CN116574300A - 一种长效抗菌的聚乙烯醇缩醛海绵及其制备方法 - Google Patents
一种长效抗菌的聚乙烯醇缩醛海绵及其制备方法 Download PDFInfo
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- CN116574300A CN116574300A CN202310535930.6A CN202310535930A CN116574300A CN 116574300 A CN116574300 A CN 116574300A CN 202310535930 A CN202310535930 A CN 202310535930A CN 116574300 A CN116574300 A CN 116574300A
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- antibacterial
- sponge
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- polyvinyl alcohol
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- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 4
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- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 claims description 3
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- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical compound C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
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- A61L15/46—Deodorants or malodour counteractants, e.g. to inhibit the formation of ammonia or bacteria
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- A—HUMAN NECESSITIES
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Abstract
本发明公开了一种长效抗菌的聚乙烯醇缩醛海绵及其制备方法。本发明利用缩醛反应在海绵中引入阳离子或者两性离子，使海绵具有长效抗菌功能。在高温和引发剂条件下，含有羟基的不饱和单体和具有阳离子或两性离子的烯烃不饱和单体发生聚合反应得到抗菌聚合物。再通过抗菌聚合物的羟基与醛基发生缩醛反应结合在海绵中。通过缩醛反应向海绵中引入抗菌基团不仅使海绵具备了长期抗菌性能，还提升了海绵的亲水性能。该方法制备海绵具有适宜的孔径结构，干态浸润速度快，吸水倍率高，具有长效抗菌性能。可以应用于日常生活，美容，医用材料等多个领域。
Description
技术领域
本发明属于高分子材料改性合成领域，具体是一种长效抗菌的聚乙烯醇缩醛海绵及其制备方法。
背景技术
近年来，随着人们健康环保意识的增强和生活水平的提高，具有抗菌功能的材料得到了越来越多的关注，以满足人们的使用需求。聚乙烯醇泡沫塑料具有发泡可控、良好的力学性能、亲水性以及化学及生物稳定性优异等特点，已经被广泛应用于包装材料，清洁美容材料，医用材料和特种用途材料。为了满足进一步的应用需求，有必要为聚乙烯醇海绵增加抗菌功能。目前聚乙烯醇海绵在医用材料领域得到广泛应用，例如PVA海绵敷料作为功能性敷料的一种，PVA海绵敷料具有以下优点：可快速吸收伤口渗液，减少伤口周围皮肤浸渍；为伤口提供湿润环境，使伤口不会形成结痂，加速伤口愈合；柔软舒适透气性好，可塑性好，适合身体各个部位；更换敷料时不造成二次损伤等。但是目前的聚乙烯醇海绵抗菌敷料功能单一，伤口容易被细菌感染造成二次损伤。因此必须研究开发具有良好抗菌功能的PVA海绵材料。专利CN101927029A《一种含纳米银的壳聚糖/聚乙烯醇海绵敷料的制备方法》中采用聚乙二醇还原银离子得到纳米银颗粒，得到纳米银溶液，再将该溶液与聚乙烯醇/壳聚糖醇溶液共混，往其中加入十二烷基硫酸钠、甲醛、碳酸氢钠和酸后高速搅拌发泡后，放入50-60℃烘箱固化一段时间后，得到壳聚糖/缩醛化聚乙烯醇医用敷料。通过物理共混的方法将纳米银颗粒引入壳聚糖/PVA复合海绵。含银的壳聚糖/PVA复合海绵可作为生物敷料使用，纳米银在与创面伤口接触时在伤口渗出液的作用下释放析出，达到杀灭细菌的目的，但是这一过程存在随着时间延长抗菌剂浓度降低，抗菌持久性差的问题，另一方面，纳米银的过量释放易对人体造成危害，安全性不确定。专利CN114106400A《一种氮丙啶交联N卤胺型抗菌PVA海绵及其制备方法与应用》将聚乙烯醇进行改性，再将改性后含碳氯键和羧基的聚乙烯醇和1-氯-2,2,5,5-四甲基-4-咪唑啉酮反应，得到含卤胺基团的PVA分子，进一步采用氮丙啶交联剂交联并乳化成型后，经过冷冻干燥获得N卤胺型抗菌PVA海绵，通过该制备方法可以得到具有长效抗菌的聚乙烯醇缩醛海绵。该种方法得到的海绵往往改性后聚乙烯醇对海绵性能产生影响，工艺过程复杂，生产成本高。Shi等人(Kai Shi,Xu Yang,Jiuduo Xu,DiSha,Baolong Wang,Xue Liu,Zhi Liu,Xiangling Ji,Reactive and FunctionalPolymers,Volume 164,2021,104916,)将制备好的聚乙烯醇缩醛海绵通过硫酸钾/六水硫酸铁(II)铵氧化还原引发体系将PDMAEMA段引入PVF骨架中，得到了具有双温度/pH响应性的PVF-g-PDMAEMA大孔水凝胶。由革兰氏阴性菌(大肠杆菌)和革兰氏阳性菌(金黄色葡萄球菌)抗菌实验测定材料的性能，发现该凝胶具有优异的抑菌活性。但是整个生产工艺复杂，周期长、对海绵自身的三维结构进行部分破坏，海绵性能发生变化。同样也不利于市面推广与应用。
发明内容
针对目前抗菌聚乙烯醇海绵存在的制作工艺复杂，抗菌持久性差，无机抗菌剂生物安全性差等问题，本发明设计并实现了一种长效抗菌的聚乙烯醇缩醛海绵。
本发明的目的在于提供一种长效抗菌的聚乙烯醇缩醛海绵及其制备方法，通过缩醛反应在海绵上接枝阳离子或两性离子，使海绵获得持久的抗菌性能。解决了目前海绵抗菌周期短、生物安全性低、改性操作复杂的不足。
本发明制备的聚乙烯醇海绵除了具备长效抗菌功能之外，由于具有抗菌功能的基团亲水性高，使海绵的浸润速率进一步提高，吸液量提升，因而可以应用于伤口敷料、止血材料、清洁、美容等多个领域。
本发明的目的通过以下技术方案实现。
一种长效抗菌的聚乙烯醇缩醛海绵的制备方法，具体包括以下制备步骤：
向聚乙烯醇中加入一定量蒸馏水，加热至90-95℃搅拌1-3h，得到聚乙烯醇水溶液；然后往其中加入含有羟基的抗菌材料、成孔剂/发泡剂、稳泡剂、固化剂、催化剂，搅拌均匀后将混合液倒入模具中，放入烘箱于50-80℃固化1-10小时，在海绵固化成型的过程中抗菌材料的羟基与醛基反应，将具有阳离子或两性离子的抗菌材料接枝在海绵上，反应结束后将海绵取出洗净，得到具有长效抗菌功能的聚乙烯醇缩醛海绵；
所述含有羟基的抗菌材料为含有羟基的抗菌单体，或者是由含有羟基的烯烃单体和含有阳离子或两性离子的烯烃不饱和单体通过引发剂引发双键自由基聚合反应生成的含有羟基的抗菌聚合物。
进一步地，所述的含有羟基的抗菌单体为三羟甲基氨基甲烷盐酸盐、4-羟基-2,2,6,6-四甲基哌啶、3-羟基吡啶、3-(N-吗啉基)-2-羟基丙磺酸钠、3-氯-2-羟丙基三甲基氯化铵中的一种或多种。
进一步地，所述含有羟基的烯烃单体为N-羟甲基丙烯酰胺、1,4-丁烯二醇、2-丁烯-1,4-二醇、N-(2-羟乙基)丙烯酰胺、甲基丙烯酸羟乙酯中的一种或多种；
所述的含有阳离子或两性离子的烯烃不饱和单体为甲基丙烯酸二甲氨乙酯、磺酸甜菜碱甲基丙烯酸酯(SBMA)、羧酸甜菜碱甲基丙烯酸酯、2-甲基丙烯酰氧乙基磷酸胆碱、二烯丙基二甲基氯化铵(DMDAAC)、丙烯酰氧乙基三甲基氯化铵、甲基丙烯酰氧乙基三甲基氯化铵中的一种或多种；
所述的引发剂为过硫酸钾、过硫酸铵、亚硫酸氢钠中的一种或多种。
进一步地，所述含有羟基的烯烃单体和所述的含有阳离子或两性离子的烯烃不饱和单体的摩尔比为1.0:(1.0-4.0)；含有羟基的烯烃单体和所述的含有阳离子或两性离子的烯烃不饱和单体的总质量与引发剂的质量比为1.0:(0.001-0.01)。
进一步地，所述聚合反应的反应温度为30-80℃，反应时间为3-10h。
进一步地，所述聚乙烯醇的聚合度为1700-2400、醇解度为88mol％-99mol％；所得聚乙烯醇水溶液的质量浓度为8％-16.67％。
进一步地，所述的成孔剂为淀粉、纤维素中的一种或多种；所述的发泡剂为曲拉通X-100、OP-10、吐温80、司盘80、十二烷基硫酸钠、十二烷基苯磺酸钠、碳酸氢钠、碳酸钠、碳酸氢铵、硼氢化钠中的一种或多种。
进一步地，所述的稳泡剂为十二烷基二甲基氧化胺、烷基醇胺、硅树脂聚醚乳液、硅油、L-580中的一种或多种。
进一步地，所述的固化剂为甲醛、乙醛、丙醛、丁醛、戊二醛中的一种或多种。
进一步地，所述的催化剂为硫酸、盐酸、硝酸中的一种或多种。
进一步地，上述各反应物配比关系如下：
含有羟基的抗菌材料总质量为聚乙烯醇质量的10％-93.3％；
发泡剂的用量为聚乙烯醇质量的3.33％-10.0％；
固化剂的用量为聚乙烯醇质量的31.31％-100.00％；
稳泡剂的用量为聚乙烯醇质量的0.2％-1％；
催化剂的用量为聚乙烯醇质量的5％-90％。
或者
含有羟基的抗菌材料总质量为聚乙烯醇质量的10％-93.3％；
成孔剂的用量为聚乙烯醇质量的3.33％-10.0％；
固化剂的用量为聚乙烯醇质量的50.00％-100.00％；
催化剂的用量为聚乙烯醇质量的5％-90％。
本发明所述的一种具有长效抗菌性能的聚乙烯醇缩醛海绵，通过以上方法制备得到。
本发明中使用的含有羟基的抗菌单体(如三羟甲基氨基甲烷盐酸盐)具有适宜的碳链结构和碳原子数目，该单体在溶液中具有优异的溶解性并且具有优异的抗菌活性；本发明中使用的具有阳离子基团的抗菌单体(如甲基丙烯酸二甲氨乙酯)具有广谱抗菌性能，并且适应范围广，细胞毒性小；本发明中使用的具有阴离子基团和氨基阳离子的抗菌单体(如二烯丙基二甲基氯化铵)具有抗污性能、高生物相容性和抗菌性能，具有显著优势。
本发明相对于现有技术具有益以下优点和有益效果：
(1)本发明通过缩醛反应在聚乙烯醇海绵上引入阳离子或两性离子抗菌基团，制备成的聚乙烯醇缩醛海绵有良好的本体抗菌性能并长久保持材料抗菌性。
(2)本发明的长效抗菌聚乙烯醇缩醛海绵具有安全无毒的特点，对皮肤不造成伤害，材料具有良好的抗菌性能、浸润速率快和良好的吸液性，可以应用于日常生活，美容，医用材料等多个领域，特别适合作为止血材料和创伤敷料使用。
(3)本发明的聚乙烯醇海绵抗菌功能在海绵制备过程中实现，不需要对海绵材料进行二次处理，制备工艺简单，克服现有抗菌聚乙烯醇海绵制备需额外浸泡并干燥的复杂工艺。
(4)本发明的抗菌聚乙烯醇海绵制备工艺过程简单，无需后处理，制作过程绿色环保，产品制造成本低。
附图说明
图1为实施例4中制备的长效抗菌的聚乙烯醇缩醛海绵的内部形貌扫描电子显微镜照片。
图2为实施例4中制备的长效抗菌的聚乙烯醇缩醛海绵的傅里叶红外光谱图。
图3为实施例4中制备的长效抗菌的聚乙烯醇缩醛海绵的干态表面水渗透动态图。
图4为实施例7中制备的长效抗菌的聚乙烯醇缩醛海绵的长效抗菌实验测试结果图。
具体实施方式
下面对本发明的较佳实施例进行详细阐述，以使本发明的优点和特征能更易于被本领域技术人员理解，从而对本发明的保护范围做出更为清楚明确的界定。
实施例1
向2.4g聚合度为1700、醇解度为99％的聚乙烯醇1799聚乙烯醇中加入27.6g蒸馏水，加热至90℃搅拌1h，得到聚乙烯醇水溶液，然后加入0.3g抗菌材料三羟甲基氨基甲烷盐酸盐，2.16g盐酸溶液、0.96g成孔剂淀粉、1.2g甲醛溶液，搅拌均匀后将混合液倒入模具中，放入60℃烘箱固化7h，在海绵固化成型的过程中抗菌材料的羟基与醛基反应，使海绵上负载阳离子基团，即将阳离子抗菌材料接枝在海绵上，反应结束后将海绵取出洗净，得到具有长效抗菌功能的聚乙烯醇缩甲醛海绵。
按照GB/T 20944.3-2008《纺织品抗菌性能的评价》标准，采用振荡法测试海绵的抗菌性能，经过测试可以得出聚乙烯醇缩甲醛抗菌材料对大肠杆菌和金黄色葡萄球菌的抑菌率在95％以上。对该海绵进行吸水测试，发现该海绵浸润速度快，吸水倍率达到7.79g/g。
实施例2
向3g聚合度为1700、醇解度为88％的聚乙烯醇1788聚乙烯醇中加入27g蒸馏水，加热至90℃搅拌2h，得到聚乙烯醇水溶液，然后加入0.5g抗菌材料3-氯-2-羟丙基三甲基氯化铵，1.5g硫酸溶液、0.7g成孔剂纤维素、2.6g丙醛溶液，搅拌均匀后将混合液倒入模具中，放入55℃烘箱固化6h，在海绵固化成型的过程中抗菌材料的羟基与醛基反应，将阳离子抗菌材料接枝在海绵上，反应结束后将海绵取出洗净，得到具有长效抗菌功能的聚乙烯醇缩丙醛海绵。
按照GB/T 20944.3-2008《纺织品抗菌性能的评价》标准，采用振荡法测试海绵的抗菌性能，经过测试可以得出聚乙烯醇缩丙醛抗菌材料对大肠杆菌和金黄色葡萄球菌的抑菌率在97％以上。对该海绵进行吸水测试，发现该海绵浸润速度快，吸水倍率到达8.87g/g。
实施例3
向3.15g聚合度为1700、醇解度为88％的聚乙烯醇1788聚乙烯醇中加入31.85g蒸馏水，加热至92℃搅拌1h，得到聚乙烯醇水溶液，然后加入1.26g抗菌材料3-(N-吗啉基)-2-羟基丙磺酸钠，0.5g硫酸溶液、0.45g成孔剂淀粉和0.09发泡剂十二烷基硫酸钠、2.8g丁醛溶液和0.35g戊二醛，搅拌均匀后将混合液倒入模具中，放入60℃烘箱固化3h，在海绵固化成型的过程中抗菌材料的羟基与醛基反应，将两性离子抗菌材料接枝在海绵上，反应结束后将海绵取出洗净，得到具有长效抗菌功能的聚乙烯醇缩丁醛海绵。
按照GB/T 20944.3-2008《纺织品抗菌性能的评价》标准，采用振荡法测试海绵的抗菌性能，经过测试可以得出聚乙烯醇缩丁醛抗菌材料对大肠杆菌和金黄色葡萄球菌的抑菌率在99.9％以上。对该海绵进行吸水测试，发现该海绵浸润速度快，吸水倍率到达9.80g/g。
实施例4
向3.92g聚合度为1700、醇解度为99％的聚乙烯醇1799聚乙烯醇中加入28.08g蒸馏水，加热至95℃搅拌1h，得到聚乙烯醇水溶液，然后加入总量为1.0014g含有羟基的抗菌聚合物，0.7g硫酸溶液、0.3g发泡剂曲拉通X-100、0.0078g稳泡剂十二烷基二甲基氧化胺、2.0g固化剂丙醛，搅拌均匀后将混合液倒入模具中，放入70℃烘箱固化1h，在海绵固化成型的过程中抗菌材料的羟基与醛基反应，将抗菌材料接枝在海绵上，反应结束后将海绵取出洗净，得到具有长效抗菌功能的聚乙烯醇缩丙醛海绵。
其中，所述含有羟基的抗菌聚合物为0.3031g N-羟甲基丙烯酰胺和0.6983g磺酸甜菜碱甲基丙烯酸酯(SBMA)在0.006g过硫酸钾的引发下于50℃反应3h得到。
按照GB/T 20944.3-2008《纺织品抗菌性能的评价》标准，采用振荡法测试海绵的抗菌性能，经过测试可以得出聚乙烯醇缩甲醛抗菌材料对大肠杆菌和金黄色葡萄球菌的抑菌率在99％以上。对该海绵进行吸水测试，发现该海绵浸润速度快，吸水倍率到达9.85g/g。
图1为实施例4中制备的长效抗菌的聚乙烯醇缩丙醛海绵的内部形貌扫描电子显微镜照片，可以看出，该海绵孔径均匀，具有优异的三维孔状结构，多数为通孔，孔径在0.05mm～0.1mm左右。
图2为实施例4中制备的长效抗菌的聚乙烯醇缩丙醛海绵PVP-SBMA的傅里叶红外光谱图。聚乙烯醇缩丙醛海绵中引入具有抗菌功能的磺酸甜菜碱甲基丙烯酸酯后，可以看到在1726cm-1处出现C＝O的伸缩振动峰，1147cm-1处对应着磺酸根阴离子基团不对称伸缩振动，这表明抗菌单体磺酸甜菜碱甲基丙烯酸酯成功引入到聚合物中，同时1542cm-1处为仲酰胺的C-N-H弯曲振动的特征峰，表明N-羟甲基丙烯酰胺成功接入海绵上。
图3为实施例4中制备的长效抗菌的聚乙烯醇缩醛海绵的表面水渗透动态图，可以看出，该海绵表面水渗透速率很快，仅需2秒，吸液性能良好。
实施例5
向5g聚合度为2400、醇解度为99％的聚乙烯醇1799聚乙烯醇中加入35g蒸馏水，加热至95℃搅拌2h，得到聚乙烯醇水溶液，然后加入总量为1.593g含有羟基的抗菌聚合物，0.5g盐酸溶液、0.15g十二烷基硫酸钠、0.005g稳泡剂烷基醇胺、3g甲醛溶液，搅拌均匀后将混合液倒入模具中，放入55℃烘箱固化6h，在海绵固化成型的过程中抗菌材料的羟基与醛基反应，将具有阳离子或两性离子的抗菌材料接枝在海绵上，反应结束后将海绵取出洗净，得到具有长效抗菌功能的聚乙烯醇缩甲醛海绵。
其中，所述含有羟基的抗菌聚合物为0.6507g甲基丙烯酸羟乙酯和0.9423g甲基丙烯酸二甲氨乙酯在0.0159g过硫酸铵的引发下于80℃反应3h得到。
按照GB/T 20944.3-2008《纺织品抗菌性能的评价》标准，采用振荡法测试海绵的抗菌性能，经过测试可以得出聚乙烯醇缩甲醛抗菌材料对大肠杆菌和金黄色葡萄球菌的抑菌率在94％以上。对该海绵进行吸水测试，发现该海绵浸润速度快，吸水倍率到达8.75g/g。
实施例6
向4g聚合度为2400、醇解度为88％的聚乙烯醇1799聚乙烯醇中加入36g蒸馏水，加热至95℃搅拌2h，得到聚乙烯醇水溶液，然后加入总量为0.8229g含有羟基的抗菌聚合物，0.5g盐酸溶液、0.4g十二烷基苯磺酸钠、0.004g稳泡剂硅油、3g甲醛溶液，搅拌均匀后将混合液倒入模具中，放入80℃烘箱固化2h，在海绵固化成型的过程中抗菌材料的羟基与醛基反应，将具有阳离子或两性离子的抗菌材料接枝在海绵上，反应结束后将海绵取出洗净，得到具有长效抗菌功能的聚乙烯醇缩甲醛海绵。
其中，所述含有羟基的抗菌聚合物为0.1762g 1,4-丁烯二醇和0.6467g二烯丙基二甲基氯化铵在0.0004g过硫酸铵和0.0004g亚硫酸氢钠的引发下于30℃反应7h得到。
按照GB/T 20944.3-2008《纺织品抗菌性能的评价》标准，采用振荡法测试海绵的抗菌性能，经过测试可以得出聚乙烯醇缩甲醛抗菌材料对大肠杆菌和金黄色葡萄球菌的抑菌率在97％以上。对该海绵进行吸水测试，发现该海绵浸润速度快，吸水倍率到达12.8g/g。
实施例7
向4.64g聚合度为2400、醇解度为99％的聚乙烯醇2499聚乙烯醇中加入28g蒸馏水，加热至95℃搅拌3h，得到聚乙烯醇水溶液，然后加入4.2685g含有羟基的抗菌物质、0.23g硝酸溶液、0.35g发泡剂碳酸钠、0.0186g稳泡剂(烷基醇胺和硅树脂聚醚乳液)、3g乙醛和0.1g戊二醛，搅拌均匀后将混合液倒入模具中，放入60℃烘箱固化3h，在海绵固化成型的过程中抗菌材料的羟基与醛基反应，将具有阳离子或两性离子抗菌材料接枝在海绵上，反应结束后将海绵取出洗净，得到具有长效抗菌功能的聚乙烯醇缩乙醛海绵。
其中，所述的含有羟基的抗菌聚合物为1.1530g N-(2-羟乙基)丙烯酰胺和4.1540g甲基丙烯酰氧乙基三甲基氯化铵(75wt％)在0.0085g过硫酸钾和0.0085g亚硫酸氢钠的引发下于45℃反应6h得到。
按照GB/T 20944.3-2008《纺织品抗菌性能的评价》标准，采用振荡法测试海绵的抗菌性能，经过测试可以得出聚乙烯醇缩乙醛抗菌材料对大肠杆菌和金黄色葡萄球菌的抑菌率在99.9％以上。对该海绵进行吸水测试，发现该海绵浸润速度快，吸水倍率到达12g/g。
图4为实施例7中制备的长效抗菌的聚乙烯醇缩醛海绵的长效抗菌实验测试结果图。通过将海绵在PBS浸泡缓冲溶液浸泡不同天数以后，由大肠杆菌进行抗菌实验可知：在PBS缓冲溶液中浸泡1天以后，抗菌率由第0天的99.9％变为99％，可能是由于部分未接枝上去的抗菌物质彻底溶出导致的。在浸泡的第3天、第5天、第7天、第10天，抗菌率分别为99.9％、99％、98％、98％，表明材料在PBS缓冲溶液中浸泡10天以后仍然具有优异的抗菌性能，材料具有长效抗菌性。
表1各实施例海绵性能测试数据
由表1可知，本发明制备得到的聚乙烯醇缩醛海绵不仅具备优异的抗菌性能，而且具有高吸水倍率，具有广阔的应用前景。阳离子或两性离子聚合物具有的优异的抗菌性能，本发明采用具有阳离子或两性离子结构的抗菌材料并将该材料在一定条件下通过化学键接枝到聚乙烯醇缩醛海绵结构中，在材料与细菌接触过程中，接枝的基团对细菌作用导致细菌的破裂死亡，表现出优异的抗菌功能；同时材料中的极性基团为亲水基团，提升了海绵的亲水性能和吸水倍率。
以上所述仅为本发明的实施例，并非因此限制本发明的专利范围，凡是利用本发明说明书所作的等效结构变换，或直接或间接运用在其他相关的技术领域，均同理包括在本发明的专利保护范围内。
Claims (10)
1.一种长效抗菌的聚乙烯醇缩醛海绵的制备方法，其特征在于，具体包括以下制备步骤：
向聚乙烯醇中加入蒸馏水，加热至90-95℃搅拌1-3h，得到聚乙烯醇水溶液；然后往其中加入含有羟基的抗菌材料、成孔剂/发泡剂、稳泡剂、固化剂、催化剂，搅拌均匀后将混合液倒入模具中，放入烘箱于50-80℃固化1-10小时，在海绵固化成型的过程中抗菌材料的羟基与醛基反应，将具有阳离子或两性离子的抗菌材料接枝在海绵上，反应结束后将海绵取出洗净，得到具有长效抗菌功能的聚乙烯醇缩醛海绵；
所述含有羟基的抗菌材料为含有羟基的抗菌单体，或者是由含有羟基的烯烃单体和含有阳离子或两性离子的烯烃不饱和单体通过引发剂引发双键自由基聚合反应生成的含有羟基的抗菌聚合物。
2.根据权利要求1所述的一种长效抗菌的聚乙烯醇缩醛海绵的制备方法，其特征在于，所述的含有羟基的抗菌单体为三羟甲基氨基甲烷盐酸盐、4-羟基-2,2,6,6-四甲基哌啶、3-羟基吡啶、3-(N-吗啉基)-2-羟基丙磺酸钠、3-氯-2-羟丙基三甲基氯化铵中的一种或多种；所述的含有羟基的烯烃单体为N-羟甲基丙烯酰胺、1,4-丁烯二醇、2-丁烯-1,4-二醇、N-(2-羟乙基)丙烯酰胺、甲基丙烯酸羟乙酯中的一种或多种；所述的含有阳离子或两性离子的烯烃不饱和单体为甲基丙烯酸二甲氨乙酯、磺酸甜菜碱甲基丙烯酸酯、羧酸甜菜碱甲基丙烯酸酯、2-甲基丙烯酰氧乙基磷酸胆碱、二烯丙基二甲基氯化铵、丙烯酰氧乙基三甲基氯化铵、甲基丙烯酰氧乙基三甲基氯化铵中的一种或多种；所述的引发剂为过硫酸钾、过硫酸铵、亚硫酸氢钠中的一种或多种。
3.根据权利要求1所述的一种长效抗菌的聚乙烯醇缩醛海绵的制备方法，其特征在于，所述含有羟基的烯烃单体和所述的含有阳离子或两性离子的烯烃不饱和单体的摩尔比为1.0:(1.0-4.0)；含有羟基的烯烃单体和所述的含有阳离子或两性离子的烯烃不饱和单体的总质量与引发剂的质量比为1.0:(0.001-0.01)；所述聚合反应的反应温度为30-80℃，时间为3-10h。
4.根据权利要求1所述的一种长效抗菌的聚乙烯醇缩醛海绵的制备方法，其特征在于，所述聚乙烯醇的聚合度为1700-2400、醇解度为88mol％-99mol％；所得聚乙烯醇水溶液的质量浓度为8％-16.67％。
5.根据权利要求1所述的一种长效抗菌的聚乙烯醇缩醛海绵的制备方法，其特征在于，所述的成孔剂为淀粉、纤维素中的一种或多种；所述的发泡剂为曲拉通X-100、OP-10、吐温80、司盘80、十二烷基硫酸钠、十二烷基苯磺酸钠、碳酸氢钠、碳酸钠、碳酸氢铵、硼氢化钠中的一种或多种。
6.根据权利要求1所述的一种长效抗菌的聚乙烯醇缩醛海绵的制备方法，其特征在于，所述的稳泡剂为十二烷基二甲基氧化胺、烷基醇胺、硅树脂聚醚乳液、硅油、L-580中的一种或多种。
7.根据权利要求1所述的一种长效抗菌的聚乙烯醇缩醛海绵的制备方法，其特征在于，所述的固化剂为甲醛、乙醛、丙醛、丁醛、戊二醛中的一种或多种。
8.根据权利要求1所述的一种长效抗菌的聚乙烯醇缩醛海绵的制备方法，其特征在于，所述的催化剂为硫酸、盐酸、硝酸中的一种或多种。
9.根据权利要求1所述的一种长效抗菌的聚乙烯醇缩醛海绵的制备方法，其特征在于，各反应物配比为：
含有羟基的抗菌材料总用量为聚乙烯醇质量的10％-93.3％；
发泡剂的用量为聚乙烯醇质量的3.33％-40.0％；
固化剂的用量为聚乙烯醇质量的31.31％-100.00％；
稳泡剂的用量为聚乙烯醇质量的0.2％-1％；
催化剂的用量为聚乙烯醇质量的5％-90％；
或者
含有羟基的抗菌材料总质量为聚乙烯醇质量的10％-93.3％；
成孔剂的用量为聚乙烯醇质量的3.33％-10.0％；
固化剂的用量为聚乙烯醇质量的50.00％-100.00％；
催化剂的用量为聚乙烯醇质量的5％-90％。
10.权利要求1-9任一项所述的制备方法制备得到的一种长效抗菌的聚乙烯醇缩醛海绵。
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