CN116084209B - 一种无氟可降解防水防油包装纸的制备方法 - Google Patents
一种无氟可降解防水防油包装纸的制备方法 Download PDFInfo
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Abstract
本发明公开了一种无氟可降解防水防油包装纸的制备方法,属于防水防油纸技术领域。所述制备方法包括:(1)第一次涂布:原纸经氯化钙溶液预处理后,涂布自制的鼠尾藻纤维素纳米纤维和十二烷基硫酸钠改性的纤维素纳米纤维的复配溶液,干燥后得到单层防油纸;(2)第二次涂布:制备改性酯化木质素,再将其和聚羟基丁酸酯复配,制备防水涂层,涂布于防油纸表面,干燥后得到防水防油纸。该方法制备的防水防油纸,采用生物基聚合物为原料,无氟环保对人体无害,可生物降解,具有极强的防水防油效果。纸张表面具有双层阻隔涂层,在保证纸张防油性能的同时,赋予纸张优良的防水效果,并提高了纸张的机械强度。
Description
技术领域
本发明属于防水防油纸技术领域,具体涉及一种无氟可降解防水防油包装纸的制备方法。
背景技术
纸张是由纤维组成的三维网状结构材料,不经处理的纸张表面存在大量的孔洞,如果将其直接用于食品包装,防水防油性能较差。市面上一些经过特殊处理的纸张,兼顾防水防油的性能,很好地解决了纸张用于食品包装存在的阻隔性能差的问题。防水防油包装纸是一种阻抗油脂与水渗透的纸张,常用于包装带油脂以及含水量较多的食物,如汉堡、糕点、传统的中式快餐等。
由于纸制品本身无法防水防油,因此,为了达到防水防油的目的,近年来大多纸制品在使用时被覆上塑料膜,而塑料膜的材质如低密度聚乙烯(LDPE)、聚氯乙烯(PVC)、聚对苯二甲酸乙二酯(PET)、乙烯醋酸乙烯共聚物(EVA)等在废弃后,都无法自行降解。即使采用焚烧处理,但在燃烧的过程中会产生大量废气,成为环境污染的一大来源,且这些塑料膜的原料来自石油,石油属于不可再生资源,大量使用塑料膜将会加剧能源危机。
随着人们对环境保护以及身体健康意识的不断增强,生物可降解材料由于其环保特性、无毒性和再生特性,逐渐成为取代传统塑料材料的研究热点,但这些生物可降解材料无法真正达到环保和经济双重效应,如聚乳酸(PLA)具有良好的生物降解性和机械性能,但其常温下硬且脆,具有极低的断裂伸长率和冲击强度;聚乙烯醇(PVA)可被细菌作为碳源和能用利用,耐油性和气体阻隔性优异,但其生产工艺复杂成本高;聚对苯二甲酸丁二醇(PBAT)具有良好的柔韧性,但其热封性较差,质地较软,拉伸易变形,极大的限制了环保可降解材料在包装领域的推广应用。
专利CN107619451A公开了一种用于防水防油纸的氟化共聚物及其乳液的制备方法,配合使用可以得到优异的防水防油协同效应。但是该方法包含氟单体,此物质会在人体中堆积,给人体带来安全影响。专利CN105694171A公开了一种在原纸表面喷射聚乙烯母料后液压成型而制造出的淋膜纸,具有防潮、防油、隔离效果佳等优点,但该方法制备的防油纸因降解和回收困难而污染环境,而且其中的有害物质会向食品中迁移。专利CN108677615A公开了一种利用阳离子淀粉、壳聚糖、海藻酸钠、聚乳酸等物质构成防水防油剂的制备方法,赋予纸张良好的防油性能,但其制备成本偏高且防水性能有待进一步提升。专利CN111636247A公开了一种由壳聚糖、水蛭石、羟丙基甲基纤维素和聚二甲基硅氧烷构成的防水防油涂层的制备方法,制备的纸张具有优异的耐水防油效果,但其使用的聚二甲基硅氧烷对人体健康的影响问题还有待商榷。
综上所述,目前防水防油包装纸还存在一些缺陷,仍有很大的改良空间。如何制备性能优异、无氟环保可降解,且对人体无害的防水防油包装纸,将成为今后食品包装的热门话题。
发明内容
为了克服现有技术存在的不足之处,本发明提供了一种无氟可降解防水防油包装纸的制备方法。该包装纸具有优异的防水防油效果,纸张的表面具有双层防护涂层,确保了纸张具有良好的的防油等级以及耐水性能。此外,本发明采用的涂层原料基于生物基聚合物,制备的防水防油纸无氟环保无毒、对人体无害、可回收降解,同时纸张的机械强度也进一步得到提升。
为了达到上述目标,本发明至少通过以下技术方案之一实现。
一种无氟可降解防水防油包装纸的制备方法,包括以下步骤:
(1)原纸预处理:将氯化钙加入水中,混合均匀,得到氯化钙溶液;将原纸浸入氯化钙溶液中,然后取出干燥,得到经氯化钙预处理的原纸。
(2)改性纳米纤维素制备:将漂白针叶木浆添加到TEMPO/NaClO/NaBr***中,调节pH然后均质化,得到纳米纤维素溶液;将乙醇与水混合加热搅拌,再加入十二烷基硫酸钠,继续搅拌,制得十二烷基硫酸钠溶液;将纳米纤维素溶液加入到十二烷基硫酸钠溶液中,加热搅拌,进行改性反应,得到改性后的纳米纤维素,然后将改性后的纤维素纳米纤维洗涤,超声处理,得到纯净的改性纳米纤维素溶液。
(3)鼠尾藻纳米纤维素制备:将鼠尾藻原材料在水中浸泡,配制NaHCO3溶液,将两者在混合反应后,干燥,洗涤,放入乙酸溶液反应,再向其中加入的H2O2溶液,充分反应后,洗涤,得到鼠尾藻产物;最后,加水到鼠尾藻产物中,均质化后得到鼠尾藻纳米纤维素溶液。
(4)内层防油涂层制备:将步骤(2)和步骤(3)中制备的改性纳米纤维素溶液和鼠尾藻纳米纤维素溶液复配,搅拌加热,再经超声处理,得到均匀的鼠尾藻-改性纳米纤维素溶液。
(5)第一次涂布:使用涂布机,将步骤(4)制备的鼠尾藻-改性纤维素纳米纤维溶液涂布在步骤(1)中制得的经氯化钙溶液预处理的原纸单面,干燥后得到单层防油纸。
(6)改性酯化木质素的制备:将2,2'-联吡啶溶解在有机溶剂中配制均匀的2,2'-联吡啶溶液;将木质素加入其中,搅拌加热,再加入硬酯酰氯,搅拌加热,反应后得到的产物用酸溶液沉淀,离心,洗涤离心产物;最后干燥离心产物,制得改性酯化木质素。
(7)单层防水涂层制备:将步骤(6)中制得的改性酯化木质素和聚羟基丁酸酯溶解在三氯甲烷中,搅拌加热,再经超声处理,制得酯化木质素-聚羟基丁酸酯溶液。
(8)第二次涂布:使用涂布机,将酯化木质素-聚羟基丁酸酯溶液涂布在步骤(5)制备的单层防油纸上,干燥后得到防水防油纸。
进一步地,步骤(1)所述氯化钙溶液的质量百分比浓度为1-4%。
进一步地,步骤(1)所述浸渍时间为3-5min;所述干燥温度为40℃-60℃;所述干燥时间为10-20min。
进一步地,步骤(2)所述TEMPO/NaClO/NaBr***为将TEMPO、NaBr和NaClO溶于水中,试剂的质量体积比为0.01g:0.1g:10mL:100mL。
进一步地,步骤(2)所述漂白针叶木浆和TEMPO/NaClO/NaBr***的质量和体积比为1g:(20~25)mL。
进一步地,步骤(2)所述调节后的pH为10。
进一步地,步骤(2)所述均质化的操作条件为均质次数为10-20次,压力为150-200MPa。
进一步地,步骤(2)所述乙醇和水的体积比为(0.6~1):1;所述加热搅拌的温度为40-60℃,搅拌时间为20-40min。
进一步地,步骤(2)所述十二烷基硫酸钠溶液的质量浓度为12~18%,纳米纤维素溶液和十二烷基硫酸钠溶液的体积比为1:(0.8~1.2)。
进一步地,步骤(2)所述改性反应的条件为加热温度为50-70℃,搅拌时间为60-180min;所述离心转速为3000-5000rpm。
进一步地,步骤(3)所述鼠尾藻和水的质量和体积比为(100~300g):1L。
进一步地,步骤(3)所述浸泡时间为24-48h;所述NaHCO3溶液质量百分比浓度为10-20%;所述干燥时间为12-24h,干燥温度为50-100℃。
进一步地,步骤(3)所述乙酸溶液质量百分比浓度为1-3%;所述的H2O2溶液浓度为30%。
进一步地,步骤(3)所述均质化的操作条件为均质次数为10-20次,压力为150-200MPa。
进一步地,步骤(4)所述改性纳米纤维素溶液的质量百分比浓度为2-10%。
进一步地,步骤(4)所述鼠尾藻-改性纳米纤维素溶液的质量百分比浓度为4-10%。
进一步地,步骤(4)所述改性纳米纤维素溶液和鼠尾藻纳米纤维素溶液,两者复配质量比为(2-8):(2-8)。
进一步地,步骤(4)所述的搅拌加热的加热温度为30-50℃,搅拌时间为20-40min,超声时间为15-30min。
进一步地,步骤(5)所述的涂布机为辊式涂布机,涂布速率为2-8cm/s,涂布量为1-6g/m2;所述干燥的温度为50℃-65℃,时间为20-40min。
进一步地,步骤(6)所述有机溶液为无水乙醇,所述的2,2'-联吡啶和有机溶剂的质量和体积比为(10-20g):200mL。
进一步地,步骤(6)所述的木质素和2,2'-联吡啶的质量比为10-50g:(10-20g)。
进一步地,步骤(6)所述的搅拌加热的条件为加热温度为50-80℃,搅拌时间为1-3h。
进一步地,步骤(6)所述的硬酯酰氯和2,2'-联吡啶的体积和质量比为(10-150mL):(10-20g)。
进一步地,步骤(6)所述的离心转速为4000-5000rpm,离心时间为10-20min;最后干燥的温度为90-100℃,时间为12-24h。
进一步地,步骤(7)所述的酯化木质素和三氯甲烷的质量和体积比为(2-10)g:100mL,所述的聚羟基丁酸酯和三氯甲烷的质量和体积比为(2-10)g:100mL。
进一步地,步骤(7)所述的加热温度为50-65℃,加热时间为40-60min;所述超声时间为15-25min。
进一步地,步骤(8)所述的涂布机为辊式涂布机;步骤(8)所述的酯化木质素-聚羟基丁酸酯溶液涂布量为1-8g/m2,涂布速率为2-8cm/s;所述干燥的温度为30℃-60℃,时间为15-35min。
本发明提供一种由上述方法制备的无氟可降解防水防油包装纸,该包装纸有单层防油涂层和单层防水涂层;所述单层防油涂层由鼠尾藻纳米纤维素、改性纳米纤维素组成;所述单层防水涂层由改性酯化木质素和聚羟基丁酸酯组成。
与现有技术相比,本发明具有如下有益效果:
(1)提供了一种无氟可降解防水防油包装纸的制备方法,其中原纸经氯化钙溶液预处理后,将自制的改性纳米纤维素溶液和鼠尾藻纳米纤维素溶液进行复配,将其涂布在纸张表面,纳米纤维素的侧链引入了疏油基团(SO4 2-,-COO-),在纸张表面形成一层疏油膜,以此来达到填充纸张表面孔隙的目的,显著提升纸张的防油效果;且Ca2+与鼠尾藻纳米纤维素中-COO-产生交联作用,防油涂层与纸张紧密结合,纸张机械性能得到提升。
(2)对木质素进行酯化改性,在侧链引入长脂肪链,赋予木质素良好的疏水性,再通过和聚羟基丁酸酯复配,赋予防油纸优异的耐水效果,纸张机械性能进一步得到提升。
(3)本发明提供的制备方法,以纤维素、鼠尾藻、木质素等为主要原料,均属于天然生物基聚合物,制备的防油防水纸无氟绿色环保,可完全生物降解,对环境和人体无害。
附图说明
图1是酯化木质素改性流程图。
具体实施方式
以下结合实例对本发明的具体实施作进一步说明,但本发明的实施与保护不限于此。若非特指,所采用的原料和设备等均可从市场购得或是本领域常用的。
测试方法
(1)防油性能测试:TAPPI T 559cm-02《Grease resistance test for paper andpaperboard》。
(2)防水性能:GB/T1540-2002《纸和纸板吸水性的测定可勃法》。
(3)抗张强度:GB/T12914-2018《纸和纸板抗张强度的测定恒速拉伸法》。
(4)透气度:GB/T458-2008《纸和纸板透气度的测定》。
(5)水蒸气透过率:GB/T22921-2008《纸和纸板薄页材料水蒸气透过率的测定动态气流法和静态气体法》。
(6)降解性能:GB/T39951-2021《一次性纸制品降解性能评价方法》。
原料来源
漂白针叶木浆:采购自青岛久诺国际贸易有限公司,原产地为加拿大;
鼠尾藻:采购自福建省连江县大江海产品公司;
木质素:采购自山东高唐多元木质素有限公司,含量为94%;
聚羟基丁酸酯:采购自广东瓮江化学试剂有限公司,含量为98%;
实施例1
一种制备无氟可降解防水防油包装纸的方法,包括如下步骤:
(1)取氯化钙加入去离子水中,混合均匀,得到质量浓度为2.5%的氯化钙溶液;将原纸放入50mL氯化钙溶液中浸渍4min,然后将纸张放入真空干燥箱,在50℃下干燥15min,得到经氯化钙预处理的原纸。
(2)将20g漂白针叶木浆添加到TEMPO/NaClO/NaBr***(0.05g TEMPO、0.5g NaBr和50mL NaClO溶于500mL去离子水)中,用0.1mol/L HCl和NaOH调节反应体系的pH值为10,然后在180MPa下均质化15次,得到纳米纤维素溶液;将50ml的乙醇与50ml去离子水加入到烧杯中,50℃加热搅拌30min,再加入15g的十二烷基硫酸钠,继续搅拌直到获得均匀溶液;将100mL纳米纤维素溶液加入到上述均匀溶液中,65℃加热搅拌120min,使得纳米纤维素与十二烷基硫酸钠充分进行改性反应,得到改性后的纳米纤维素,然后将改性后的纳米纤维素进行离心操作,再用去离子水洗涤以除去未反应的试剂,得到纯净的改性纳米纤维素。
(3)将200g鼠尾藻放入1L去离子水中浸泡36h,同时配制质量浓度为15%的NaHCO3溶液,将浸泡后的鼠尾藻放入1L NaHCO3溶液中均匀混合1h后,之后放入70℃的烘箱干燥20h;干燥后的鼠尾藻经过去离子水充分洗涤,放入质量百分比浓度为1.5%的500mL乙酸溶液中,充分反应2h后,加入40mL的质量浓度为30%的H2O2溶液,反应8h后,用去离子水充分洗涤。最后,将去离子水加入到鼠尾藻产物中,然后在200MPa下均质化15次,得到纯净的鼠尾藻纳米纤维素溶液。
(4)将制备的改性纳米纤维素配制为质量浓度为6%的溶液,将制备的鼠尾藻纳米纤维素配制为质量浓度为6%的溶液,两者按照4:6的质量比进行复配,在40℃的温度下磁力搅拌30min,再超声25min制备出鼠尾藻-改性纳米纤维素溶液。
(5)在辊式涂布机上将制备的鼠尾藻-改性纳米纤维素溶液均匀涂布在经氯化钙溶液处理的原纸正面,涂布速率为5cm/s,所述涂层的涂布量为5g/m2,将纸张放入真空干燥箱中,干燥温度为55℃,干燥时间为30min,制得所述单层防油纸。
(6)将15g的2,2'-联吡啶溶解在200mL无水乙醇中,配制均匀的质量分数为7.5%的2,2'-联吡啶溶液;将30g的木质素加入其中,在600rpm的转速下搅拌,70℃水浴加热1h;再加入60mL的硬酯酰氯,搅拌加热3h;反应后得到的产物用0.2mol·L-1的盐酸沉淀,在离心机中以4500rpm的转速离心15min后,再用去离子水洗涤离心产物5次;最后将产物在烘箱中90℃干燥18h,制备出改性酯化木质素。
(7)将6g改性酯化木质素和4g聚羟基丁酸酯溶解在100mL三氯甲烷中,55℃搅拌加热50min后,再经超声处理20min,制备出酯化木质素-聚羟基丁酸酯溶液。
(8)在辊式涂布机上将酯化木质素-聚羟基丁酸酯溶液均匀涂布在步骤(5)中制备的单层防油纸的正面,涂布速率为6cm/s,所述涂层的涂布量为6g/m2,结束后将纸张放入真空干燥箱中,干燥温度为50℃,干燥时间为25min,制得所述无氟可降解防水防油包装纸。
实施例2
一种制备无氟可降解防水防油包装纸的方法,包括如下步骤:
(1)取适量氯化钙加入去离子水中,混合均匀,得到质量浓度为2.5%的氯化钙溶液;将原纸放入50mL氯化钙溶液中浸渍4min,然后将纸张放入真空干燥箱,在50℃下干燥15min,得到经氯化钙预处理的原纸。
(2)将20g漂白针叶木浆添加到TEMPO/NaClO/NaBr***(0.05g TEMPO、0.5g NaBr和50mL NaClO溶于500mL去离子水)中,用0.1mol/L HCl和NaOH调节反应体系的pH值为10中,然后在180MPa下均质化15次,得到纳米纤维素溶液;将50ml的乙醇与50ml去离子水加入到烧杯中,50℃加热搅拌30min,再加入15g的十二烷基硫酸钠,继续搅拌直到获得均匀溶液;将一定量(100mL)的纤维素纳米纤维溶液加入到上述均匀溶液中,65℃加热搅拌120min,使得纤维素纳米纤维与十二烷基硫酸钠进行改性反应,得到改性后的纳米纤维素,然后将改性后的纤维素纳米纤维进行离心操作,再用去离子水洗涤以除去未反应的试剂,得到纯净的改性纳米纤维素。
(3)将150g鼠尾藻放入1L去离子水中浸泡48h,同时配制质量百分比浓度为15%的NaHCO3溶液,将浸泡后的鼠尾藻放入1L NaHCO3溶液中均匀混合1h后,放入70℃的烘箱干燥20h;干燥后的鼠尾藻经过去离子水充分洗涤,放入质量百分比浓度为1.5%的500mL乙酸溶液中,充分反应2h后,加入30mL的质量浓度为30%的H2O2溶液,反应10h后,用去离子水充分洗涤。最后,将去离子水加入到鼠尾藻产物中,然后在200MPa下均质化15次,得到纯净的鼠尾藻纳米纤维素溶液。
(4)将制备的改性纳米纤维素配制为质量浓度为5%的溶液,将制备的鼠尾藻纳米纤维素配制为质量浓度为5%的溶液,两者按照4:6的质量比进行复配,在40℃的温度下磁力搅拌30min,再超声25min制备出鼠尾藻-改性纳米纤维素。
(5)在辊式涂布机上将制备的鼠尾藻-改性纳米纤维素溶液均匀涂布在经氯化钙溶液处理的原纸正面,涂布速率为5cm/s,所述涂层的涂布量为4g/m2,将纸张放入真空干燥箱中,干燥温度为55℃,干燥时间为30min,制得所述单层防油纸。
(6)将15g的2,2'-联吡啶溶解在200mL无水乙醇中,配制均匀的质量分数为7.5%的2,2'-联吡啶溶液;将30g的木质素加入其中,在600rpm的转速下搅拌,70℃水浴加热1h;再加入60mL的硬酯酰氯,搅拌加热3h;反应后得到的产物用0.2mol·L-1的盐酸沉淀,在离心机中以4500rpm的转速离心15min后,再用去离子水洗涤离心产物5次;最后将产物在烘箱中90℃干燥18h,制备出改性酯化木质素。
(7)将5g改性酯化木质素和5g聚羟基丁酸酯溶解在100mL三氯甲烷中,55℃搅拌加热50min后,再经超声处理20min,制备出酯化木质素-聚羟基丁酸酯溶液。
(8)在辊式涂布机上将酯化木质素-聚羟基丁酸酯溶液均匀涂布在步骤(5)中制备的单层防油纸的正面,涂布速率为6cm/s,所述涂层的涂布量为5g/m2,将纸张放入真空干燥箱中,干燥温度为50℃,干燥时间为25min,制得所述无氟可降解防水防油包装纸。
实施例3
一种制备无氟可降解防水防油包装纸的方法,包括如下步骤:
(1)取适量氯化钙加入去离子水中,混合均匀,得到质量浓度为2.5%的氯化钙溶液;将原纸放入50mL氯化钙溶液中浸渍4min,然后将纸张放入真空干燥箱,在50℃下干燥15min,得到经氯化钙预处理的原纸。
(2)将20g漂白针叶木浆添加到TEMPO/NaClO/NaBr***(0.05g TEMPO、0.5g NaBr和50mL NaClO溶于500mL去离子水)中,用0.1mol/L HCl和NaOH调节反应体系的pH值为10中,然后在180MPa下均质化15次,得到纳米纤维素溶液;将50ml的乙醇与50ml去离子水加入到烧杯中,50℃加热搅拌30min,再加入15g的十二烷基硫酸钠,继续搅拌直到获得均匀溶液;将一定量(100mL)的纤维素纳米纤维溶液加入到上述均匀溶液中,65℃加热搅拌120min,使得纤维素纳米纤维与十二烷基硫酸钠进行改性反应,得到改性后的纳米纤维素,然后将改性后的纤维素纳米纤维进行离心操作,再用去离子水洗涤以除去未反应的试剂,得到纯净的改性纳米纤维素。
(3)将200g鼠尾藻放入1L去离子水中浸泡36h,同时配制质量百分比浓度为15%的NaHCO3溶液,将浸泡后的鼠尾藻放入1L NaHCO3溶液中均匀混合1h后,放入70℃的烘箱干燥20h;干燥后的鼠尾藻经过去离子水充分洗涤,放入质量百分比浓度为1.5%的500mL乙酸溶液中,充分反应2h后,加入40mL的质量浓度为30%的H2O2溶液,反应8h后,用去离子水充分洗涤。最后,将去离子水加入到鼠尾藻产物中,然后在200MPa下均质化15次,得到纯净的鼠尾藻纳米纤维素溶液。
(4)将制备的改性纳米纤维素配制为质量浓度为6%的溶液,将制备的鼠尾藻纳米纤维素配制为质量浓度为6%的溶液,两者按照6:4的质量比进行复配,在40℃的温度下磁力搅拌30min,再超声25min制备出鼠尾藻-改性纳米纤维素。
(5)在辊式涂布机上将制备的鼠尾藻-改性纳米纤维素均匀涂布在经氯化钙溶液处理的原纸正面,涂布速率为5cm/s,所述涂层的涂布量为5g/m2,将纸张放入真空干燥箱中,干燥温度为55℃,干燥时间为30min,制得所述单层防油纸。
(6)将15g的2,2'-联吡啶溶解在200mL无水乙醇中,配制均匀的质量分数为7.5%的2,2'-联吡啶溶液;将30g的木质素加入其中,在600rpm的转速下搅拌,70℃水浴加热1h;再加入60mL的硬酯酰氯,搅拌加热3h;反应后得到的产物用0.2mol·L-1的盐酸沉淀,在离心机中以4500rpm的转速离心15min后,再用去离子水洗涤离心产物5次;最后将产物在烘箱中90℃干燥18h,制备出改性酯化木质素。
(7)将8g改性酯化木质素和2g聚羟基丁酸酯溶解在100mL三氯甲烷中,55℃搅拌加热50min后,再经超声处理20min,制备出酯化木质素-聚羟基丁酸酯溶液。
(8)在辊式涂布机上将酯化木质素-聚羟基丁酸酯溶液均匀涂布在步骤(5)中制备的单层防油纸的正面,涂布速率为6cm/s,所述涂层的涂布量为5g/m2,将纸张放入真空干燥箱中,干燥温度为50℃,干燥时间为25min,制得所述无氟可降解防水防油包装纸。
实施例4
一种制备无氟可降解防水防油包装纸的方法,包括如下步骤:
(1)取适量氯化钙加入去离子水中,混合均匀,得到质量浓度为2.5%的氯化钙溶液;将原纸放入50mL氯化钙溶液中浸渍4min,然后将纸张放入真空干燥箱,在50℃下干燥15min,得到经氯化钙预处理的原纸。
(2)将20g漂白针叶木浆添加到TEMPO/NaClO/NaBr***(0.05g TEMPO、0.5g NaBr和50mL NaClO溶于500mL去离子水)中,用0.1mol/L HCl和NaOH调节反应体系的pH值为10中,然后在180MPa下均质化15次,得到纳米纤维素溶液;将50ml的乙醇与50ml去离子水加入到烧杯中,50℃加热搅拌30min,再加入15g的十二烷基硫酸钠,继续搅拌直到获得均匀溶液;将一定量的纤维素纳米纤维溶液加入到上述均匀溶液中,65℃加热搅拌120min,使得纤维素纳米纤维与十二烷基硫酸钠进行改性反应,得到改性后的纳米纤维素,然后将改性后的纤维素纳米纤维进行离心操作,再用去离子水洗涤以除去未反应的试剂,得到纯净的改性纳米纤维素。
(3)将200g鼠尾藻放入1L去离子水中浸泡36h,同时配制质量百分比浓度为15%的NaHCO3溶液,将浸泡后的鼠尾藻放入1L NaHCO3溶液中均匀混合1h后,放入70℃的烘箱干燥20h;干燥后的鼠尾藻经过去离子水充分洗涤,放入质量百分比浓度为1.5%的500mL乙酸溶液中,充分反应2h后,加入40mL的质量浓度为30%的H2O2溶液,反应8h后,用去离子水充分洗涤。最后,将去离子水加入到鼠尾藻产物中,然后在200MPa下均质化15次,得到纯净的鼠尾藻纳米纤维素溶液。
(4)将制备的改性纳米纤维素配制为质量浓度为8%的溶液,将制备的鼠尾藻纳米纤维素配制为质量浓度为8%的溶液,两者按照4:6的质量比进行复配,在40℃的温度下磁力搅拌30min,再超声25min制备出鼠尾藻-改性纳米纤维素。
(5)在辊式涂布机上将制备的鼠尾藻-改性纳米纤维素溶液均匀涂布在经氯化钙溶液处理的原纸正面,涂布速率为5cm/s,所述涂层的涂布量为5g/m2,将纸张放入真空干燥箱中,干燥温度为55℃,干燥时间为30min,制得所述单层防油纸。
(6)将15g的2,2'-联吡啶溶解在200mL无水乙醇中,配制均匀的质量分数为7.5%的2,2'-联吡啶溶液;将30g的木质素加入其中,在600rpm的转速下搅拌,70℃水浴加热1h;再加入60mL的硬酯酰氯,搅拌加热3h;反应后得到的产物用0.2mol·L-1的盐酸沉淀,在离心机中以4500rpm的转速离心15min后,再用去离子水洗涤离心产物5次;最后将产物在烘箱中90℃干燥18h,制备出改性酯化木质素。
(7)将4g改性酯化木质素和6g聚羟基丁酸酯溶解在100mL三氯甲烷中,55℃搅拌加热50min后,再经超声处理20min,制备出酯化木质素-聚羟基丁酸酯溶液。
(8)在辊式涂布机上将酯化木质素-聚羟基丁酸酯溶液均匀涂布在步骤(5)中制备的单层防油纸的正面,涂布速率为6cm/s,所述涂层的涂布量为6g/m2,将纸张放入真空干燥箱中,干燥温度为50℃,干燥时间为25min,制得所述无氟可降解防水防油包装纸。
对比例1
省略实施例1中制备改性纳米纤维素溶液的操作,即防油层只由鼠尾藻纳米纤维素溶液构成,其他操作和实施例1保持一致,制得无氟可降解防水防油包装纸。
对比例2
省略实施例1中制备鼠尾藻纳米纤维素溶液的操作,即防油层只由改性纳米纤维素溶液构成,其他操作和实施例1保持一致,制得无氟可降解防水防油包装纸。
对比例3
省略实施例1中的聚羟基丁酸酯的使用,即防水层只由改性酯化木质素溶液构成,其他操作和实施例1保持一致,制得无氟可降解防水防油包装纸。
对比例4
省略实施例1中的改性酯化木质素的使用,即防水层只由聚羟基丁酸酯溶液构成,其他操作和实施例1保持一致,制得无氟可降解防水防油包装纸。
对比例5
将实施例1中的防油层和防水层的涂布顺序进行调换,即内层防水层由改性酯化木质素-聚羟基丁酸酯溶液构成,外层防油层由鼠尾藻-改性纳米纤维素溶液构成,其他操作和实施例1保持一致,制得无氟可降解防水防油包装纸。
将实施例与对比例得到的防水防油包装纸进行性能测试,测试结果如下:
表1无氟可降解防水防油包装纸性能指标
从表1可以看出:
对比例1与实施例1的区别在于:防油层只涂覆了鼠尾藻纳米纤维素溶液;由于防油层并没有改性纳米纤维溶液,原纸表面孔洞并没能得到充分填充,导致防水防油纸的防油性能、抗张强度呈现下降趋势,水蒸气透过率、透气度、呈现上升趋势,防水防油纸整体性能降低。
对比例2与实施例1的区别在于:防油层只涂覆了改性纳米纤维素溶液;由于防油层并没有鼠尾藻纳米纤维素溶液,原纸表面并没有形成稳定的防油涂层,且无-COO-与纸张表面的Ca2+产生叫交联反应,导致防水防油纸的防油性能、抗张强度呈现下降趋势,水蒸气透过率、透气度、呈现上升趋势,防水防油纸整体性能降低。
对比例3与实施例1的区别在于:防水层只涂覆了改性酯化木质素溶液,并没有使用聚羟基丁酸酯溶液,导致防水防油纸的防水性能、抗张强度呈现下降趋势,水蒸气透过率、透气度、呈现上升趋势,防水防油纸整体性能降低。
对比例4与实施例1的区别在于:防水层只涂覆了聚羟基丁酸酯溶液,并没有使用改性酯化木质素溶液,导致防水防油纸的防水性能、抗张强度呈现下降趋势,水蒸气透过率、透气度、呈现上升趋势,防水防油纸整体性能降低。
对比例5与实施例1的区别在于:将防油层和防水层涂覆顺序交换,即内层为防水层,外层为防油层,由于防油层在外层,起不到防水的效果,导致防水防油纸的防水性能、抗张强度呈现下降趋势,水蒸气透过率、透气度、呈现上升趋势,防水防油纸整体性能降低。
综上,本发明的无氟可降解防水防油包装纸采用单层防油层及单层防水层,涂层与纸张结合更加紧密,具有高防油等级、高抗张强度,低水蒸气透过率、低透气度,良好的耐水性能以及降解性能。
Claims (9)
1.一种无氟可降解防水防油包装纸的制备方法,其特征在于,包括以下步骤:
(1)原纸预处理:将氯化钙加入水中,混合均匀,得到氯化钙溶液;将原纸浸入氯化钙溶液中,然后取出干燥,得到经氯化钙预处理的原纸;
(2)改性纳米纤维素制备:将漂白针叶木浆添加到TEMPO/NaClO/NaBr***中,调节pH然后均质化,得到纳米纤维素溶液;将乙醇与水混合加热搅拌,再加入十二烷基硫酸钠,继续搅拌,制得十二烷基硫酸钠溶液;将纳米纤维素溶液加入到十二烷基硫酸钠溶液中,加热搅拌,进行改性反应,得到改性后的纳米纤维素,然后将改性后的纤维素纳米纤维洗涤,超声处理,得到纯净的改性纳米纤维素溶液;
(3)鼠尾藻纳米纤维素制备:将鼠尾藻原材料在水中浸泡,配制NaHCO3溶液,将两者在混合反应后,干燥,洗涤,放入乙酸溶液反应,再向其中加入的H2O2溶液,充分反应后,洗涤,得到鼠尾藻产物;最后,加水到鼠尾藻产物中,均质化后得到鼠尾藻纳米纤维素溶液;
(4)内层防油涂层制备:将步骤(2)和步骤(3)中制备的改性纳米纤维素溶液和鼠尾藻纳米纤维素溶液复配,搅拌加热,再经超声处理,得到均匀的鼠尾藻-改性纳米纤维素溶液;
(5)第一次涂布:使用涂布机,将步骤(4)制备的鼠尾藻-改性纳米纤维素溶液涂布在步骤(1)中制得的经氯化钙溶液预处理的原纸单面,干燥后得到单层防油纸;
(6)改性酯化木质素的制备:将2,2'-联吡啶溶解在有机溶剂中配制均匀的2,2'-联吡啶溶液;将木质素加入其中,搅拌加热,再加入硬酯酰氯,搅拌加热,反应后得到的产物用酸溶液沉淀,离心,洗涤离心产物;最后干燥离心产物,制得改性酯化木质素;
(7)单层防水涂层制备:将步骤(6)中制得的改性酯化木质素和聚羟基丁酸酯溶解在三氯甲烷中,搅拌加热,再经超声处理,制得酯化木质素-聚羟基丁酸酯溶液;
(8)第二次涂布:使用涂布机,将酯化木质素-聚羟基丁酸酯溶液涂布在步骤(5)制备的单层防油纸上,干燥后得到防水防油纸;
步骤(3)所述鼠尾藻和水的质量和体积比为(100~300g):1L;所述NaHCO3溶液质量百分比浓度为10-20%;所述乙酸溶液质量百分比浓度为1-3%;所述的H2O2溶液浓度为30%。
2.根据权利要求1所述的制备方法,其特征在于,步骤(1)所述氯化钙溶液的质量百分比浓度为1-4%;所述浸入时间为3-5min;所述干燥温度为40℃-60℃;所述干燥时间为10-20min。
3.根据权利要求1所述的制备方法,其特征在于,步骤(2)所述TEMPO/NaClO/NaBr***为将TEMPO、NaBr、NaClO溶入水中;所述漂白针叶木浆和TEMPO/NaClO/NaBr***的质量和体积比为1g:(20~25)mL;所述十二烷基硫酸钠溶液的质量浓度为12~18%,纳米纤维素溶液和十二烷基硫酸钠溶液的体积比为1:(0.8~1.2)。
4.根据权利要求1所述的制备方法,其特征在于,步骤(4)所述改性纳米纤维素溶液的质量百分比浓度为2-10%;所述鼠尾藻纳米纤维素溶液的质量百分比浓度为4-10%;所述两者复配质量比为(2-8):(2-8)。
5.根据权利要求1所述的制备方法,其特征在于,步骤(5)所述的涂布机为辊式涂布机,涂布速率为2-8cm/s,涂布量为1-6g/m2;所述干燥的温度为50℃-65℃,时间为20-40min。
6.根据权利要求1所述的制备方法,其特征在于,步骤(6)所述有机溶剂为无水乙醇,所述的2,2'-联吡啶和有机溶剂的质量和体积比为(10-20g):200mL;所述的木质素和2,2'-联吡啶的质量比为10-50g:(10-20g);所述的硬酯酰氯和2,2'-联吡啶的体积和质量比为(10-150mL):(10-20g)。
7.根据权利要求1所述的制备方法,其特征在于,步骤(7)所述的改性酯化木质素和三氯甲烷的质量和体积比为(2-10)g:100mL,所述的聚羟基丁酸酯和三氯甲烷的质量和体积比为(2-10)g:100mL。
8.一种由权利要求1~7任一所述方法制备的无氟可降解防水防油包装纸,其特征在于,该包装纸有单层防油涂层和单层防水涂层;所述单层防油涂层由鼠尾藻纳米纤维素、改性纳米纤维素组成;所述单层防水涂层由改性酯化木质素和聚羟基丁酸酯组成。
9.权利要求8所述的无氟可降解防水防油包装纸在包装领域的应用。
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