CN105143516A - 在碱性次氯酸盐水性组合物中作为腐蚀抑制剂的高分子量聚丙烯酸和其方法 - Google Patents
在碱性次氯酸盐水性组合物中作为腐蚀抑制剂的高分子量聚丙烯酸和其方法 Download PDFInfo
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Abstract
本发明涉及一种水性组合物，其pH是至少11并且包含2wt％-15wt％的金属次氯酸盐和0.2wt％到4wt％的重量平均分子量为至少40,000的聚丙烯酸。
Description
背景技术
本发明大体上涉及含有聚丙烯酸作为腐蚀抑制剂的高度碱性和氧化性组合物。
己经使用低分子量分散剂聚合物作为腐蚀抑制剂。举例来说，美国专利5,976,414揭示分子量在500到15,000范围内的聚丙烯酸在轻度碱性水性组合物中作为腐蚀抑制包装的一部分。然而，需要在更高度碱性和氧化性系统中进行腐蚀抑制。
由本发明解决的问题是提供在高度碱性和氧化性组合物中改进的耐腐蚀性。
发明内容
本发明是针对一种水性组合物，其pH是至少11并且包含：(a)2wt％-15wt％的金属次氯酸盐和(b)0.2wt％到4wt％的重量平均分子量(Mw)为至少40,000的聚丙烯酸。
本发明进一步是针对一种用于在pH是至少11并且具有2wt％-15wt％的金属次氯酸盐的水性组合物中抑制腐蚀的方法，其通过添加0.2wt％到4wt％的数量平均分子量为至少40,000的聚丙烯酸来进行。
具体实施方式
除非另外指明，否则所有百分比都是重量百分比(wt％)，所有级分都是按重量计并且所有温度都是以℃为单位。聚合物中聚合单体残基的百分比是按固体聚合物的全部重量计，并且单体百分比是按总单体重量计。在“室温(roomtemperature)”(roomtemp.)下进行的测量是在20℃到25℃下进行。如所属领域中己知的，重量平均分子量Mw和数量平均分子量Mn都是通过凝胶渗透色谱法(GPC)使用聚丙烯酸标准品来测量。GPC的技术在《现代尺寸排阻色谱》(ModernSizeExclusionChromatography)，W.W.姚(W.W.Yau)，J.J.柯克兰(J.JKirkland)，D.D.布莱(D.D.Bly)；威利跨学科出版社(Wiley-Interscience)，1979和《材料表征和化学分析指南》(AGuidetoMaterialsCharacterizationandChemicalAnalysis)，J.P.希比利亚(J.P.Sibilia)；VCH，1988，第81到84页中详细论述。本文所报告的分子量是以道尔顿(dalton)为单位。
交联剂是具有两个或更多个非共轭烯系不饱和基团的单体。交联剂的实例包括例如二醇或多元醇的二烯丙基醚或三烯丙基醚以及二(甲基)丙烯酰酯或三(甲基)丙烯酰酯(例如，三羟甲基丙烷二烯丙基醚(TMPDAE)和三羟甲基丙烷三甲基丙烯酸酯(TMPTMA))、二酸或三酸的二烯丙基酯或三烯丙基酯、(甲基)丙烯酸烯丙基酯、二乙烯基砜、磷酸三烯丙酯、二乙烯基芳香族化合物(例如，二乙烯基苯)。
优选地，聚丙烯酸的Mw是至少50,000，优选地至少60,000，优选地至少80,000，优选地至少100,000，优选地至少150,000，优选地至少200,000，优选地至少250,000，优选地至少300,000，优选地至少350,000。优选地，聚丙烯酸的Mw不超过1,000,000，优选地不超过800,000，优选地不超过700,000，优选地不超过600,000，优选地不超过500,000。如本文所用的术语“聚丙烯酸”是指聚丙烯酸和其盐，例如将存在于含有氢氧化钠的高pH水性调配物中的聚丙烯酸钠盐。聚丙烯酸的分子量是针对酸形式所测量的，并且重量百分比是基于酸形式。
优选地，组合物中聚丙烯酸的量是至少0.3wt％，优选地至少0.4wt％，优选地至少0.5wt％，优选地至少0.6wt％，优选地至少0.7wt％，优选地至少0.8wt％。优选地，组合物中聚丙烯酸的量不超过3wt％，优选地不超过2.5wt％，优选地不超过2wt％，优选地不超过1.7wt％，优选地不超过1.4wt％。
优选地，金属次氯酸盐是碱金属或碱土金属盐或其组合；优选地是钠、钾、镁或钙盐；优选地是次氯酸钠。优选地，金属次氯酸盐的量是至少3wt％，优选地至少4wt％，优选地至少5wt％；优选地不超过13wt％，优选地不超过12wt％，优选地不超过11wt％，优选地不超过10wt％。在一个优选实施例中，组合物进一步包含最多3wt％、优选地0.1wt％到2.5wt％、优选地0.5wt％到2wt％的过氧化氢或其盐。
优选地，水性组合物的pH是至少11.5，优选地至少12，优选地至少12.3，优选地至少12.6。优选地，水性组合物的pH不超过14，优选地不超过13.5。优选地，水性组合物含有0.2wt％到5wt％的一种或多种碱金属氢氧化物，优选地氢氧化钠或氢氧化钾，优选地氢氧化钠。优选地，碱金属氢氧化物的量是至少0.3wt％，优选地至少0.4wt％，优选地至少0.5wt％，优选地至少0.6wt％；优选地不超过3wt％，优选地不超过2.5wt％，优选地不超过2wt％。
优选地，水性组合物包含至少75wt％、优选地至少78wt％、优选地至少80wt％、优选地至少82wt％、优选地至少83wt％、优选地至少84wt％、优选地至少85wt％、优选地至少86wt％的水。优选地，水性组合物包含不超过95wt％、优选地不超过93wt％、优选地不超过91wt％并且优选地不超过90wt％的水。优选地，水性组合物含有小于10wt％；优选地小于7wt％、优选地小于5wt％、优选地小于4wt％、优选地小于3wt％的除水、聚丙烯酸、金属次氯酸盐以及碱金属氢氧化物之外的成分。
优选地，聚丙烯酸包含不超过0.3wt％、优选地不超过0.2wt％、优选地不超过0.1wt％、优选地不超过0.05wt％、优选地不超过0.03wt％、优选地不超过0.02wt％、优选地不超过0.01wt％、优选地不超过0.005wt％、优选地不超过0.001wt％的交联剂聚合残基。优选地，聚丙烯酸包含不超过5wt％、优选地不超过3wt％、优选地不超过2wt％、优选地不超过1wt％、优选地不超过0.5wt％、优选地不超过0.2wt％的除丙烯酸之外单体的聚合残基。聚丙烯酸链的端基不重要。
本发明的水性组合物的实例是液体排放口清洁剂和液体氯漂白剂，优选地是液体排放口清洁剂。可以存在于液体排放口清洁剂中的其它组分包括表面活性剂、增稠剂、硅酸盐以及磷酸盐。优选地，氧化胺表面活性剂优选地以1wt％到3wt％的量存在。不含有本文所描述的高分子量聚丙烯酸的液体排放口清洁剂可能造成金属管道，尤其那些由镀锌钢制成的金属管道的过度腐蚀。
实例
购买LIQUIDPLUMR排放口清洁剂的商业样品并且用于本文所描述的测试。LIQUIDPLUMR排放口清洁剂的pH是13。测量为7.62cm×1.27cm×0.17cm的镀锌钢试片用于测试。以1wt％(以固体形式)的含量向排放口清洁剂中添加各种聚丙烯酸，并且在室温下在静态条件下将试片浸没在排放口清洁剂中持续6天。通过实验室浸渍腐蚀测试来测定腐蚀。制备可商购的金属样本并且将其浸没在测试溶液中持续预定的时间段和温度。在测试结束时，清洗样本，称重，并且使用立体变焦显微镜以肉眼进行检查。计算均一腐蚀速率，并且以用mpy为单位的渗透率形式报告(mpy-毫英寸/年)。也常常以mm/y的SI单位报告腐蚀速率(mm/y-毫米/年)，其中1mpy相当于0.0254mm/y。根据ASTMG1-03，《用于制备、清洗和评估腐蚀测试样本的标准实践》(“StandardPracticeforPreparing，Cleaning，andEvaluatingCorrosionTestSpecimens”)和ASTMG31-72《金属的实验室浸渍腐蚀测试的标准实践》(“StandardPracticeforLaboratoryImmersionCorrosionTestingofMetals”)来进行测试。下表描述所测试的排放口清洁剂样品和结果。
聚丙烯酸A具有膦基端基，B和D具有磺酸酯端基，并且C具有膦酰基端基。也使用碳钢试片进行上文所描述的测试。在样品当中没有观察到腐蚀速率差异。
Claims (10)
1.一种水性组合物，其pH是至少11并且包含：(a)2wt％-15wt％的金属次氯酸盐和(b)0.2wt％到4wt％的重量平均分子量为至少40,000的聚丙烯酸。
2.根据权利要求1所述的组合物，其中所述水性组合物的pH是至少12。
3.根据权利要求2所述的组合物，其中所述聚丙烯酸的重量平均分子量为至少100,000。
4.根据权利要求3所述的组合物，其包含0.5wt％到2wt％的所述聚丙烯酸。
5.根据权利要求4所述的组合物，其中所述金属次氯酸盐是次氯酸钠。
6.根据权利要求5所述的组合物，其包含4wt％到11wt％次氯酸钠。
7.一种用于在pH是至少11并且具有2wt％-15wt％的金属次氯酸盐的水性组合物中抑制腐蚀的方法，其通过添加0.2wt％到4wt％的数量平均分子量为至少40,000的聚丙烯酸来进行。
8.根据权利要求7所述的方法，其中所述水性组合物是液体排放口清洁剂。
9.根据权利要求8所述的方法，其中所述排放口清洁剂的pH是至少12。
10.根据权利要求9所述的方法，其中所述聚丙烯酸的重量平均分子量是至少100,000，所述水性组合物包含0.5wt％到2wt％的聚丙烯酸并且所述水性组合物包含4wt％到11wt％的次氯酸钠。
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| PCT/US2014/034094 WO2014172318A1 (en) | 2013-04-17 | 2014-04-15 | High molecular weight polyacrylic acids as corrosion inhibitors in an alkaline hypochlorite aqueous composition and method thereof |
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| AU2014254124A1 (en) | 2015-11-12 |
| AU2014254124B2 (en) | 2018-05-17 |
| BR112015025070A2 (pt) | 2017-07-18 |
| JP2016518491A (ja) | 2016-06-23 |
| EP2956571A1 (en) | 2015-12-23 |
| WO2014172318A1 (en) | 2014-10-23 |
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