CN111138614A - 一种用于低模量高强度超薄聚氨酯安全套的水性聚氨酯乳液及其制备方法 - Google Patents

一种用于低模量高强度超薄聚氨酯安全套的水性聚氨酯乳液及其制备方法 Download PDF

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CN111138614A
CN111138614A CN201911320711.6A CN201911320711A CN111138614A CN 111138614 A CN111138614 A CN 111138614A CN 201911320711 A CN201911320711 A CN 201911320711A CN 111138614 A CN111138614 A CN 111138614A
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mass
polyurethane emulsion
parts
aqueous polyurethane
prepolymer
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CN201911320711.6A
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Inventor
李维虎
郭文鹤
朱保凌
汪飞
戴家兵
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Lanzhou Keshi Sicily Health Technology Co.,Ltd.
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Lanzhou Scisky Aqueous Polymer Material Co ltd
Hefei Scisky Technology Co ltd
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Application filed by Lanzhou Scisky Aqueous Polymer Material Co ltd, Hefei Scisky Technology Co ltd filed Critical Lanzhou Scisky Aqueous Polymer Material Co ltd
Priority to CN201911320711.6A priority Critical patent/CN111138614A/zh
Publication of CN111138614A publication Critical patent/CN111138614A/zh
Priority to EP20902064.3A priority patent/EP4079778A4/en
Priority to PCT/CN2020/137262 priority patent/WO2021121323A1/zh
Priority to US17/787,171 priority patent/US20230029922A1/en
Priority to CN202080085071.XA priority patent/CN115298240A/zh
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Abstract

本发明公开了一种用于低模量高强度超薄聚氨酯安全套的水性聚氨酯乳液及其制备方法，其中，水性聚氨酯乳液包括：15～18质量份数的大份子二元醇，4～6质量份数的二异氰酸酯，0.6～0.9质量份数的亲水扩链剂，0.4～0.8质量份数的小分子扩链剂等。本发明制备的水性聚氨酯乳液具有低模量、高强度和高回弹等特性。

Description

一种用于低模量高强度超薄聚氨酯安全套的水性聚氨酯乳液 及其制备方法
技术领域
本发明属于聚氨酯制备领域，具体涉及一种用于低模量高强度超薄聚氨酯安全套的水性聚氨酯乳液及其制备方法。
背景技术
现有的安全套主要是采用天然乳胶为原材料制备安全套，但天然乳胶安全套中存在水溶性蛋白质，会引起过敏反应；天然乳胶在硫化过程中残留亚硝胺，存在引发癌症的隐患。以天然乳胶为原材料制备的安全套厚度均在36μm以上，膜厚用户体验差，做成36μm以下时天然乳胶安全套存在强度差，使用时易破损的缺点。
水性聚氨酯安全套的研究已有十余年历史，现有技术中虽然有些制备的聚氨酯安全套强度符合要求，但使用高沸点溶剂毒性大，且难以烘干。也有一些所制备的水性聚氨酯安全套爆破强度和最大力较小，实际使用过程总存在产品破裂的风险。因此，对于制备水性聚氨酯安全套所需水性聚氨酯乳液的制备方法存在进一步改进和优化需求，这也是该领域的研究热点和难点。
发明内容
本发明旨在提供一种用于低模量高强度超薄聚氨酯安全套的水性聚氨酯乳液及其制备方法，使制备的水性聚氨酯乳液具有低模量、高强度、高回弹的特性，解决了天然乳胶安全套水溶性蛋白质致敏、含致癌亚硝胺、膜厚用户体验差以及病毒隔离差等缺点。
为解决上述问题，本发明是通过以下技术方案实现的：本发明提供一种水性聚氨酯乳液，包括：
15～18质量份数的大份子二元醇，4～6质量份数的二异氰酸酯，0.6～0.9质量份数的亲水扩链剂，0.4～0.8质量份数的小分子扩链剂，0.5～0.68质量份数的成盐剂，0.3～0.5质量份数的交联剂，0.1～2.0质量份数的改性物质，50～55质量份数的冰水混合物和21～23质量份数的丙酮；
其中，所述改性物质为使水性聚氨酯分子链的端基形成交联结构的聚醚类物质。
在一实施例中，所述改性物质为聚醚多胺。
在一实施例中，所述交联剂为潜伏型异氰酸酯类交联剂。
在一实施例中，所述大分子二元醇为聚丙二醇、聚四氢呋喃醚二醇和聚己二酸新戊二醇酯中的一种或多种组合。
在一实施例中，所述大分子二元醇的分子量为2000～3000。
在一实施例中，所述二异氰酸酯为异佛尔酮二异氰酸酯，氢化苯基甲烷二异氰酸酯和或六亚甲基二异氰酸酯中的一种或多种组合。
在一实施例中，所述水性聚氨酯乳液的固含量为30～32％，pH值为6.5～7.5。
在一实施例中，所述亲水性扩链剂为二羟甲基丙酸和/或二羟甲基丁酸。
本发明的另一个目的在于提供一种水性聚氨酯乳液的制备方法，至少包括以下步骤：
提供一反应器；
向所述反应器中加入15～18质量份数的大份子二元醇，4～6质量份数的二异氰酸酯，0.6～0.9质量份数的亲水扩链剂，0.4～0.8质量份数的小分子扩链剂，0.5～0.68质量份数的成盐剂和4～23质量份数的丙酮，获得预聚体；
将所述预聚体、0.3～0.5质量份数的交联剂和50～55质量份数的冰水混合物进行混合，获得开链的预聚体；
在所述开链的预聚体中加入0.1～2.0质量份数的改性物质，使所述开链的预聚体的端基形成交联结构，获得所述水性聚氨酯乳液。
在一实施例中，所述改性物质滴加到所述开链的预聚体中，滴加所用的时间为25～35分钟。
在一实施例中，所述21～23质量份数的丙酮分三次加入所述反应器中。
在一实施例中，在使所述开链的预聚体的端基形成交联结构后，进行脱溶处理除去丙酮。
本发明的另一个目的还在于提供一种所述的一种水性聚氨酯乳液在聚氨酯安全套领域的应用。
本发明制备的水性聚氨酯乳液具有低模量、高强度、高回弹的特性，使用本发明中水性聚氨酯乳液制备的水性聚氨酯安全套无毒、无特殊气味、不致敏、致密性好、可有效隔绝各种病毒、安全套更薄、导热性好、模量低、强度高、用户体验感好，解决了天然乳胶安全套水溶性蛋白质致敏、含致癌亚硝胺、膜厚用户体验差、病毒隔离差等缺点。同时解决了现有水性聚氨酯安全套模量高、强度低、延伸率差的缺点。以该水性聚氨酯乳液按照水性聚氨酯安全套制备方法制备的水性聚氨酯安全套单层厚度薄至30μm以下，膜的断裂伸长率不低于1000％，断裂强度不低于30MPa，100％模量不超过1.8MPa，安全套爆破压力大于2.5kPa，爆破体积不低于6L。
附图说明
图1：本发明一实施例中的方法流程示意图。
具体实施方式
下面通过几个具体的实施例对本发明作进一步的说明，但需要指出的是本发明的实施例中所描述的具体的物料配比、工艺条件及结果等仅用于说明本发明，并不能以此限制本发明的保护范围，凡是根据本发明的精神实质所作的等效变化或修饰，都应该涵盖在本发明的保护范围内。注意，如没有特别说明，本文中描述所示的“％”是指“质量份数”。
本发明将使水性聚氨酯分子链的端基形成交联结构的聚醚胺类物质作为后扩链剂使用，使得制备的水性聚氨酯乳液具有低模量、高强度和高回弹等特性。
请参阅图1，为本发明一实施例中水性聚氨酯乳液的方法流程示意图，本发明提供一种水性聚氨酯乳液的制备方法，至少包括以下步骤：
S1、提供一反应器；
S2、向所述反应器中加入15～18质量份数的大份子二元醇，4～6质量份数的二异氰酸酯，0.6～0.9质量份数的亲水扩链剂，0.4～0.8质量份数的小分子扩链剂，0.5～0.68质量份数的成盐剂和4～23质量份数的丙酮，获得预聚体；
S3、将所述预聚体、0.3～0.5质量份数的交联剂和50～55质量份数的冰水混合物进行混合，获得开链的预聚体；
S4、在所述开链的预聚体中加入0.1～2.0质量份数的改性物质，使所述开链的预聚体的端基形成交联结构，获得所述水性聚氨酯乳液。
具体的，在步骤S1中，所述反应器例如为反应釜。
具体的，在步骤S2中，将15～18％的大分子二元醇投入反应器例如反应釜，搅拌加热至100～110℃，-0.1MPa条件下真空脱水至大分子二元醇中水含量在0.03％以下，降温至35～40℃，投入4～6％的二异氰酸酯，搅拌升温至80～90℃，保温反应2～3小时，降温至45-50℃，投入0.6～0.9％的亲水扩链剂和7％的丙酮，搅拌升温至80℃反应3～4小时，降温至50～55℃，投入0.4～0.8％的小分子扩链剂和4％丙酮，搅拌升温至70～75℃反应2～3小时，然后降温至10～20℃，加入0.5～0.68％的成盐剂和10～12％的丙酮，搅拌30分钟，获得预聚体。其中，所使用的大分子二元醇为聚丙二醇(PPG)，聚四氢呋喃醚二醇(PTMEG)和/或聚己二酸新戊二醇酯(PNA)中一种或多种。所述大分子二元醇分子量为2000～3000，大分子二元醇分子量过大，水性聚氨酯乳液成膜后回弹性和断裂强度下降，如果分子量过小，水性聚氨酯乳液成膜易开裂，且模量大。所使用的二异氰酸酯为异佛尔酮二异氰酸酯(IPDI)，氢化苯基甲烷二异氰酸酯(H12MDI)和或六亚甲基二异氰酸酯(HDI)中一种或多种，如果选择芳香族二异氰酸酯，所获得水性聚氨酯成膜后存在黄变的风险。当二异氰酸酯为IPDI或HDI时，异氰酸酯反应活性低，在S1步骤中二异氰酸酯与大分子二元醇反应温度为90℃，当二异氰酸酯为H12MDI时，二异氰酸酯活性高，二异氰酸酯与大分子二元醇反应温度为80℃。所使用的亲水性扩链剂为二羟甲基丙酸(DMPA)和或二羟甲基丁酸(DMBA)，所使用小分子扩链剂为环己二甲醇(CHDM)，1，4-丁二醇(BD)和或甲基丙二醇(MPD)中一种或多种。在本发明中，降温至35～40℃，投入4～6％的二异氰酸酯，搅拌升温至80～90℃，保温反应2～3小时，降温至45～50℃，投入0.6～0.9％的亲水扩链剂和7％的丙酮，搅拌升温至80℃反应3～4小时，降温至50-55℃，投入0.4～0.8％的小分子扩链剂和4％丙酮，搅拌升温至70～75℃反应2～3小时，然后降温至10～20℃，加入0.5～0.68％的成盐剂和10～12％的丙酮，其中，采用三段式降温加料的目的是为了使水性聚氨酯的分子链更加规整以及微相分离程度高，从而使得制备的水性聚氨酯的机械性能例如拉伸强度得以提升。
具体的，在步骤S3中，将预聚体转移至乳化器中，加入0.3～0.5％的交联剂，以300转/分钟的转速搅拌30-35分钟，调整1000～1400转/分钟高速搅拌下匀速将50～55％的冰水混合物加入预聚体中。
具体的，在步骤S4中，预聚体打开后继续搅拌5分钟，然后将转速调整至400转/分钟，加入0.1～2.0％的改性物质水溶液，继续搅拌3～5小时。所使用的交联剂为潜伏型异氰酸酯交联剂例如荷拓纳潜伏型异氰酸酯交联剂ACRAFIX FAE和或ACRAFIX FAX中任意一种，潜伏型交联剂交联温度为90～110℃，保证水性聚氨酯乳液常温贮存稳定性，同时该种交联发生在水性聚氨酯成膜过程中，有利于粒子间的融合和聚氨酯膜性能的提升。所述改性物质例如为聚醚多胺，聚醚多胺属于柔性固化剂，在本发明中的作用也起到后扩链剂的作用，其作为后扩链使用时存在端基交联，不会提高聚氨酯膜的模量，同时交联结构可增加聚氨酯膜的回弹性能和强度。另外，本发明还能另外加入其他后扩链剂，例如乙二胺和异佛尔酮二胺，乙二胺对称性好，其作为后扩链可提供聚氨酯膜更高的强度，异佛尔酮二胺结构中含有脂肪族六元环结构，脂肪族六元环存在“船式”和“椅式”构象转化，其作为后扩链剂可提高聚氨酯膜回弹性能。将步骤S4获得的乳液升温至40～45℃，-0.09MPa条件下脱去乳液中的丙酮，制得低模量高强度的水性聚氨酯乳液。所制得的水性聚氨酯乳液固含量为30～32％。所制得的水性聚氨酯乳液pH值为6.5～7.5。
在本发明中，例如聚醚多胺以及其他后扩链加入速度要慢，控制在25～35分钟左右加完，速度过快会导致局部放热严重，增加了水参与程度，导致所获得水性聚氨酯分子中脲键含量增大且分子量分布不均。
下面列举一些实施例来具体说明本发明。同时列举一些对比例，例如加入后扩链剂例如乙二胺或者异佛尔酮二胺来跟加入聚醚类物质进行对比。
在一实施例中，将16-16.67％的PTMEG 3000投入反应釜，搅拌加热至100～110℃，-0.1MPa条件下真空脱水至大分子二元醇中水含量在0.03％以下，降温至35～40℃，投入4.16％的IPDI，搅拌升温至90℃，保温反应2.5小时，降温至45～50℃，投入0.67％的DMPA和7％的丙酮，搅拌升温至80℃反应3-4小时，降温至50～55℃，投入0.73％的CHDM和4％丙酮，搅拌升温至75℃反应3～4小时，然后降温至15℃，加入0.5％的成盐剂和10％的丙酮，搅拌30～35分钟，获得第一预聚体。将第一预聚体转移至乳化器中，加入0.3％的交联剂，以300转/分钟的转速搅拌30～35分钟，调整1200转/分钟高速搅拌下匀速将53.32％的冰水混合物加入预聚体中，获得开链后的第一预聚体。第一预聚体打开后继续搅拌5-10分钟，然后将转速调整至400转/分钟，滴加入2.5～2.65％聚醚多胺，控制在25-35分钟左右加完，继续搅拌5～5.5小时，将获得的乳液升温至40～45℃，-0.09MPa条件下脱去乳液中的丙酮，制得水性聚氨酯乳液A。
在一实施例中，将15.38％的PNA 2000投入反应釜，搅拌加热至100～110℃，-0.1MPa条件下真空脱水至大分子二元醇中水含量在0.03％以下，降温至35～40℃，投入2.0％的IPDI和2.0％的HDI，搅拌升温至90℃，保温反应2.5小时，降温至45～50℃，投入0.72％的DMPA和7％的丙酮，搅拌升温至80℃反应3～4小时，降温至50～55℃，投入0.4％的BDO和4％丙酮，搅拌升温至75℃反应3～4小时，然后降温至15℃，加入0.54％的成盐剂和12％的丙酮，搅拌30-35分钟，获得第二预聚体。将第二预聚体转移至乳化器中，加入0.3％的交联剂，以300转/分钟的转速搅拌30～35分钟，调整1200转/分钟高速搅拌下匀速将53.5％的冰水混合物加入预聚体中，获得开链后的第二预聚体。第二预聚体打开后继续搅拌5～10分钟，然后将转速调整至400转/分钟，滴加入1.8-2.0％聚醚多胺，控制在25～35分钟左右加完，搅拌5～5.5小时，将获得的乳液升温至40～45℃，-0.09MPa条件下脱去乳液中的丙酮，制得水性聚氨酯乳液B。
在一对比例中，将16.67％的PTMEG 3000和PPG3000投入反应釜，搅拌加热至100～110℃，-0.1MPa条件下真空脱水至大分子二元醇中水含量在0.03％以下，降温至35～40℃，投入4.16％的IPDI，搅拌升温至90℃，保温反应2.5小时，降温至45～50℃，投入0.67％的DMPA和7％的丙酮，搅拌升温至80℃反应3-4小时，降温至50～55℃，投入0.73％的CHDM和4％丙酮，搅拌升温至75℃反应3～4小时，然后降温至15℃，加入0.5％的成盐剂和10.8％的丙酮，搅拌30分钟，获得第三预聚体。将第三预聚体转移至乳化器中，加入0.3％的交联剂，以300转/分钟的转速搅拌30～35分钟，调整1200转/分钟高速搅拌下匀速将53.32％的冰水混合物加入预聚体中，获得开链后的第三预聚体。第三预聚体打开后继续搅拌5～10分钟，然后将转速调整至400转/分钟，滴加入1.5～1.84％异佛尔酮二胺水溶液，控制在25～35分钟左右加完，继续搅拌3～3.5小时。将获得的乳液升温至40～45℃，-0.09MPa条件下脱去乳液中的丙酮，制得水性聚氨酯乳液C。
在一对比例中，将16.07％的PPG3000投入反应釜，搅拌加热至100～110℃，-0.1MPa条件下真空脱水至大分子二元醇中水含量在0.03％以下，降温至35～40℃，投入3.27％的IPDI和1.4％的H12MDI，搅拌升温至80℃，保温反应2.5小时，降温至45～50℃，投入0.82％的DMPA和7％的丙酮，搅拌升温至80℃反应3小时，降温至50～55℃，投入0.75％的CHDM和4％丙酮，搅拌升温至75℃反应3小时，然后降温至10℃，加入0.61％的成盐剂和12％的丙酮，搅拌30分钟，获得第四预聚体。将第四预聚体转移至乳化器中，加入0.5％的交联剂，以300转/分钟的转速搅拌30-35分钟，调整1200转/分钟高速搅拌下匀速将53.43％的冰水混合物加入预聚体中，获得开链后的第四预聚体。第四预聚体打开后继续搅拌5分钟，然后将转速调整至400转/分钟，滴加入0.1～0.15％乙二胺水溶液，控制在25-35分钟左右加完，继续搅拌3～3.5小时。将获得的乳液升温至40～45℃，-0.09MPa条件下脱去乳液中的丙酮，制得水性聚氨酯乳液D。
使用以上各实施案例所制备的水性聚氨酯乳液按CN 103640133A公开的水性聚氨酯安全套制备方法制备聚氨酯安全套，对所制得的安全套依据GB7544-1992、GB/T7546-1992和GB/T7547-1992进行性能检测，测试结果如下表1所示。
在本发明中，将制得的水性聚氨酯乳液用于制备水性聚氨酯安全套工艺步骤如下：对不锈钢模具进行清洗、干燥，模具浸入纳米级水性聚氨酯交联粒子乳液，取出滴胶后干燥，将经处理的模具浸入水性聚氨酯乳液，取出滴胶后干燥，在模具表面得到水性聚氨酯胶膜，对模具表面水性聚氨酯胶膜开口端进行卷边处理，将经处理的模具浸入50±5℃的热水中，浸泡后干燥，然后浸入脱模剂中，取出干燥，采用干法电检，对经处理的胶膜进行电检，电检合格后脱模，即得到聚氨酯安全套。
表1.一些实施例样品制成的安全套的性能测试结果
Figure BDA0002327071390000061
Figure BDA0002327071390000071
从表1中的数据分析得出，加入聚醚多胺作为后扩链剂比加入乙二胺和异佛尔酮二胺作为后扩链剂，所得的水性聚氨酯乳液制备的聚氨酯安全套的性能整体要高。聚醚多胺属于柔性固化剂，其作为后扩链使用存在端基交联，其一方面不会提高聚氨酯膜的模量，同时交联结构可增加聚氨酯膜的回弹性能和断裂强度等性能。
本发明制备的水性聚氨酯乳液具有低模量、高强度、高回弹的特性，使用本发明中水性聚氨酯乳液制备的水性聚氨酯安全套无毒、无特殊气味、不致敏、致密性好、可有效隔绝各种病毒、安全套更薄、导热性好、模量低、强度高、用户体验感好，解决了天然乳胶安全套水溶性蛋白质致敏、含致癌亚硝胺、膜厚用户体验差、病毒隔离差等缺点。同时解决了现有水性聚氨酯安全套模量高、强度低、延伸率差的缺点。以该水性聚氨酯乳液按照水性聚氨酯安全套制备方法制备的水性聚氨酯安全套单层厚度薄至30μm以下，膜的断裂伸长率不低于1000％，断裂强度不低于30MPa，100％模量不超过1.8MPa，安全套爆破压力大于2.5kPa，爆破体积不低于6L。
以上所述，仅为本发明的较佳实施例，并非对本发明任何形式上和实质上的限制，应当指出，对于本技术领域的普通技术人员，在不脱离本发明方法的前提下，还将可以做出若干改进和补充，这些改进和补充也应视为本发明的保护范围。凡熟悉本专业的技术人员，在不脱离本发明的精神和范围的情况下，当可利用以上所揭示的技术内容而做出的些许更动、修饰与演变的等同变化，均为本发明的等效实施例；同时，凡依据本发明的实质技术对上述实施例所作的任何等同变化的更动、修饰与演变，均仍属于本发明的技术方案的范围内。

Claims (10)

1.一种水性聚氨酯乳液，其特征在于，包括：
15～18质量份数的大份子二元醇，4～6质量份数的二异氰酸酯，0.6～0.9质量份数的亲水扩链剂，0.4～0.8质量份数的小分子扩链剂，0.5～0.68质量份数的成盐剂，0.3～0.5质量份数的交联剂，0.1～2.0质量份数的改性物质，50～55质量份数的冰水混合物和21～23质量份数的丙酮；
其中，所述改性物质为使水性聚氨酯分子链的端基形成交联结构的聚醚类物质。
2.根据权利要求1所述的一种水性聚氨酯乳液，其特征在于，所述改性物质为聚醚多胺。
3.根据权利要求1所述的一种水性聚氨酯乳液，其特征在于，所述交联剂为潜伏型异氰酸酯类交联剂。
4.根据权利要求1所述的一种水性聚氨酯乳液，其特征在于，所述大分子二元醇为聚丙二醇、聚四氢呋喃醚二醇和聚己二酸新戊二醇酯中的一种或多种组合。
5.根据权利要求1所述的一种水性聚氨酯乳液，其特征在于，所述大分子二元醇的分子量为2000～3000。
6.根据权利要求1所述的一种水性聚氨酯乳液，其特征在于，所述二异氰酸酯为异佛尔酮二异氰酸酯，氢化苯基甲烷二异氰酸酯和或六亚甲基二异氰酸酯中的一种或多种组合。
7.根据权利要求1所述的一种水性聚氨酯乳液，其特征在于，所述亲水性扩链剂为二羟甲基丙酸和/或二羟甲基丁酸。
8.一种水性聚氨酯乳液的制备方法，其特征在于，至少包括以下步骤：
提供一反应器；
向所述反应器中加入15～18质量份数的大份子二元醇，4～6质量份数的二异氰酸酯，0.6～0.9质量份数的亲水扩链剂，0.4～0.8质量份数的小分子扩链剂，0.5～0.68质量份数的成盐剂和4-23质量份数的丙酮，获得预聚体；
将所述预聚体、0.3～0.5质量份数的交联剂和50～55质量份数的冰水混合物进行混合，获得开链的预聚体；
在所述开链的预聚体中加入0.1～2.0质量份数的改性物质，使所述开链的预聚体的端基形成交联结构，获得所述水性聚氨酯乳液。
9.根据权利要求8所述的一种水性聚氨酯乳液，其特征在于，所述改性物质滴加到所述开链的预聚体中，滴加所用的时间为25～35分钟。
10.一种如权利要求1-7任一项所述的一种水性聚氨酯乳液在聚氨酯安全套领域的应用。
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