CN111253588A - 一种改性云母粉/水性丙烯酸酯微纳复合乳液的制备方法 - Google Patents
一种改性云母粉/水性丙烯酸酯微纳复合乳液的制备方法 Download PDFInfo
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Abstract
本发明涉及一种改性云母粉/水性丙烯酸酯微纳复合乳液的制备方法,包括:将碳酸氢钠、去离子水进行恒温搅拌,并加入部分预乳化液和部分引发剂水溶液,恒温搅拌,滴加剩余预乳化液和改性云母粉的混合液及剩余引发剂水溶液,然后保温,降温,调pH,然后加入有机硅,搅拌,过滤,即得。本发明具有操作简单、环境友好、可大量生产、成本低的特点,制备的乳液稳定性好,改性云母粉在基体中分散性优异,涂膜力学性能强,适用范围广,防紫外线性能强,具有良好的应用前景。
Description
技术领域
本发明属于功能性丙烯酸酯复合乳液的制备领域,特别涉及一种改性云母粉/水性丙烯酸酯微纳复合乳液的制备方法。
背景技术
水性聚丙烯酸酯涂料具有许多突出的优点,如卓越的耐候性、耐光性,以及户外耐久性强,紫外光照射不易分解和变色,能长时间保持原有的色光,耐热性好;耐腐蚀,有较好的耐酸、碱、盐、油脂、洗涤剂等化学品粘污及污染的能力,因此,已成为最受关注与青睐的一类涂料。但由于其强度较低、耐水性差等缺点的存在,一定程度上限制了丙烯酸酯涂料的发展。无机粉体材料作为涂料工业中常见的填料物质,复配于乳液中,起到改善涂料强度、刚性并赋予涂料其它独特性能的作用,引起人们广泛的研究兴趣。针对无机材料与涂料表面性质差异大,相容性差,难以在乳液中稳定或大量存在,一般要对其进行表面修饰处理,提高无机粉体材料在涂料中的分散性;专利申请号为201811119320.3公开了一种将改性石墨烯添加于水性丙烯酸酯乳液制备抗辐射涂料的方法,得到了易成膜、柔性、附着力强的防辐射涂料,体现了无机粉体材料在提高水性丙烯酸酯乳液性能方面具有的优异性能。云母粉作为一种亲水性的无机微纳米材料,其独特的层状结构与优良的力学、光学等性能,使其作为一种性能优良的无机填料较为广泛的应用于高聚物材料中。专利申请号为201810455184.9公开了一种通过氧化石墨烯改性绢云母粉的聚合物水泥防水涂料及其制备方法,通过氧化石墨烯对绢云母粉进行改性,使其能促进聚合物乳液成膜并加速水泥化,另一方面利用氧化石墨烯的插层作用及绢云母粉的片状结构来改善涂料的施工性能,由于云母粉与水性丙烯酸酯乳液相容性欠佳,将两者复合并取得有效增益效果的专利较少,本文通过将改性后云母粉添加于水性丙烯酸酯乳液中,显著提高乳液强度与断裂延伸率,且制备的复合乳液性能稳定,分散性优异。
发明内容
本发明所要解决的技术问题是提供一种改性云母粉/水性丙烯酸酯微纳复合乳液的制备方法,克服现有技术中云母粉与水性丙烯酸酯乳液相容性差的缺陷,该方法采用原位聚合与乳液聚合的方法,在种子乳液形成之后,将改性后的云母粉添加与单体混合液中,制备出改性云母粉/水性丙烯酸酯复合乳液,该乳液综合性能优异,实用性强。
本发明的一种改性云母粉/水性丙烯酸酯微纳复合乳液,所述复合乳液由包含下列组分的原料获得;其中原料组分包括:预乳化液、碳酸氢钠、引发剂、改性云母粉、有机硅。
所述预乳化液由丙烯酸正丁酯、苯乙烯、甲基丙烯酸甲酯、甲基丙烯酸,乳化剂,双丙酮丙烯酰胺和去离子水混匀,乳化获得;有机硅为聚有机硅氧烷;改性云母粉为:云母粉、硅烷偶联剂分散于去离子水中,加入聚丙烯酸酯溶液,超声分散;恒温匀速滴加盐酸溶液、氯化钠溶液,将混合液静置分离并收集絮凝状固体,水洗产物至中性,超声分散,冻干机干燥。
本发明的一种改性云母粉/水性丙烯酸酯微纳复合乳液的制备方法,包括:
(1)将单体丙烯酸正丁酯、苯乙烯、甲基丙烯酸甲酯、甲基丙烯酸,乳化剂,双丙酮丙烯酰胺和去离子水混匀,然后预乳化,得到预乳化液;
(2)将碳酸氢钠、去离子水进行恒温搅拌,并加入质量分数8:92%的部分预乳化液和质量分数45:55%的引发剂水溶液,恒温搅拌,滴加剩余预乳化液和改性云母粉的混合液及剩余引发剂水溶液,然后保温,降温,调pH,然后加入有机硅,充分搅拌溶解后停止加热,过滤,即得。
所述步骤(1)中乳化剂为占十二烷基硫酸钠总质量的70-90%、占聚氧乙烯辛基苯酚醚-10总质量的70-90%。
所述步骤(1)中乳化剂为十二烷基硫酸钠和聚氧乙烯辛基苯酚醚-10;其中十二烷基硫酸钠的质量为单体(丙烯酸正丁酯、苯乙烯、甲基丙烯酸甲酯、甲基丙烯酸,下同)总质量的1-3%;聚氧乙烯辛基苯酚醚-10的质量为单体总质量的2-4%。
进一步,优选地,所述十二烷基硫酸钠的质量为单体总质量的2.0%;聚氧乙烯辛基苯酚醚-10的质量为单体总质量的3.0%。
所述步骤(1)中丙烯酸正丁酯、苯乙烯、甲基丙烯酸甲酯、甲基丙烯酸的质量比为43-46:22-21:32-31:3-2;双丙酮丙烯酰胺的质量为单体总质量的1-4%。
进一步,优选地,所述步骤(1)中双丙酮丙烯酰胺的质量为单体总质量的1.9%。
所述步骤(1)中预乳化具体为:先用高速分散均质机搅拌0.5-1min,再磁力搅拌20min。
所述步骤(2)中引发剂为过硫酸钾;有机硅为国药集团生产聚有机硅氧烷,化学纯。
所述步骤(2)中碳酸氢钠的质量为单体总质量的3-7‰;引发剂的质量为单体总质量的0.5-1.5%;改性云母粉为单体总质量的1-7%;有机硅的质量为单体总质量的4-9%。
进一步,优选地,所述改性云母粉质量为单体总质量的1.25%、2.50%、3.75%、5.0%、6.25%;碳酸氢钠的质量为单体总质量的4.0‰;引发剂的质量为单体总质量的0.70%;有机硅的质量为单体总质量的6.0%。
所述步骤(2)中恒温搅拌温度均为80-84℃,搅拌转速为200-400rpm;保温时间为1-3h,保温温度为80-84℃。
所述恒温搅拌时间为15-30min。
进一步,优选地,所述恒温搅拌温度为82℃,保温时间为1.5h。
所述步骤(2)中部分预乳化液和部分引发剂水溶液均一次性加入,剩余预乳化液和改性云母粉的混合液及剩余引发剂水溶液均在2.5-3h滴完;其中部分预乳化溶液为预乳化液总质量的6%-12%;部分引发剂为引发剂总质量的45%-55%。
所述剩余预乳化液和改性云母粉的混合液具体为:将改性云母粉与剩余预乳化液室温混合,磁力搅拌20min。
所述步骤(2)中降温至55℃±5℃;氨水调节pH值为8.0-9.0。
所述步骤(2)中搅拌溶解时间为30-60min后停止加热。
所述改性云母粉的具体制备方法为:将市售云母粉、硅烷偶联剂分散于去离子水中,加入聚丙烯酸酯溶液,超声分散;恒温匀速滴加盐酸溶液、氯化钠溶液,将混合液静置分离并收集絮凝状固体,水洗产物至中性,超声分散,冻干机干燥,即得。
本发明提供一种所述方法制备的改性云母粉/水性丙烯酸酯微纳复合乳液。
本发明提供一种所述改性云母粉/水性丙烯酸酯微纳复合乳液的应用。
有益效果
(1)本发明采用预乳化半连续工艺制备了功能性改性云母粉/水性丙烯酸酯微纳复合乳液,本发明具有操作简单、环境友好、可大量生产、成本低的特点。
(2)本发明制备的高分散性的改性云母粉/水性丙烯酸酯微纳复合乳液,与添加未改性云母粉的对比样相比,具有以下优良特性:
①所制备的复合乳液,如制备过程中,反应体系的凝胶率为0.68%。
②所制备的复合乳液中,改性云母粉在复合乳液中分散性好,如常温静置放置30天,乳液未出现明显沉淀、分层的现象。
③所制备的复合乳液干燥后形成的涂膜具有一定的耐水性,如涂膜接触角可达40.12°,而纯水性聚丙烯酸酯漆膜为28.17°。
④所制备的复合乳液干燥成膜后,形成的涂膜拉伸强度可达11.5MPa、段裂延伸率可达1054%;
⑤所制备的复合乳液具有优异的抗紫外性能,参见图4;
⑥所制备的复合乳液干燥成膜后,涂膜可剥性能优异。
附图说明
图1本发明的工艺流程图;
图2是产物的接触角;其中a:纯水性聚丙烯酸酯漆膜;b:实施例3产物;
图3是实施例3产物的分散性能图片(室温静置30天),其中a为添加改性后云母粉的复合乳液,b为添加未改性云母粉的复合乳液,云母粉添加量为3.75%;
图4是实施案例3产物紫外吸光度;其中a:纯水性聚丙烯酸酯漆膜;b:实施例3产物;
图5是实施案例3产物的可剥性图片。
具体实施方式
下面结合具体实施例,进一步阐述本发明。应理解,这些实施例仅用于说明本发明而不用于限制本发明的范围。此外应理解,在阅读了本发明讲授的内容之后,本领域技术人员可以对本发明作各种改动或修改,这些等价形式同样落于本申请所附权利要求书所限定的范围。
所使用改性云母粉制备方法:取5g市售2000目云母粉、0.01g硅烷偶联剂KH-570、2g聚丙烯酸酯溶液和25g去离子水在烧杯中混合均匀,磁力搅拌10min,超声分散20min分钟;取0.75g盐酸溶液,匀速加入到混合溶液中,1-2min滴加完毕,取0.075g氯化钠加入到混合溶液中,20℃下磁力搅拌15min。将混合液静置分液,过滤收集絮凝状复合物,去离子水洗至中性。收集产物分散于15g去离子水中,超声分散30min;-80℃下预冻,冻干机干燥,收集产物。
聚丙烯酸酯的具体制备方法:取10g丙烯酸正丁酯、4.8g苯乙烯、7.3g甲基丙烯酸甲酯、0.7g丙烯酸、0.4g十二烷基硫酸钠、0.06g聚氧乙烯辛基苯酚醚-10和11g去离子水于烧杯中混合均匀,磁力搅拌20min进行预乳化。分别取0.072g过硫酸钾溶于2g去离子水中,0.09g过硫酸钾于5.4g去离子水中,备用;取0.09g碳酸氢钠、9.6g去离子水、0.046g十二烷基硫酸钠和0.07g聚氧乙烯辛基苯酚醚-10于四口烧瓶内混匀,控温82℃,恒温搅拌15min,转速为350rpm;待乳化剂溶解完全,一次性加入2.8g预乳化液和2.2g过硫酸钾水溶液,恒温搅拌30min;分别同时向四口烧瓶内滴加剩余乳化液和5.5g过硫酸钾溶液,3h内滴完,然后保温1.5h,降温至55℃,用氨水调pH值为8-9;加入1.4g聚有机硅氧烷,充分搅拌30min后停止加热,过滤,出料。
所用云母粉来自麦克林集团,干法2000目云母粉,其它单体及乳化剂等添加剂来自国药集团,化学纯。
实施例1
(1)取16.65g丙烯酸正丁酯、8.14g苯乙烯、12.21g甲基丙烯酸甲酯、1.24g甲基丙烯酸、0.76g十二烷基硫酸钠、1.10g聚氧乙烯辛基苯酚醚-10、0.73g双丙酮丙烯酰胺和18.2g去离子水于烧杯中混合均匀,先用高速分散均质机搅拌0.5-1min,再磁力搅拌20min进行预乳化。分别取0.12g过硫酸钾溶于3.5g去离子水中,0.15g过硫酸钾于9.0g去离子水中,备用。
(2)取0.15g碳酸氢钠、16g去离子水于四口烧瓶内混匀,控温82℃,恒温搅拌15min,转速为220rpm;待乳化剂溶解完全,一次性加入4.7g预乳化液和3.62g过硫酸钾水溶液,恒温搅拌30min。
(3)取0.48g改性云母粉与剩余预乳化液均匀混合,磁力搅拌20min制备均匀分散的混合液,备用。
(4)分别同时向四口烧瓶内滴加改性云母粉-预乳化液混合液和9.15g过硫酸钾溶液,2.5-3h内滴完,然后82℃保温1.5h,降温至55℃,用氨水调pH值为8-9。
(5)加入2.3g聚有机硅氧烷,充分搅拌30min后停止加热,过滤,出料。
图1为本发明的工艺流程图。
实施例2
(1)取16.65g丙烯酸正丁酯、8.14g苯乙烯、12.21g甲基丙烯酸甲酯、1.24g甲基丙烯酸、0.76g十二烷基硫酸钠、1.10g聚氧乙烯辛基苯酚醚-10、0.73g双丙酮丙烯酰胺和18.2g去离子水于烧杯中混合均匀,先用高速分散均质机搅拌0.5-1min,再磁力搅拌20min进行预乳化。分别取0.12g过硫酸钾溶于3.5g去离子水中,0.15g过硫酸钾于9.0g去离子水中,备用。
(2)取0.15g碳酸氢钠、16g去离子水于四口烧瓶内混匀,控温82℃,恒温搅拌15min,转速为220rpm;待乳化剂溶解完全,一次性加入4.7g预乳化液和3.62g过硫酸钾水溶液,恒温搅拌30min.
(3)取0.95g改性云母粉与剩余预乳化液均匀混合,磁力搅拌20min制备均匀分散的混合液,备用。
(4)分别同时向四口烧瓶内滴加改性云母粉-预乳化液混合液和9.15g过硫酸钾溶液,2.5-3h内滴完,然后82℃保温1.5h,降温至55℃,用氨水调pH值为8-9。
(5)加入2.3g聚有机硅氧烷,充分搅拌30min后停止加热,过滤,出料。
实施例3
(1)取16.65g丙烯酸正丁酯、8.14g苯乙烯、12.21g甲基丙烯酸甲酯、1.24g甲基丙烯酸、0.76g十二烷基硫酸钠、1.10g聚氧乙烯辛基苯酚醚-10、0.73g双丙酮丙烯酰胺和18.2g去离子水于烧杯中混合均匀,先用高速分散均质机搅拌0.5-1min,再磁力搅拌20min进行预乳化。分别取0.12g过硫酸钾溶于3.5g去离子水中,0.15g过硫酸钾于9.0g去离子水中,备用。
(2)取0.15g碳酸氢钠、16g去离子水于四口烧瓶内混匀,控温82℃,恒温搅拌15min,转速为220rpm;待乳化剂溶解完全,一次性加入4.7g预乳化液和3.62g过硫酸钾水溶液,恒温搅拌30min.
(3)取1.4g改性云母粉与剩余预乳化液均匀混合,磁力搅拌20min制备均匀分散的混合液,备用。
(4)分别同时向四口烧瓶内滴加改性云母粉-预乳化液混合液和9.15g过硫酸钾溶液,2.5-3h内滴完,82℃保温1.5h,降温至55℃,用氨水调pH值为8-9。
(5)加入2.3g聚有机硅氧烷,充分搅拌30min后停止加热,过滤,出料。
产物接触角如图2所示,纯水性聚丙烯酸酯漆膜的接触角为28.17°,本实例产物涂膜的接触角为40.12°,表明本实施例所得制备的复合乳液干燥后形成的涂膜具有一定的耐水性。
室温静置30天,物质分散性能如图3所示,可以看出本实施例添加改性后云母粉的复合乳液较添加未改性云母粉的复合乳液,具有更好的分散性能。
如图2-图5分别展示了产品的耐水性、分散稳定性、抗紫外性及可剥性能,接触角的增加有助于提升涂膜耐水性;室温静置30天,改性云母粉在乳液中分散性好;在紫外-可见光度区间内吸光度的提升,使涂膜可起到降低被涂覆物受到紫外损伤的作用;且涂膜在多种漆板表面可剥性好。
实施例4
(1)取16.65g丙烯酸正丁酯、8.14g苯乙烯、12.21g甲基丙烯酸甲酯、1.24g甲基丙烯酸、0.76g十二烷基硫酸钠、1.10g聚氧乙烯辛基苯酚醚-10、0.73g双丙酮丙烯酰胺和18.2g去离子水于烧杯中混合均匀,先用高速分散均质机搅拌0.5-1min,再磁力搅拌20min进行预乳化。分别取0.12g过硫酸钾溶于3.5g去离子水中,0.15g过硫酸钾于9.0g去离子水中,备用。
(2)取0.15g碳酸氢钠、16g去离子水于四口烧瓶内混匀,控温82℃,恒温搅拌15min,转速为220rpm;待乳化剂溶解完全,一次性加入4.7g预乳化液和3.62g过硫酸钾水溶液,恒温搅拌30min.
(3)取1.91g改性云母粉与剩余预乳化液均匀混合,磁力搅拌20min制备均匀分散的混合液,备用。
(4)分别同时向四口烧瓶内滴加改性云母粉-预乳化液混合液和9.15g过硫酸钾溶液,2.5-3h内滴完,然后82℃保温1.5h,降温至55℃,用氨水调pH值为8-9。
(5)加入2.3g聚有机硅氧烷,充分搅拌30min后停止加热,过滤,出料。
对比例1
(1)取16.65g丙烯酸正丁酯、8.14g苯乙烯、12.21g甲基丙烯酸甲酯、1.24g甲基丙烯酸、0.76g十二烷基硫酸钠、1.10g聚氧乙烯辛基苯酚醚-10、0.73g双丙酮丙烯酰胺和18.2g去离子水于烧杯中混合均匀,先用高速分散均质机搅拌0.5-1min,再磁力搅拌20min进行预乳化。分别取0.12g过硫酸钾溶于3.5g去离子水中,0.15g过硫酸钾于9.0g去离子水中,备用。
(2)取0.15g碳酸氢钠、16g去离子水于四口烧瓶内混匀,控温82℃,恒温搅拌15min,转速为220rpm;待乳化剂溶解完全,一次性加入4.7g预乳化液和3.62g过硫酸钾水溶液,恒温搅拌30min.
(3)取4.2g云母粉与剩余预乳化液均匀混合,磁力搅拌20min制备均匀分散的混合液,备用。
(4)分别同时向四口烧瓶内滴加改性云母粉-预乳化液混合液和9.15g过硫酸钾溶液,2.5-3h内滴完,然后82℃保温1.5h,降温至55℃,用氨水调pH值为8-9。
(5)加入2.3g聚有机硅氧烷,充分搅拌30min后停止加热,过滤,出料。
对实施例1-4和对比例1制备的水性丙烯酸酯微纳复合乳液依据HG/T 4758-2014《水性丙烯酸树脂涂料》进行各项性能测试,其中:
凝胶率:乳液聚合反应结束后,采用200目尼龙过滤纱网对乳液进行过滤,收集滤渣及附着反应设备与器材上的固体凝聚物,去离子水充分洗涤后置于90℃鼓风干燥箱内烘干至恒重,称量,按公式计算乳液凝胶率。
式中:W1—固体凝聚物烘干后的质量(g);
W0—单体的总质量(g)。
转化率:精确称取2.50g乳液放置于已经干燥至恒重的表面皿中,试样均匀置于表面皿底部表面,放入105℃鼓风干燥箱内干燥4h,每隔1h称重一次,直至两次质量差不大于0.001g为止,按照公式计算乳液的转化率。
式中:B—转化率(%);
W1--反应器内原料总质量(g);
W2—原料中不挥发性物质总质量(g);
W3—单体总质量(g)。
拉伸强度与断裂伸长率:
将水性涂料漆膜剪裁成(10±1)mm×(50±5)mm的规格,游标卡尺精确测量厚度。并置于恒温恒湿箱中24h,采用英国Hounsfied的H5K-S型万能材料试验机测定其拉伸强度和断裂伸长率。拉伸速度为50mm/min,每类样品平行测量三次,记录平均值。结果如下:
表1为实施案例1-4与对比例1所制备的复合乳液制备过程中凝胶率与乳液成膜后的拉伸强度与段裂伸长率。
表1
实施例1 | 实施例2 | 实施例3 | 实施例4 | 对比例1 | |
凝胶率(%) | 0.10 | 0.34 | 0.68 | 1.0 | 3.5 |
拉伸强度(MPa) | 10.5 | 11.1 | 11.5 | 12.2 | 8.6 |
断裂伸长率(%) | 1110 | 1149 | 1174 | 1186 | 897 |
接触角(°) | 31.7 | 37.9 | 40.12 | 35.4 | 34.9 |
由表可知,与对比例相比,本专利所得产品,凝胶率低、拉伸强度高,断裂伸长率大,耐水性好。
Claims (11)
1.一种改性云母粉/水性丙烯酸酯微纳复合乳液,其特征在于,所述复合乳液由包含下列组分的原料获得;其中原料组分包括:预乳化液、碳酸氢钠、引发剂、改性云母粉、有机硅。
2.根据权利要求1所述复合乳液,其特征在于,所述预乳化液由丙烯酸正丁酯、苯乙烯、甲基丙烯酸甲酯、甲基丙烯酸,乳化剂,双丙酮丙烯酰胺和去离子水混匀,乳化获得;有机硅为聚有机硅氧烷;改性云母粉为:云母粉、硅烷偶联剂分散于去离子水中,加入聚丙烯酸酯溶液,超声分散;恒温匀速滴加盐酸溶液、氯化钠溶液,将混合液静置分离并收集絮凝状固体,水洗产物至中性,超声分散,冻干机干燥。
3.一种改性云母粉/水性丙烯酸酯微纳复合乳液的制备方法,包括:
(1)将单体丙烯酸正丁酯、苯乙烯、甲基丙烯酸甲酯、甲基丙烯酸,乳化剂,双丙酮丙烯酰胺和去离子水混匀,然后预乳化,得到预乳化液;
(2)将碳酸氢钠、水进行恒温搅拌,并加入部分预乳化液和部分引发剂水溶液,恒温搅拌,滴加剩余预乳化液和改性云母粉的混合液及剩余引发剂水溶液,然后保温,降温,调节pH,然后加入有机硅,搅拌溶解,过滤,得到改性云母粉/水性丙烯酸酯微纳复合乳液。
4.根据权利要求3所述制备方法,其特征在于,所述步骤(1)中乳化剂为十二烷基硫酸钠和聚氧乙烯辛基苯酚醚-10;其中十二烷基硫酸钠的质量为单体总质量的1-3%;聚氧乙烯辛基苯酚醚-10的质量为单体总质量的2-4%。
5.根据权利要求3所述制备方法,其特征在于,所述步骤(1)中丙烯酸正丁酯、苯乙烯、甲基丙烯酸甲酯、甲基丙烯酸的质量比为43-46:22-21:32-31:3-2;双丙酮丙烯酰胺的质量为单体总质量的1-4%。
6.根据权利要求3所述制备方法,其特征在于,所述步骤(2)中引发剂为过硫酸钾;有机硅为聚有机硅氧烷;改性云母粉为:云母粉、硅烷偶联剂分散于去离子水中,加入聚丙烯酸酯溶液,超声分散;恒温匀速滴加盐酸溶液、氯化钠溶液,将混合液静置分离并收集絮凝状固体,水洗产物至中性,超声分散,冻干机干燥。
7.根据权利要求3所述制备方法,其特征在于,所述步骤(2)中碳酸氢钠的质量为单体总质量的3-7‰;引发剂的质量为单体总质量的0.5-1.5%;改性云母粉为单体总质量的1-7%;有机硅的质量为单体总质量的4-9%。
8.根据权利要求3所述制备方法,其特征在于,所述步骤(2)中恒温搅拌温度均为80-84℃,搅拌转速为200-400rpm;保温时间为1-3h,保温温度为80-84℃。
9.根据权利要求3所述制备方法,其特征在于,所述步骤(2)中部分预乳化溶液为预乳化液总量的6%-12%;部分引发剂为引发剂总量的45%-55%。
10.一种权利要求3所述方法制备的改性云母粉/水性丙烯酸酯微纳复合乳液。
11.一种权利要求1所述改性云母粉/水性丙烯酸酯微纳复合乳液的应用。
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