CN110157362A - 一种水性阻燃型纳米复合黏合剂的制备方法 - Google Patents
一种水性阻燃型纳米复合黏合剂的制备方法 Download PDFInfo
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- CN110157362A CN110157362A CN201910495378.6A CN201910495378A CN110157362A CN 110157362 A CN110157362 A CN 110157362A CN 201910495378 A CN201910495378 A CN 201910495378A CN 110157362 A CN110157362 A CN 110157362A
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Abstract
本发明公开了一种水性阻燃型纳米复合黏合剂的制备方法,所述方法包括以下步骤:(1)将疏水乙烯基单体、极性乙烯基单体、阻燃功能单体、共稳定剂混溶形成油相溶液;(2)将表面乙烯基改性的无机纳米粒子分散于水中,得到无机纳米粒子的水分散液,用pH调节剂将分散液的pH值调节到4~11;(3)将油相溶液加至无机纳米粒子的水分散液中,预乳化得到粗乳液;于冰水浴中超声处理制得单体细乳液;通氮除氧后,在氮气保护下反应制得水性阻燃型纳米复合黏合剂。本发明在无机粒子为胶体稳定剂的细乳液聚合体系中,通过单体液滴内阻燃功能单体参与的自由基共聚合反应,制得了胶体稳定好、综合粘接性能和阻燃性能优异的阻燃型纳米复合黏合剂。
Description
(一)技术领域
本发明涉及一种水性黏合剂的制备方法。
(二)背景技术
随着黏合剂绿色化发展的需求增加,用水性黏合剂替代溶剂型黏合剂已成为黏合剂行业的发展趋势,其中开发高性能的水性黏合剂乳液已成为黏合剂相关领域的重要发展方向。但是,与溶剂型黏合剂相比,水性黏合剂在综合粘接性能、耐水性等方面仍存在不足【Langmuir 2011,27,3878–3888.】。究其原因,除了黏合剂聚合物本身的分子结构设计外,在合成水性黏合剂乳液时添加的小分子乳化剂也会对黏合剂的粘接性能产生重要的影响【Journal of Applied Polymer Science2010,115,1125–1130.】。通过反复离心-洗涤的方法能减少黏合剂乳液中乳化剂的残留,但是该处理方法仍存在:(1)工序繁琐,会产生大量的废水;(2)去除部分乳化剂后,黏合剂乳液的稳定性下降;(3)残留的乳化剂仍会劣化黏合剂的粘接性能。
随着科技的进步和经济的发展,为了满足建筑高层化、汽车轻量化、家具高档化等需要,粘合连接正在越来越多的代替机械连接。上述应用领域都要求所用的材料必须具有优异的阻燃性能,因此在保持黏合剂高粘接性能的同时,赋予其优异的阻燃性能已成为黏合剂开发领域的研究热点【ACS Sustainable Chemistry&Engineering2017,5,3353–3361.】。
针对小分子乳化剂的使用劣化水性黏合剂粘接性能的问题以及黏合剂阻燃性能提升的需求,本发明提出,在细乳液聚合体系中,以表面乙烯基改性的无机粒子替代小分子乳化剂为胶体稳定剂,并通过引入含乙烯基的阻燃功能单体,通过其与通用单体的自由基共聚合反应,制备水性阻燃型纳米复合黏合剂。
(三)发明内容
本发明旨在提供一种新型水性阻燃型纳米复合黏合剂的制备方法,在无机粒子为胶体稳定剂的细乳液聚合体系中,通过单体液滴内阻燃功能单体参与的自由基共聚合反应,制备胶体稳定好、综合粘接性能和阻燃性能优异的纳米复合黏合剂。
为实现上述发明目的,本发明采用的技术方案是:
一种水性阻燃型纳米复合黏合剂的制备方法,所述方法包括以下步骤:
(1)将疏水乙烯基单体、极性乙烯基单体、阻燃功能单体、共稳定剂混溶形成油相溶液,其中疏水乙烯基单体质量用量为单体总质量用量的30%~95%,极性乙烯基单体的质量用量为单体总质量用量的0.5%~15%,阻燃单体的质量用量为单体总质量用量的1%~40%;共稳定剂的质量用量为单体总质量用量的0%~12%;
所述单体总质量为疏水乙烯基单体、极性乙烯基单体和阻燃功能单体的总质量;
所述疏水乙烯基单体选自下列至少一种:式(I)所示的丙烯酸酯或甲基丙烯酸脂类单体、醋酸乙烯酯、苯乙烯;
式(I)中,R1为H或CH3;R2为C1~C20的脂肪直链或支链烷基或-(CH2)3-Si(OCH3)3;
所述极性乙烯基单体选自下列至少一种:甲基丙烯酸羟烷基酯、丙烯酸羟烷基酯、丙烯酰胺、N-羟烷基丙烯酰胺、甲基丙烯酸、丙烯酸、甲基丙烯酸二甲胺基乙酯、丙烯酸缩水甘油酯、甲基丙烯酸缩水甘油酯;
所述阻燃单体选自下列阻燃-1至阻燃-37单体中的至少一种:
所述共稳定剂选自下列至少一种:C14~C22的脂肪直链或支链烷烃、C14~C22的脂肪醇;
(2)将表面乙烯基改性的无机纳米粒子分散于水中,得到无机纳米粒子的水分散液,其中表面乙烯基改性的无机纳米粒子的质量用量为步骤(1)中单体总质量用量的1%~20%,水的质量用量为步骤(1)中单体总质量用量的60%~1900%,用pH调节剂将分散液的pH值调节到4~11;所述无机纳米粒子选自下列至少一种:SiO2纳米粒子、TiO2纳米粒子、ZnO纳米粒子,所述无机纳米粒子的表面改性剂选自下列至少一种:含乙烯基硅烷偶联剂、甲基丙烯酸2-异氰酸乙酯,所述表面乙烯基改性的无机纳米粒子的偶联密度的范围为0.2μmol·(m2无机纳米粒子)-1~2.0μmol·(m2无机纳米粒子)-1,其中偶联密度的定义为每单位平方米的无机纳米粒子表面修饰的改性剂的摩尔量;所述pH调节剂选自下列至少一种:盐酸、柠檬酸、乳酸、酒石酸、柠檬酸钠、氢氧化钠、碳酸钠、碳酸氢钠、氨水、磷酸氢二钠、磷酸二氢钠、硼砂;
(3)将步骤(1)制得的油相溶液加至步骤(2)得到的无机纳米粒子的水分散液中,在100~1000rpm的搅拌强度下预乳化得到粗乳液;最后将装有粗乳液的容器置于冰水浴中,在30W~900W的功率下超声处理0.5min~120min,制得单体细乳液;通氮除氧后,将温度调至25℃~95℃,并在氮气保护下反应0.5h~24h,制得阻燃型纳米复合黏合剂;
并且通过下列方式a或b引入引发剂:
方式a:步骤(1)中,往单体混合液中加入油溶性引发剂,其中油溶性引发剂的质量用量为单体总质量用量的0.05%~5%;
方式b:步骤(3)中,向单体细乳液添加水溶性引发剂,其中水溶性引发剂的质量用量为单体总质量用量的0.05%~5%。
在本发明中,以表面改性的无机纳米粒子替代有机小分子乳化剂作为稳定剂,稳定细乳液聚合体系,在单体液滴内,疏水乙烯基单体、极性乙烯基单体与阻燃功能单体经自由基共聚合反应,制得具有阻燃性能的纳米复合黏合剂。
本发明步骤(1)中,综合考虑黏合剂的粘接性能和阻燃效果,所述疏水乙烯基单体优选为下列至少一种:丙烯酸异辛酯、丙烯酸丁酯、甲基丙烯酸甲酯、醋酸乙烯酯、苯乙烯。所述极性乙烯基单体优选为下列至少一种:甲基丙烯酸羟乙酯、丙烯酸羟乙酯、甲基丙烯酸、丙烯酸、甲基丙烯酸缩水甘油酯、丙烯酸缩水甘油酯、N-羟甲基丙烯酰胺。所述阻燃功能单体优选下列至少一种:阻燃-8单体、阻燃-17单体、阻燃-22单体、阻燃-23单体、阻燃-28单体、阻燃-32单体;所述阻燃功能单体的质量用量优选为单体总质量用量的5%~30%。
本发明步骤(1)中,考虑到单体液滴的稳定性,所述共稳定剂优选为下列至少一种:C16~C22的脂肪直链或支链烷烃,更优选为正十六烷。
发明人经深入研究发现,疏水乙烯基单体/极性乙烯基单体/阻燃单体的组合及配比、体系pH值、无机纳米粒子的选择和用量等反应参数均会对细乳液聚合体系的稳定性、纳米复合黏合剂粒子的尺寸及其分布、纳米复合黏合剂的微结构、粘接性能和阻燃性能等方面产生重要影响。
一方面,引入一定量的阻燃单体,能赋予黏合剂阻燃性能,且随其用量的增加,黏合剂的阻燃性能显著提高。但使用双乙烯基阻燃单体是,如其用量过高,会导致黏合剂的粘接性能下降。在合适的单体组合及配比条件下,所制备得到的黏合剂能使聚合反应顺利进行且较好地兼顾产品的黏结性能和阻燃性能。
另一方面,在本发明无机粒子稳定的细乳液聚合体系中,由于不添加小分子乳化剂,使得乳液的后期处理过程大大简化,同时添加的无机粒子还能提高黏合剂胶膜的内聚力,增强胶膜强度。但发明人经深入研究发现,为保证乙烯基修饰的无机纳米粒子自发地吸附到油水界面,需严格控制其表面改性剂的偶联密度。具有适宜油水两亲性的无机纳米粒子能够比较稳定地存在于油水界面上,形成致密的单层或多层固体膜,防止液滴之间的粘并聚集,最终起到稳定细乳液液滴的作用。表面偶联密度过高的无机粒子难以均匀地分散于水相,无法为细乳液聚合体系提供足够的胶体稳定性。而且,无机粒子的添加量需严格控制在一定的区间内,添加量过低,其稳定能力不足,细乳液聚合体系易失稳;随着无机纳米粒子添加量的增加,黏合剂的阻燃效果也有所提升,但添加量过高,胶膜内聚力过强,黏合剂的黏性下降。在本发明步骤(2)的表面改性的无机纳米粒子的偶联密度和用量限定范围内,可以为细乳液聚合体系提供足够的胶体稳定性且不会因为胶膜内聚力过强而造成黏合剂黏性降低。作为优选,所述无机纳米粒子的尺寸范围为10nm~50nm,无机纳米粒子的尺寸在10nm~30nm之间对细乳液液滴的稳定效果最佳。所述的无机纳米粒子优选SiO2纳米颗粒,表面改性剂优选为3-甲基丙烯酰氧丙基三(三甲基硅氧烷基)硅烷或甲基丙烯酸2-异氰酸乙酯。所述SiO2纳米粒子可通过现有方法制备,例如:(1)用法合成粒径在10nm~50nm的SiO2纳米粒子或(2)直接购买市售该粒径范围内的SiO2纳米粒子。
再一方面,发明人发现,通过控制聚合反应体系的pH值可控制无机粒子与液滴的相互作用,从而控制聚合体系的稳定性。当将聚合反应体系的pH值维持在4~11的范围内,可获得较好的聚合体系稳定性。当聚合反应体系的pH值维持在6.0~10.0的范围内,无机粒子与液滴的作用最强,聚合体系的稳定性较好。因此,优选步骤(2)中用pH调节剂将分散液的pH值调节到6.0~10.0。
本发明步骤(3)中,考虑到引发剂的引发温度,聚合反应温度优选为40℃~75℃;反应时间优选1h~24h。为防止超声过程中细乳液过热,将装粗乳液的容器置于冰水浴中进行超声处理,超声功率优选60~500W,超声时间优选5min~45min。
本发明中,所述油溶性引发剂选自下列至少一种:偶氮二异丁腈、偶氮二异庚腈、过氧化二苯甲酰、过氧化二碳酸二异丙酯。所述水溶性引发剂选自下列至少一种:2,2’-偶氮二异丁基脒二盐酸盐、偶氮二氰基戊酸、过硫酸盐、氧化剂与还原剂构成的氧化还原体系;所述还原剂为亚硫酸盐、硫代硫酸盐、亚硫酸氢盐、抗坏血酸盐或草酸;所述的氧化剂为过氧化氢或过硫酸盐。所述过硫酸盐优选为过硫酸铵或过硫酸钾。所述还原剂优选为抗坏血酸盐或亚硫酸盐。
与现有技术相比,本发明的有益效果主要体现在:本发明的目的在于在细乳液聚合技术的框架内,通过采用一种表面修饰的无机纳米粒子作为稳定剂,替代小分子乳化剂,来稳定细乳液聚合体系,并通过引入含乙烯基的阻燃单体参与自由基共聚合反应,制备水性阻燃型纳米复合黏合剂。该方法的优点是:(1)不使用小分子乳化剂,简化了乳液的后处理工艺,避免了小分子乳化剂对黏合剂综合粘接性能的影响;(2)赋予黏合剂优异的阻燃性能,使其在军工、电子元器件、汽车、建筑等领域具有更高的应用价值;(3)黏合剂配方设计多样,制备工艺简单,易工业实施。
(四)具体实施方式
下面结合具体实施例对本发明进行进一步描述,但本发明的保护范围并不限于此:
实施例1:
分别称取8.87g丙烯酸异辛酯、1.4g苯乙烯、0.86g甲基丙烯酸-2-羟乙酯、0.33g丙烯酸缩水甘油酯、4.34g阻燃-22单体和1.06g正十八烷混合后得到油相溶液。
将1.0g乙烯基修饰的SiO2纳米粒子【数均粒径为20nm,表面改性剂为3-甲基丙烯酰氧丙基三(三甲基硅氧烷基)硅烷,偶联密度为1.2μmol·(m2SiO2)-1】预分散于95g水中,随后称取1.54g柠檬酸钠制成pH调节剂,得到pH值为8.9的SiO2水分散液。
将油相溶液加到SiO2水分散液中,在500rpm的磁力搅拌下预乳化得到粗乳液,再将装有粗乳液的容器置于冰水浴中,在300W的功率下超声处理8min,制得稳定的单体细乳液;随后向单体细乳液添加0.27g水溶性引发剂过硫酸钾,通氮除氧后,将反应温度调至70℃,并在氮气保护下反应8h,制得阻燃型聚合物/SiO2纳米复合黏合剂乳液。
所制备的黏合剂乳液具有高的胶体稳定性,在5000rpm条件下离心15min后无沉淀生成。用动态光散射纳米粒度仪测得纳米复合黏合剂粒子的Z均粒径为234nm,PDI为0.110。
将乳液的固含量调至20wt%后,取3g乳液,加入1.5g固含量为3.0wt%的PTE增稠剂(佛山市三水大唐树脂有限公司),制得黏合剂工作液。将聚对苯二甲酸乙二醇酯(PET)薄膜裁剪成20cm×26cm样片,置于等离子体处理设备(HD-1B,常州中科常泰等离子体科技有限公司)中,在氧气气氛和200W的功率下,处理5min,制得PET亲水膜。将PET亲水膜放在自动涂覆机(K control Coater model 202,R K Print Coat Instruments Ltd)上,选取3号滚轮,在100mm·min-1的条件下涂覆黏合剂工作液,随后在100℃条件下烘焙2min。将施胶后的PET膜裁剪成2.5cm×26cm的条形样品,进行面积为2.5cm×25cm的平角对接。用万能拉伸机测定胶膜的剪切强度,结果显示在100mm·min-1的拉伸速率下,胶膜的剪切强度为24.6MPa。将施胶后的PET膜裁剪成2.5cm×12.5cm条形样品,保持胶带的有胶一侧向外,制成周长为98mm的标准环形样品,与GB/T3280-2007规定的试验钢板接触,并以300mm·min-1向上拉,测得该样品的初粘力为0.78N。将PET胶膜裁剪成2.5cm×26cm的条形样品,在拉伸速率为300mm·min-1的条件下进行T-剥离强度测试,测得该样品的剥离强度为22.8N·m-1。
将制备的黏合剂乳液置于带凹槽的四氟乙烯模具中,于70℃,60%RH的恒温恒湿箱中放置一周后,得到完整的黏合剂胶膜。按照GB/T2406-80要求将黏合剂胶膜裁剪成70mm×6mm×3.2mm尺寸,将试样垂直固定在燃烧筒中,使氧、氮混合气流由下向上流过,点燃试样顶端,同时记时和观察试样燃烧长度,与所规定的标准判据相比较。在不同的氧浓度中试验一组试样,测定黏合剂刚好维持平稳燃烧时的最低氧浓度,用混合气中氧的体积百分数表示,测得该样品的极限氧指数为28.2%,阻燃效果好。
对比例1:
分别称取8.87g丙烯酸异辛酯、1.4g苯乙烯、0.86g甲基丙烯酸-2-羟乙酯、0.33g丙烯酸缩水甘油酯和1.06g正十八烷混合后得到油相溶液。
将1.0g乙烯基修饰的SiO2纳米粒子【数均粒径为20nm,表面改性剂为3-甲基丙烯酰氧丙基三(三甲基硅氧烷基)硅烷,偶联密度为1.2μmol·(m2SiO2)-1】预分散于95g水中,随后称取1.54g柠檬酸钠制成pH调节剂,得到pH值为8.9的SiO2水分散液。
将油相溶液加到SiO2水分散液中,在500rpm的磁力搅拌下预乳化得到粗乳液,再将装有粗乳液的容器置于冰水浴中,在300W的功率下超声处理8min,制得稳定的单体细乳液;随后向单体细乳液添加0.27g水溶性引发剂过硫酸钾,通氮除氧后,将反应温度调至70℃,并在氮气保护下反应8h,制得聚合物/SiO2纳米复合黏合剂乳液。
所制备的黏合剂乳液具有高的胶体稳定性,在5000rpm条件下离心15min后无沉淀生成。用动态光散射纳米粒度仪测得纳米复合黏合剂粒子的Z均粒径为210nm,PDI为0.100。
采用与实施例1相同的施胶工艺和测试方法,该胶膜的剪切强度为23.9MPa,样品的初粘力和剥离强度分别为0.82N和23.0N·m-1,样品的极限氧指数为18.4%,无阻燃效果。
对比例2:
分别称取8.87g丙烯酸异辛酯、1.4g苯乙烯、0.86g甲基丙烯酸-2-羟乙酯、0.33g丙烯酸缩水甘油酯、4.34g阻燃-22单体和1.06g正十八烷混合后得到油相溶液。
将0.5g十二烷基硫酸钠溶解于95g水中,随后称取1.54g柠檬酸钠制成pH调节剂,得到pH值为8.9的乳化剂水溶液。
将油相溶液加到乳化剂水溶液中,在500rpm的磁力搅拌下预乳化得到粗乳液,再将装有粗乳液的容器置于冰水浴中,在300W的功率下超声处理8min,制得稳定的单体细乳液;随后向单体细乳液添加0.27g水溶性引发剂过硫酸钾,通氮除氧后,将反应温度调至70℃,并在氮气保护下反应12h,制得阻燃型聚合物黏合剂乳液。
所制备的黏合剂乳液具有高的胶体稳定性,在5000rpm条件下离心15min后无沉淀生成。用动态光散射纳米粒度仪测得聚合物黏合剂粒子的Z均粒径为139nm,PDI为0.080。
采用与实施例1相同的施胶工艺和测试方法,该胶膜的剪切强度为18.9MPa,样品的初粘力和剥离强度分别为0.65N和19.6N·m-1,样品的极限氧指数为26.8%,阻燃效果好。
对比例3:
分别称取8.87g丙烯酸异辛酯、1.4g苯乙烯、0.86g甲基丙烯酸-2-羟乙酯、0.33g丙烯酸缩水甘油酯、4.34g阻燃-22单体和1.06g正十八烷混合后得到油相溶液。
将1.0g乙烯基修饰的SiO2纳米粒子【数均粒径为20nm,表面改性剂为3-甲基丙烯酰氧丙基三(三甲基硅氧烷基)硅烷,偶联密度为1.2μmol·(m2SiO2)-1】预分散于95g水中,随后用0.1mol/L的盐酸溶液将SiO2水分散液的pH调节至3。
将油相溶液加到SiO2水分散液中,在500rpm的磁力搅拌下预乳化得到粗乳液,再将装有粗乳液的容器置于冰水浴中,在300W的功率下超声处理8min,制得稳定的单体细乳液;随后向单体细乳液添加0.27g水溶性引发剂过硫酸钾,通氮除氧后,将反应温度调至70℃,并在氮气保护下反应,聚合过程中体系失去稳定性,无法制得稳定的阻燃型聚合物/SiO2纳米复合黏合剂乳液。
实施例2:
分别称取5.9g丙烯酸丁酯、1.6g醋酸乙烯酯、0.05g丙烯酰胺、0.03g丙烯酸-2-羟乙酯、2.42g阻燃-23单体、0.36g正十六烷和0.25g过氧化二苯甲酰混合后得到油相混合溶液。
将1.2g乙烯基修饰的SiO2纳米颗粒【数均粒径为12nm,表面改性剂为3-甲基丙烯酰氧丙基三(三甲基硅氧烷基)硅烷,偶联密度为1.4μmol·(m2SiO2)-1】预分散于120g水中,随后称取0.41g磷酸氢二钠和0.39g磷酸二氢钠制成pH调节剂,得到pH值为6.8的SiO2水分散液。
将油相溶液加到SiO2水分散液中,在800rpm的磁力搅拌下预乳化得到粗乳液,再将装有粗乳液的容器置于冰水浴中,在400W的功率下超声处理7min,制得稳定的单体细乳液;通氮除氧后,将反应温度调至78℃,并在氮气保护下反应20h,制得阻燃型聚合物/SiO2纳米复合黏合剂乳液。
所制备的黏合剂乳液具有高的胶体稳定性,在5000rpm条件下离心15min后无沉淀生成。用动态光散射纳米粒度仪测得纳米复合黏合剂粒子的Z均粒径为230nm,PDI为0.133。
采用与实施例1相同的施胶工艺和测试方法,该胶膜的剪切强度为22.4MPa,样品的初粘力和剥离强度分别为0.77N和23.7N·m-1,样品的极限氧指数为29.6%,阻燃效果好。
实施例3:
分别称取2.75g甲基丙烯酸甲酯、3.00g丙烯酸甲酯、5.5g丙烯酸丁酯、0.27g甲基丙烯酸-2-羟丙酯、0.03g丙烯酸缩水甘油酯、1.65g阻燃-28单体、0.26g十六烷和0.45g偶氮二异丁腈混合后得到油相溶液。
将0.5g乙烯基修饰的SiO2纳米颗粒【数均粒径为30nm,表面改性剂为甲基丙烯酸2-异氰酸乙酯,偶联密度为1.0μmol·(m2SiO2)-1】预分散于100g水中,随后称取0.055g磷酸氢二钠和0.985g磷酸二氢钠配制成pH调节剂,得到pH值为8.0的SiO2水分散液。
将油相溶液加到SiO2水分散液中,在700rpm的磁力搅拌下预乳化得到粗乳液,再将装有粗乳液的容器置于冰水浴中,在450W的功率下超声处理5min,制得稳定的单体细乳液;通氮除氧后,将反应温度调至65℃,并在氮气保护下反应10h,制得阻燃型聚合物/SiO2纳米复合黏合剂乳液。
所制备的黏合剂乳液具有高的胶体稳定性,在5000rpm条件下离心15min后无沉淀生成。用动态光散射纳米粒度仪测得纳米复合黏合剂粒子的Z均粒径为208nm,PDI为0.102。
采用与实施例1相同的施胶工艺和测试方法,该胶膜的剪切强度为28.4MPa,样品的初粘力和剥离强度分别为0.68N和22.3N·m-1,样品的极限氧指数为28.2%,阻燃效果好。
实施例4:
分别称取2.6g醋酸乙烯酯、1.33g甲基丙烯酸甲酯、5.6g丙烯酸异辛酯、0.1g甲基丙烯酸二甲氨基乙酯、0.06g甲基丙烯酸、0.41g阻燃-32单体、0.79g正十六烷和0.04g偶氮二异庚腈混合后得到油相混合溶液。
将0.8g乙烯基修饰的SiO2纳米颗粒【数均粒径为25nm,表面改性剂为甲基丙烯酸2-异氰酸乙酯,偶联密度为0.6μmol·(m2SiO2)-1】预分散于105g水中,随后称取0.215g碳酸钠、2.1g碳酸氢钠制成pH调节剂,得到pH值为9.0的SiO2水分散液。
将单体分散液加到SiO2水分散液中,在600rpm的磁力搅拌下预乳化得到粗乳液,再将装有粗乳液的容器置于冰水浴中,在200W的功率下超声处理12min,制得稳定的单体细乳液;通氮除氧后,将反应温度调至62℃,并在氮气保护下反应7h,制得阻燃型聚合物/SiO2纳米复合黏合剂乳液。
所制备的黏合剂乳液具有高的胶体稳定性,在5000rpm条件下离心15min后无沉淀生成。用动态光散射纳米粒度仪测得纳米复合黏合剂粒子的Z均粒径为215nm,PDI为0.115。
采用与实施例1相同的施胶工艺和测试方法,该胶膜的剪切强度为23.2MPa,样品的初粘力和剥离强度分别为0.78N和24.3N·m-1,样品的极限氧指数为23.8%,有一定阻燃效果。
实施例5:
分别称取3.75g甲基丙烯酸甲酯、2.0g丙烯酸乙酯、3.3g丙烯酸丁酯、2.2g醋酸乙烯酯、0.27g甲基丙烯酸-2-羟丙酯、0.03g甲基丙烯酸、0.95g阻燃-8单体和0.26g正十六烷混合后得到油相混合溶液。
将0.75g乙烯基修饰的SiO2纳米颗粒【数均粒径为25nm,表面改性剂为3-甲基丙烯酰氧丙基三(三甲基硅氧烷基)硅烷,偶联密度为0.8μmol·(m2SiO2)-1】预分散于100g水中,随后称取0.16g碳酸钠和0.29g碳酸氢钠制成pH调节剂,得到pH值为9.6的SiO2水分散液。
将油相溶液加到SiO2水分散液中,在700rpm的磁力搅拌下预乳化得到粗乳液,再将装有粗乳液的容器置于冰水浴中,在450W的功率下超声处理5min,制得稳定的单体细乳液;随后向单体细乳液添加0.08g的水溶性氧化剂过硫酸钾和0.08g的水溶性还原剂亚硫酸钠,通氮除氧后,将反应温度调至40℃,并在氮气保护下反应10h,制得阻燃型聚合物/SiO2纳米复合黏合剂乳液。
所制备的黏合剂乳液具有高的胶体稳定性,在5000rpm条件下离心15min后无沉淀生成。用动态光散射纳米粒度仪测得纳米复合黏合剂粒子的Z均粒径为226nm,PDI为0.106。
采用与实施例1相同的施胶工艺和测试方法,该胶膜的剪切强度为23.8MPa,样品的初粘力和剥离强度分别为0.72N和22.5N·m-1,样品的极限氧指数为26.3%,阻燃效果好。
实施例6:
分别称取1.67g甲基丙烯酸甲酯、3.0g丙烯酸乙酯、2.0g丙烯酸异辛酯、1.41g丙烯酸丁酯、0.64g甲基丙烯酸十八烷基酯、1.03g丙烯酸羟乙酯、0.22g丙烯酸缩水甘油酯和2.56g阻燃-17单体、混合后得到油相混合溶液。
将1.4g乙烯基修饰的SiO2纳米颗粒【数均粒径为28nm,表面改性剂为3-甲基丙烯酰氧丙基三(三甲基硅氧烷基)硅烷,偶联密度为0.5μmol·(m2SiO2)-1】预分散于110g水中,随后称取0.23g磷酸氢二钠和0.98g磷酸二氢钠制成pH调节剂,得到pH值为7.4的SiO2水分散液。
将油相溶液加到SiO2水分散液中,在650rpm的磁力搅拌下预乳化得到粗乳液,再将装有粗乳液的容器置于冰水浴中,在280W的功率下超声处理10min,制得稳定的单体细乳液;随后向单体细乳液添加0.15g的水溶性氧化剂过硫酸铵和0.15g的水溶性还原剂抗坏血酸钠,通氮除氧后,将反应温度调至45℃,并在氮气保护下反应6h,制得阻燃型聚合物/SiO2纳米复合黏合剂乳液。
所制备的黏合剂乳液具有高的胶体稳定性,在5000rpm条件下离心15min后无沉淀生成。用动态光散射纳米粒度仪测得纳米复合黏合剂粒子的Z均粒径为220nm,PDI为0.147。
采用与实施例1相同的施胶工艺和测试方法,该胶膜的剪切强度为23.4MPa,样品的初粘力和剥离强度分别为0.75N和23.8N·m-1,样品的极限氧指数为28.9%,阻燃效果好。
本发明的上述实施例是对本发明的说明而不能限制本发明,在于本发明的权利要求书相当的含义和范围内的任何变化,都应认为是包括在权利要求书的范围内。
Claims (10)
1.一种水性阻燃型纳米复合黏合剂的制备方法,其特征在于:所述方法包括以下步骤:
(1)将疏水乙烯基单体、极性乙烯基单体、阻燃功能单体、共稳定剂混溶形成油相溶液,其中疏水乙烯基单体质量用量为单体总质量用量的30%~95%,极性乙烯基单体的质量用量为单体总质量用量的0.5%~15%,阻燃单体的质量用量为单体总质量用量的1%~40%;共稳定剂的质量用量为单体总质量用量的0%~12%;
所述单体总质量为疏水乙烯基单体、极性乙烯基单体和阻燃功能单体的总质量;
所述疏水乙烯基单体选自下列至少一种:式(I)所示的丙烯酸酯或甲基丙烯酸脂类单体、醋酸乙烯酯、苯乙烯;
式(I)中,R1为H或CH3;R2为C1~C20的脂肪直链或支链烷基或-(CH2)3-Si(OCH3)3;
所述极性乙烯基单体选自下列至少一种:甲基丙烯酸羟烷基酯、丙烯酸羟烷基酯、丙烯酰胺、N-羟烷基丙烯酰胺、甲基丙烯酸、丙烯酸、甲基丙烯酸二甲胺基乙酯、丙烯酸缩水甘油酯、甲基丙烯酸缩水甘油酯;
所述阻燃单体选自下列阻燃-1至阻燃-37单体中的至少一种:
所述共稳定剂选自下列至少一种:C14~C22的脂肪直链或支链烷烃、C14~C22的脂肪醇;
(2)将表面乙烯基改性的无机纳米粒子分散于水中,得到无机纳米粒子的水分散液,其中表面乙烯基改性的无机纳米粒子的质量用量为步骤(1)中单体总质量用量的1%~20%,水的质量用量为步骤(1)中单体总质量用量的60%~1900%,用pH调节剂将分散液的pH值调节到4~11;所述无机纳米粒子选自下列至少一种:SiO2纳米粒子、TiO2纳米粒子、ZnO纳米粒子,所述无机纳米粒子的表面改性剂选自下列至少一种:含乙烯基硅烷偶联剂、甲基丙烯酸2-异氰酸乙酯,所述表面乙烯基改性的无机纳米粒子的偶联密度的范围为0.2μmol·(m2无机纳米粒子)-1~2.0μmol·(m2无机纳米粒子)-1,其中偶联密度的定义为每单位平方米的无机纳米粒子表面修饰的改性剂的摩尔量;所述pH调节剂选自下列至少一种:盐酸、柠檬酸、乳酸、酒石酸、柠檬酸钠、氢氧化钠、碳酸钠、碳酸氢钠、氨水、磷酸氢二钠、磷酸二氢钠、硼砂;
(3)将步骤(1)制得的油相溶液加至步骤(2)得到的无机纳米粒子的水分散液中,在100~1000rpm的搅拌强度下预乳化得到粗乳液;最后将装有粗乳液的容器置于冰水浴中,在30W~900W的功率下超声处理0.5min~120min,制得单体细乳液;通氮除氧后,将温度调至25℃~95℃,并在氮气保护下反应0.5h~24h,制得水性阻燃型纳米复合黏合剂;
并且通过下列方式a或b引入引发剂:
方式a:步骤(1)中,往单体混合液中加入油溶性引发剂,其中油溶性引发剂的质量用量为单体总质量用量的0.05%~5%;
方式b:步骤(3)中,向单体细乳液添加水溶性引发剂,其中水溶性引发剂的质量用量为单体总质量用量的0.05%~5%。
2.如权利要求1所述的制备方法,其特征在于:步骤(1)中,所述疏水乙烯基单体为下列至少一种:丙烯酸异辛酯、丙烯酸丁酯、甲基丙烯酸甲酯、醋酸乙烯酯、苯乙烯。
3.如权利要求1所述的制备方法,其特征在于:所述极性乙烯基单体为下列至少一种:甲基丙烯酸羟乙酯、丙烯酸羟乙酯、甲基丙烯酸、丙烯酸、甲基丙烯酸缩水甘油酯、丙烯酸缩水甘油酯、N-羟甲基丙烯酰胺。
4.如权利要求1所述的制备方法,其特征在于:所述阻燃功能单体选自下列至少一种:阻燃-8单体、阻燃-17单体、阻燃-22单体、阻燃-23单体、阻燃-28单体、阻燃-32单体;所述阻燃功能单体的质量用量为单体总质量用量的5%~30%。
5.如权利要求1所述的制备方法,其特征在于:步骤(1)中,所述共稳定剂为下列至少一种:C16~C22的脂肪直链或支链烷烃,优选为正十六烷。
6.如权利要求1所述的制备方法,其特征在于:所述无机纳米粒子的尺寸范围为10nm~50nm,优选在10nm~30nm之间。
7.如权利要求1所述的制备方法,其特征在于:所述的无机纳米粒子为SiO2纳米颗粒,表面改性剂为3-甲基丙烯酰氧丙基三(三甲基硅氧烷基)硅烷或甲基丙烯酸2-异氰酸乙酯。
8.如权利要求1所述的制备方法,其特征在于:步骤(2)中用pH调节剂将分散液的pH值调节到6.0~10.0。
9.如权利要求1所述的制备方法,其特征在于:步骤(3)中,聚合反应温度为40℃~75℃,反应时间为1h~24h。
10.如权利要求1所述的制备方法,其特征在于:所述油溶性引发剂选自下列至少一种:偶氮二异丁腈、偶氮二异庚腈、过氧化二苯甲酰、过氧化二碳酸二异丙酯;
所述水溶性引发剂选自下列至少一种:2,2’-偶氮二异丁基脒二盐酸盐、偶氮二氰基戊酸、过硫酸盐、氧化剂与还原剂构成的氧化还原体系;所述还原剂为亚硫酸盐、硫代硫酸盐、亚硫酸氢盐、抗坏血酸盐或草酸;所述的氧化剂为过氧化氢或过硫酸盐。
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