CN109137540B - 一种耐水解腐蚀的聚氨酯合成革及其加工方法 - Google Patents
一种耐水解腐蚀的聚氨酯合成革及其加工方法 Download PDFInfo
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- CN109137540B CN109137540B CN201811229059.2A CN201811229059A CN109137540B CN 109137540 B CN109137540 B CN 109137540B CN 201811229059 A CN201811229059 A CN 201811229059A CN 109137540 B CN109137540 B CN 109137540B
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Abstract
本发明公开了一种耐水解腐蚀的聚氨酯合成革及其加工方法，该聚氨酯合成革采用水性聚氨酯浆液对改性竹纤维无纺布层进行浸渍，使得具有良好防水、耐腐蚀、阻燃性能的水性聚氨酯浆液在挤压作用下，充分渗透进入无纺布层的间隙中，同时在溶剂四氢呋喃的作用下凝固发泡，干燥吸纹后得到。该水性聚氨酯浆液包括：水性聚碳树脂、甲醇醚化氨基树脂、正硅酸乙酯、双季戊四醇、开孔剂、泡沫稳定剂、轻质碳酸钙、硅藻土包覆木质素磺酸钠。本发明的聚氨酯合成革表面细腻、触感舒适，保持了良好的断裂伸长率、抗拉强度、抗压强度等力学性能，在耐水、耐腐蚀环境下的耐久性好。
Description
技术领域
本发明属于人造革技术领域，具体涉及一种耐水解腐蚀的聚氨酯合成革及其加工方法。
背景技术
聚氨酯合成革属于聚氨酯弹性体的一类，由于具有光泽柔和、手感柔软、真皮感强、与基材粘接性能优异、抗磨损、耐挠曲、抗老化等优异性能，广泛应用在衣服、鞋帽、汽车内饰件、箱包手袋领域。随着向环保、节能、减排方向的发展，水性聚氨酯合成革、无溶剂聚氨酯合成革、TPU等逐渐成为该行业研究热点。
目前聚氨酯合成革的工艺化合成方法主要有干法和湿法两类。干法一般以离型纸为载体，将聚氨酯树脂浆料刮涂在离型纸上，加热烘干除去溶剂后形成连续均匀的聚氨酯薄膜，薄膜上刮涂粘结剂，与基布贴合，烘干固化后利用剥离装置将离型纸剥离并将成品人造革与离型纸分别成卷。干法制备的合成革致密、强度好、粘接牢固，但废气污染严重。湿法主要通过挤压使浆料充分渗透到非织造布间隙中，非织造布置于凝固浴中，利用“DMF-H2O”体系形成固体膜。湿法制备的合成革具有良好的透湿、透气性能，手感柔软轻盈。
目前的水性聚氨酯合成革虽然已经具备了良好的耐水解性，但是在加工过程中仍然会使用到挥发性溶剂，导致成品的VOC(挥发性有机物)含量高，而且耐酸碱腐蚀性能差，沾上水份、酸碱后会大大降低合成革的耐久性，促进聚氨酯树脂的分解反应，导致合成革表面开裂破损，大大降低了使用寿命。申请号201510761921.4的专利公开了一种水性聚氨酯合成革的制造方法，采用湿法工艺，以甲酸钙和氯化钙的混合液浸渍基布，水性表面处理和真空吸纹后整理，得到的合成革具有良好的手感和力学性能。但是研究发现，水性聚氨酯与凝聚剂、填料的相容性较差，虽然处理液中的甲酸钙和氯化钙提高了耐水性，耐腐蚀性仍有待于进一步提高。
发明内容
为了克服上述的技术问题，本发明的目的在于提供一种耐水解腐蚀的聚氨酯合成革及其加工方法，该聚氨酯合成革采用水性聚氨酯浆液对改性竹纤维无纺布层进行浸渍，使得具有良好防水、耐腐蚀、阻燃性能的水性聚氨酯浆液在挤压作用下，充分渗透进入无纺布层的间隙中，同时在良好溶剂四氢呋喃的作用下凝固发泡，干燥吸纹后得到的聚氨酯合成革表面细腻、触感舒适，保持了良好的断裂伸长率、抗拉强度、抗压强度等力学性能，在耐水、耐腐蚀环境下的牢度好。
本发明的目的可以通过以下技术方案实现：
本发明提供了一种耐水解腐蚀的聚氨酯合成革，包括改性竹纤维无纺布层，用于浸渍该改性竹炭纤维无纺布层的水性聚氨酯浆液；所述水性聚氨酯浆液包括以下重量份的成分：水性聚碳树脂100-120份、甲醇醚化氨基树脂25-36份、正硅酸乙酯12-18份、双季戊四醇6-11份、开孔剂5-12份、泡沫稳定剂3-9份、轻质碳酸钙12-20份、硅藻土包覆木质素磺酸钠8-15份；其中，所述水性聚碳树脂的100％模量为26-30MPa，粘度为200-400mPa·s，PH值为7.8，断裂伸长率为140％；所述甲醇醚化氨基树脂的粘度为5000-6000mPa·s，游离甲醛含量≤0.8％；所述泡沫稳定剂为Si-C类侧链型有机硅表面活性剂；
所述水性聚氨酯浆液的制备方法包括以下步骤：
1)混合树脂制备：将水性聚碳树脂、甲醇醚化氨基树脂加入反应釜中，盖上釜盖，使用氮气排出反应釜内的空气后再进行两次氮气吹扫，升温至70-80℃，搅拌30min后，沿加料口加入泡沫稳定剂，待体系温度降低至40-50℃后，于-0.1～-0.085MPa的真空度下真空脱泡2h得到混合树脂；
2)混料均质：向混合树脂中加入轻质碳酸钙、硅藻土包覆木质素磺酸钠，升温至45℃，搅拌均匀后加入正硅酸乙酯，再缓慢滴加开孔剂，滴加完毕后，升温至80℃，加入双季戊四醇，得到粘稠的混料体系，混料体系送入高压均质机，在15-20MPa的压力下均质5min得到该水性聚氨酯浆液。
本发明的聚氨酯合成革在水性聚氨酯浆液的原料筛选过程中，考虑到常用的水性聚碳树脂具有环保低毒、附着力强、硬度高的优点，但是耐水性差，在高温碱性条件下容易发生聚碳聚酯分子的分解，降低了产品质量。选择高固体份-低粘度、相容性好、挥发份低的甲醇醚化氨基树脂，在氮气保护的作用下发生反应。由于氨基树脂中存在高反应活性的氨基，会与水性聚碳树脂中的氨酯基发生交联反应，生成规整度高的三维交联网状大分子结构，在改善水性聚碳树脂韧性的基础上，提高了其反应活性，结构的规整性提高了抗拉强度、抗压强度等力学性能，同时由于疏水基团氨酯基的存在，保持了良好的耐水性，酸碱条件下也不容易发生水解。该三维交联网状大分子结构仍然具备聚碳树脂良好的附着性和粘结性，防火阻燃型的轻质填料轻质碳酸钙、硅藻土包覆木质素磺酸钠会填充在大分子的网状结构间和网状结构内，与混合树脂发挥复合协同作用，不仅可以发挥轻质碳酸钙受热膨胀的特性，还可以发挥硅藻土缓释木质素磺酸钠净化、抗菌除臭的作用。
作为本发明进一步的方案，所述改性竹纤维素无纺布层的制备方法包括以下步骤：
1)选用α-纤维素含量在80％以上、聚合度介于400-800的竹浆，将预先粉碎至粒径为600-1000nm的竹炭活性炭加入竹浆中，竹炭活性炭的添加量为竹浆重量的5％，搅拌均匀形成浆液，于80-100℃无菌干燥至含水量小于等于10％形成纺丝粘液；
2)纺丝粘液使用干喷湿式纺丝法进行纺丝，经凝固浴、水洗、干燥得到改性竹纤维，改性竹纤维经开松、梳理成网后，采用高针刺密度上下反复穿刺得到预成型无纺布；
3)预成型无纺布在浸渍液浸渍30-50min后，轧液烘干，得到该改性竹纤维素无纺布层。
本发明的改性竹纤维素无纺布层采用在高α-纤维素含量的竹浆中加入竹炭活性炭，α-纤维素在低浓度的强碱溶液中不容易发生溶解，且具有良好的韧性、吸附作用，良好吸附除臭性能的竹炭活性炭均匀分散在竹浆中，经过湿式纺丝得到高针高密度的无纺布层，同时由乙腈、聚乙烯吡咯烷酮、硫酸镁组成的浸渍液的浸渍，无毒环保的聚乙烯吡咯烷酮会与无纺布层的间隙相容，改善其成膜性、相容性，同时在水份存在的情况下，会生成致密的微孔，促进聚氨酯乳液在无纺布层间隙的渗透。
作为本发明进一步的方案，所述浸渍液由乙腈、聚乙烯吡咯烷酮、硫酸镁按照质量比10:0.15:3混合配制而成。
作为本发明进一步的方案，所述硅藻土包覆木质素磺酸钠的制备方法包括以下步骤：
1)硅藻土酸化：取25g的硅藻土原土，加入200g的10wt％的稀盐酸，35℃搅拌均匀，离心分离5min，过滤，干燥得到酸化硅藻土；
2)取10g木质素磺酸钠加入85g酸化硅藻土中，20-30KHz频率下超声搅拌均匀后，无菌干燥50min，送入干法辊压造粒机，在转速15-25r/min、成型压力1300KN的条件下得到粒度3-6mm的硅藻土包覆木质素磺酸钠颗粒。
本发明的硅藻土包覆木质素磺酸钠，硅藻土具有独特的壳体结构，兼具生物骨架中的大孔以及二氧化硅球体间隙构成的纳米级微孔，稀盐酸浸泡使得氢离子置换出硅藻土中的钠离子、钙离子、钾离子等大粒径离子，微孔的粒度增大，木质素磺酸钠会包覆渗透到硅藻土的骨架中。在水性聚氨酯溶液浸渍的过程中，硅藻土包覆木质素磺酸钠会降低液体界面表面张力，降低合成革的空隙率，增强合成革的强度和抗渗性。
本发明还提供了一种耐水解腐蚀的聚氨酯合成革的加工方法，包括以下步骤：
1)湿法浸渍：将改性竹纤维无纺布层浸渍在水性聚氨酯浆液的底部，相邻的改性竹纤维无纺布层间隔5-10cm，使用辊筒以20-40KPa的压力分别挤压改性竹纤维无纺布层的两面；
2)刮涂发泡：使用刮刀对浸渍后的改性竹纤维无纺布层进行刮涂处理，保留两面的浆液厚度为1-2mm，通入20wt％的四氢呋喃水溶液凝固发泡，水洗后得到多孔聚氨酯无纺布底基；
3)干燥吸纹：将多孔聚氨酯无纺布底基先于120-130℃干燥2h后，-0.09～-0.08MPa的真空度下真空吸纹得到合成革半成品，合成革半成品于160-180℃干燥5min后，冷却养护24h即可。
本发明的聚氨酯合成革的加工方法，并没有采用常见的聚氨酯浆液刮涂工艺，而是采用湿法浸渍将水性聚氨酯浆液浸渍在改性纤维无纺布层中，保持无纺布层的间距，同时压力均匀地挤压无纺布层的两面，有利于浆液渗透和粘附在无纺布层的间隙内和表面；然后使用无毒溶剂四氢呋喃使浆液凝固发泡；最后干燥、真空吸纹得到，避免了传统的转移膜贴合、离型纸剥离的工艺，制备得到的聚氨酯合成革表面细腻、触感舒适、透气性好。
本发明的有益效果：
1、本发明的聚氨酯合成革采用水性聚氨酯浆液对改性竹纤维无纺布层进行浸渍，使得具有良好防水、耐腐蚀、阻燃性能的水性聚氨酯浆液在挤压作用下，充分渗透进入无纺布层的间隙中，同时在良好溶剂四氢呋喃的作用下凝固发泡，干燥吸纹后得到的聚氨酯合成革表面细腻、触感舒适，保持了良好的断裂伸长率、抗拉强度、抗压强度等力学性能，在耐水、耐腐蚀环境下牢度好。
2、本发明的水性聚氨酯浆液，选择高固体份-低粘度、相容性好、挥发份低的甲醇醚化氨基树脂，在氮气保护的作用下发生反应，生成规整度高的三维交联网状大分子结构，在改善水性聚碳树脂韧性的基础上，提高了其反应活性，结构的规整性提高了抗拉强度、抗压强度等力学性能，同时由于疏水基团氨酯基的存在，保持了良好的耐水性，酸碱条件下也不容易发生水解；防火阻燃型的轻质填料轻质碳酸钙、硅藻土包覆木质素磺酸钠会填充在大分子的网状结构间和网状结构内，不仅可以发挥轻质碳酸钙受热膨胀的特性，还可以发挥硅藻土缓释木质素磺酸钠净化、抗菌除臭的作用。
3、本发明的改性竹纤维素无纺布层，采用在高α-纤维素含量的竹浆中加入竹炭活性炭，α-纤维素在低浓度的强碱溶液中不容易发生溶解，且具有良好的韧性、吸附作用，良好吸附除臭性能的竹炭活性炭均匀分散在竹浆中，经过湿式纺丝得到高针高密度的无纺布层，同时由于浸渍液的浸渍，聚乙烯吡咯烷酮会与无纺布层的间隙相容，改善其成膜性、相容性，生成致密的微孔，促进聚氨酯乳液在无纺布层间隙的渗透。
具体实施方式
下面将结合本发明实施例，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其它实施例，都属于本发明保护的范围。
实施例1
一种耐水解腐蚀的聚氨酯合成革，包括改性竹纤维无纺布层，用于浸渍该改性竹炭纤维无纺布层的水性聚氨酯浆液。水性聚氨酯浆液包括以下重量份的成分：水性聚碳树脂107份、甲醇醚化氨基树脂32份、正硅酸乙酯16份、双季戊四醇9份、开孔剂9份、泡沫稳定剂6份、轻质碳酸钙15份、硅藻土包覆木质素磺酸钠12份。其中，所述水性聚碳树脂的100％模量为26-30MPa，粘度为200-400mPa·s，PH值为7.8，断裂伸长率为140％；所述甲醇醚化氨基树脂的粘度为5000-6000mPa·s，游离甲醛含量≤0.8％；所述泡沫稳定剂为Si-C类侧链型有机硅表面活性剂。
所述水性聚氨酯浆液的制备方法包括以下步骤：
1)混合树脂制备：将水性聚碳树脂、甲醇醚化氨基树脂加入反应釜中，盖上釜盖，使用氮气排出反应釜内的空气后再进行两次氮气吹扫，升温至70-80℃，搅拌30min后，沿加料口加入泡沫稳定剂，待体系温度降低至40-50℃后，于-0.1～-0.085MPa的真空度下真空脱泡2h得到混合树脂；
2)混料均质：向混合树脂中加入轻质碳酸钙、硅藻土包覆木质素磺酸钠，升温至45℃，搅拌均匀后加入正硅酸乙酯，再缓慢滴加开孔剂，滴加完毕后，升温至80℃，加入双季戊四醇，得到粘稠的混料体系，混料体系送入高压均质机，在15-20MPa的压力下均质5min得到该水性聚氨酯浆液。
所述改性竹纤维素无纺布层的制备方法包括以下步骤：
1)选用α-纤维素含量在80％以上、聚合度介于400-800的竹浆，将预先粉碎至粒径为600-1000nm的竹炭活性炭加入竹浆中，竹炭活性炭的添加量为竹浆重量的5％，搅拌均匀形成浆液，于80-100℃无菌干燥至含水量小于等于10％形成纺丝粘液；
2)纺丝粘液使用干喷湿式纺丝法进行纺丝，经凝固浴、水洗、干燥得到改性竹纤维，改性竹纤维经开松、梳理成网后，采用高针刺密度上下反复穿刺得到预成型无纺布；
3)预成型无纺布在浸渍液浸渍30-50min后，轧液烘干，得到该改性竹纤维素无纺布层。其中，浸渍液由乙腈、聚乙烯吡咯烷酮、硫酸镁按照质量比10:0.15:3混合配制而成。
所述硅藻土包覆木质素磺酸钠的制备方法包括以下步骤：
1)硅藻土酸化：取25g的硅藻土原土，加入200g的10wt％的稀盐酸，35℃搅拌均匀，离心分离5min，过滤，干燥得到酸化硅藻土；
2)取10g木质素磺酸钠加入85g酸化硅藻土中，20-30KHz频率下超声搅拌均匀后，无菌干燥50min，送入干法辊压造粒机，在转速15-25r/min、成型压力1300KN的条件下得到粒度3-6mm的硅藻土包覆木质素磺酸钠颗粒。
本实施例耐水解腐蚀的聚氨酯合成革的加工方法，包括以下步骤：
1)湿法浸渍：将改性竹纤维无纺布层浸渍在水性聚氨酯浆液的底部，相邻的改性竹纤维无纺布层间隔5-10cm，使用辊筒以20-40KPa的压力分别挤压改性竹纤维无纺布层的两面；
2)刮涂发泡：使用刮刀对浸渍后的改性竹纤维无纺布层进行刮涂处理，保留两面的浆液厚度为1-2mm，通入20wt％的四氢呋喃水溶液凝固发泡，水洗后得到多孔聚氨酯无纺布底基；
3)干燥吸纹：将多孔聚氨酯无纺布底基先于126℃干燥2h后，-0.09～-0.08MPa的真空度下真空吸纹得到合成革半成品，合成革半成品于175℃干燥5min后，冷却养护24h即可。
实施例2
一种耐水解腐蚀的聚氨酯合成革，包括改性竹纤维无纺布层，用于浸渍该改性竹炭纤维无纺布层的水性聚氨酯浆液。水性聚氨酯浆液包括以下重量份的成分：水性聚碳树脂112份、甲醇醚化氨基树脂29份、正硅酸乙酯15份、双季戊四醇10份、开孔剂10份、泡沫稳定剂8份、轻质碳酸钙19份、硅藻土包覆木质素磺酸钠13份。其中，所述水性聚碳树脂的100％模量为26-30MPa，粘度为200-400mPa·s，PH值为7.8，断裂伸长率为140％；所述甲醇醚化氨基树脂的粘度为5000-6000mPa·s，游离甲醛含量≤0.8％；所述泡沫稳定剂为Si-C类侧链型有机硅表面活性剂。
所述水性聚氨酯浆液的制备方法与实施例1相同。
所述改性竹纤维素无纺布层的制备方法与实施例1相同。
所述硅藻土包覆木质素磺酸钠的制备方法与实施例1相同。
本实施例耐水解腐蚀的聚氨酯合成革的加工方法，包括以下步骤：
1)湿法浸渍：将改性竹纤维无纺布层浸渍在水性聚氨酯浆液的底部，相邻的改性竹纤维无纺布层间隔5-10cm，使用辊筒以20-40KPa的压力分别挤压改性竹纤维无纺布层的两面；
2)刮涂发泡：使用刮刀对浸渍后的改性竹纤维无纺布层进行刮涂处理，保留两面的浆液厚度为1-2mm，通入20wt％的四氢呋喃水溶液凝固发泡，水洗后得到多孔聚氨酯无纺布底基；
3)干燥吸纹：将多孔聚氨酯无纺布底基先于128℃干燥2h后，-0.09～-0.08MPa的真空度下真空吸纹得到合成革半成品，合成革半成品于178℃干燥5min后，冷却养护24h即可。
实施例3
一种耐水解腐蚀的聚氨酯合成革，包括改性竹纤维无纺布层，用于浸渍该改性竹炭纤维无纺布层的水性聚氨酯浆液。水性聚氨酯浆液包括以下重量份的成分：水性聚碳树脂102份、甲醇醚化氨基树脂30份、正硅酸乙酯15份、双季戊四醇7份、开孔剂11份、泡沫稳定剂8份、轻质碳酸钙18份、硅藻土包覆木质素磺酸钠13份。其中，所述水性聚碳树脂的100％模量为26-30MPa，粘度为200-400mPa·s，PH值为7.8，断裂伸长率为140％；所述甲醇醚化氨基树脂的粘度为5000-6000mPa·s，游离甲醛含量≤0.8％；所述泡沫稳定剂为Si-C类侧链型有机硅表面活性剂。
所述水性聚氨酯浆液的制备方法与实施例1相同。
所述改性竹纤维素无纺布层的制备方法与实施例1相同。
所述硅藻土包覆木质素磺酸钠的制备方法与实施例1相同。
本实施例耐水解腐蚀的聚氨酯合成革的加工方法，包括以下步骤：
1)湿法浸渍：将改性竹纤维无纺布层浸渍在水性聚氨酯浆液的底部，相邻的改性竹纤维无纺布层间隔5-10cm，使用辊筒以20-40KPa的压力分别挤压改性竹纤维无纺布层的两面；
2)刮涂发泡：使用刮刀对浸渍后的改性竹纤维无纺布层进行刮涂处理，保留两面的浆液厚度为1-2mm，通入20wt％的四氢呋喃水溶液凝固发泡，水洗后得到多孔聚氨酯无纺布底基；
3)干燥吸纹：将多孔聚氨酯无纺布底基先于130℃干燥2h后，-0.09～-0.08MPa的真空度下真空吸纹得到合成革半成品，合成革半成品于170℃干燥5min后，冷却养护24h即可。
实施例4
一种耐水解腐蚀的聚氨酯合成革，包括改性竹纤维无纺布层，用于浸渍该改性竹炭纤维无纺布层的水性聚氨酯浆液。水性聚氨酯浆液包括以下重量份的成分：水性聚碳树脂118份、甲醇醚化氨基树脂35份、正硅酸乙酯18份、双季戊四醇11份、开孔剂12份、泡沫稳定剂9份、轻质碳酸钙20份、硅藻土包覆木质素磺酸钠14份。其中，所述水性聚碳树脂的100％模量为26-30MPa，粘度为200-400mPa·s，PH值为7.8，断裂伸长率为140％；所述甲醇醚化氨基树脂的粘度为5000-6000mPa·s，游离甲醛含量≤0.8％；所述泡沫稳定剂为Si-C类侧链型有机硅表面活性剂。
所述水性聚氨酯浆液的制备方法与实施例1相同。
所述改性竹纤维素无纺布层的制备方法与实施例1相同。
所述硅藻土包覆木质素磺酸钠的制备方法与实施例1相同。
本实施例耐水解腐蚀的聚氨酯合成革的加工方法，包括以下步骤：
1)湿法浸渍：将改性竹纤维无纺布层浸渍在水性聚氨酯浆液的底部，相邻的改性竹纤维无纺布层间隔5-10cm，使用辊筒以20-40KPa的压力分别挤压改性竹纤维无纺布层的两面；
2)刮涂发泡：使用刮刀对浸渍后的改性竹纤维无纺布层进行刮涂处理，保留两面的浆液厚度为1-2mm，通入20wt％的四氢呋喃水溶液凝固发泡，水洗后得到多孔聚氨酯无纺布底基；
3)干燥吸纹：将多孔聚氨酯无纺布底基先于130℃干燥2h后，-0.09～-0.08MPa的真空度下真空吸纹得到合成革半成品，合成革半成品于168℃干燥5min后，冷却养护24h即可。
对比例1
与实施例1的区别在于，本对比例的聚氨酯合成革中水性聚氨酯浆液中缺少甲醇醚化氨基树脂的添加，制备方法相同。
对比例2
与实施例1的区别在于，本对比例的聚氨酯合成革中改性竹纤维无纺布层采用聚丙烯纤维制成的无纺布层，制备方法相同。
对比例3
与实施例1的区别在于，本对比例的聚氨酯合成革中缺少硅藻土包覆木质素磺酸钠的添加，制备方法相同。
对比例4
参照申请号201510761921.4的专利中实施例1制备的水性聚氨酯合成革。
性能测试
参照行业标准CAB1001-2013《水性聚氨酯合成革》，本标准适用于以基布、水性聚氨酯树脂等为主要原料，经湿法或干法加工工艺制成的水性聚氨酯合成革。将实施例、对比例制备的聚氨酯合成革裁剪成3cm×3cm的尺寸，通过该标准进行断裂伸长率、拉伸负荷、撕裂负荷、耐水收缩率的测试。耐腐蚀性分别采用40wt％的氢氧化钠溶液和20wt％的盐酸溶液浸泡合成革，记录表面发生明显破裂的时间。具体测试结果见下表：
由上表可以看出，本发明实施例的聚氨酯合成革与对比例相比，在断裂伸长率、拉伸负荷、撕裂负荷等力学性能方面较优异，耐水收缩率较低，说明耐水性好，对强酸、强碱的耐腐蚀性较好。对比例1由于缺少甲醇醚化氨基树脂，附着性、粘结性较低，无法与聚碳树脂形成规整的网状大分子结构，在力学性能、耐水耐腐蚀性上降低显著；对比例2由于采用聚丙烯纤维制成的无纺布层，不具备改性竹纤维无纺布层的良好吸附除臭效果，水性聚氨酯浆液的渗透性降低，聚氨酯浆液无法完全渗透入无纺布间隙中，使得力学性能、耐水性、耐腐蚀性大大降低；对比例3由于缺少硅藻土包覆木质素磺酸钠，无法通过硅藻土、木质素磺酸钠的粘结性和吸附性增加合成革的强度、抗渗透性，耐水、耐腐蚀性能上有一定的降低。
在本说明书的描述中，参考术语“一个实施例”、“示例”、“具体示例”等的描述意指结合该实施例或示例描述的具体特征、结构、材料或者特点包含于本发明的至少一个实施例或示例中。在本说明书中，对上述术语的示意性表述不一定指的是相同的实施例或示例。而且，描述的具体特征、结构、材料或者特点可以在任何的一个或多个实施例或示例中以合适的方式结合。
以上内容仅仅是对本发明所作的举例和说明，所属本技术领域的技术人员对所描述的具体实施例做各种各样的修改或补充或采用类似的方式替代，只要不偏离发明或者超越本权利要求书所定义的范围，均应属于本发明的保护范围。
Claims (5)
1.一种耐水解腐蚀的聚氨酯合成革，其特征在于，包括改性竹纤维素无纺布层，用于浸渍该改性竹纤维素无纺布层的水性聚氨酯浆液；所述水性聚氨酯浆液包括以下重量份的成分：水性聚碳树脂100-120份、甲醇醚化氨基树脂25-36份、正硅酸乙酯12-18份、双季戊四醇6-11份、开孔剂5-12份、泡沫稳定剂3-9份、轻质碳酸钙12-20份、硅藻土包覆木质素磺酸钠8-15份；其中，所述水性聚碳树脂的100%模量为26-30MPa，粘度为200-400mPa·s，pH值为7.8，断裂伸长率为140%；所述甲醇醚化氨基树脂的粘度为5000-6000mPa·s，游离甲醛含量≤0.8%；所述泡沫稳定剂为Si-C类侧链型有机硅表面活性剂；
所述水性聚氨酯浆液的制备方法包括以下步骤：
混合树脂制备：将水性聚碳树脂、甲醇醚化氨基树脂加入反应釜中，盖上釜盖，使用氮气排出反应釜内的空气后再进行两次氮气吹扫，升温至70-80℃，搅拌30min后，沿加料口加入泡沫稳定剂，待体系温度降低至40-50℃后，于-0.1~-0.085MPa的真空度下真空脱泡2h得到混合树脂；
混料均质：向混合树脂中加入轻质碳酸钙、硅藻土包覆木质素磺酸钠，升温至45℃，搅拌均匀后加入正硅酸乙酯，再缓慢滴加开孔剂，滴加完毕后，升温至80℃，加入双季戊四醇，得到粘稠的混料体系，混料体系送入高压均质机，在15-20MPa的压力下均质5min得到该水性聚氨酯浆液。
2.根据权利要求1所述的耐水解腐蚀的聚氨酯合成革，其特征在于，所述改性竹纤维素无纺布层的制备方法包括以下步骤：
1）选用α-纤维素含量在80%以上、聚合度介于400-800的竹浆，将预先粉碎至粒径为600-1000nm的竹炭活性炭加入竹浆中，竹炭活性炭的添加量为竹浆重量的5%，搅拌均匀形成浆液，于80-100℃无菌干燥至含水量小于等于10%形成纺丝粘液；
2）纺丝粘液使用干喷湿式纺丝法进行纺丝，经凝固浴、水洗、干燥得到改性竹纤维，改性竹纤维经开松、梳理成网后，采用高针刺密度上下反复穿刺得到预成型无纺布；
3）预成型无纺布在浸渍液浸渍30-50min后，轧液烘干，得到该改性竹纤维素无纺布层。
3.根据权利要求2所述的耐水解腐蚀的聚氨酯合成革，其特征在于，所述浸渍液由乙腈、聚乙烯吡咯烷酮、硫酸镁按照质量比10:0.15:3混合配制而成。
4.根据权利要求1所述的耐水解腐蚀的聚氨酯合成革，其特征在于，所述硅藻土包覆木质素磺酸钠的制备方法包括以下步骤：
1）硅藻土酸化：取25g的硅藻土原土，加入200g的10wt%的稀盐酸，35℃搅拌均匀，离心分离5min，过滤，干燥得到酸化硅藻土；
2）取10g木质素磺酸钠加入85g酸化硅藻土中，20-30kHz频率下超声搅拌均匀后，无菌干燥50min，送入干法辊压造粒机，在转速15-25r/min、成型压力1300kN的条件下得到粒度3-6mm的硅藻土包覆木质素磺酸钠颗粒。
5.根据权利要求1-4任一项所述的耐水解腐蚀的聚氨酯合成革的加工方法，其特征在于，包括以下步骤：
1）湿法浸渍：将改性竹纤维素无纺布层浸渍在水性聚氨酯浆液的底部，相邻的改性竹纤维素无纺布层间隔5-10cm，使用辊筒以20-40kPa的压力分别挤压改性竹纤维素无纺布层的两面；
2）刮涂发泡：使用刮刀对浸渍后的改性竹纤维素无纺布层进行刮涂处理，保留两面的浆液厚度为1-2mm，通入20wt%的四氢呋喃水溶液凝固发泡，水洗后得到多孔聚氨酯无纺布底基；
3）干燥吸纹：将多孔聚氨酯无纺布底基先于120-130℃干燥2h后，-0.09~-0.08MPa的真空度下真空吸纹得到合成革半成品，合成革半成品于160-180℃干燥5min后，冷却养护24h即可。
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