CN109689807A - 用氨基醇中和的丙烯酸类聚合物 - Google Patents

用氨基醇中和的丙烯酸类聚合物 Download PDF

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CN109689807A
CN109689807A CN201780056091.2A CN201780056091A CN109689807A CN 109689807 A CN109689807 A CN 109689807A CN 201780056091 A CN201780056091 A CN 201780056091A CN 109689807 A CN109689807 A CN 109689807A
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acrylic polymer
acrylic
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amino alcohol
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M·洛可
A·A·佩拉
M·舒密尔
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Rohm and Haas Co
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Abstract

一种丙烯酸聚合物,其包含3wt%至17wt%的羧酸单体聚合单元。所述聚合物至少部分地用具有伯氨基的氨基醇中和。

Description

用氨基醇中和的丙烯酸类聚合物
技术领域
本发明涉及一种特别适用作地板面漆的水性涂料组合物。
背景技术
在某些情况下,在地板和其他表面上使用的水性涂料组合物包含双组分聚氨酯系统。举例来说,美国专利第7,452,935公开了一种系统,其包含用含有羟基的叔胺中和的多羟基聚丙烯酸酯树脂。但是,这一参考文献没有公开可去除的地板面漆,也没有公开本发明的已中和聚合物。
本发明所解决的问题是提供一种改进的可去除的涂料组合物。
发明内容
本发明提供一种丙烯酸类聚合物,其包含3wt%至17wt%的羧酸单体聚合单元;所述聚合物至少部分地用具有伯氨基的氨基醇中和。
本发明还涉及一种用于涂覆基材的方法,其通过将包含所述丙烯酸类聚合物的水性涂料组合物施用到所述基材上来进行。
具体实施方式
除非另有说明,否则百分比是重量百分比(wt%),温度单位以℃为单位,并且操作在环境温度(通常为20-25℃)下进行。单体单元或氨基醇的重量百分比是按干燥聚合物的总重量计。与某些配制物成分一起列出的百分比是水性乳液或分散液中的固体百分比。所有聚合物Tg值通过差示扫描量热法(DSC)测量,使用每分钟20℃的加热速率,Tg在转变的中点处取得。
“羧酸单体”是指具有至少一个、优选一个或两个、优选一个羧酸基团的单烯键式不饱和化合物。优选地,羧酸单体具有3至8个、优选3至5个、优选3或4个碳原子。
如本文所用,术语“(甲基)丙烯酸”是指“丙烯酸”和/或“甲基丙烯酸”,并且术语“(甲基)丙烯酸酯”是指“丙烯酸酯”和/或“甲基丙烯酸酯”。术语“(甲基)丙烯酰胺”是指丙烯酰胺(AM)和/或甲基丙烯酰胺(MAM)。“丙烯酸类单体”的实例包括丙烯酸(AA)、甲基丙烯酸(MAA)、AA和MAA的酯、衣康酸(IA)、巴豆酸(CA)、丙烯酰胺(AM)、甲基丙烯酰胺(MAM)以及AM和MAM的衍生物,例如烷基(甲基)丙烯酰胺。AA和MAA的酯包括但不限于烷基酯、苄基酯、羟烷基酯、磷酸烷基酯和磺烷基酯,例如甲基丙烯酸甲酯(MMA)、甲基丙烯酸乙酯(EMA)、甲基丙烯酸丁酯(BMA)、甲基丙烯酸异丁酯(iBMA)、甲基丙烯酸羟乙酯(HEMA)、丙烯酸羟乙酯(HEA)、丙烯酸甲酯(MA)、丙烯酸乙酯(EA)、丙烯酸丁酯(BA)、丙烯酸乙基己酯(EHA)和甲基丙烯酸磷酸乙酯(PAM)。术语“乙烯基单体”是指含有碳-碳双键的单体,所述碳-碳双键与杂原子,如氮或氧连接。乙烯基单体的实例包括但不限于乙酸乙烯酯、乙烯基甲酰胺、乙烯基乙酰胺、乙烯基吡咯烷酮、乙烯基己内酰胺和长链链烷酸乙烯酯,如新癸酸乙烯酯和硬脂酸乙烯酯。术语“苯乙烯类单体”是指苯乙烯和乙烯基甲苯。“丙烯酸类聚合物”包含至少50wt%、优选至少75wt%、优选至少85wt%的丙烯酸类单体聚合单元,优选至少85wt%、更优选至少90wt%、并且最优选至少95wt%的选自(甲基)丙烯酸和(甲基)丙烯酸烷基酯的单体的聚合单元。优选地,任何剩余的单体单元衍生自乙烯基单体。优选地,丙烯酸类聚合物包含不超过10wt%、优选不超过5wt%、优选不超过3wt%、优选不超过2wt%、优选0wt%的苯乙烯类单体聚合单元。
为了本发明的目的,烷基是直链或支链烷基。在本发明的一些实施方案中,烷基是合成来源并且可以含有一系列链长。优选地,烷基是直链或支链无环烷基。
丙烯酸类聚合物包含具有伯胺官能度,即至少一个氨基,-NH2;优选不超过两个,优选一个氨基的氨基醇。优选地,氨基醇具有3至12个;优选至少4个;优选不超过10个、优选不超过8个、优选不超过6个碳原子。优选地,氨基醇包含1至5个,优选2至4个、优选3个羟基。优选地,氨基醇包含至少一个,优选至少两个、优选三个伯羟基。优选的氨基醇是2-氨基-2-羟甲基-1,3-丙二醇(CAS No.77-86-1)。优选地,丙烯酸类聚合物包含1wt%至10wt%;优选至少1.5wt%、优选至少2wt%、优选至少2.5wt%;优选不超过8wt%、优选不超过6wt%、优选不超过5wt%的氨基醇。优选地,丙烯酸类聚合物的pH为6至8.5、优选6.5至8、优选7至8。聚合物中可存在超过一种氨基醇。
优选地,聚合物包含不超过2wt%、优选不超过1wt%、优选不超过0.5wt%、优选0wt%的氨。优选地,聚合物包含不超过2wt%的叔氨基醇,即具有叔氨基的氨基醇,优选不超过1wt%、优选不超过0.5wt%、优选0wt%的叔氨基醇。优选地,聚合物包含不超过2wt%,优选不超过1wt%、优选不超过0.5wt%、优选0wt%的烷基胺。
优选地,聚合物还包含(甲基)丙烯酸C1-C8烷基酯的单体残基。优选地,(甲基)丙烯酸C1-C8烷基酯包含甲基丙烯酸烷基酯和丙烯酸烷基酯,优选甲基丙烯酸C1-C2烷基酯(MMA或EMA)和丙烯酸C4-C8烷基酯(例如,BA或EHA),优选MMA和丙烯酸C4-C8烷基酯,优选MMA和BA。优选地,聚合的(甲基)丙烯酸C1-C8烷基酯单体单元的总量为83wt%至97wt%。优选地,(甲基)丙烯酸C1-C8烷基酯单体单元的总量为至少85wt%、优选至少87wt%、优选至少89wt%;优选不超过95wt%、优选不超过93wt%、优选不超过91wt%。优选地,聚合物包含15wt%至40wt%;优选地至少18wt%、优选地至少21wt%、优选地至少24wt%;优选地不超过37wt%、优选地不超过34wt%、优选地不超过32wt%的丙烯酸C4-C8烷基酯聚合单元。优选地,聚合物包含45wt%至80wt%;优选至少48wt%、优选至少51wt%、优选至少54wt%、优选至少57wt%;优选不超过77wt%、优选不超过74wt%、优选不超过71wt%、优选不超过68wt%的甲基丙烯酸C1-C2烷基酯。
优选地,聚合物的Tg为至少30℃、优选至少40℃、优选至少50℃、优选至少60℃;优选不超过80℃、优选不超过90℃、优选不超过95℃、优选不超过100℃。本领域技术人员将能够根据本文所述的那些来选择单体以达到任何期望的Tg值。
优选地,羧酸单体是(甲基)丙烯酸,优选甲基丙烯酸。优选地,聚合物包含至少5wt%;优选至少6wt%、优选至少7wt%、优选至少8wt%;优选不超过15wt%、优选不超过13wt%、优选不超过12wt%、优选不超过11wt%的羧酸单体聚合单元。
交联剂是具有两个或更多个烯属不饱和基团的单体,并且可包括,例如二乙烯基芳香族化合物,二-、三-和四-(甲基)丙烯酸酯,二-、三-和四-烯丙基醚或酯化合物和(甲基)丙烯酸烯丙基酯。此类单体的实例包括二乙烯基苯(DVB)、三羟甲基丙烷二烯丙基醚、四烯丙基季戊四醇、三烯丙基季戊四醇、二烯丙基季戊四醇、邻苯二甲酸二烯丙基酯、顺丁烯二酸二烯丙基酯、氰脲酸三烯丙基酯、双酚A二烯丙基醚、烯丙基蔗糖、亚甲基双丙烯酰胺、三羟甲基丙烷三丙烯酸酯、甲基丙烯酸烯丙基酯(ALMA)、乙二醇二甲基丙烯酸酯(EGDMA)、己烷-1,6-二醇二丙烯酸酯(HDDA)和丁二醇二甲基丙烯酸酯(BGDMA)。优选地,聚合物中聚合的交联剂单元的量不超过1wt%、优选不超过0.5wt%、优选不超过0.2wt%、优选不超过0.1wt%、优选不超过0.05wt%、优选不超过0.01wt%。
优选地,聚合物以均匀的水性分散液,即胶乳形式分散在水中。优选地,水性分散液包含30wt%至60wt%;优选至少35wt%;优选不超过55wt%、优选不超过50wt%的聚合物。可存在超过一种根据本发明的聚合物,其中聚合物的总量在上文指定的量内。
优选地,水性涂料组合物包含至少45wt%;优选至少50wt%、优选至少55wt%、优选至少60wt%、优选至少65wt%;优选不超过80wt%、优选不超过75wt%的丙烯酸类聚合物。优选地,所述水性组合物含有不超过10wt%,优选不超过8wt%、优选不超过6wt%;优选至少2wt%的有机溶剂。
乳液聚合物颗粒的平均粒径通常为40纳米至1000纳米,优选40纳米至300纳米。本文中的粒径是通过Brookhaven BI-90分析仪上的动态光散射测量的粒径。用1N KCl(水溶液)将胶乳样品稀释至合适的浓度。
本发明的地板涂料组合物任选地可以包括其他成分,例如蜡、碱溶性树脂、增塑剂、润湿助剂、消泡剂、可溶或分散的杀生物剂、聚氨酯分散剂、硅酸盐等。优选地,蜡的含量为0.5wt%至10wt%,优选1wt%至7wt%(基于固体的量)。
在本发明的方法中,将水性组合物施用于表面,例如地板、墙壁、台面、屋顶等。可以施用组合物的材料包括石头、混凝土、沥青、屋顶基材、油毡、瓷砖、木材、颗粒或纤维板、玻璃、皮革、纸张和纸板。优选地,将组合物施用于地板。优选地,组合物在没有外部加热、通风或湿度控制的环境条件下固化,尽管这些可按需要使用。
评价地板抛光涂料的性能
为了适当地评价打算用于抛光媒剂中的乳液聚合物的性能,必须将聚合物配制成抛光剂。本发明的乳液聚合物的配制以本领域技术人员常用并且充分理解的方式进行。使用的成分以及其比例和添加方式与常规技术乳液聚合物通常使用的相同。所配制地板抛光剂中使用的成分由乳液聚合物、蜡乳液、碱溶性树脂(ASR)、成膜助剂、调平剂和润湿剂组成。用于抛光配制物中的聚结溶剂、增塑溶剂和调平剂的水平取决于乳液聚合物(聚合物的总组合物)与所选溶剂和添加剂的相容性以及乳液聚合物的最低成膜温度。对于此处列出的实例的乳液聚合物,聚结剂、增塑剂和添加剂水平如配制物细节中给出,尽管酌情进行了微小调整以确保每个聚合物实例形成光泽的、明显粘附的膜。
测试方法:
在本发明中,使用各种测试来评价乳液聚合物媒剂作为可去除地板抛光剂(或地板涂料)的性能。用于施用涂料组合物的方法描述于《ASTM标准年刊(Annual Book of ASTMStandards)》,第15部分,第15.04卷,测试程序ASTM D 3153中,除了向基材上施用每平方英寸0.04mL涂料。共施用2层。地板抛光配制物如下:
耐黑色鞋跟印和磨损性能
用于测定耐黑色鞋跟和磨损性能的方法描述于《化学专用品制造商协会公告(Chemical Specialty Manufacturers Association Bulletin)》第9-73期中,除了使用商购的橡胶鞋跟代替推荐的2"(5.1cm)橡胶方块。我们测定了经过涂布的基材区域中由黑色鞋跟印和磨损痕迹覆盖的百分比;这可以用透明方格纸方便地进行。黑色鞋跟印是橡胶在涂层上或涂层中的实际沉积。另一方面,磨损痕迹是由涂层的物理位移引起的,并且呈现为光泽度降低的区域。在鞋跟撞击基材的位置可能同时发生磨损痕迹和黑色鞋跟印;即,在去除黑色鞋跟印后,可能存在磨损。
光泽和再涂层光泽
用于测定抛光剂配制物的光泽性能和再涂层光泽性能的方法描述于《ASTM标准年刊(Annual Book of ASTM Standards)》,第15部分,第15.04卷,测试程序ASTM D 1455中。光泽在黑色乙烯基复合瓷砖上进行测定。
耐洗涤剂性
用于测定耐洗涤剂性的方法描述于《ASTM标准年刊》,第15部分,第15.04卷,测试程序ASTM D 3207中,除了使用GP Forward通用清洁剂(General Purpose Cleaner)(Diversey Inc.Sturtevant,Wis.53177USA)于水中的1/20稀释液作为测试洗涤剂溶液。
可去除性
用于测定抛光剂可去除性的方法描述于《ASTM标准年刊》,第15部分,第15.04卷,测试程序ASTM D 1792中,除了使用FREEDOM(Diversey Inc.Sturtevant,Wis.53177USA)于水中的1/4稀释液作为测试剥离溶液。
粘性消失时间测试方法
表面涂层粘性消失时间使用ZAPON粘性测试仪来测定。粘性测试仪由1/16英寸(1.6mm)厚的铝金属片的1英寸(2.54cm)宽弯曲条制成。对它进行尺寸化以使得1平方英寸部分将平坦地放置在表面上。将其称重以使得当五克砝码放置在铝条带的中心上时它将直立。如果低于五克的砝码放置在铝条带的中心上,则它将倒下。将粘性测试仪放置在膜的表面上,其中500克砝码放置在测试仪上。将砝码在测试仪上保持五秒然后去除。如果测试仪在五秒内倒下,则涂料通过Zapon粘性消失测试。从当施用涂料时开始经过的的时间记录为Zapon粘性消失时间。条件:73℉(23℃)和16%相对湿度。
台架测试:
本发明的聚合物和对比聚合物均具有组成28BA/62MMA/10MAA。
表1:当在70℉&50%RH的典型条件下施用时,基于本发明聚合物(用TRIS AMINOTA-40;2-氨基-2-羟甲基-1,3-丙二醇中和)的配制物MS-1126-10W表现出相对于基于对比聚合物的类似对照配制物N-24-9(典型商业聚合物)更高的施用光泽度
表2:当在50℉&30%RH的低温度和湿度条件下施用,基于本发明聚合物(用TRISAMINO TA-40;2-氨基-2-羟甲基-1,3-丙二醇中和)的配制物MS-1126-10W表现出相对于基于典型商业聚合物的类似对照配制物N-24-9更高的施用光泽度。
地板测试数据
表3:当在50℉&30%RH的低温度和湿度下施用时,基于本发明聚合物(用TRISAMINOTA-40;2-氨基-2-羟甲基-1,3-丙二醇中和)的配制物MS-1126-10W表现出相对于基于典型商业聚合物的类似对照配制物N-24-9更高的施用光泽度。
其它测试方法
在适用的情况下,采用由陶氏化学公司(Dow Chemical Company)的家庭、机构和个人护理解决方案(Home,Institutional&Personal Care Solutions)业务开发的用于评估地板面漆的标准测试方法。
防滑性
如由詹姆斯测量机(James Machine)所测量,用于抛光-涂覆地板表面的静摩擦系数的ASTM D2047标准测试方法。
防污性通过将已涂覆的白色乙烯基复合瓷砖暴露于标准AATAC土壤后的颜色变化来测量。ΔE越低,相对于参考瓷砖样品的颜色变化越小。测量值<+/-1.0单位并不显著,因为它处于测试方法的精度范围内。
加速磨损测试机(AWT)是陶氏公司具有专利的机器人高通量测试机,其可以在数天内生成数月的地板磨损测试数据。它能够在复制现场趋势的不同维护条件下测试各种基材上的抛光剂和清洁剂。
光泽保持和防污性的附加(AWT)图表用于适度的维护系统,其中地板每周维护3至4次。每个维护周期包括2次操作,弄脏、研磨和用标准全功能清洁剂(All PurposeCleaner)(1oz/gal)擦洗经过涂覆的测试基材。然后使用地板机和高速磨光垫进行一次磨光操作。在每个循环后记录并绘制光泽度和颜色测量值(ΔE)。
一般评级系统:
评级描述符
加速磨损测试机结果
表4:在弄脏、磨损、擦洗和磨光之前和之后,基于本发明聚合物(用TRIS AMINOTA-40;2-氨基-2-羟甲基-1,3-丙二醇中和)的地板面漆配制物表现出相对于基于典型商业聚合物的类似对照配制物更高的光泽度。
配制物详情:
表5:
*使用1.21%TRIS AMINO TA-40
聚合物/蜡比率 89/11。

Claims (10)

1.一种丙烯酸类聚合物,其包含3wt%至17wt%的羧酸单体聚合单元;所述聚合物至少部分地用具有伯氨基的氨基醇中和。
2.根据权利要求1所述的丙烯酸类聚合物,其中所述丙烯酸类聚合物包含83wt%至97wt%的聚合的(甲基)丙烯酸C1-C8烷基酯单体单元。
3.根据权利要求2所述的丙烯酸类聚合物,其中所述氨基醇具有3至12个碳原子。
4.根据权利要求3所述的丙烯酸类聚合物,其包含1wt%至8wt%的所述氨基醇。
5.根据权利要求4所述的丙烯酸类聚合物,其中所述氨基醇具有2至4个羟基。
6.根据权利要求5所述的丙烯酸类聚合物,其中所述聚合物包含85wt%至95wt%的(甲基)丙烯酸C1-C8烷基酯聚合单元和5wt%至15wt%的羧酸单体聚合单元。
7.根据权利要求6所述的丙烯酸类聚合物,其中所述羧酸单体具有3至5个碳原子。
8.根据权利要求7所述的丙烯酸类聚合物,其中所述氨基醇具有从2至4个伯羟基和一个伯氨基。
9.根据权利要求8所述的丙烯酸类聚合物,其中所述(甲基)丙烯酸C1-C8烷基酯包含甲基丙烯酸C1-C2烷基酯酯和丙烯酸C4-C8烷基酯。
10.根据权利要求9所述的丙烯酸类聚合物,其包含15wt%至40wt%的丙烯酸C4-C8烷基酯聚合单元和45wt%至80wt%的甲基丙烯酸C1-C2烷基酯聚合单元。
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