CN116836328A - 一种抗水解抗冻融型烯基琥珀酸酐施胶剂乳液及其制备方法 - Google Patents
一种抗水解抗冻融型烯基琥珀酸酐施胶剂乳液及其制备方法 Download PDFInfo
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Abstract
本发明提供了一种烯基琥珀酸酐施胶剂乳液的制备方法:将纳米纤维素与4‑苯甲酰苯甲酸混合于DMF中,然后加入DCC作为催化剂,反应后离心并洗涤干燥沉淀,获得CNF/4‑BBA纳米颗粒;将其分散到水中,作为水相;将ASA与水相混合,乳化后再加入丙烯酰胺和甲基丙烯酸混合,在紫外光照射下再次乳化,即得。该制备方法简单,无需复杂的化学改性和添加高成本助剂;此外,紫外光引发交联聚合技术具有环境友好、反应速率快等优点;同时,所制备的ASA施胶剂乳液具有很长的冷冻保质期。
Description
技术领域
本发明属于材料化学技术领域,具体涉及一种抗水解抗冻融型烯基琥珀酸酐造纸施胶剂乳液及其制备方法。
背景技术
紫外光引发交联聚合技术近年来在高分子材料制备领域得到了广泛的关注。通过紫外光引发剂的作用,可实现高分子材料的迅速交联固化,具有操作简便、反应速率快、环境友好等优点。然而,传统的紫外光引发剂在烯基琥珀酸酐施胶剂的制备过程中,可能导致不稳定的乳液,从而影响制品的性能。因此,开发一种适用于烯基琥珀酸酐施胶剂制备的紫外光引发剂具有重要意义。
纳米纤维素(CNF)作为一种生物基高分子材料,具有优异的力学性能、生物相容性和可生物降解性。在高分子材料领域得到了广泛的关注。将纳米纤维素与其他功能性材料结合,可发挥其在各种领域的优势。尤其是在紫外光引发剂的设计中,结合纳米纤维素的特性可以发挥出优异的引发效果。
发明内容
针对目前紫外引发剂导致烯基琥珀酸酐施胶剂不稳定的问题,本发明提供一种烯基琥珀酸酐(ASA)施胶剂乳液的制备方法,以CNF/4-BBA为引发剂,在乳化稳定ASA乳液的基础上在紫外线下引发单体分子聚合获得抗水解、抗冻融的ASA施胶剂乳液。
本发明还提供了一种上述方法制备的ASA施胶剂乳液,具有良好的抗冻、抗水解性能。
为实现上述目的,本发明采用如下技术方案。
一种烯基琥珀酸酐施胶剂乳液的制备方法,包括以下步骤:
(1)将纳米纤维素(CNF)与4-苯甲酰苯甲酸(4-BBA)混合于N,N’-二甲基甲酰胺(DMF)溶剂中,然后加入N,N’-二环己基碳二亚胺(DCC)作为催化剂,反应后离心,沉淀洗涤、干燥,获得CNF/4-BBA纳米颗粒;
(2)将CNF/4-BBA纳米颗粒分散到水中,作为水相;将烯基琥珀酸酐(ASA)与水相混合,乳化后获得乳液A;
(3)乳液A中加入丙烯酰胺(AAm)和甲基丙烯酸(MAAc)得混合液,在紫外光照射下再次乳化,得到乳液B,即抗冻融抗水解的烯基琥珀酸酐施胶剂乳液。
步骤(1)中,CNF与4-BBA质量比为10:1-10,更为优选的是5:2。
步骤(1)中,DMF与CNF质量比为100:1-20,更为优选的是100:9。
步骤(1)中,DCC与CNF的质量比为1:1-15,更为优选的是1:5。
步骤(2)中,CNF/4-BBA在水相中的质量分数为0.1-5%wt,更为优选的是1.2%wt。
步骤(2)中,ASA与水相质量比为4:1-1:10;更为优选的是2:3。
步骤(3)中,AAm与MAAc质量比为1:1-1:5,更为优选的是1:2。
步骤(3)中,AAm在混合液中的质量分数为1%wt-10wt%,更为优选的是3%wt。
一种上述制备方法获得的烯基琥珀酸酐施胶剂乳液。
上述烯基琥珀酸酐施胶剂乳液可耐至少-20℃冷冻,分散相的平均液滴粒径不大于6μm。
本发明的机理如下:
4-苯甲酰苯甲酸(4-BBA)作为一种芳香酮类光引发剂,具有羰基和羧基官能团,可以与纳米纤维素发生酯化反应,形成共价键。以CNF/4-BBA为紫外光引发剂,引发AAm(丙烯酰胺)和MAAc(甲基丙烯酸)交联聚合,乳化稳定ASA乳液。
首先,4-苯甲酰苯甲酸(4-BBA)是一种芳香酮类光引发剂,同时具有羰基和羧基官能团。羧基通过酯化作用与CNF表面的羟基形成共价键,而羰基则参与光引发过程。第一步涉及CNF表面的羟基与4-BBA的羧基之间的酯化反应。为实现这一点,可将CNF和4-BBA在溶剂中混合,并可添加催化剂如DCC(N,N’-二环己基碳二亚胺)以促进酯化反应。反应后,CNF将通过酯键接枝4-BBA分子。
其次,暴露于紫外线(UV)光后,CNF/4-BBA中的羰基吸收紫外线能量并形成激发单线态。这种激发态可以进行系统间交叉以形成反应性三重态。三重态可以从合适的氢供体中提取氢原子以形成自由基。然后,产生的自由基通过攻击单体的双键来引发AAm和MAAc的聚合。自由基继续传播,导致单体连接在一起并形成聚合物网络。当聚合物链通过次级相互作用(例如氢键或疏水相互作用)相互作用时,发生交联。
本发明中,利用4-BBA可制备双功能光引发剂,其中羧基允许与CNF共价连接形成具有乳化稳定ASA的CNF/4-BBA纳米颗粒;在油水界面处的CNF/4-BBA纳米颗粒周围聚集的AAm和MAAc在紫外光照射时,羰基在暴露于紫外光时引发AAm和MAAc的聚合,形成具有抗冻融抗水分子渗透的凝胶层,在低温下进一步阻止水分子越过界面颗粒进入油相,从而产生ASA抗水解的性能。
本发明具有以下优点:
本发明制备CNF/4-BBA作为ASA乳液乳化剂,同时作为紫外光引发剂使液滴在油水界面处形成AAm/MAAc水凝胶层,可以有效改善烯基琥珀酸酐施胶剂的抗水解和抗冻融性能;该制备方法简单,无需复杂的化学改性和添加高成本助剂;此外,紫外光引发交联聚合技术具有环境友好、反应速率快等优点;同时,所制备的ASA施胶剂乳液具有很长的冷冻保质期。
附图说明
图1是CNF/4-BBA原子力显微图像;
图2是抗水解抗冻融型ASA乳液的显微图片;
图3是抗水解抗冻融型ASA乳液在冻融前后状态对比图片。
具体实施方式
下面结合实施例和附图对本发明做进一步说明,但本发明不受下述实施例的限制。
实施例1 ASA施胶剂乳液的制备
(1)CNF/4-BBA的制备:将10质量份CNF与1质量份4-BBA混合在1000质量份DMF溶剂中,然后加入10质量份的DCC作为催化剂,室温下搅拌24小时,离心后用DMF洗涤,干燥后得到CNF/4-BBA纳米颗粒;
CNF/4-BBA红外谱图显示,3400-3500 cm⁻¹:羟基(OH)的弯曲振动,表明纳米纤维素的存在;2920-2980cm-1:烷基(C-H)的拉伸振动,表明纳米纤维素的存在;1710-1720cm-1:酰胺(C=O)的拉伸振动,表明4-苯甲酰苯甲酸的存在;1630-1640cm-1:羧酸(C=O)的拉伸振动,表明4-苯甲酰苯甲酸的存在;1600-1620 cm-1:芳香环(C=C)的拉伸振动,表明4-苯甲酰苯甲酸的存在;1300-1310cm-1:酯基(C-O)的拉伸振动,表明纳米纤维素与4-苯甲酰苯甲酸之间形成的酯键;上述红外光谱特征峰,可以确认纳米纤维素与4-苯甲酰苯甲酸的成功反应获得酯;
其原子力显微图像如图1所示,CNF/4-BBA复合纳米纤维呈现出棒状结构,具有较大的长径比;
(2)将CNF/4-BBA纳米颗粒分散到水中形成质量分数为0.1%wt的水分散液,搅拌均匀,作为水相;取100质量份水相与400质量份ASA混合,第一次乳化得到均匀乳液;再分别加入1质量份AAm和1质量份MAAc,在紫外光照射下继续进行第二次乳化,得到抗冻融抗水解烯基琥珀酸酐施胶乳液,如图2所示;
使用光学显微镜自带的粒径统计软件统计显微镜下观察到的100个乳液液滴的直径,取平均值,获得乳液平均粒径为5μm;
将制备好的乳液在-20℃冷冻,然后在80-100℃下解冻,冻融前后状态如图3所示,前后状态未发生变化,说明该乳液后具有良好的稳定性。
实施例2 ASA施胶剂乳液的制备
(1)CNF/4-BBA的制备:将100质量份CNF与40质量份4-BBA混合在800质量份DMF溶剂中,然后加入9质量份DCC作为催化剂,室温下搅拌24小时,离心后用DMF洗涤,干燥后得到CNF/4-BBA纳米颗粒;
(2)将CNF/4-BBA纳米颗粒分散到水中形成质量分数为1.2%wt的水分散液,搅拌均匀,作为水相;取200质量份水相与300质量份ASA混合,第一次乳化得到均匀乳液后,分别加入6质量份AAm和12质量份MAAc,在紫外光照射下继续进行第二次乳化,得到抗冻融抗水解烯基琥珀酸酐施胶乳液,乳液平均粒径4.2μm;
乳液在-20℃冷冻,在80-100℃下解冻后状态未发生改变,具有良好的稳定性。
实施例3 ASA施胶剂乳液的制备
(1)CNF/4-BBA的制备:将100质量份CNF与100质量份4-BBA混合在500质量份DMF溶剂中,然后加入7质量份DCC作为催化剂,室温下搅拌24小时,离心后用DMF洗涤,干燥后得到CNF/4-BBA纳米颗粒;
(2)将CNF/4-BBA纳米颗粒分散到水中形成质量分数为5%wt的水分散液,搅拌均匀,作为水相;取100质量份水相与1000质量份ASA混合,第一次乳化得到均匀乳液后,分别加入10质量份AAm和50质量份MAAc,在紫外光照射下继续进行第二次乳化,得到抗冻融抗水解烯基琥珀酸酐施胶乳液,乳液平均粒径5.7μm;
乳液在-20℃冷冻,在80-100℃下解冻后状态未发生改变,具有良好的稳定性。
应用例1 ASA施胶剂乳液在纸张的抄造中的应用
采用浆内施胶法施胶。施胶前,将AKD/ASA复合型造纸施胶剂乳液稀释至0.5%,纸浆浓度调至1%,在1000rpm搅拌速率下先向纸浆中加入1%硫酸铝(相对于绝干纸浆的质量百分数),然后用1 mol/L的氢氧化钠溶液将浆料pH值调节至7-8.5,再依次加入稀释后的ASA施胶剂乳液(用量为0.15%,ASA总质量相对于绝干纸浆的总质量的百分数)、0.03%(相对于绝干纸浆的质量百分数)用量的阳离子聚丙烯酰胺,然后用搅拌器在1000rpm剪切速率下搅拌2分钟后,静置30秒,再用PTI纸片抄造器(型号:RK3AKWT,产地:奥地利)抄造手抄片,手抄片定量为60g/m2(T205 om-88,TAPPI),抄片系统按照ISO5289/2和DIN54358的标准,选择凯塞法手动抄纸模式进行抄纸。抄造的手抄片在105℃下烘干,然后于室温下平衡纸张水份24h,环境湿度为50%。施胶性能通过测量抄造纸张施胶度(GB/T5405-2002)来评价。测量前,将纸张裁剪成30×30mm方形纸片,置于25℃、50%湿度环境下平衡水分24小时。将纸片四边折起,使其形成底面面积约20×20mm的船型结构,然后将其漂浮于浓度为2%的硫氰酸铵稀溶液中,用胶头滴管在船型纸片上部滴一滴0.5μL质量浓度1%的氯化铁溶液,同时用秒表计时,当氯化铁液滴中部出现红色斑点时,计时结束,时间为该纸样的施胶度。测试样品正反面各测10次,取平均值。
表1 不同施胶剂的性能
根据表1数据可知,本发明制备的ASA乳液的液滴平均粒径较小,-20℃乳液放置30天无任何相体析出、无破乳现象,说明本发明所制备的ASA乳液的稳定性良好。在用量为0.15%时(ASA与绝干浆的质量比)浆内施胶纸张的纸页施胶度为353-421秒,说明乳液的施胶性能优异,并且在乳液存放30天后使用,所施胶纸张得施胶度仍然很高,说明乳液的抗水解性能很好;低温冷冻储存时,由于Amm/MAAc抗冻凝胶层的保护,使得乳液具有明显的抗冻融抗水解性能。而由纯CNF或者纯4-BBA乳化的ASA乳液不稳定,在放置1小时后丧失所有的施胶性能,并且也不具有低温稳定性,乳液冻融后会破乳。
Claims (5)
1.一种烯基琥珀酸酐施胶剂乳液的制备方法,其特征在于,包括以下步骤:
(1)将CNF与4-BBA混合于DMF溶剂中,然后加入DCC作为催化剂,反应后离心,沉淀洗涤、干燥,获得CNF/4-BBA纳米颗粒;
(2)将CNF/4-BBA纳米颗粒分散到水中,作为水相;将ASA与水相混合,乳化后获得乳液A;
(3)乳液A中加入AAm和MAAc得混合液,在紫外光照射下再次乳化,得到乳液B,即抗冻融抗水解的烯基琥珀酸酐施胶剂乳液。
2.根据权利要求1所述的制备方法,其特征在于,步骤(1)中,CNF与4-BBA质量比为10:1-10;
步骤(1)中,DMF与CNF质量比为100:1-20;
步骤(1)中,DCC与CNF的质量比为1:1-15;
步骤(2)中,CNF/4-BBA在水相中的质量分数为0.1-5%wt;
步骤(2)中,ASA与水相质量比为4:1-1:10;
步骤(3)中,AAm与MAAc质量比为1:1-1:5;
步骤(3)中,AAm在混合液中的质量分数为1%wt-10wt%。
3.根据权利要求1所述的制备方法,其特征在于,步骤(1)中,CNF与4-BBA质量比为5:2;
步骤(1)中,DMF与CNF质量比为100:9;
步骤(1)中,DCC与CNF的质量比为1:5;
步骤(2)中,CNF/4-BBA在水相中的质量分数为1.2%wt;
步骤(2)中,ASA与水相质量比为2:3;
步骤(3)中,AAm与MAAc质量比为1:2;
步骤(3)中,AAm在混合液中的质量分数为3%wt。
4.一种权利要求1-3任一所述的制备方法获得的烯基琥珀酸酐施胶剂乳液。
5.根据权利要求4所述的烯基琥珀酸酐施胶剂乳液,其特征在于,烯基琥珀酸酐施胶剂乳液耐至少-20℃冷冻,分散相的平均液滴粒径不大于6μm。
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