CN112552779B - 一种环保型低表面处理水性环氧厚浆型耐酸碱涂料及其制备方法 - Google Patents
一种环保型低表面处理水性环氧厚浆型耐酸碱涂料及其制备方法 Download PDFInfo
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Abstract
本发明属于涂料化工领域,具体的说是一种环保型低表面处理水性环氧厚浆型耐酸碱涂料及其制备方法及其可用于金属或建筑,尤其为钢铁材质在化工环境下应用于耐酸碱、耐化学介质等领域的防腐蚀涂料。涂料由组分A和组分B两组分按质量比4‑8:1组成;其中,组分A为水性环氧树脂分散体、活性稀释剂、颜填料和助剂组成;组分B为水性改性酚醛酰胺环氧固化剂。与现有的水性涂料相比,本发明的环保型低表面处理水性环氧厚浆型耐酸碱涂料具有低VOCs、高固体分,可一次厚膜涂装200‑300μm,柔韧性好,抗开裂性强,对基材附着力良好,可低表面处理带锈涂装,亦对焊缝等不易附着的金属表面有较好的附着力,耐腐蚀性好,具有优异的耐酸、耐碱、耐油、耐溶剂等耐化学介质性,可在腐蚀环境较严苛的条件下使用,提高设备使用寿命,尤其适用于化工环境的金属及建筑的防护。
Description
技术领域:
本发明属于涂料化工领域,具体的说是一种环保型低表面处理水性环氧厚浆型耐酸碱涂料及其制备方法及其可用于金属或建筑,尤其为钢铁材质在化工环境下应用于耐酸碱、耐化学介质等领域的防腐蚀涂料。
背景技术
随着我国经济的快速发展和人民生活水平的迅速提高,全社会的环保意识也随之增强。环境友好型的新技术、新材料受到越来越多的关注。在多个领域,更健康、更环保的材料正在淘汰高污染、高能耗的落后技术,到目前为止,水性涂料为环保涂料之一正不断被开发及应用。但相对于传统油性漆或环保型涂料如粉末涂料、高固体分涂料等,水性涂料因技术制约,其理化性能在一定程度上相较于上述涂料仍有欠缺。
目前,我国主要水性防腐涂料因水性树脂原料技术制约,往往通过不同水性树脂复配以达到物理及化学性能的平衡。但不同树脂的冷拼导致了其在干燥成膜时不同结构及分子量的聚合物分子与固化剂交联时形成不均一的高聚物膜,结果会导致性能虽有增加但达不到较高的技术要求。另外,由于目前水性工业涂料的固体分较低,难以单道施工达到较高膜厚,或即使能单道施工达到较高膜厚,由于体系内溶剂量(水)较多,导致涂膜挥发较慢而产生流挂或涂膜多空隙导致性能下降,达不到性能技术要求。
针对传统的水性涂料的弊端,需要提供环保型低表面处理水性环氧耐酸碱涂料。
发明内容:
本发明目的在于提供一种环保型低表面处理水性环氧厚浆型耐酸碱涂料及其制备方法。
为实现上述目的,本发明采用技术方案为:
一种环保型低表面处理水性环氧厚浆型耐酸碱涂料,涂料由组分A和组分B两组分按质量比4-8:1组成;其中,组分A为水性环氧树脂分散体、活性稀释剂、颜填料和助剂组成;组分B为水性改性酚醛酰胺环氧固化剂。
所述的组分A各组分质量分数为:水性环氧树脂分散体25-40%,活性稀释剂E10p-DPOMA 2.5-12.5%,颜填料氧化铁红7.5-15%、白云母粉10-20%、改性磷酸锌5-10%、改性三聚磷酸铝2.5-5%、多磷酸硅酸钙铝2.5-5%、沉淀硫酸钡7.5-15%、硅土2.5-7.5%,混合助剂1.5-5.5%及去离子水2.5-5%。
所述水性环氧树脂分散体为环氧当量450-550、固含量50-55%的E20环氧树脂改性的水分散体和/或环氧当量180-220、固含量98-100%的E51环氧树脂改性的水分散体;
多种水性树脂复配可调整交联密度,提高耐性,平衡力学性能,即两者混合时按质量百分比计,85-70%的E20环氧树脂改性的水分散体与15-30%的E51环氧树脂改性的水分散体。
所述E10p-DPOMA为由叔碳酸缩水甘油酯,顺丁烯二酸,DPOMA合成的具有增韧作用的水性/油性两用的增韧树脂;
所得E10p-DPOMA有增加涂膜柔韧性、降低涂料体系粘度、提高涂料固含量、增加涂膜耐候性和增加涂膜耐化学介质性能。
其中,按质量百分比计,叔碳酸缩水甘油酯50-60%,顺丁烯二酸10-15%,DPOMA25-35%。
所得E10p-DPOMA为外观为透明液体,黏度为0.015-0.020(mPa·s),22℃折光系数为1.496,一个大气压下沸点为350℃,玻璃化温度为40-50℃,环氧值0.05-0.10mol/100g。
所得E10p-DPOMA有少量环氧基团,可与胺类固化剂(组分B)交联,提高水性环氧分散体和改性酚醛酰胺固化剂的交联密度,且具有双键可被氧化交联,作为活性稀释剂可部分代替水性涂料中作为稀释剂的水,可解决涂膜因水分的挥发造成的涂膜内空隙而产生的易开裂性。
所述去离子水为经反渗透-离子交换设备制取的,电阻值≥18M。
所述混合助剂是由流平剂5-10份、消泡剂10-20份、润湿剂5-10份、分散剂20-30份、增稠剂10-30份、防腐防霉剂1-10份、pH调节剂1-6份、防闪锈剂5-20份组成。
所述流平剂为丙烯酸酯均(低)聚物、丙烯酸酯共聚物、有机硅改性丙烯酸酯聚合物、聚硅氧烷中的一种或几种;例如硅碳猫ThAdd 2020聚氨酯流平剂、斯洛柯Silok 350聚醚改性聚二甲基硅烷、Silok 310聚酯改性聚有机硅氧烷
所述消泡剂为有机硅消泡剂、矿物油基含硅及多种混合物、脂肪烃的乳化物、非硅酮有机酯碳氢化合物、非硅酮胺类碳氢化合物、含疏水粒子矿物油混合物中的一种或几种;例如AFCONA 2507含硅类消泡聚合物、AFCONA 2503含硅类消泡聚合物、斯洛柯Silok 4680憎水固体和聚醚有机硅破泡聚合物乳液、Silok 4635水性非硅消泡剂、先创SYNTHRONSD4950不含硅消泡聚合物乳液。
所述湿润剂为聚氧乙烯烷芳基醚、聚氧乙烯多元醇醚、聚氧乙酯聚氧丙烯酸嵌段共聚物、脂肪酸聚乙二醇酯、多元醇酯、脂肪胺聚氧乙烯醚加成物、非离子表面活性稀释剂中的一种或几种;例如斯洛柯Silok 8104E炔二醇表面活性剂、Silok 8000聚醚改性聚有机硅氧烷,AFCONA 3570氟碳改性聚丙烯酸酯水溶液。
所述分散剂为高分子共聚物、聚羧酸铵、油酰基环氧烷共聚物、聚硅氧烷、聚丙烯酸铵中的一种或几种;例如AFCONA PF152改性聚丙烯酸酯聚合物、AFCONA 6506脂肪酸改性聚酯高分子聚合物溶液,斯洛柯Silok 7112W含颜料亲和基团的嵌段共聚物、Silok 7456多元羧酸酯,先创SYNTHRON SD1790改性聚丙烯酸有机盐类分散剂。
所述增稠剂为聚氨酯增稠剂和/或改性聚脲增稠剂;例如ALBORTA EDW720缔合型聚氨酯增稠剂、EDW750聚醚多元醇缔合型流变助剂,浙江丰虹PA670水性聚酰胺蜡触变防沉剂。
所述反腐防霉剂为1,2-苯并异噻唑啉-3-酮(BIT)、2-甲基-5-氯-4-异噻咪唑-3-酮和2-甲基-4-异噻咪唑-3-酮(CMIT/MIT)、碘代丙炔基氨基甲酸酯、苯并咪唑氨基甲酸甲酯与N/-(3,4-二氯苯基)-N,N-二甲基脲的复配体中的一种或几种;例如生达化工的SD-100含氮、硫环状的有机物,百洁化工的BCH复合型高效快速防腐防霉剂、液体防腐剂BIT-20;
所述pH调节剂为2-氨基-2-甲基-1-丙醇,例如苏维SOVE-95胺中和剂,ELEMENTISDeuAdd MA-95胺中和剂。
所述防闪锈剂,其活性成分主要为螯合锌化合物,例如先创SYNTHRON SD6760防闪锈剂,苏维SOVE190防闪锈助剂。
上述中,所述氧化铁红为红色颜料,本产品不局限于红色。通过变化颜料,如钛白粉、炭黑、铈红、钛镍黄、镍绿等颜料,或直接更换水性通用色浆可达到白色、黑色、红色、黄色、绿色、蓝色、灰色等表观颜色。
所述氧化铁红为湿法制得,吸油量为20-30g/100g,密度为5.2g/cm3。
所述改性磷酸锌、改性三聚磷酸铝、多磷酸硅酸钙铝为防锈颜料,对于钢铁底材有更好的保护性,通过其可对金属表面形成钝化膜或将铁锈转化为更为稳定的络合物膜,以防止钢铁的腐烂。产品不局限于钢铁基材,亦可用于其他非金属建筑材料。
其中,改性磷酸锌、改性三聚磷酸铝、多磷酸硅酸钙铝均为市购产品;
改性磷酸锌,其水分≤1.5%,含锌量在45%以上,吸油量为30±5g左右,pH值为5-7,细度为325目、500目、1000目中的任意一种或几种。
改性三聚磷酸铝为白色粉末、水分≤1%,pH值为5.5-7,吸油量为25-35,白度≥90的工业级高纯三聚磷酸铝,细度为325目、500目、1000目中的任意一种或几种。
多磷酸硅酸钙铝为灰白色粉末,吸油量为35g/100g,平均粒径为2.5-4.0μm,密度为2.6g/cm3,氧化铝含量为6-8%,二氧化硅含量28.5-31.5%,五氧化二磷含量为24.5-27.5%,氧化钙含量为26.5-29.5%。
所述白云母粉,为不同直径、厚度复配的混合体系,通过不同的片状结构堆叠而形成的涂膜,变相增加了污染物对涂层穿透的路径而达到防腐蚀效果。
所述白云母粉为单斜晶系,吸油量为40-50g/100g,密度为2.8g/cm3,细度为1250目、800目、600目、325目中的一种或几种。
所述沉淀硫酸钡为填料,其他同质填料有滑石粉、碳酸钙、石英粉、长石粉。填料细度为400目、600目、800目、1250目。选用的填料为以上的一种或几种。
所述硅土为功能填料,是以氨基硅烷或烷基硅烷进行表面改性的或不改性的微粒状的二氧化硅、煅烧级高岭土和无定型相矿物组成的,选用的功能填料以上的一种或几种。
所述的硅土为白色微黄粉末,是以氨基硅烷或烷基硅烷进行表面改性的微粒状的二氧化硅、煅烧级高岭土和无定型相矿物组成的,主要化学组成为80%以上的SiO2和10%以上的Al2O3,以上的一种或几种。
所述的组分B为水性改性酚醛酰胺环氧固化剂,其活泼氢当量为270,通过加去离子水稀释得到不同当量的组分B。
一种涂料的制备方法:
(1)按上述比例将水性环氧分散体,E10p-DPOMA,混合助剂、颜填料,加入至分散缸,分散为均匀的浆料,而后将物料研磨至细度小于等于50μm,即得组分A;
(2)将水性改性酚醛酰胺环氧固化剂70-90%,经去离子水30-10%混合均匀,即为组分B;
(3)使用时将上述获得的组分A与组分B,按照质量比为4-8:1比例混合,即为涂料。
所述步骤(2)中将水性改性酚醛酰胺环氧固化剂经去离子水混合采用800-1000r分散5-10分钟,至液体混合均匀。
所述涂料中组分A(主料环氧树脂)和B(与固化剂(胺类))按比例混合在5℃以上进行化学交联反应得环保型低表面处理水性环氧厚浆型耐酸碱涂料;而后采用喷涂、刷涂、辊涂、淋涂的方式进行涂装。
本发明所具有的优点:
1.本发明涉及的环保型低表面处理水性环氧厚浆型耐酸碱涂料,其具有低VOCs、高固体分,可一次厚膜涂装200-300μm,柔韧性好,抗开裂性强,对基材附着力良好,可低表面处理带锈涂装,亦对焊缝等不易附着的金属表面有较好的附着力,耐腐蚀性好,柔韧性好,具有优异的耐酸、耐碱、耐油、耐溶剂等耐化学介质性,可在腐蚀环境较严苛的条件下使用,提高设备使用寿命,尤其适用于化工环境的金属及建筑的防护。
2.本发明涉及的涂料相对于传统水性涂料具有较高的固体份,挥发分较少,干燥过程中体积收缩率小,可进行一次性厚膜涂装200-300μm,缩短施工工期。
3.本发明涉及的涂料可进行低表面处理涂装,仅需进行初步打磨除锈/除油方式即可进行涂装,且涂装后的漆膜具有较好的附着力及防锈性;基材可喷砂至表面Sa 2.5级或手工St 2级后进行涂装,降低施工前基材处理成本。另因其具有良好的附着力,可以在焊缝等不易附着处具有良好的附着力。
4.本发明涉及的涂料可在腐蚀环境比较苛刻的条件下使用,提高设备的使用寿命,尤其适用于化工防腐领域的新建设备及设备维护及维修的表面涂装防护。
附图说明:
图1为锈板状态;
图2为锈板表面处理后状态;
图3为锈板涂刷后状态;
图4为焊接板状态;
图5为焊接板涂刷后状态。
具体实施方式:
下面结合实施实例对本发明进行详细说明,应当指出的是,此处所描述的具体实施方式只是为了说明和解释本发明,并不局限于本发明。
本发明涂料其通过功能性单体活性稀释剂E10p-DPOMA与预聚物树脂及固化剂产生网状交联结构,使涂料的防腐性效果更好,附着力增强,方便于施工,延迟了使用年限,同时避免了溶剂的挥发,可一次厚膜涂装,缩短施工时间。该涂料具有耐候性好、抗开裂性强、对基材附着力好、防腐性能好、可带锈涂装等一系列的特点,有着非常可观的应用前景。
本发明的环保型低表面处理水性环氧厚浆型耐酸碱涂料具有低VOCs、高固体分,可一次厚膜涂装200-300μm,柔韧性好,抗开裂性强,对基材附着力良好,可低表面处理带锈涂装,亦对焊缝等不易附着的金属表面有较好的附着力,耐腐蚀性好,具有优异的耐酸、耐碱、耐油、耐溶剂等耐化学介质性,可在腐蚀环境较严苛的条件下使用,提高设备使用寿命,尤其适用于化工环境的金属及建筑的防护。
本发明涂料的涂装方法可以采用刷涂、喷涂、辊涂、淋涂等多种施工方式。
下述各实施例配方为重量百分比。
下述记载试剂除特定记载,均为市购产品;例如,E20环氧树脂改性的水分散体(佛山市高明同德化工有限公司/无锡洪汇新材料有限公司)、环氧当量450-550,E51环氧树脂改性的水分散体(佛山市高明同德化工有限公司)、环氧当量180-220;改性三聚磷酸铝(汇金集团),改性磷酸锌(汇金集团),沉淀硫酸钡(南风化工集团股份有限公司)。
下述实施例所采用的E10p-DPOMA为叔碳酸缩水甘油酯50g、顺丁烯二酸12g、偶氮二异丁腈0.2g,准确称量后混合均匀,在氮气保护下,用四口烧瓶在搅拌状态下升温DPOMA25g,乙酸丁酯25g至90℃,匀速滴加上述混合物,在恒温状态下滴加上述混合物匀速搅拌,1.5-2小时滴加完毕,保温30分钟后,降温至30℃,滴加二甲基乙醇胺6g,分散30分钟,用减压蒸馏去除乙酸丁酯,得到100%的E10p-DPOMA。
实例1-20:
按照表1-3中各成分配制涂料,以实例6为例,在移动缸中加入由E20改性环氧分散体30g与E51改性环氧分散体5g组成的水性环氧分散体,E10p-DPOMA 5g,用高速分散机分散10分钟,加入由流平剂(ThAdd 2020)0.3g、消泡剂(AFCONA 2503)0.7g、润湿剂(Silok8104E)0.4g、分散剂(Silok 7112W)1.3g、增稠剂(EDW750)1g、防腐防霉剂(百洁化工BCH)0.2g、pH调节剂(SV-95)0.1g、防闪锈剂(SD6760)1g组成的混合助剂(混合助剂添加比例详见表表3),分散均匀后依次加入氧化铁红7.5g、改性三聚磷酸铝2.5g、改性磷酸锌7.5g、白云母粉12.5g、多磷酸硅酸钙铝2.5g、沉淀硫酸钡12.5g、硅土5g,去离子水5g,1000-2000r/min高速分散15分钟,用卧式砂磨研磨至细度≤50μm后,过滤出料,得到100g组分A。将改性酚醛酰胺环氧固化剂80g,去离子水20g加入至分散缸,用800-1000r/min转速分散10min,过滤出料,得到100g组分B。将所得的组分A与组分B按5:1质量比混合均匀。在标准测试碳钢板上进行200-300μm喷涂,根据HG/T5176-2017《钢结构用水性防腐涂料》、HG/T 4759-2014《水性环氧树脂防腐涂料》,7天养护后进行性能测试,硬度、柔韧性、耐冲击性、耐中性盐雾、耐水性、耐油性(3#溶剂油)、耐酸性(50g/L H2SO4)、耐碱性(50g/L NaOH)。涂层性能结果见表2。
由上述表4中记载可见,本实施例1-20均超过上述标准HG/T 4759-2014《水性环氧树脂防腐涂料》的相关性能要求,同时也超过国内其他厂家样漆的性能参数。同时,添加E10p-DPOMA活性稀释剂的实施例5-20的性能优于未添加的实施例1-4,对耐酸性影响较大,是由于活性稀释剂的添加使树脂交联密度增加,耐化学品性提高。以耐盐雾性作为防腐性能的判断标准,实施例5-20的防腐效果均超过上述标准;其中,颜填料添加量不同对结果有影响,实施例15-20较实施例6-14效果较差,实施例6性能最佳。
同时,选用上述实施例的涂料进行涂装,具体为:
施工实例1:按标准HG/T5173-2017带锈涂装用水性底漆中要求制作锈板后按标准要求进行表面处理(参见图1和2)。在标准环境中选用实施例6的涂料进行涂刷,总干膜厚度控制100-200μm(如图3)。由图3可见涂装后表面无返锈、透锈现象。检测后各项性能达到标准。
施工实例:选择2块喷砂碳钢75*150*5mm标准钢板进行90°垂直电焊(参见图4)。在标准环境中选用实施例6的涂料,进行涂刷,总干膜厚度控制100-200μm(参见图5)。由图5可见涂装后表面无返锈、透锈、露底等现象,焊缝处附着牢固,润湿性优良。检测后各项性能达到标准。
表1实施例1-20组分A配方表(以组分A为100g计)
表2实施例1-20组分B配方用量表(为100份计)
表3实施例1-20组分A配方内混合助剂用量表(为100份计,总量为5g)
表4实施例1-20组分性能表
对比样漆选用晨阳水漆的水性灰环氧底漆及固化剂配套(HG/T 5176),涂装方法同实施例1-20工艺。
Claims (10)
1.一种环保型低表面处理水性环氧厚浆型耐酸碱涂料,其特征是:涂料由组分A和组分B两组分按质量比4-8:1组成;其中,
组分B为水性改性酚醛酰胺环氧固化剂和去离子水;
所述的组分A各组分质量分数为:水性环氧树脂分散体 25-40%,活性稀释剂2.5-12.5%,氧化铁红7.5-15%、白云母粉 10-20%、改性磷酸锌 5-10%、改性三聚磷酸铝 2.5-5%、多磷酸硅酸钙铝 2.5-5%、沉淀硫酸钡 7.5-15%、硅土 2.5-7.5%、混合助剂 1.5-5.5%及去离子水 2.5-5%;
所述活性稀释剂为E10p-DPOMA,E10p-DPOMA为由叔碳酸缩水甘油酯,顺丁烯二酸,DPOMA合成的具有增韧作用的水性/油性两用的增韧树脂;其中,按质量百分比计,叔碳酸缩水甘油酯50-60%,顺丁烯二酸10-15%,DPOMA25-35%。
2.根据权利要求1所述的涂料,其特征是:所述水性环氧树脂分散体为环氧当量450-550的E20环氧树脂改性的水分散体和/或环氧当量180-220的E51环氧树脂改性的水分散体。
3.根据权利要求1所述的涂料,其特征是:所述混合助剂是由流平剂5-10份、消泡剂10-20份、润湿剂5-10份、分散剂20-30份、增稠剂10-30份、防腐防霉剂1-10份、pH调节剂1-6份、防闪锈剂5-20份组成。
4.根据权利要求3所述的涂料,其特征是:所述流平剂为丙烯酸酯均聚物、丙烯酸酯共聚物、聚硅氧烷中的一种或几种;
所述消泡剂为有机硅消泡剂、脂肪烃的乳化物、非硅酮有机酯碳氢化合物、非硅酮胺类碳氢化合物、含疏水粒子矿物油混合物中的一种或几种;
所述润湿剂为聚氧乙烯烷芳基醚、聚氧乙烯多元醇醚、聚氧乙酯聚氧丙烯酸嵌段共聚物、多元醇酯、脂肪胺聚氧乙烯醚加成物中的一种或几种;
所述分散剂为聚羧酸铵、聚硅氧烷中的一种或几种;
所述增稠剂为聚氨酯增稠剂和/或改性聚脲增稠剂;
所述防腐防霉剂为1,2-苯并异噻唑啉-3-酮(BIT)、2-甲基-5-氯-4-异噻咪唑-3-酮和2-甲基-4-异噻咪唑-3-酮(CMIT/MIT)、碘代丙炔基氨基甲酸酯、苯并咪唑氨基甲酸甲酯与N-(3,4-二氯苯基)-N,N-二甲基脲的复配体中的一种或几种;
所述防闪锈剂为螯合锌化合物。
5.根据权利要求3所述的涂料,其特征是:所述润湿剂为脂肪酸聚乙二醇酯。
6.根据权利要求3所述的涂料,其特征是:所述流平剂为丙烯酸酯低聚物或有机硅改性丙烯酸酯聚合物。
7.根据权利要求1所述的涂料,其特征是:所述的组分B中固化剂为水性改性酚醛酰胺环氧固化剂,其活泼氢当量为270。
8.一种权利要求1所述涂料的制备方法,其特征在于:
(1)按权利要求1的比例将组分A各组分加入至分散缸,分散为均匀的浆料,而后将物料研磨至细度小于等于50μm,即得组分A;
(2)将水性改性酚醛酰胺环氧固化剂70-90%,经去离子水30-10%混合均匀,即为组分B;
(3)使用时将上述获得的组分A与组分B,按照质量比为4-8:1比例混合,即为涂料。
9.根据权利要求8所述涂料的制备方法,其特征在于:所述步骤(2)中将水性改性酚醛酰胺环氧固化剂经去离子水混合采用800-1000r/min分散5-10分钟,至液体混合均匀。
10.根据权利要求8所述涂料的制备方法,其特征在于:所述涂料中组分A和B按比例混合在5℃以上反应得环保型低表面处理水性环氧厚浆型耐酸碱涂料;而后采用喷涂、刷涂、辊涂、淋涂的方式进行涂装。
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