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CN106866915B - 一种画布涂料用生物基水性纳米乳液及其制备方法 - Google Patents

一种画布涂料用生物基水性纳米乳液及其制备方法 Download PDF

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CN106866915B
CN106866915B CN201710118543.7A CN201710118543A CN106866915B CN 106866915 B CN106866915 B CN 106866915B CN 201710118543 A CN201710118543 A CN 201710118543A CN 106866915 B CN106866915 B CN 106866915B
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water
chain extender
parts
canvas
mixture
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CN106866915A (zh
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杜娟
顾洪溪
田梅娟
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Baoji University of Arts and Sciences
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Abstract

一种画布涂料用生物基水性纳米乳液及其制备方法，向反应器中加入低聚物二元醇和含羟基的天然植物油，真空脱水后，加入异氰酸酯化合物、扩链剂、溶剂和催化剂，在60‑90℃下反应1‑4小时后，加入中和剂后在室温下搅拌15‑60分钟后加入去离子水，静置后真空脱除溶剂，得到水性树脂a；将水性树脂a加入反应器中，在40‑50℃下滴加丙烯酸酯单体和引发剂，滴加完毕后45‑55℃下保温反应2‑3小时，最后浓缩，本发明的生物基水性纳米乳液具有优异的附着力，耐久性好，耐老化，适合画布涂料用水性乳液。

Description

一种画布涂料用生物基水性纳米乳液及其制备方法
技术领域
本发明涉及高分子材料技术领域，尤其涉及一种画布涂料用生物基水性纳米乳液及其制备方法。
背景技术
乳液作为涂料的“心脏”，对涂料性能起着至关重要的作用。画布涂料也不例外，画布涂料质量的好坏是决定画作表现力及画作品质的关键，也影响画作寿命的长短，画布涂料除了满足涂层表面最基本性能要求之外，还要满足对画布有较强的附着力，抗渗油性，抗拉伸性，不龟裂，不能有针眼，耐老化和耐候性等特点。
目前，许多科研院所工作者在乳液聚合领域开展了诸多工作，但在画布涂料用水性乳液领域研究较少，且国内没有一家专门的企业，针对画布特性，研发一种适于画布涂料且综合性能完美的乳液，国内多数画布工厂只能借用建筑行业用乳液暂时替代用作画布涂料的制作，不仅综合性能不尽如人意，且价格昂贵。
公开号为CN201010278991.1，名称为“画布涂料用苯丙乳液及其制备方法”的发明专利的公开了一种画布涂料用苯丙乳液及其制备方法，采用苯乙烯与(甲基)丙烯酸系单体和(甲基)丙烯酸酯系单体进行聚合，并且使苯乙烯-丙烯酸-丙烯酸酯共聚物(即苯丙乳液)在交联剂作用下进行部分交联的乳液，具有优良的弹性，粘合力强，拉伸强度好，抗油渗透率强，耐久性好，耐老化等特性。
公开号为CN201310175127.9，名称为“画布涂料用高光苯丙乳液及其制备方法”的发明专利，该专利在专利CN201010278991.1基础之上，公开了一种画布涂料用高光苯丙乳液及其制备方法，乳液体系中通过双丙酮丙烯酰胺和失水山梨酸醇油酸酯聚氧乙烯醚磺基琥珀酸二钠添加，重点突出了乳液的高光性。
但是使用苯丙乳液作为画布涂料用乳液，交联度不高，容易“热粘冷脆”，耐热性不佳，且残留乳化剂不能完全除净，稳定性不好，所以，目前急需提供一种满足画布涂料用水性乳液。
发明内容
为了克服以上问题，本发明的目的是提供一种画布涂料用生物基水性纳米乳液及其制备方法，此生物基水性纳米乳液对画布交联度高，具有较强的附着力，不龟裂，并且具有较好的抗拉伸性、耐热性好以及稳定性。
为实现上述目的，本发明采用以下技术方案来实现：
一种画布涂料用生物基水性纳米乳液的制备方法，包括以下步骤：
1)按质量份数称取：低聚物二元醇10-20份，含羟基的天然植物油3-5份，异氰酸酯化合物12-24份，扩链剂2-8份，中和剂1-5份，去离子水40-60份，丙烯酸酯类单体10-20份以及引发剂0.1-0.2份；
向反应器中加入低聚物二元醇和含羟基的天然植物油，真空脱水后，加入异氰酸酯化合物、扩链剂、溶剂和催化剂，在60-90℃下反应1-4小时后，加入中和剂后在室温下搅拌15-60分钟后加入去离子水，静置后真空脱除溶剂，得到水性树脂a；
2)将水性树脂a加入反应器中，在40-50℃下滴加丙烯酸酯单体和引发剂，滴加完毕后45-55℃下保温反应2-3小时，得到水性树脂b；
3)将水性树脂b在真空下浓缩，得到画布涂料用生物基水性纳米乳液。
本发明进一步的改进在于，所述低聚物二元醇分子量为500～2000。
本发明进一步的改进在于，所述低聚物二元醇为聚己内酯二元醇、聚四氢呋喃二元醇、聚碳酸酯二元醇、聚己二酸己二醇酯二元醇、聚己二酸丁二醇酯二醇中的一种或两种任意配比的混合物。
本发明进一步的改进在于，所述含羟基的天然植物油为橄榄油、蓖麻油、棕榈油、菜籽油、椰子油、花生油中的一种或两种任意配比的混合物；
所述二异氰酸酯化合物为甲苯二异氰酸、4，4'－二苯基甲烷二异氰酸酯、环己基二异氰酸酯中的一种或两种任意配比的混合物。
本发明进一步的改进在于，所述扩链剂为二元醇亲水扩链剂和三元醇扩链剂的混合物。
本发明进一步的改进在于，所述二元醇亲水扩链剂和三元醇扩链剂的质量比为1:2；
所述二元醇亲水扩链剂为二羟甲基丙酸、二羟甲基丁酸、二羟基丙磺酸钠、2－氨基乙基氨基乙磺酸钠、二氨基苯磺酸钠、N-甲基二乙醇胺中的一种或两种任意配比的混合物；
所述三元醇扩链剂为三羟甲基丙烷、1，2，4-丁三醇中的一种或两种任意配比的混合物。
本发明进一步的改进在于，所述中和剂为三乙胺、二乙烯三胺、N，N-二甲基乙醇胺、盐酸、醋酸中的一种或两种任意配比的混合物；
所述丙烯酸酯类单体为甲基丙烯酸甲酯、丙烯酸甲酯、丙烯酸丁酯中的一种或两种任意配比的混合物；
所述引发剂为过硫酸钾、过硫酸铵、偶氮二异丁腈、叔丁基过氧化氢中的一种或两种任意配比的混合物。
本发明进一步的改进在于，所述催化剂为二月桂酸二丁基锡、环烷酸锡、环烷酸铋中的一种或多种；
催化剂的加入量为低聚物二元醇、含羟基的天然植物油、异氰酸酯化合物、扩链剂、中和剂、去离子水、丙烯酸酯类单体以及引发剂的总质量的1％；
所述溶剂为丙酮或丁酮；
溶剂的加入量为低聚物二元醇、含羟基的天然植物油、异氰酸酯化合物、扩链剂、中和剂、去离子水、丙烯酸酯类单体以及引发剂的总质量的40％。
本发明进一步的改进在于，步骤1)中真空脱水的温度为110-120℃，时间为1-2小时；
步骤1)中搅拌的速度为750-850rmp。
一种画布涂料用生物基水性纳米乳液。
与现有技术相比，本发明具有的有益效果：
(1)本发明以生物材料含羟基的天然植物油作为原料，代替部分多元醇制备成水性纳米乳液为画布成膜物质，以水作为溶剂，不含有毒的有机溶剂，无刺激性气味，绿色环保。
(2)本发明的制备过程分为两步，第一步，以低聚物二元醇、含羟基的天然植物油、异氰酸酯化合物、扩链剂、中和剂等原料经过逐步聚合反应制得水性聚氨酯乳液，第二步，加入丙烯酸酯单体和引发剂，经过自由基聚合反应制得水性聚氨酯和丙烯酸树脂复合的画布涂料用生物基水性纳米乳液，因此，涂膜比单纯使用苯乙烯和丙烯酸酯类单体自由基聚合的苯丙乳液交联度高，耐热性好，不会热粘冷脆，性能优于交联度不高的苯丙乳液，兼具了水性聚氨酯和水性丙烯酸树脂两者的优点。
(3)本发明先制得水性聚氨酯乳液，再将水性聚氨酯乳液和丙烯酸乳液复合得到了水性纳米级乳液，克服了一般画布涂料固含量低的缺点，有较强的附着力，不龟裂，无针眼，耐老化和耐候性等特点，满足画布用乳液的要求。本发明制备方法简单易行，
进一步的，本发明的制备过程中不需要加乳化剂，只加入含羧基的亲水性扩链剂，制备完毕加入胺类中和剂中和成盐，分散在水中，因此不存在乳化剂残留问题。
本发明制备的画布涂料用生物基水性纳米乳液，具有良好的乳液稳定性、耐候性以及耐老化性，并且固含量达40％以上。对画布交联度高，具有较强的附着力，不龟裂。
附图说明
图1为棉布画布扫描电镜图，其中，(a)为放大600倍；(b)为放大1200倍；
图2为实施例1画布用水性纳米乳液涂布扫描电镜图，其中，(a)为放大600倍；(b)为放大1200倍；
图3为实施例2画布用水性纳米乳液涂布扫描电镜图，其中，(a)为放大600倍；(b)为放大1200倍。
具体实施方式
下面结合附图对本发明进行详细描述。
本发明所述的画布的材质为长纤织物层或无纺布层。所述长纤织物层为涤纶、尼龙、聚丙烯腈纤维、聚乙烯醇缩甲醛纤维、聚丙烯纤维、氨纶、棉、毛、亚麻中的一种或多种构成的织物层。本发明中低聚物二元醇分子量为500～2000。
下面通过具体实施例进行说明。
实施例1(此配方是最优配方，扫描电镜没有任何针孔)
1)按质量份数称取：低聚物二元醇10份，含羟基的天然植物油3份，异氰酸酯化合物15份，扩链剂2份，中和剂5份，去离子水40份，丙烯酸酯类单体15份以及引发剂0.1份；
向反应器中加入低聚物二元醇和含羟基的天然植物油，在110℃下真空脱水2小时后，加入异氰酸酯化合物、扩链剂、溶剂和催化剂，在60℃下反应4小时后，加入中和剂后在室温下750rmp搅拌60分钟后加入去离子水，静置后真空脱除溶剂，得到水性树脂a；
2)将水性树脂a加入反应器中，在40℃下滴加丙烯酸酯单体和引发剂，滴加完毕后45℃下保温反应3小时，得到水性树脂b；
3)将水性树脂b在真空下脱单体1小时，以脱除微量残留单体，得到画布涂料用生物基水性纳米乳液。
所述低聚物二元醇为聚己内酯二元醇。
所述含羟基的天然植物油为橄榄油；
所述二异氰酸酯化合物为甲苯二异氰酸。
所述扩链剂为二元醇亲水扩链剂和三元醇扩链剂的混合物。
所述二元醇亲水扩链剂和三元醇扩链剂的质量比为1:2；
所述二元醇亲水扩链剂为二羟甲基丙酸；
所述三元醇扩链剂为三羟甲基丙烷；
所述丙烯酸酯类单体为；
所述引发剂为过硫酸钾。
所述催化剂为二月桂酸二丁基锡；
所述催化剂的加入量为低聚物二元醇、含羟基的天然植物油、异氰酸酯化合物、扩链剂、中和剂、去离子水、丙烯酸酯类单体以及引发剂的总质量的1％；
所述溶剂为丙酮；
所述溶剂的加入量为低聚物二元醇、含羟基的天然植物油、异氰酸酯化合物、扩链剂、中和剂、去离子水、丙烯酸酯类单体以及引发剂的总质量的40％。
实施例2
1)按质量份数称取：低聚物二元醇15份，含羟基的天然植物油5份，异氰酸酯化合物12份，扩链剂5份，中和剂4份，去离子水50份，丙烯酸酯类单体10份以及引发剂0.2份；
向反应器中加入低聚物二元醇和含羟基的天然植物油，在120℃下真空脱水1小时后，加入异氰酸酯化合物、扩链剂、溶剂和催化剂，在90℃下反应1小时后，加入中和剂后在室温下850rmp搅拌15分钟后加入去离子水，静置后真空脱除溶剂，得到水性树脂a；
2)将水性树脂a加入反应器中，在50℃下滴加丙烯酸酯单体和引发剂，滴加完毕后55℃下保温反应2小时，得到水性树脂b；
3)将水性树脂b在真空下脱单体1小时，以脱除微量残留单体，得到画布涂料用生物基水性纳米乳液。
所述低聚物二元醇为聚四氢呋喃二元醇与聚碳酸酯二元醇的混合物。
所述含羟基的天然植物油为蓖麻油与棕榈油的混合物；
所述二异氰酸酯化合物为4，4'－二苯基甲烷二异氰酸酯与环己基二异氰酸酯的混合物。
所述扩链剂为二元醇亲水扩链剂和三元醇扩链剂的混合物。
所述二元醇亲水扩链剂和三元醇扩链剂的质量比为1:2；
所述二元醇亲水扩链剂为二羟甲基丁酸与二羟基丙磺酸钠的混合物；
所述三元醇扩链剂为三羟甲基丙烷与1，2，4-丁三醇中的混合物。
所述中和剂为二乙烯三胺与N，N-二甲基乙醇胺的混合物；
所述丙烯酸酯类单体为丙烯酸甲酯与丙烯酸丁酯的混合物；
所述引发剂为过硫酸铵与偶氮二异丁腈的混合物。
所述催化剂为环烷酸锡与环烷酸铋中的混合物；
催化剂的加入量为低聚物二元醇、含羟基的天然植物油、异氰酸酯化合物、扩链剂、中和剂、去离子水、丙烯酸酯类单体以及引发剂的总质量的1％；
所述溶剂为丁酮；
溶剂的加入量为低聚物二元醇、含羟基的天然植物油、异氰酸酯化合物、扩链剂、中和剂、去离子水、丙烯酸酯类单体以及引发剂的总质量的40％。
实施例3
1)按质量份数称取：低聚物二元醇20份，含羟基的天然植物油4份，异氰酸酯化合物20份，扩链剂7份，中和剂3份，去离子水60份，丙烯酸酯类单体20份以及引发剂0.1份；
向反应器中加入低聚物二元醇和含羟基的天然植物油，在115℃下真空脱水1.5小时后，加入异氰酸酯化合物、扩链剂、溶剂和催化剂，在70℃下反应3小时后，加入中和剂后在室温下800rmp搅拌20分钟后加入去离子水，静置后真空脱除溶剂，得到水性树脂a；
2)将水性树脂a加入反应器中，在45℃下滴加丙烯酸酯单体和引发剂，滴加完毕后50℃下保温反应2小时，得到水性树脂b；
3)将水性树脂b在真空下脱单体1小时，以脱除微量残留单体，得到画布涂料用生物基水性纳米乳液。
所述低聚物二元醇为聚己二酸己二醇酯二元醇与聚己二酸丁二醇酯二醇的混合物。
所述含羟基的天然植物油为菜籽油与椰子油的混合物；
所述二异氰酸酯化合物为甲苯二异氰酸与环己基二异氰酸酯的混合物。
所述扩链剂为二元醇亲水扩链剂和三元醇扩链剂的混合物。
所述二元醇亲水扩链剂和三元醇扩链剂的质量比为1:2；
所述二元醇亲水扩链剂为2－氨基乙基氨基乙磺酸钠与二氨基苯磺酸钠的混合物；
所述三元醇扩链剂为1，2，4-丁三醇。
所述中和剂为盐酸与醋酸中的混合物；
所述丙烯酸酯类单体为丙烯酸丁酯；
所述引发剂为叔丁基过氧化氢。
所述催化剂为环烷酸锡；
催化剂的加入量为低聚物二元醇、含羟基的天然植物油、异氰酸酯化合物、扩链剂、中和剂、去离子水、丙烯酸酯类单体以及引发剂的总质量的1％；
所述溶剂为丙酮；
溶剂的加入量为低聚物二元醇、含羟基的天然植物油、异氰酸酯化合物、扩链剂、中和剂、去离子水、丙烯酸酯类单体以及引发剂的总质量的40％。
实施例4
1)按质量份数称取：低聚物二元醇12份，含羟基的天然植物油3份，异氰酸酯化合物24份，扩链剂8份，中和剂1份，去离子水45份，丙烯酸酯类单体18份以及引发剂0.2份；
向反应器中加入低聚物二元醇和含羟基的天然植物油，在110℃下真空脱水1.5小时后，加入异氰酸酯化合物、扩链剂、溶剂和催化剂，在80℃下反应2小时后，加入中和剂后在室温下820rmp搅拌40分钟后加入去离子水，静置后真空脱除溶剂，得到水性树脂a；
2)将水性树脂a加入反应器中，在50℃下滴加丙烯酸酯单体和引发剂，滴加完毕后55℃下保温反应2小时，得到水性树脂b；
3)将水性树脂b在真空下脱单体1小时，以脱除微量残留单体，得到画布涂料用生物基水性纳米乳液。
所述低聚物二元醇为聚己内酯二元醇与聚己二酸丁二醇酯二醇的混合物。
所述含羟基的天然植物油为橄榄油与花生油的混合物；
所述二异氰酸酯化合物为甲苯二异氰酸与环己基二异氰酸酯的混合物。
所述扩链剂为二元醇亲水扩链剂和三元醇扩链剂的混合物。
所述二元醇亲水扩链剂和三元醇扩链剂的质量比为1:2；
所述二元醇亲水扩链剂为二氨基苯磺酸钠与N-甲基二乙醇胺的混合物；
所述三元醇扩链剂为1，2，4-丁三醇。
所述中和剂为三乙胺与N，N-二甲基乙醇胺的混合物；
所述丙烯酸酯类单体为丙烯酸甲酯；
所述引发剂为偶氮二异丁腈。
所述催化剂为二月桂酸二丁基锡、环烷酸锡与环烷酸铋的混合物；
催化剂的加入量为低聚物二元醇、含羟基的天然植物油、异氰酸酯化合物、扩链剂、中和剂、去离子水、丙烯酸酯类单体以及引发剂的总质量的1％；
所述溶剂为丙酮；
溶剂的加入量为低聚物二元醇、含羟基的天然植物油、异氰酸酯化合物、扩链剂、中和剂、去离子水、丙烯酸酯类单体以及引发剂的总质量的40％。
从图1可以看出，未经过涂布的棉织物画布表面纤维束很松散，而且之间有较多的空隙。
从图2可以看出，涂覆画布涂料最优配方的棉织物画布表面相对较平整，纤维束基本都被涂层紧紧地黏附在一起，纤维束之间的空隙消失，这说明画布涂料最优配方涂层穿过了纤维织物并把它们黏结为一体。
从图3可以看出，涂覆画布涂料非最优配方的棉织物画布表面不平整，纤维束之间仍有少量空隙。
下面对本发明制备的画布涂料用生物基水性纳米乳液进行了性能测试：
本发明适用的画布的材质为长纤织物层或无纺布层。所述长纤织物层为涤纶、尼龙、聚丙烯腈纤维、聚乙烯醇缩甲醛纤维、聚丙烯纤维、氨纶、棉、毛、亚麻中的一种或多种构成的织物层。
1.耐候性
将本发明制备的乳液放入温度20-40℃范围内的测试箱中，放置24小时，然后观察其凝结情况。
2.耐老化性
借助紫外线加速老化试验机，参阅测试标准GB/T4522-2008，通过在特定标准测试条件下促进胶膜劣化，进行试样暴露前后的性能值比较，以暴露后的关键性能值(如白度，透明度及弹性等)为暴露前的80％以上者判为合格。
3.乳液稳定性
采用肉眼目测有无破乳，分层，絮凝和沉淀的现象，没有则为良好。
4.涂膜外观测试
采用肉眼观察涂膜有无龟裂，采用扫描电子显微镜观察涂膜有无针孔。
5.差示扫描量热法
采用日本NETZSOH-DSC204型示差扫描量热仪测试，测试范围为–40℃～100℃，试样重8～12mg，在液氮保护下样品被冷却到-40℃，然后以10℃/min的升温速率加热，测试其玻璃化转变温度，玻璃化转变温度高则交联度增大，反之则减小。性能测试结果，见表1。
表1实施例1-4制备的画布涂料用生物基水性纳米乳液的性能
Figure BDA0001236333840000111
本发明以低聚物二元醇、含羟基的天然植物油、异氰酸酯化合物、扩链剂、中和剂、去离子水、丙烯酸酯类单体、以及引发剂为原料，经过反应制得画布涂料用生物基水性纳米乳液。本发明的生物基水性纳米乳液具有优异的附着力，耐久性好，耐老化，适合画布涂料用水性乳液。

Claims (5)

1.一种画布涂料用生物基水性纳米乳液的制备方法，其特征在于，包括以下步骤：
1）按质量份数称取：低聚物二元醇10份，含羟基的天然植物油3份，异氰酸酯化合物15份，扩链剂2份，中和剂5份，去离子水40份，丙烯酸酯类单体15份以及引发剂0.1份；
向反应器中加入低聚物二元醇和含羟基的天然植物油，真空脱水后，加入异氰酸酯化合物、扩链剂、溶剂和催化剂，在60-90℃下反应1-4小时后，加入中和剂后在室温下搅拌15-60分钟后加入去离子水，静置后真空脱除溶剂，得到水性树脂a；
2）将水性树脂a加入反应器中，在40-50℃下滴加丙烯酸酯单体和引发剂，滴加完毕后45-55℃下保温反应2-3小时，得到水性树脂b；
3）将水性树脂b在真空下浓缩，得到画布涂料用生物基水性纳米乳液；
所述低聚物二元醇分子量为500～2000；
所述扩链剂为二元醇亲水扩链剂和三元醇扩链剂的混合物，并且二元醇亲水扩链剂和三元醇扩链剂的质量比为1:2；
溶剂的加入量为低聚物二元醇、含羟基的天然植物油、异氰酸酯化合物、扩链剂、中和剂、去离子水、丙烯酸酯类单体以及引发剂的总质量的40%；所述溶剂为丙酮或丁酮；
所述低聚物二元醇为聚己内酯二元醇、聚四氢呋喃二元醇、聚碳酸酯二元醇、聚己二酸己二醇酯二元醇、聚己二酸丁二醇酯二醇中的一种或两种任意配比的混合物；
所述含羟基的天然植物油为橄榄油、蓖麻油、棕榈油、菜籽油、椰子油、花生油中的一种或两种任意配比的混合物；
所述异氰酸酯化合物为甲苯二异氰酸酯、4，4'－二苯基甲烷二异氰酸酯、环己基二异氰酸酯中的一种或两种任意配比的混合物；
所述二元醇亲水扩链剂为二羟甲基丙酸、二羟甲基丁酸中一种或两种任意配比的混合物；
所述三元醇扩链剂为三羟甲基丙烷、1，2，4-丁三醇中的一种或两种任意配比的混合物；
所述催化剂为二月桂酸二丁基锡、环烷酸锡、环烷酸铋中的一种或多种。
2.根据权利要求1所述的一种画布涂料用生物基水性纳米乳液的制备方法，其特征在于，所述中和剂为三乙胺、二乙烯三胺、N，N-二甲基乙醇胺中的一种或两种任意配比的混合物；
所述丙烯酸酯类单体为甲基丙烯酸甲酯、丙烯酸甲酯、丙烯酸丁酯中的一种或两种任意配比的混合物；
所述引发剂为过硫酸钾、过硫酸铵、偶氮二异丁腈、叔丁基过氧化氢中的一种或两种任意配比的混合物。
3.根据权利要求1所述的一种画布涂料用生物基水性纳米乳液的制备方法，其特征在于，催化剂的加入量为低聚物二元醇、含羟基的天然植物油、异氰酸酯化合物、扩链剂、中和剂、去离子水、丙烯酸酯类单体以及引发剂的总质量的1%。
4.根据权利要求1所述的一种画布涂料用生物基水性纳米乳液的制备方法，其特征在于，步骤1）中真空脱水的温度为110-120℃，时间为1-2小时；
步骤1）中搅拌的速度为750-850rmp。
5.一种根据权利要求1-4中任意一项制备方法制备的画布涂料用生物基水性纳米乳液。
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