于结构粘接应用的水基非铬酸盐底漆 |
US20130017612A1 (en) * | 2011-07-11 | 2013-01-17 | United States Of America As Represented By The Administrator Of The National Aeronautics And Spac | pH-Sensitive Microparticles with Matrix-Dispersed Active Agent |
Family Cites Families (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2853423B2 (ja) * | 1990-11-16 | 1999-02-03 | 東洋インキ製造株式会社 | 反応性マイクロゲルの製造方法 |
DE59711017D1 (de) * | 1996-07-02 | 2003-12-24 | Vantico Ag | Härter für Epoxidharze |
US6436508B1 (en) * | 1997-07-25 | 2002-08-20 | The Procter & Gamble Company | Absorbent articles having a liquid swellable material coated breathable backsheet |
TW457284B (en) | 1997-09-12 | 2001-10-01 | Cytec Tech Corp | Water based primer compositions and their use for treating metal surfaces |
US6387497B1 (en) | 1997-12-19 | 2002-05-14 | Matsumoto Yushi-Seiyaku Co Ltd | Synthetic organic particles, process for the production of the same, and use thereof |
US6075072A (en) * | 1998-03-13 | 2000-06-13 | 3M Innovative Properties Company | Latent coating for metal surface repair |
JP2001158843A (ja) * | 1999-09-24 | 2001-06-12 | Nof Corp | 水分散型の徐放性製剤及びその製造方法 |
US6174964B1 (en) * | 1999-09-24 | 2001-01-16 | 3M Innovative Properties Company | Fluorochemical oligomer and use thereof |
US6794317B2 (en) * | 2000-04-26 | 2004-09-21 | Creare Inc. | Protective cover system including a corrosion inhibitor |
AU2001290007A1 (en) | 2000-09-18 | 2002-03-26 | Rhodia Chimie | Active latex comprising a corrosion inhibiting agent |
JP3753964B2 (ja) * | 2001-09-17 | 2006-03-08 | 大日本インキ化学工業株式会社 | 着色塗料用樹脂組成物及び積層塗装方法 |
US6933046B1 (en) | 2002-06-12 | 2005-08-23 | Tda Research, Inc. | Releasable corrosion inhibitor compositions |
US6758887B2 (en) | 2002-11-29 | 2004-07-06 | United Technologies Corporation | Chromate free waterborne epoxy corrosion resistant primer |
JP2006161027A (ja) * | 2004-11-09 | 2006-06-22 | Shiseido Co Ltd | 有機溶媒膨潤性ミクロゲル及びその製造方法 |
DE102005014271A1 (de) * | 2005-03-24 | 2006-09-28 | Rhein Chemie Rheinau Gmbh | Mikrogele in Kombination mit funktionalen Additiven |
KR100738056B1 (ko) * | 2005-05-18 | 2007-07-12 | 삼성에스디아이 주식회사 | Fed의 제조방법 |
EP1832629B1 (en) * | 2006-03-10 | 2016-03-02 | Max-Planck-Gesellschaft zur Förderung der Wissenschaften e.V. | Corrosion inhibiting pigment comprising nanoreservoirs of corrosion inhibitor |
US20130196173A1 (en) * | 2010-04-09 | 2013-08-01 | Postech Academy-Industry Foundation | Organic Corrosion Inhibitor-Embedded Polymer Capsule, Preparation Method Thereof, Composition Containing Same, and Surface Treated Steel Sheet Using Same |
-
2013
- 2013-12-18 RU RU2015131104A patent/RU2622419C2/ru active
- 2013-12-18 WO PCT/US2013/075910 patent/WO2014105540A1/en active Application Filing
- 2013-12-18 MY MYPI2015001275A patent/MY170423A/en unknown
- 2013-12-18 EP EP13815927.2A patent/EP2938682B1/en active Active
- 2013-12-18 CN CN201380062932.2A patent/CN105102551A/zh active Pending
- 2013-12-18 KR KR1020157016020A patent/KR102163064B1/ko active IP Right Grant
- 2013-12-18 JP JP2015550477A patent/JP6429281B2/ja active Active
- 2013-12-18 MX MX2015008218A patent/MX363157B/es unknown
- 2013-12-18 US US14/132,547 patent/US10240048B2/en active Active
- 2013-12-18 AU AU2013368218A patent/AU2013368218B2/en active Active
- 2013-12-18 ES ES13815927.2T patent/ES2635551T3/es active Active
- 2013-12-18 BR BR112015015253-8A patent/BR112015015253B1/pt active IP Right Grant
- 2013-12-18 CA CA2896653A patent/CA2896653C/en active Active
- 2013-12-27 TW TW102148872A patent/TWI618762B/zh not_active IP Right Cessation
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5574377A (en) * | 1994-08-10 | 1996-11-12 | Marquez-Lucero; Alfredo | Device for the detection and localization of organic solvent leakages and fabrication process |
CN1269710A (zh) * | 1997-07-25 | 2000-10-11 | 普罗克特和甘保尔公司 | 具有涂敷有液体可溶胀材料的透气底片的吸湿用品 |
US20080254133A1 (en) * | 2005-11-25 | 2008-10-16 | The University Of Manchester | Microgel Particle |
CN102365337A (zh) * | 2009-03-31 | 2012-02-29 | 塞特克技术公司 | 用于结构粘接应用的水基非铬酸盐底漆 |
US20130017612A1 (en) * | 2011-07-11 | 2013-01-17 | United States Of America As Represented By The Administrator Of The National Aeronautics And Spac | pH-Sensitive Microparticles with Matrix-Dispersed Active Agent |
Non-Patent Citations (3)
Title |
---|
杨玉霞等: "聚丙烯酸类水凝胶的制备及其在碱性溶液中的pH敏感性", 《材料研究学报》 * |
耿耀宗等: "《合成聚合物乳液制造与应用技术》", 30 June 1999, 中国轻工业出版社 * |
马建标等: "《功能高分子材料》", 31 July 2000, 化学工业出版社 * |
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AU2013368218A1 (en) | 2015-05-28 |
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