CN105693916A - 一种含氟纯丙乳液的制备方法 - Google Patents
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Abstract
本发明涉及乳液聚合技术领域,特别涉及一种含氟纯丙乳液的制备方法:将乳化剂、硬单体、软单体、功能单体、含氟单体、水溶性热引发剂、螯合剂、子量调节剂混合在一起,搅拌;高速剪切,搅拌速度为800-1000rpm;反应;加阻聚剂终止反应。利用乳液自由基聚合来制备水性含氟纯丙乳液,该工艺反应步骤简单,所用化学品清洁环保,单体转化率高,凝胶率低,得到的乳液粒径分布均匀、状态稳定。可用于纸张的表面施胶,能显著提高纸张的防水、耐油和表面强度等性能。
Description
技术领域
本发明涉及乳液聚合技术领域,特别涉及一种含氟纯丙乳液的制备方法。
背景技术
纯丙乳液已广泛用到建筑和工业涂料中,是目前较为高档的一种水性涂料。其聚合主要采用乳液自由基聚合方式,所用单体主要为烷基丙烯酸酯,分为软单体和硬单体,丙烯酸由于含有极性基团,在聚合时能起到稳定乳液的作用,并能有助于交联形成热固涂层,其主要作为功能性单体来进行添加。
通常,功能性单体也属于硬单体,硬单体的玻璃化温度(Tg)较高,例如,甲基丙烯酸丁酯的Tg为20℃,醋酸乙烯酯的Tg为30℃,甲基丙烯酸甲酯的Tg为105℃,丙烯酸的Tg为106℃,甲基丙烯酸的Tg为130℃,硬单体的主要作用是增加涂层的光泽度和硬度;软单体的玻璃化温度(Tg)较低,例如,丙烯酸丁酯的Tg为-54℃,甲基丙烯酸乙酯的Tg为-22℃,丙烯酸羟乙酯的Tg为-15℃,软单体的主要作用是增加涂层的粘弹性和柔韧性。
但研究发现,用这些单体合成的纯丙乳液对水分很敏感,防水性弱,进而降低涂层的表面强度,强化纯丙乳液的防水性和表面强度,已是一个迫在眉睫、亟待开发的课题。
有些研究者试图通过添加有机溶剂的方法来解决纯丙乳液的防水问题,主要包括:醚类、酯类、酮类、乙二醇醚酯类或它们混和物,例如,甲醇、乙醇、异丙醇、丙酮、乙二醇甲醚等。这些有机溶剂主要作为功能助剂起到交联作用,能增加乳液涂料的成膜性,但在生产和应用过程中会大量排放挥发性有机化合物(VOC),造成环境污染并对人类健康造成极大危害。有些研究者通过合成含氟的表面活性剂再添加到纯丙乳液中,因乳液聚合物中含有氟烷基侧链而具有较低的表面自由能,所以含氟聚合物乳胶膜具有独特的表面性能(抗水、防油),但乳液中的含氟量很难提高,防水防油效果受限,提高含氟表面活性剂的添加量可增加乳液含氟量,若添加量太大,反而会降低乳液涂料的防水性。有些研究者通过在乳液聚合时添加含氟单体来提高乳液中的含氟量,进而增加纯丙乳液涂料的防水性,但由于含氟单体很难乳化,致使乳液聚合的单体转化率低、凝胶率高。
现在水性乳液的制备工艺基本都是采用滴定聚合,这种反应方式更加容易控制聚合速率,能够提高单体转化率,减少凝胶率。但这种聚合工艺对含氟单体含量高的乳液来说,反应转化率和凝胶率结果却并不理想。
发明内容
为了解决以上含氟量高的乳液聚合时存在的单体转化率低、凝胶率高的问题,本发明提供了一种提高单体转化率,减少凝胶率的含氟纯丙乳液的制备方法。
该工艺特点是:首先借助于非离子和阴离子的复合乳化剂在水相中分散成几个纳米粒径的胶束,将所有硬单体、软单体、功能单体、含氟单体、水溶性热引发剂、螯合剂、分子量调节剂添加到水相中,通过高速搅拌将各疏水性单体均匀溶解到胶束中,有一部分水溶性单体、分子量调节剂、引发剂和螯合剂也分散到胶束中,再加热引发聚合,随着聚合的进行,水溶性单体、分子量调节剂、引发剂和螯合剂等水溶性物质会慢慢地向胶束中迁移,随着自由基聚合反应的进行,透明胶束会逐渐转变成灰色半透明色、兰色、兰白色、乳白色,乳白色状态保持一段时间后,再添加阻聚剂终止反应,加水调节乳液浓度,得到含氟纯丙乳液。采用此乳液聚合工艺后,制备了单体转化率高于98%和凝胶率低于3%的含氟纯丙乳液。
本发明是通过以下措施实现的:
一种含氟纯丙乳液的制备方法,操作工艺分为四段,即混合段、高速剪切段、反应段和终止段,各段具体工艺条件如下:
(1)混合段的工艺条件为:将乳化剂、硬单体、软单体、功能单体、含氟单体、水溶性热引发剂、螯合剂、子量调节剂混合在一起,加去离子水调节软硬单体的质量浓度为30%,Tmax=50±5℃,保温时间10~60分钟,通氮气,搅拌速度为50-300rpm;
(2)高速剪切段的工艺条件为:Tmax=50±5℃,保温时间10~120分钟,搅拌速度为800-1000rpm;
(3)反应段的工艺条件为:Tmax=80±5℃,保温时间120~360分钟,搅拌速度为50-300rpm;
(4)终止段的工艺条件为:加阻聚剂终止反应,加水(60-70℃)调节软硬单体的质量浓度为20%,降温至30±5℃,搅拌速度为50-300rpm,再搅拌10-60分钟,放料并经100目筛子过滤。测试单体转化率和凝胶率。
优选步骤(1)中保温时间30分钟,搅拌速度为200rpm;
步骤(2)中保温时间30分钟,搅拌速度为900rpm;
步骤(3)中保温时间320分钟,搅拌速度为200rpm;
步骤(4)中搅拌速度为200rpm,再搅拌20分钟。
原料配方为:
软硬单体总质量共为100份,软单体与硬单体质量比为1:(1-2),优选1:2;功能性单体质量为软硬单体总质量的1-10%,优选3%,含氟单体质量为软硬单体总质量的5-20%,优选5-10%,更优选10%。
引发剂为软硬单体总质量的0.2-0.8%,优选0.2%,乳化剂用量为软硬单体总质量的0.4-2.0%,优选0.4-0.8%,螯合剂用量为软硬单体总质量0.05-0.1%,优选0.05%,分子量调节剂的用量为软硬单体总质量的0.05-0.1%,优选0.05%,;阻聚剂用量为软硬单体总质量的0.01-0.1%,优选0.01%。
软单体为甲基丙烯酸乙酯、丙烯酸丁酯和丙烯酸羟乙酯的混和物,各单体的质量比均为1:1:1;硬单体为甲基丙烯酸甲酯、甲基丙烯酸丁酯和醋酸乙烯酯的混和物,各单体的质量比均为1:1:1;功能性单体为甲基丙烯酸和丙烯酸的混和物,各单体的质量比均为1:1;含氟单体为丙烯酸十二氟庚酯、甲基丙烯酸六氟丁酯和甲基丙烯酸三氟乙酯的混和物,各单体的质量比均为1:1:1。
引发剂为过硫酸钾、过硫酸钠和过硫酸铵的混和物,各引发剂的质量比均为1:1:1。
乳化剂为十二烷基硫酸钠、十二烷基苯磺酸钠、十二烷基磺酸钠、油酸钠、OP-10、OP-13和OP-15的混和物,各乳化剂的质量比均为1:1:1:1:2:2:2。
螯合剂为多聚磷酸钠、EDTA二钠和DTPA的混合物,各螯合剂的质量比均为1:1:1。
分子量调节剂为叔丁硫醇;阻聚剂为对苯二酚。
上述单体转化率和凝胶率的计算公式(1)和(2)如下:
C=(W×W2/W1-W3)/W4(1)
其中:C—单体转化率,%
W—加入反应器的原料的总质量,g
W1—所取乳液样品质量,g
W2—干燥后样品质量,g
W3—原料中不挥发组分的质量,g
W4—单体的总质量,g
G=M1/M(2)
其中:G—凝胶率,%
M1—烘干后的固体凝胶的质量,g
M—单体的总质量,g
具体分析方法为:
(1)准确称取乳液2-3g于恒重的称量瓶中,然后将其置于真空干燥箱中,于80-100℃下干燥至恒重,按式(1)计算单体转化率。
(2)聚合反应结束后,将乳液用100目尼龙过滤网过滤,小心收集滤渣及附着在瓶壁、搅拌桨上的固体凝聚物,水洗后放到真空干燥箱于80-100℃烘干至至恒重称量,按式(2)计算凝胶率。
本发明的有益效果:
(1)首先借助于非离子和阴离子复合乳化剂在水相中分散成微胶束,再通过高速搅拌将全部疏水性单体和部分水溶性单体、分子量调节剂、引发剂和螯合剂均匀溶解到胶束中,加热引发自由基聚合,从而得到单体转化率高、凝胶率低的含氟纯丙乳液;
(2)利用乳液自由基聚合来制备水性含氟纯丙乳液,该工艺反应步骤简单,所用化学品清洁环保,单体转化率高,凝胶率低,得到的乳液粒径分布均匀、状态稳定。可用于纸张的表面施胶,能显著提高纸张的防水、耐油和表面强度等性能。
具体实施方式
为了更好的理解本发明,下面结合具体实例来进一步说明。
实施例1:
含氟纯丙乳液各组分百分比含量如表1:
表1各组分百分比
项目 | 百分比(%) |
水 | 80 |
软单体 | 6.67 |
硬单体 | 13.33 |
功能性单体 | 0.6 |
含氟单体 | 1.0 |
引发剂 | 0.04 |
乳化剂 | 0.08 |
螯合剂 | 0.01 |
特丁硫醇 | 0.01 |
对苯二酚 | 0.002 |
制备方法如下:
1.混合段:加水调节软硬单体浓度30%,Tmax=50±5℃,保温时间30分钟,通氮气,搅拌速度为200rpm,
2.高速剪切段:Tmax=50±5℃,保温时间30分钟,搅拌速度为900rpm,
3.反应段:Tmax=80±5℃,保温时间320分钟,搅拌速度为200rpm,
4.终止段:添加对苯二酚终止反应,加剩余水(65±5℃)调节软硬单体的质量浓度为20%,降温至30±5℃,搅拌速度为200rpm,再搅拌20分钟,放料并经100目筛子过滤。
通过上述步骤制备的含氟纯丙乳液的测试结果为:
单体转化率:98.9%;凝胶率2.4%;外观:蓝光乳白色液体;固含量:22.6%;平均粒径0.58μm;pH=4.2;贮存稳定性:存放6个月无分层、破乳和沉淀现象。
实施例2:
含氟纯丙乳液各组分百分比含量如表2:
表2各组分百分比
项目 | 百分比(%) |
水 | 80 |
软单体 | 6.67 |
硬单体 | 13.33 |
功能性单体 | 0.6 |
含氟单体 | 2.0 |
引发剂 | 0.04 |
乳化剂 | 0.08 |
螯合剂 | 0.01 |
特丁硫醇 | 0.01 |
对苯二酚 | 0.002 |
制备方法见实施例1。
通过上述步骤制备的含氟纯丙乳液的测试结果为:
单体转化率:99.0%;凝胶率2.5%;外观:蓝光乳白色液体;固含量:23.8%;平均粒径0.67μm;pH=4.1;贮存稳定性:存放6个月无分层、破乳和沉淀现象。
实施例3:
含氟纯丙乳液各组分百分比含量如表3:
表3各组分百分比
项目 | 百分比(%) |
水 | 80 |
软单体 | 6.67 |
硬单体 | 13.33 |
功能性单体 | 0.6 |
含氟单体 | 1.0 |
引发剂 | 0.04 |
乳化剂 | 0.16 |
螯合剂 | 0.01 |
特丁硫醇 | 0.01 |
对苯二酚 | 0.002 |
制备方法见实施例1。
通过上述步骤制备的含氟纯丙乳液的测试结果为:
单体转化率:99.1%;凝胶率1.5%;外观:蓝光乳白色液体;固含量:22.8%;平均粒径0.35μm;pH=4.2;贮存稳定性:存放6个月无分层、破乳和沉淀现象。
实施例4:
含氟纯丙乳液各组分百分比含量如表4:
表4各组分百分比
项目 | 百分比(%) |
水 | 80 |
软单体 | 6.67 |
硬单体 | 13.33 |
功能性单体 | 0.6 |
含氟单体 | 2.0 |
引发剂 | 0.04 |
乳化剂 | 0.16 |
螯合剂 | 0.01 |
特丁硫醇 | 0.01 |
对苯二酚 | 0.002 |
制备方法见实施例1。
通过上述步骤制备的含氟纯丙乳液的测试结果为:
单体转化率:99.6%;凝胶率1.6%;外观:蓝光乳白色液体;固含量:23.4%;平均粒径0.43μm;pH=4.1;贮存稳定性:存放6个月无分层、破乳和沉淀现象。
对比实施例1:
同实施例4相比,将乳化剂中的OP-13替换为OP-10,十二烷基磺酸钠替换为十二烷基苯磺酸钠,其余同实施例4相同。
制备的含氟纯丙乳液的测试结果为:
单体转化率:89.5%;凝胶率5.7%;外观:蓝光乳白色液体;固含量:20.6%;平均粒径0.78μm;pH=3.9;贮存稳定性:存放6个月无分层、破乳和沉淀现象。
对比实施例2:
同实施例4相比,将乳化剂中的OP-13、OP-10替换为OP-15,十二烷基硫酸钠、十二烷基磺酸钠替换为十二烷基苯磺酸钠,其余同实施例4相同。
制备的含氟纯丙乳液的测试结果为:
单体转化率:88.1%;凝胶率6.0%;外观:蓝光乳白色液体;固含量:19.7%;平均粒径0.86μm;pH=3.6;贮存稳定性:存放6个月无分层、破乳和沉淀现象。
实施例5:应用实例
将实施例1-4和对比实施例1-2的含氟乳液用到纸张的表面施胶,原纸为定量为70g/m2的未表面施胶纸,控制施胶量为1.2g/m2(单面),施胶温度为54℃,测试纸张的表面接触角(水/油)、表面强度和表面吸收性,结果见表5。
表5原纸表面施胶前后的抗水、耐油和表面强度变化
项目 | 水接触角(度) | 油接触角(度) | 表面吸收性(g/m2) | 表面强度(干拉毛,m/s) |
空白(未施胶) | 10 | 3 | 73.0 | 0.94 |
实施例1乳液施胶 | 77 | 36 | 24.3 | 2.73 |
实施例2乳液施胶 | 90 | 54 | 18.4 | 3.84 |
实施例3乳液施胶 | 80 | 43 | 22.2 | 2.98 |
实施例4乳液施胶 | 98 | 65 | 15.6 | 4.43 |
对比实施例1 | 60 | 30 | 32.4 | 2.64 |
对比实施例2 | 56 | 26 | 28.5 | 2.43 |
从表5可以看出,本发明的含氟乳液,能显著提高纸张的防水、耐油和表面强度性能。
上述实施例为本发明较佳的实施方式,但本发明的实施方式并不受实施例的限制,其它任何未背离本发明的精神实质与原理下所做的改变、修饰、组合、替代、简化均应为等效替换方式,都包含在本发明的保护范围之内。
Claims (10)
1.一种含氟纯丙乳液的制备方法,其特征在于包括以下步骤:
(1)混合:将乳化剂、硬单体、软单体、功能单体、含氟单体、水溶性热引发剂、螯合剂、分子量调节剂混合,加去离子水调节软硬单体的质量浓度为30%,温度50±5℃,保温时间10~60分钟,通氮气,搅拌速度为50-300rpm;
(2)高速剪切:温度50±5℃,时间10~120分钟,搅拌速度为800-1000rpm;
(3)反应:温度80±5℃,保温时间120~360分钟,搅拌速度为50-300rpm;
(4)终止:加阻聚剂终止反应,加入60-70℃的水调节软硬单体的质量浓度为20%,降温至30±5℃,搅拌速度为50-300rpm,再搅拌10-60分钟,放料过滤即得。
2.根据权利要求1所述的制备方法,其特征在于软单体与硬单体质量比为1:(1-2),功能性单体质量为软硬单体总质量的1-10%,含氟单体质量为软硬单体总质量的5-20%。
3.根据权利要求1所述的制备方法,其特征在于引发剂为软硬单体总质量的0.2-0.8%,乳化剂用量为软硬单体总质量的0.4-2.0%,螯合剂用量为软硬单体总质量0.05-0.1%,分子量调节剂的用量为软硬单体总质量的0.05-0.1%;阻聚剂用量为软硬单体总质量的0.01-0.1%。
4.根据权利要求1所述的制备方法,其特征在于软单体为甲基丙烯酸乙酯、丙烯酸丁酯和丙烯酸羟乙酯的混和物,质量比为1:1:1;硬单体为甲基丙烯酸甲酯、甲基丙烯酸丁酯和醋酸乙烯酯的混和物,质量比为1:1:1;功能性单体为甲基丙烯酸和丙烯酸的混和物,质量比为1:1;含氟单体为丙烯酸十二氟庚酯、甲基丙烯酸六氟丁酯和甲基丙烯酸三氟乙酯的混和物,质量比为1:1:1。
5.根据权利要求1所述的制备方法,其特征在于乳化剂为十二烷基硫酸钠、十二烷基苯磺酸钠、十二烷基磺酸钠、油酸钠、OP-10、OP-13和OP-15的混和物,质量比为1:1:1:1:2:2:2。
6.根据权利要求1所述的制备方法,其特征在于引发剂为过硫酸钾、过硫酸钠和过硫酸铵的混和物,质量比为1:1:1;螯合剂为多聚磷酸钠、EDTA二钠和DTPA的混合物,质量比为1:1:1;分子量调节剂为叔丁硫醇;阻聚剂为对苯二酚。
7.根据权利要求1所述的制备方法,其特征在于软单体与硬单体质量比为1:(1-2),功能性单体质量为软硬单体总质量的3%,含氟单体质量为软硬单体总质量的5-10%。
8.根据权利要求1所述的制备方法,其特征在于引发剂为软硬单体总质量的0.2%,乳化剂用量为软硬单体总质量的0.4-0.8%,螯合剂用量为软硬单体总质量0.05%,分子量调节剂的用量为软硬单体总质量的0.05%;阻聚剂用量为软硬单体总质量的0.01%。
9.根据权利要求1所述的制备方法,其特征在于步骤(4)用100目筛子过滤。
10.根据权利要求1所述的制备方法,其特征在于
步骤(1)中保温时间30分钟,搅拌速度为200rpm;
步骤(2)中保温时间30分钟,搅拌速度为900rpm;
步骤(3)中保温时间320分钟,搅拌速度为200rpm;
步骤(4)中搅拌速度为200rpm,再搅拌20分钟。
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