CN106459622A - 涂覆管节段的方法 - Google Patents
涂覆管节段的方法 Download PDFInfo
- Publication number
- CN106459622A CN106459622A CN201580027003.7A CN201580027003A CN106459622A CN 106459622 A CN106459622 A CN 106459622A CN 201580027003 A CN201580027003 A CN 201580027003A CN 106459622 A CN106459622 A CN 106459622A
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- Prior art keywords
- methyl
- ethylenically unsaturated
- group
- polymer
- coating
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- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
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- CJOBVZJTOIVNNF-UHFFFAOYSA-N cadmium sulfide Chemical compound [Cd]=S CJOBVZJTOIVNNF-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
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- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
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- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 1
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- 229920000126 latex Polymers 0.000 description 1
- MOUPNEIJQCETIW-UHFFFAOYSA-N lead chromate Chemical compound [Pb+2].[O-][Cr]([O-])(=O)=O MOUPNEIJQCETIW-UHFFFAOYSA-N 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
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- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
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- 150000002978 peroxides Chemical class 0.000 description 1
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- NVKTUNLPFJHLCG-UHFFFAOYSA-N strontium chromate Chemical compound [Sr+2].[O-][Cr]([O-])(=O)=O NVKTUNLPFJHLCG-UHFFFAOYSA-N 0.000 description 1
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- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
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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
- C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
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- C—CHEMISTRY; METALLURGY
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Abstract
公开了一种涂覆管节段的方法。该方法包括通过电沉积来将涂料组合物施涂到该管节段上,其中该涂料组合物包含:(i)分散在含水介质中的(甲基)丙烯酸类聚合物,其是通过在含有阳离子盐基团的聚合物型分散剂的存在下,将可聚合的烯属不饱和单体组合物聚合来制备的,该单体组合物包含烯属不饱和单体的混合物,该烯属不饱和单体中至少之一包含至少两个烯属不饱和基团/分子;(ii)含有活性氢基团的可电沉积的阳离子树脂质载体;和(iii)与该活性氢基团有反应性的固化剂。
Description
发明领域
本发明涉及一种涂覆用于传输饮用水的管节段的方法。更具体地,本发明涉及通过电沉积的方法,向管表面上施涂防腐蚀涂料。
发明背景
已知的是石油沥青基涂料用于涂覆传输饮用水所用的管。这样的涂层的厚度不同,特别是在接合处,在这里管节段(segment)接合在一起来进行装配。这种厚度的差异是不期望的,因为它会导致接合处差的密封和潜在的泄漏。为了克服这个问题,已知的是通过电沉积方法来施涂保护涂层,该方法沿着整个管节段施涂了均匀厚度的涂层。但是,为了最佳的耐腐蚀性,据信该电沉积组合物需要用衍生自双酚A的环氧树脂配制。但是,这样的组合物是有问题的,因为双酚A据报道是雌激素材料。所以,将它用于传输可饮用的或饮用水的管中被认为是有害的。
发明内容
本发明提供了一种用电沉积组合物涂覆管节段的方法,该组合物具有优异的耐腐蚀性,并且可以配制以使得它基本上没有双酚A及其衍生物。具体地,本发明提供下面的:
一种方法,其包括通过电沉积将涂料组合物施涂到管节段上,其中该涂料组合物包含:
(i)分散在含水分散介质中的(甲基)丙烯酸类聚合物,其是通过在含有阳离子盐基团的聚合物型分散剂存在下,将可聚合的烯属不饱和单体组合物聚合来制备的,该单体组合物包含烯属不饱和单体的混合物,该烯属不饱和单体中至少之一包含至少两个烯属不饱和基团/分子;
(ii)含有活性氢基团的可电沉积的阳离子树脂质载体;和
(iii)与该活性氢基团有反应性的固化剂。
具体实施方式
出于以下详细说明的目的,应理解本发明可采用各种替代变化和步骤顺序,除了其中明确有相反的规定之外。另外,除了在任何操作实施例中,或其中另外说明,所有表达,例如说明书和权利要求中使用的成分的量的数字,应被理解为在所有情况下由术语“约”来修饰。因此,除非有相反指示,下述说明书和附加的权利要求中陈述的数字参数是近似值,其可根据本发明获得的期望性能而变化。最起码,并且不试图限制将等同原则应用到权利要求范围,每个数字参数应至少按照所报告的有效数字的位数并通过应用普通的四舍五入方法来解释。
虽然陈述本发明宽广范围的数字范围和参数是近似值,但在具体实施例中称述的数值是尽可能精确地报告的。然而,任何数值必然固有地包含在它们各自测试方法中发现的标准偏差必然造成的一定误差。
同样,应当理解的是,本文中引用的任何数值范围旨在包括全部包括在其中的子范围。例如,“1至10”的范围旨在包括所述的最小值1和所述的最大值10之间(并且包括端值)的全部子范围,也就是说,具有最小值等于或大于1,和最大值等于或小于10。
在本申请中,单数的使用包括复数和复数包括单数,除非另有明确规定。另外,在本申请中,使用“或者”表示“和/或”,除非另有明确规定,即使在某些情况中可以明确使用“和/或”。
本发明的管节段典型地是由黑色金属例如铸铁或者钢制成的。为了传输可饮用的或饮用水,该管节段的内径通常是10-100厘米(cm)。该管通常呈节段的形式例如直型(linear)和非直型节段例如肘形节段。所述段典型的长度是10-30cm。节段是通过挤进装配(jamfitting)而结合在一起的,其中管部分(section)的一端是锥形的,并且安装到稍大尺寸的待连接的管的轴环(collar)中,这在内锥形表面和外轴环表面之间形成了密封。
如所述的,本发明的某些实施方案涉及可电沉积的涂料组合物。作为此处使用的,术语“可电沉积的涂料组合物”指的是这样的组合物,其能够在所施加的电势的影响下沉积到导电基材上。
用于本发明的涂料组合物包含分散在含水介质中的非离子(甲基)丙烯酸类聚合物,其是可聚合的烯属不饱和单体组合物的聚合产物。术语“丙烯酸类”包括丙烯酸及其衍生物例如其酯,所谓的丙烯酸酯。术语“(甲基)丙烯酸类”或者“甲基丙烯酸酯”目的是覆盖丙烯酸类/丙烯酸酯和甲基丙烯酸类/甲基丙烯酸酯二者。除了水之外,该分散介质还包含含阳离子盐基团的聚合物型分散剂以分散该非离子(甲基)丙烯酸类聚合物。
作为此处使用的,术语“含阳离子盐基团的聚合物型分散剂”和“聚合物型分散剂”指的是包含赋予正电荷的至少部分中和的阳离子基团例如锍基团和胺盐基团的阳离子聚合物。作为此处使用的,术语“聚合物”包括但不限于低聚物以及均聚物和共聚物二者。“树脂”和“聚合物”是可互换使用的。典型地,该聚合物型分散剂的Z平均分子量(Mz)是200000-2000000。
在某些实施方案中,非离子(甲基)丙烯酸类聚合物和/或聚合物型分散剂包含活性氢官能团。作为此处使用的,术语“活性氢官能团”指的是与异氰酸酯有反应性的那些基团,这是通过Zerewitnoff测试来测定的,如JOURNAL OF THE AMERICAN CHEMICALSOCIETY,第49卷,第3181页(1927)所述。在某些实施方案中,活性氢官能团衍生自羟基,伯胺基和/或仲胺基。
在某些实施方案中,该聚合物型分散剂本身是(甲基)丙烯酸类树脂,并且例如通过传统的自由基引发的聚合技术(例如溶液聚合技术)来制备的,其中使含有一种或多种乙烯基单体的烯属不饱和可聚合的单体组合物经历自由基引发的加聚条件,例如通过在自由基引发剂存在下加热。合适的聚合物型分散剂和它们的制备描述在US2013/0306477,第[0016]-[0026]段中,该部分通过引用并入。
该可聚合的烯属不饱和单体组合物包含烯属不饱和单体的混合物,该烯属不饱和单体中至少之一包含至少两个或更多个可聚合的烯属不饱和基团/分子。
包含两个或更多个烯属不饱和基团/分子的单体的非限定性例子是多(甲基)丙烯酸酯,其包括二(甲基)丙烯酸酯,三(甲基)丙烯酸酯和/或四(甲基)丙烯酸酯。例子包括乙二醇二甲基丙烯酸酯,甲基丙烯酸烯丙基酯,己二醇二丙烯酸酯,甲基丙烯酸酐,四甘醇二丙烯酸酯,三丙二醇二丙烯酸酯,季戊四醇四丙烯酸酯,二季戊四醇三丙烯酸酯,二季戊四醇五丙烯酸酯,乙氧基化的三羟甲基丙烷三丙烯酸酯(具有0-20个乙氧基单元)和乙氧基化的三羟甲基丙烷三甲基丙烯酸酯(具有0-20个乙氧基单元)。在某些实施方案中,具有大于一个不饱和位点的烯属不饱和单体的用量为至多10重量%,例如0.1-5重量%,基于该烯属不饱和可聚合的单体组合物的总重量计。
其他可聚合的烯属不饱和单体的例子(其可以存在于该可聚合的烯属不饱和单体组合物中)包括(甲基)丙烯酸C1-C18烷基酯。具体的例子包括但不限于(甲基)丙烯酸甲基酯,(甲基)丙烯酸乙基酯,(甲基)丙烯酸丁基酯,(甲基)丙烯酸己基酯,(甲基)丙烯酸辛基酯,(甲基)丙烯酸异癸基酯,(甲基)丙烯酸硬脂基酯,(甲基)丙烯酸2-乙基己基酯,(甲基)丙烯酸异冰片酯和(甲基)丙烯酸叔丁基酯。在某些实施方案中,该(甲基)丙烯酸C1-C18烷基酯的用量至多为90重量%,例如30至70重量%,基于该烯属不饱和可聚合的单体组合物的总重量计。
该可聚合的烯属不饱和单体组合物还可以包含一种或多种取代的(甲基)丙烯酸C1-C8烷基酯,例如羟烷基酯,例如(甲基)丙烯酸羟乙基酯,(甲基)丙烯酸羟丙基酯和/或(甲基)丙烯酸羟丁基酯。在某些实施方案中,这样的单体的用量至多为20重量%,例如5-15重量%,基于该烯属不饱和可聚合的单体组合物的总重量计。
该可聚合的烯属不饱和单体组合物可以包含一种或多种乙烯基芳族化合物,例如苯乙烯,α-甲基苯乙烯,α-氯甲基苯乙烯和乙烯基甲苯。在某些实施方案中,该乙烯基芳族化合物的用量至多为80重量%,例如20-60重量%,基于该烯属不饱和可聚合的单体组合物的总重量计。
该(甲基)丙烯酸类聚合物可以经由烯属不饱和可聚合的单体组合物在分散介质(其包含水和典型的前述聚合物型分散剂)中聚合来制备。在某些实施方案中,该单体组合物是在聚合物型分散剂存在下分散于水中,并且通过在自由基引发剂存在下加热而经历加聚条件。聚合的时间和温度将取决于彼此,所选择的成分和在一些情况中反应的规模。在某些实施方案中,该聚合是在40℃-100℃进行2-20小时。
用于该聚合的自由基引发剂可以选自用于含水胶乳聚合技术的任意那些,包括氧化还原对引发剂,过氧化物,氢过氧化物,过氧二碳酸盐,偶氮化合物等。
该自由基引发剂典型的存在量是0.01重量%-5重量%,例如0.05重量%-2.0重量%,或者在一些情况中0.1重量%-大约1.5重量%,基于该可聚合的烯属不饱和单体组合物的重量计。可溶于该单体组合物中的链转移剂例如烷基硫醇,例如叔十二烷基硫醇,2-巯基乙醇,巯基丙酸异辛基酯,正辛基硫醇或者3-巯基乙酸可以用于该可聚合的烯属不饱和单体组合物的聚合中。可以使用其他链转移剂例如酮例如甲乙酮,和氯烃例如氯仿。在某些实施方案中,链转移剂(如果有的话)的量是0.1-6.0重量%,基于该烯属不饱和可聚合的单体组合物的重量计。
用于本发明的涂料组合物典型地包含2-50重量%,例如20-35重量%的聚合物型分散剂和50-98重量%,例如65-80重量%的可聚合的烯属不饱和单体组合物,其中这些重量%是基于该聚合物型分散剂和可聚合的烯属不饱和单体组合物的总重量计。
水的存在量是40-90,例如50-75重量%,基于该分散介质的总重量计。
除了水之外,该分散介质在某些实施方案中还可以包含一些有机助溶剂。在某些实施方案中,该有机助溶剂至少部分地可溶于水。这样的溶剂的例子包括氧化的有机溶剂,例如乙二醇,二甘醇,丙二醇和二丙二醇的单烷基醚,其在烷基中包含1-10个碳原子,例如这些二醇的单乙基醚和单丁基醚。其他至少部分水可混溶的溶剂的例子包括醇例如乙醇,异丙醇,丁醇和双丙酮醇。如果使用,该有机助溶剂在某些实施方案中的用量小于10重量%,例如小于5重量%,基于该分散介质的总重量计。
用于本发明的可电沉积的涂料组合物还包含可电沉积的阳离子树脂质载体,其不同于上述的聚合物型分散剂。这样的聚合物的例子(其适用于本发明)包括含阳离子盐基团的树脂,其衍生自多缩水甘油醚,(甲基)丙烯酸类聚合物和聚酯等。这样的聚合物包含活性氢基团,例如羟基和伯和仲胺基团,包括其组合。
用作本发明所用的可电沉积的涂料组合物中的组分(ii)的合适的含有阳离子盐基团的聚合物还包括例如阳离子(甲基)丙烯酸类树脂,例如描述在美国专利No.3455806的第2栏第18行到第3栏第61行和美国专利No.3928157的第2栏第29行到第3栏第21行中的那些,其二者的这些部分在此通过引用并入。
该阳离子盐基团可以是胺盐基团和/或锍盐基团。典型地,该可电沉积的阳离子树脂质载体是在有机溶剂中制备的,至少部分地用酸中和,并且反转(invert)到含水介质中。
用于本发明的可电沉积的涂料组合物包含固化剂,其与该含阳离子盐基团的树脂质载体的活性氢基团反应。合适的固化剂的非限定性例子是封闭的多异氰酸酯,氨基塑料树脂和酚醛树脂,例如苯酚甲醛缩合物,包括其烯丙基醚衍生物。
合适的封闭多异氰酸酯包括封闭的脂肪族多异氰酸酯,芳族多异氰酸酯及其混合物。在某些实施方案中,该固化剂包含封闭的脂肪族多异氰酸酯。合适的封闭的脂肪族多异氰酸酯包括例如完全封闭的脂肪族多异氰酸酯,例如描述在美国专利No.3984299第1栏第57行到第3栏第15行的那些,其的这个部分在此通过引用并入。
合适的氨基塑料树脂的例子包括描述在美国专利No.3937679第16栏第3行到第17栏第47行的那些,其的这个部分在此通过引用并入。如'679专利前述部分所公开的,氨基塑料可以与羟甲基酚醚组合使用。
配制用于本发明的涂料组合物,以使得它们基本上没有,可以实质上没有和可以完全没有双酚A及其衍生物或者残留物,包括双酚A(“BPA”)和双酚A二缩水甘油基醚(“BADGE”)。这样的组合物有时候称作“非有意BPA”,因为BPA(包括其衍生物或者残留物)并非有意加入的,但是可以以痕量存在,这归因于来自于环境的不可避免的污染。该组合物还可以是基本上没有和可以实质上没有和可以完全没有双酚F及其衍生物或者残留物,包括双酚F和双酚F二缩水甘油基醚(“BPFG”)。作为本文上下文中所用的,术语“基本上没有”表示该组合物包含小于1000份/百万份(ppm),“实质上没有”表示小于100ppm和“完全没有”表示小于20份/十亿份(ppb)的任何上述化合物,其衍生物或者残留物。
用于本发明的可电沉积的涂料组合物中的树脂固体含量是至少1重量%,例如5-40重量%或者5-20重量%的树脂固体。树脂固体表示该组合物的非挥发性有机含量,即,有机材料,其当加热到110℃持续15分钟时将不挥发,并且会排除有机溶剂。
在本发明所用的涂料组合物中,聚合物型分散剂和非离子(甲基)丙烯酸类聚合物的总和典型地是5-50,例如15-30重量%。该可电沉积的树脂质载体典型地是25-90,例如50-80重量%。该固化剂典型的存在量是5-52,例如18-30重量%。该重量百分比基于涂料组合物中树脂固体的总重量计。
用于本发明的涂料组合物可以包含催化剂来催化固化剂和活性氢之间的反应。合适的固化催化剂包括但不限于有机锡化合物(例如二丁基氧化锡和二辛基氧化锡)及其盐(例如二乙酸二丁基锡);其他金属氧化物(例如铈,锆和铋的氧化物)及其盐(例如氨基磺酸铋和乳酸铋)。在某些实施方案中,该固化催化剂包含环状胍,如美国专利No.7842762第1栏第53行到第4栏第18行和第16栏第62行到第19栏第8行所述,其引用部分在此通过引用并入。
在一些情况中,颜料组合物和如果期望,不同的添加剂例如填料,增塑剂,抗氧化剂,UV光吸收剂,消泡剂,杀真菌剂,流动控制剂,表面活性剂或者润湿剂包括在本发明所用的涂料组合物中。该颜料组合物可以是常规类型,包含例如铁氧化物,铅氧化物,铬酸锶,炭黑,煤尘,二氧化钛,滑石,硫酸钡以及着色颜料例如镉黄,镉红,铬黄等。所述分散体的颜料含量通常表达为颜料与树脂的重量比。在本发明的实践中,当使用颜料时,颜料与树脂的重量比有时候是0.03-0.35。上述的其他添加剂通常在分散体中的量是0.01-3重量%,基于树脂固体总重量计。
用于本发明的涂料组合物是通过将该组合物放置以与导电阳极接触,并且所述管节段充当了阴极,来沉积到管节段上的。在与该组合物接触之后,该涂料组合物的粘着膜沉积在所述管节段上,并且在电极之间施加足够的电压。电沉积在其下进行的条件通常类似于用于其他类型的涂料电沉积中的那些。所施加的电压可以变化,并且可以例如低至1伏到高达几千伏,但是经常是50-500伏。电流密度经常是0.5安培-15安培/平方英尺,并且倾向于在电沉积过程中降低,这表示形成了绝缘膜。
一旦该可电沉积的涂料组合物电沉积在所述管节段上,将该经涂覆的基材加热到足以固化基材上的电沉积涂层的温度和时间。典型地,该经涂覆的基材加热到250℉(121℃)-450℉(232℃)的温度。固化时间可取决于固化温度以及其他变量,例如该电沉积涂层的膜厚度,存在于组合物中的催化剂的水平和类型等。出于本发明的目的,所必需的是所述时间足以进行基材上的涂层的固化。例如该固化时间可以是10分钟-60分钟,例如20-40分钟。所得的固化涂层的厚度典型地是15-50微米。
下面的实施例说明本发明,但是其不被认为将本发明限制到它们的细节。除非另有指示,否则下面的实施例以及整个说明书中全部的份数和百分比是以重量计的。
实施例
首字母缩写定义:
实施例1:合成可电沉积的阳离子树脂质载体
*聚氨酯交联剂-用丁基溶纤剂和丁基卡必醇封闭的聚合物异氰酸酯。
**单酮亚胺-与1当量的酮反应的酮亚胺。
将加料1加入到安装有热电偶,氮气鼓泡器(sparge)和机械搅拌器的4颈烧瓶中。在氮气层和搅拌下,将该烧瓶加热到回流。将加料2和3从加料漏斗在150分钟内逐滴加入,随后保持30分钟。逐滴加入加料3,并且保持30分钟,随后加入加料4。将Dean-Stark分水器(trap)安装到所述烧瓶上,并且随后升温到145℃。在加热过程中,逐滴加入加料5,同时经由D-S分水器收集蒸馏物。在145℃持续保持2小时。在保持后,冷却到110℃和将加料6加入该反应器中。在产生峰值放热曲线之后,开始2小时的保持。在该保持后,冷却到105℃和在搅拌下反向稀释(reverse thinned)到加料7中,并且保持30分钟。将加料8在搅拌下加入该分散体中,并且保持另外30分钟。加入最后的加料9,使得该混合物持续冷却到环境温度。
该树脂质材料的固体百分比是30.4%。测定聚合物Z均分子量的GPC分析显示出43050的值,并且是在DMF中使用聚苯乙烯标准物来进行的。
实施例2:合成包含阳离子盐基团的聚合物型分散剂
*在含水条件下乳酸浓度是88%。
将加料1加入到安装有热电偶,氮气鼓泡器和机械搅拌器的4颈烧瓶中。在氮气层和搅拌下,将该烧瓶加热到回流。将加料2和3从加料漏斗在150分钟内逐滴加入,随后保持30分钟。在升温到120℃之后,加料4随后在15分钟内加入,随后保持10分钟。降温到90℃,同时加入加料5来帮助冷却该反应。加入加料6,并且在85℃保持3小时。在保持过程中,将加料7在装备有机械搅拌器的另一容器中加热到大约35-40℃。在保持后,将来自反应器的内容物在快速搅拌下分散到加料7中,然后保持60分钟。随着分散剂持续冷却到环境温度,将加料8在搅拌下加入。
该聚合物型分散剂的固体百分比是17.0%。测定聚合物Z均分子量的GPC分析显示出620000的值,并且是用DMF使用聚苯乙烯标准物来进行的。
实施例3:
在实施例2的聚合物型分散剂存在下合成(甲基)丙烯酸类聚合物
将加料1加入到安装有热电偶,氮气鼓泡器和机械搅拌器的4颈烧瓶中。在氮气层和强力(rigorous)搅拌下,将该烧瓶加热到50℃。在50℃,将该溶液在氮气下鼓泡另外30分钟。然后将加料2和3混合加入到加料漏斗中;该溶液使用氮气鼓泡器连续搅拌。将加料4加入到另外的漏斗中。将两种溶液在50℃在180分钟内加入,然后保持30分钟。加入加料5和6,并且在50℃保持30分钟。
测定聚合物Z均分子量的GPC分析显示出650000的值,并且是用DMF使用聚苯乙烯标准物来进行的。最终粒度产生40nm的Z均尺寸。
实施例4(对比):
没有实施例3的添加剂的阳离子可电沉积的涂料组合物的配方
加料 | 成分 | 重量(以g计) |
1 | 实施例1 | 1004.9 |
2 | 实施例3 | 0.0 |
3 | CP934D1 | 96.3 |
4 | 去离子水 | 1398.8 |
5 | E61652 | 7.4 |
1蓝色阳离子丙烯酸类糊料,市售自PPG Industries Inc。
2阳离子锡催化剂糊料,市售自PPG Industries,Inc。
将加料1加入1加仑容器中,并且用一部分的加料4来稀释。这然后置于搅拌下。将加料3用一部分的加料4稀释,并且加入到稀释的加料1中。将加料5用一部分的加料4稀释,并且加入到先前的混合物中。加入其余的加料4。
实施例5:具有实施例3的添加剂的阳离子可电沉积的涂料组合物的配方
加料 | 成分 | 重量(以g计) |
1 | 实施例1 | 1004.9 |
2 | 实施例3 | 413.6 |
3 | CP 934D | 115.6 |
4 | 去离子水 | 1398.8 |
5 | E6165 | 8.7 |
将加料1加入1加仑容器中,并且用一部分的加料4来稀释。这然后置于搅拌下。将加料2用一部分的加料4稀释,并且加入到稀释的加料1中。将加料3用一部分的加料4稀释,并且加入到先前的混合物中。将加料5用一部分的加料4稀释,并且加入到先前的混合物中。加入其余的加料4。
实施例6(对比):衍生自双酚A的二缩水甘油基醚的阳离子可电沉积的涂料组合物
的配方
加料 | 成分 | 重量(g) |
1 | CR451A1 | 870.2 |
2 | HALLCOMID M-8-102 | 62.5 |
3 | CP 573B3 | 122.8 |
4 | 去离子水 | 1507 |
1含阳离子锍盐基团的树脂,衍生自双酚A的二缩水甘油基醚和完全封闭的多异氰酸酯固化剂,市售自PPG Industries,Inc。
2成膜添加剂,获自Stepan。
3阳离子环氧颜料糊料,市售自PPG Industries,Inc。
将加料1加入1加仑容器中,并且用一部分的加料4来稀释。这然后置于搅拌下。将加料2加入到稀释的加料1中,并且进行搅拌大约15分钟。将加料3用一部分的加料4稀释,并且加入到先前的混合物中。加入其余的加料4。
用于电涂测试浴的涂覆(coat out)条件和随后的经涂覆的样品的测试
涂料组合物 | 浴温1 | 电压 | 总库伦 | 成膜厚2 |
实施例4 | 92 | 300 | 105 | 2.9 |
实施例5 | 92 | 300 | 105 | 3.1 |
实施例6 | 92 | 200 | 90 | 2.4 |
1以华氏度测量。
2以密耳测量。
制备用于腐蚀测试的面板
使用磁搅拌棒进行搅拌,在塑料管中涂覆面板。浴温是使用连接到温度控制器(根据需要将热或者冷水传送通过不锈钢管)的热电偶控制的。这个管也充当电沉积方法的阳极。用于涂覆的基材是4”x6”x3/8”铸铁,其是用重(heavy)(7-10gm/m2)磷酸锌(GardobondZ 3650,来自于Chemetall)预处理的。在涂覆之后,将该面板冲洗,并然后焙烤10'@170℉。该烘箱然后升温到356℉,并且使得该面板焙烤另外40分钟。
腐蚀测试
腐蚀测试使用了ASTM B117(盐雾测试)所述的测试。在这个测试中,将涂层是使用划线工具切割,并且以单个垂直线来曝露裸露的金属基材。将经划线的基材放入测试室中,在这里将盐的水溶液持续雾化到该基材上。所述室保持在恒定的温度。将该经涂覆的基材曝露于盐雾环境2000小时。在曝露之后,将该经涂覆的基材从测试室除去,并且评价沿着划线的腐蚀。划线蔓延(creep)是腐蚀沿着划线行进的总距离,以毫米测量。还注意了表面和边缘腐蚀。胶带粘附性是通过紧靠着涂层下压来消除空隙和气穴(air pocket),来将Scotch细胶带(filament tape)施加到经涂覆的基材的表面上来进行的。然后将该胶带以与经涂覆的表面的平面呈直角的角度急速(sharply)拉开。附着性是通过从基材上除去的涂层的量来报告的。
测试结果报告在下表I中。
表I
测试结果
该测试结果显示实施例5(其包含实施例3的组分)的耐腐蚀性优于实施例4(其不含实施例3的组分)。同样,实施例5的耐腐蚀性类似于用衍生自双酚A的环氧树脂配制的阳离子电沉积树脂(实施例6),并且另外具有优异的边缘腐蚀。
虽然上面出于说明的目的描述了本发明的具体实施方案,但是对本领域技术人员来说显然的是可以对本发明的细节进行诸多改变,而不脱离所附的权利要求所限定的本发明。
虽然本发明不同的实施方案已经按照“包含”进行了描述,但是“基本由……组成”或者“由……组成”的实施方案也处于本发明的范围内。
Claims (16)
1.一种包括通过电沉积将涂料组合物施涂到管节段上的方法,其中该涂料组合物包含:
(i)分散在含水分散介质中的(甲基)丙烯酸类聚合物,其是通过在含有阳离子盐基团的聚合物型分散剂存在下,将可聚合的烯属不饱和单体组合物聚合来制备的,该可聚合的烯属不饱和单体组合物包含烯属不饱和单体的混合物,该烯属不饱和单体中至少之一包含至少两个烯属不饱和基团/分子;
(ii)含有活性氢基团的可电沉积的阳离子树脂质载体;和
(iii)与该活性氢基团有反应性的固化剂。
2.权利要求1的方法,其中该节段是将管的两个直型部分结合的管节段。
3.权利要求2的方法,其中该节段是非直型的。
4.权利要求3的方法,其中该节段是肘形的。
5.权利要求1的方法,其中该含有至少两个烯属不饱和单体的单体包括多(甲基)丙烯酸酯。
6.权利要求5的方法,其中该多(甲基)丙烯酸酯包括三和/或四(甲基)丙烯酸酯。
7.权利要求1的方法,其中该烯属不饱和单体的混合物包含含活性氢基团的(甲基)丙烯酸类单体。
8.权利要求1的方法,其中该分散介质包含水、有机溶剂和含阳离子盐基团的聚合物型分散剂,该含阳离子盐基团的聚合物型分散剂不同于所述可电沉积的阳离子树脂质载体。
9.权利要求1的方法,其中该含阳离子盐基团的聚合物型分散剂包括(甲基)丙烯酸类树脂。
10.权利要求9的方法,其中该阳离子盐基团包括胺盐基团和/或锍盐基团。
11.权利要求1的方法,其中(i)的Mz是至少500000。
12.权利要求1的方法,其中(ii)包括(甲基)丙烯酸类聚合物。
13.权利要求1的方法,其中(ii)是在有机溶剂中制备的,并且反转到含水介质中。
14.权利要求1的方法,其中该涂料组合物基本上没有双酚A及其衍生物。
15.一种管节段,其是根据权利要求1的方法涂覆的。
16.一种管节段,其是根据权利要求14的方法涂覆的。
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US14/223,181 US9499918B2 (en) | 2014-03-24 | 2014-03-24 | Method for coating pipe segments |
US14/223,181 | 2014-03-24 | ||
PCT/US2015/022153 WO2015148447A1 (en) | 2014-03-24 | 2015-03-24 | Method for coating pipe segments |
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CN106459622A true CN106459622A (zh) | 2017-02-22 |
CN106459622B CN106459622B (zh) | 2019-11-05 |
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US (1) | US9499918B2 (zh) |
EP (1) | EP3122823B1 (zh) |
CN (1) | CN106459622B (zh) |
AU (1) | AU2015236343B2 (zh) |
BR (1) | BR112016022154A2 (zh) |
CA (1) | CA2944013A1 (zh) |
MX (1) | MX2016012513A (zh) |
PL (1) | PL3122823T3 (zh) |
RU (1) | RU2650950C1 (zh) |
WO (1) | WO2015148447A1 (zh) |
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FR2992708B1 (fr) * | 2012-06-29 | 2015-03-27 | Saint Gobain Pont A Mousson | Revetement exterieur pour element de tuyauterie enterre a base de fer, element de tuyauterie revetu et procede de depot du revetement |
US11407905B2 (en) | 2017-03-01 | 2022-08-09 | Ppg Industries Ohio, Inc. | Electrodepositable coating compositions |
EP4301819A1 (en) * | 2021-03-05 | 2024-01-10 | PPG Industries Ohio Inc. | Electrodepositable coating compositions |
Citations (3)
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US5356679A (en) * | 1991-12-24 | 1994-10-18 | Pont-A-Mousson S.A. | Pipe surface coating with conversion and thermosetting resin layer, and process for the coating application |
US20070015873A1 (en) * | 2005-07-13 | 2007-01-18 | Fenn David R | Electrodepositable aqueous resinous dispersions and methods for their preparation |
US20130306477A1 (en) * | 2012-05-16 | 2013-11-21 | Ppg Industries Ohio, Inc. | Cationic electrodepositable coating compositions capable of forming low gloss coatings |
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US3159558A (en) | 1960-08-26 | 1964-12-01 | American Bitumuls & Asphalt Co | Process for electro-deposition of bituminous materials |
BRPI0822764A2 (pt) * | 2008-09-25 | 2017-05-09 | Du Pont | composição eletrodepositável, dispersão aquosa eletrodepositável, substrato revestido com uma camada de uma composição de revestimento eletrodepositável, substrato revestido com uma camada seca e curada de uma composição de revestimento eletrodepositável e processo para a produção de uma camada de uma composição de revestimento em um substrato |
US8486538B2 (en) * | 2009-01-27 | 2013-07-16 | Ppg Industries Ohio, Inc | Electrodepositable coating composition comprising silane and yttrium |
AU2013217087B2 (en) | 2012-02-07 | 2015-10-22 | Swimc Llc | Compositions for containers and other articles and methods of using same |
US9505937B2 (en) | 2012-05-16 | 2016-11-29 | Ppg Industries Ohio, Inc. | Anionic electrodepositable coating compositions capable of forming low gloss coatings |
-
2014
- 2014-03-24 US US14/223,181 patent/US9499918B2/en active Active
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2015
- 2015-03-24 RU RU2016141483A patent/RU2650950C1/ru active
- 2015-03-24 CN CN201580027003.7A patent/CN106459622B/zh active Active
- 2015-03-24 BR BR112016022154A patent/BR112016022154A2/pt not_active Application Discontinuation
- 2015-03-24 WO PCT/US2015/022153 patent/WO2015148447A1/en active Application Filing
- 2015-03-24 CA CA2944013A patent/CA2944013A1/en not_active Abandoned
- 2015-03-24 EP EP15715575.5A patent/EP3122823B1/en active Active
- 2015-03-24 PL PL15715575T patent/PL3122823T3/pl unknown
- 2015-03-24 AU AU2015236343A patent/AU2015236343B2/en not_active Ceased
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US5356679A (en) * | 1991-12-24 | 1994-10-18 | Pont-A-Mousson S.A. | Pipe surface coating with conversion and thermosetting resin layer, and process for the coating application |
US20070015873A1 (en) * | 2005-07-13 | 2007-01-18 | Fenn David R | Electrodepositable aqueous resinous dispersions and methods for their preparation |
US20130306477A1 (en) * | 2012-05-16 | 2013-11-21 | Ppg Industries Ohio, Inc. | Cationic electrodepositable coating compositions capable of forming low gloss coatings |
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Publication number | Publication date |
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CN106459622B (zh) | 2019-11-05 |
MX2016012513A (es) | 2017-04-27 |
PL3122823T3 (pl) | 2019-12-31 |
BR112016022154A2 (pt) | 2017-08-15 |
RU2650950C1 (ru) | 2018-04-18 |
US9499918B2 (en) | 2016-11-22 |
CA2944013A1 (en) | 2015-10-01 |
AU2015236343B2 (en) | 2017-03-16 |
EP3122823A1 (en) | 2017-02-01 |
AU2015236343A1 (en) | 2016-11-03 |
WO2015148447A1 (en) | 2015-10-01 |
US20150267856A1 (en) | 2015-09-24 |
EP3122823B1 (en) | 2019-05-08 |
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