CN105462523B - 一种基于聚合物复合物制备高粘合性能水基胶黏剂的方法 - Google Patents

一种基于聚合物复合物制备高粘合性能水基胶黏剂的方法 Download PDF

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CN105462523B
CN105462523B CN201610004475.7A CN201610004475A CN105462523B CN 105462523 B CN105462523 B CN 105462523B CN 201610004475 A CN201610004475 A CN 201610004475A CN 105462523 B CN105462523 B CN 105462523B
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孙俊奇
王梓霖
李想
李洋
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Jilin University
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Abstract

一种基于聚合物复合物制备高粘合性能水基胶黏剂的方法，属于水基胶黏剂制备技术领域。具体涉及一种通过溶液共混形成聚合物复合物，制备具有高粘合性能的水基胶黏剂方法。本发明制备方法简便，仅通过溶液共混即可以得到聚合物复合物水凝胶，离心可得到致密的水基胶黏剂。这种水基胶黏剂是基于聚合物之间的多重弱相互作用而形成的，形成过程简单高效，不涉及复杂的仪器和设备；制备过程中无需添加有机溶剂，无异味无毒环保，所用原料常见，价格低廉。这种水基胶黏剂可以应用于光学玻璃、金属、木材、塑料等多种材料的粘合，并且具有很高的粘合强度，材料(除塑料外)表面无需进行预先处理或修饰，可直接粘接。本发明所制备的水基胶黏剂有望在广泛的领域中得到应用。

Description

一种基于聚合物复合物制备高粘合性能水基胶黏剂的方法
技术领域
本发明属于水基胶黏剂制备技术领域，具体涉及一种通过溶液共混形成聚合物复合物，进而制备具有高粘合性能的水基胶黏剂方法。这种水基胶黏剂可以应用于多种材料表面，如光学玻璃、金属、木材、塑料等，对各种材料都有很强的胶接强度。
背景技术
由能分散或能溶解于水中的成膜材料制成的胶黏剂就是水基胶黏剂，也常常称为水性胶黏剂。其中，成膜材料一般都是有机聚合物，动物胶、淀粉、糊精、血清蛋白、白蛋白、甲基纤维素及聚乙烯醇都属于此类胶黏剂，还有一些酚醛与脲醛树脂的可溶性中间体亦属于此类。
水基胶黏剂并不是简单地用水作分散介质代替溶剂型胶黏剂中的溶剂，水基胶黏剂与溶剂型胶黏剂的主要差别在于：溶剂型胶黏剂是以苯、甲苯等有机溶剂作为分散介质的均相体系，物相是连续的。水基胶黏剂是以水作为分散介质的非均相体系；溶剂型胶黏剂的分子质量较低以保持可涂覆性，而水基胶黏剂的粘度与分子质量无关，它的粘度不随聚合物分子质量的改变有明显差异，可把聚合物的分子质量做得较大以提高其内聚强度。
胶接强度(Bonding strength)不仅仅是评价一种胶黏剂品质好坏的重要指标，而且几乎是目前判断一个胶接接头是否可靠的唯一依据。为了定量的表征胶黏剂的强度，需要特定的方法对其进行检测。在诸多强度表征方法中，搭接拉伸剪切测试(Lap sheartest)应用最为普遍：将胶黏剂粘在待粘合材料的一端，另一块待粘合材料平行覆盖，使两块待粘合材料平行粘接，粘接面积为S，在拉伸仪上进行拉伸试验，测出断裂时的最大应力Fmax。用最大应力除以粘接面积，即Fmax/S可计算出拉伸剪切强度(单位：Pa，一般用kPa或MPa)，通过比较拉伸剪切强度的大小可以衡量胶黏剂的胶接强度。(A waja F.；GilbertM.；Kelly G.；et al.Adhesion of polymers[j].Prog Polym Sci.2009,34:948)
聚合物复合物是基于静电、氢键、配位键、主客体相互作用等分子间弱相互作用力而形成的超分子聚集体。聚合物复合物主要包括由聚阴阳离子形成的聚电解质-聚电解质复合物，不带电荷的聚合物-聚合物复合物，聚合物-表面活性剂分子复合物以及聚合物-无机物复合物等。
聚合物在非化学等量的条件下复合，所形成的复合物表面含有丰富的剩余作用位点，这样的复合物可以作为构筑基元方便地进行层层组装构筑聚合物复合膜。与非复合的聚合物相比，聚合物复合物具有相对较大的尺寸，更加丰富的组成，并且聚合物复合物在溶液中的结构可以通过改变复合物的复合比例、温度、溶液pH值以及离子强度等参数来进行调控。因此，利用聚合物复合物和与其具有相互作用的化学物质进行交替沉积可以容易地实现复合膜材料的快速构筑，而且聚合物复合物多样可调的结构为层层组装复合膜的结构调控提供了极大的空间。
发明内容
本发明的目的是提供一种基于聚合物复合物制备高粘合性能的水基胶黏剂的方法。此水基胶黏剂制备方法简便，仅通过溶液共混即可以得到聚合物复合物水凝胶，离心可得到致密的水基胶黏剂。这种水基胶黏剂是基于聚合物之间的多重弱相互作用而形成的，形成过程简单高效，不涉及复杂的仪器和设备；制备过程中无需添加有机溶剂，无异味无毒环保，所用原料常见，价格低廉。这种水基胶黏剂可以应用于光学玻璃、金属、木材、塑料等多种材料的粘合，并且具有很高的粘合强度，材料(除塑料外)表面无需进行预先处理或修饰，可直接粘接。本发明所制备出水基胶黏剂有望在广泛的领域中得到应用。
本发明所述方法的步骤如下：
(1)构筑溶液的制备：将聚合物溶于去离子水中，超声20～60分钟，加热直至完全溶解，配成浓度为1.0～10.0mg/mL的聚合物溶液，用0.5～2M的盐酸或氢氧化钠水溶液调节pH值在1～8之间；然后将纳米填料溶于去离子水中，超声20～60分钟，加热至完全溶解，配成浓度为0.01～1mg/mL的纳米填料溶液；
(2)聚合物复合物溶液的制备：将步骤(1)得到的聚合物溶液及纳米填料溶液以一定的滴速(1～10mL/min)混合在一起，纳米填料质量用量是聚合物总质量用量的0～5％，上述混合过程充分搅拌，防止由于局部物质浓度过大而产生不均匀的复合；
(3)水基胶黏剂的收集：将步骤(2)制得到的聚合物复合物静置，使水凝胶充分析出，离心使聚合物复合物水凝胶作用更加充分，结构更加致密，弃去上清液即得到具有很高粘合性能的水基胶黏剂；
本发明所述的聚合物为透明质酸、聚甲基丙烯酸、聚丙烯酸、聚乙二醇、聚乙烯醇、聚乙烯基吡咯烷酮、聚乙烯基吡啶中任意两种或两种以上的组合；当为两种聚合物的组合时，其质量比为1：10～10：1；
本发明所述的纳米填料为氧化石墨烯、碳纳米管、蒙脱土或纤维素纳米晶中的一种，粒径在10～50纳米之间；
与现有技术相比，本发明的优点在于：
1.工艺简单，原料易得，成本低；
2.所用材料无毒，无需使用有机溶剂，环保；
3.可粘接多种基底材料，如光学玻璃、金属(如铁、铝)、木材(包括家具用的木制材料)或被亲水化处理过的塑料(如有机玻璃、聚四氟乙烯材料)等，大部分基底材料无需处理或修饰，可直接粘合。
本发明基于聚合物之间的多重弱相互作用制备聚合物复合物，实现了高粘合性能水基胶黏剂的制备。本方法中使用的聚合物复合物的制备方法，不需要采用复杂的仪器和原料，制备过程简单高效，无需添加有机溶剂，无毒环保，所用原料常见，价格低廉。这种水基胶黏剂可以在多种类型的材料上使用，材料(除塑料外)表面无需进行预先处理或修饰，可直接粘接，干燥后具有很高的粘合强度。本发明利用快速简便的制备方式，所制备出水基胶黏剂无毒环保并且具有很高的粘合性能，有望在广泛的领域中得到应用。
附图说明
图1：基于聚合物复合物制备的水基胶黏剂的状态照片，对应实施例1；
图2：a)图为镊子取出小块水基胶黏剂的状态照片，b)图为基于聚合物复合物制备的水基胶黏剂在常温条件下对金属有很强粘合力的状态照片，对应实施例1；
图3：基于聚合物复合物制备的水基胶黏剂粘合两片铁片的状态照片，可应用于搭接拉伸剪切测试，对应实施例1；
图4：基于聚合物复合物制备的水基胶黏剂粘合两片木片的状态照片，可应用于搭接拉伸剪切测试，对应实施例2；
图5：基于聚合物复合物制备的水基胶黏剂粘合两片玻璃片的状态照片，粘合后的玻璃样品两侧各固定一片铁片，应用于搭接拉伸剪切测试，对应实施例3；
图6：基于聚合物复合物制备的水基胶黏剂应用于不同基底时的拉伸剪切强度柱状图，由左向右依次对应铁片、木条和玻璃，分别对应实施例1，2和3。
图7：基于聚合物复合物制备的水基胶黏剂粘合两片亲水化处理的聚四氟乙烯薄片，可以挂载三个500g砝码，挂重约1500g。
具体实施方式
以下通过一些实例来进一步阐明本发明的具体实施例和结果，而不是要用这些实施例来限制本发明。
实施例1
a.构筑溶液的制备：分别配制浓度为1mg/mL的聚丙烯酸PAA去离子水溶液10mL以及浓度为1mg/mL的聚乙烯基吡咯烷酮PVPON去离子水溶液10mL，两种溶液中所含有聚合物的质量比为1：1，用1M的HCl水溶液调节聚合物溶液的pH值分别为4。
b.聚合物复合物的制备：将配好的溶液按体积比1：1以10mL/min的速度混合在一起，混合的过程中溶液需要充分搅拌，防止由于局部聚合物浓度过大而产生不均匀的复合物。
c.水基胶黏剂的收集：聚合物复合物混合结束后静置，使聚合物复合物水凝胶充分析出，通过离心得到致密的水凝胶，弃去上清液即得到所需要的水基胶黏剂，如图1所示，小瓶顶部部分就是刚离心得到的水基胶黏剂，这种水基胶黏剂是一种半透明状的水凝胶，即使倒立放置，水凝胶也不会流淌。这种水基胶黏剂可以很容易的取出，如图2(a)所示，用镊子可以方便的取出小块凝胶，张开镊子两脚，可发现此凝胶对不锈钢镊子有很强的粘合力，如图2(b)所示。
d.样品的粘结：将制得的水基胶黏剂取下适量的小块，如图2(a)，置于铁片一端，另一块铁片平行覆盖，如图3，粘接面积为0.5cm*1cm，对粘接部位施以5N的压力，使两条铁片紧密接触，待水基胶黏剂中的水分挥发干后即可以粘接牢固。
e.将此粘合后的铁片应用于搭接拉伸剪切测试，测试此水基胶黏剂的胶接强度。本实施例测得拉伸断裂应力Fmax＝215N，计算得到本实施例水基胶黏剂应用于铁片表面的拉伸剪切强度为Fmax/S＝4.3MPa，如图6。
实施例2
a.构筑溶液的制备：配制浓度为5mg/mL的透明质酸HA去离子水溶液10mL以及1mg/mL聚乙烯醇PVA去离子水溶液10mL，用1M的NaOH水溶液调节复合物溶液的pH值分别为7。配制浓度为0.12mg/mL(HA和PVA总质量的2％)的纤维素纳米晶CNC去离子水溶液10mL，超声40分钟，使其分散均匀。
b.聚合物复合物的制备：将配置好的溶液按照1：1：1体积比等速混合，滴速为5mL/min，混合的过程中复合物需要充分搅拌，防止局部浓度过大形成不均匀的复合物。
c.水基胶黏剂的收集：复合物混合结束后静置，使水凝胶充分析出，通过离心得到致密的水凝胶，弃去上清液得到可以应用的水基胶黏剂，此水基胶黏剂状态与图1中水基胶黏剂的状态类似。
d.样品的粘接：取下适量大小的水基胶黏剂，应用于1cm宽木条，平行覆盖另一块木条，保证粘接面积为1cm*1cm，要求水基胶黏剂均匀覆盖全部粘结面，用长尾夹固定样品，待水基胶黏剂干燥后木条可粘结牢固，如图4。
e.将此粘合后的木条应用于搭接拉伸剪切测试，测试此水基胶黏剂的胶接强度。本实施例测得拉伸断裂应力Fmax＝115N，计算得本实施例水基胶黏剂应用于木条的拉伸剪切强度为Fmax/S＝11.5MPa，如图6。
实施例3
a.构筑溶液的制备：配制浓度为1mg/mL的聚甲基丙烯酸PMAA去离子水溶液10mL以及9mg/mL聚乙二醇PEG去离子水溶液10mL，完全溶解后，用1M的HCl水溶液调节聚合物溶液的pH值为1。配制浓度为0.4mg/mL(PMAA和PVA总质量的4％)的蒙脱土MMT去离子水溶液10mL，超声60分钟，使其分散均匀。
b.聚合物复合物的制备：将配置好的溶液按照1：1：1体积比等速混合，滴速为1mL/min，混合的过程中复合物需要充分搅拌，防止局部浓度过大形成不均匀的复合物。
c.水基胶黏剂的收集：复合物混合结束后静置，使水凝胶充分析出，通过离心得到致密的水凝胶，弃去上清液得到可以应用的水基胶黏剂，此水基胶黏剂状态与图1中水基胶黏剂类似。
d.样品的粘接：取下适量大小的水基胶黏剂，应用于0.5cm宽的玻璃片，平行覆盖另一块玻璃片，保证粘接面积为0.5cm*0.5cm，要求水基胶黏剂均匀覆盖全部粘结面，用长尾夹固定样品，待水基胶黏剂干燥后玻璃可粘结牢固。
e.由于玻璃没有足够的强度来做搭接拉伸剪切测试，所以在粘合后的玻璃样品的两侧表面上应用商业化的氰基丙烯酸胶水，将玻璃和铁片粘合起来，如图5。将固定有铁片的粘合玻璃应用于搭接拉伸剪切测试，在保证玻璃与玻璃之间的胶接打开的前提下采集实验数据，测得拉伸断裂应力Fmax＝172.5N，计算得本实施例水基胶黏剂应用于玻璃表面的拉伸剪切强度为Fmax/S＝6.9MPa，如图6。
f.塑料材料的表面经亲水化处理后也可以应用此水基胶黏剂进行粘接。如图7所示，亲水化处理的两片聚四氟乙烯薄片(1cm宽)被本发明所制备的水基胶黏剂胶接，胶接面积1cm*0.7cm，待水分蒸发，此胶接头可以承受约1500g的挂重。
这些实施例表明，由本发明所述制备水基胶黏剂的方法简单便捷，所使用的材料安全无毒，粘合效果好，应用范围广，具有广阔的应用前景和商业价值。

Claims (5)

1.一种基于聚合物复合物制备高粘合性能水基胶黏剂的方法，其步骤如下：
(1)构筑溶液的制备：将聚合物溶于去离子水中，超声20～60分钟，加热直至完全溶解，配成浓度为1.0～10.0mg/mL的聚合物溶液，调节pH值在1～8之间；然后将纳米填料溶于去离子水中，超声20～60分钟，加热至完全溶解，配成浓度为0.01～1mg/mL的纳米填料溶液；聚合物为透明质酸、聚甲基丙烯酸、聚丙烯酸、聚乙二醇、聚乙烯醇、聚乙烯基吡咯烷酮、聚乙烯基吡啶中任意两种或两种以上的组合；
(2)聚合物复合物溶液的制备：将步骤(1)得到的聚合物溶液及纳米填料溶液混合在一起，纳米填料质量用量是聚合物总质量用量的0～5％；
(3)水基胶黏剂的收集：将步骤(2)制得到的聚合物复合物溶液静置，使水凝胶充分析出，离心弃去上清液即得到基于聚合物复合物制备的高粘合性能水基胶黏剂。
2.如权利要求1所述的一种基于聚合物复合物制备高粘合性能水基胶黏剂的方法，其特征在于：当为两种聚合物的组合时，其质量比为1：10～10：1。
3.如权利要求1所述的一种基于聚合物复合物制备高粘合性能水基胶黏剂的方法，其特征在于：纳米填料为氧化石墨烯、碳纳米管、蒙脱土或纤维素纳米晶中的一种，粒径在10～50纳米之间。
4.如权利要求1所述的一种基于聚合物复合物制备高粘合性能水基胶黏剂的方法，其特征在于：步骤(1)中是用0.5～2M的盐酸或氢氧化钠水溶液调节pH值在1～8之间。
5.如权利要求1所述的一种基于聚合物复合物制备高粘合性能水基胶黏剂的方法，其特征在于：步骤(2)中聚合物溶液及纳米填料溶液混合过程充分搅拌。
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