CN107236285B - 一种石墨烯水性聚氨酯安全套用水性聚氨酯乳液及其制备方法和应用 - Google Patents

一种石墨烯水性聚氨酯安全套用水性聚氨酯乳液及其制备方法和应用 Download PDF

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CN107236285B
CN107236285B CN201710368650.5A CN201710368650A CN107236285B CN 107236285 B CN107236285 B CN 107236285B CN 201710368650 A CN201710368650 A CN 201710368650A CN 107236285 B CN107236285 B CN 107236285B
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戴家兵
王武生
李维虎
郭文鹤
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Lijieshealth Co ltd
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Abstract

本发明公开了一种石墨烯水性聚氨酯安全套用水性聚氨酯乳液及其制备方法和应用。本发明的石墨烯水性聚氨酯安全套用水性聚氨酯乳液是封闭型石墨烯改性的水性聚氨酯乳液，由本发明所述石墨烯水性聚氨酯安全套用水性聚氨酯乳液制得的安全套强度、回弹性、耐化学性、耐穿刺性等均优异。

Description

一种石墨烯水性聚氨酯安全套用水性聚氨酯乳液及其制备方 法和应用
技术领域
本发明涉及聚合物材料领域，具体涉及一种石墨烯水性聚氨酯安全套用水性聚氨酯乳液及其制备方法和应用。
背景技术
安全套是目前使用最为广泛的用于避孕和防止性病传播的性生活医疗卫生用品，现有安全套主要为天然乳胶安全套，然而天然乳胶中存在水溶性蛋白质，会引起过敏反应；用于制备安全套的天然乳胶需经过硫化处理，在硫化过程中会产生亚硝胺，存在引发癌症的隐患；并且天然乳胶安全套存在约5μm的本征空隙，可以有效隔绝精子却无法隔绝直径更小的乙肝和艾滋等病毒；天然乳胶安全套的极限厚度为36μm，无法给用户更好的体验。
水性聚氨酯是一种绿色高分子材料，安全、无毒、强度高、导热性好、成膜致密性好，被广泛应用在医疗领域，以水性聚氨酯为原材料制备的安全套更薄、无毒、无硫化过程，无水溶性蛋白质，导热性能好，病毒隔离效果好，用户体验好。
石墨烯是一种新型的二维平面材料，其碳原子以SP2杂化轨道组成六角形蜂窝结构，厚度仅为0.3354 nm。石墨烯既是最薄的材料，也是最强韧的材料，具有优异的延伸性、导热性和致密性，并且石墨烯对光线的吸收率仅2.3%，几乎完全透明。将石墨烯以共混或化学键的方式添加到水性聚氨酯乳液中，可提高水性聚氨酯胶膜的强度、耐热性、耐磨性、耐化学性和耐穿刺性能的同时，保持透明性和光泽度。但报道显示石墨烯在水性聚氨酯中分散性及相容性还不够充分。
CN 103382244 A通过原位复合的方法制备石墨烯改性水性聚氨酯材料，在石墨烯中引进氨基与聚氨酯预聚体末端NCO基团反应，通过化学键合制备石墨烯改性水性聚氨酯乳液，但石墨烯表面氨基基团数难以控制，其与聚氨酯预聚体反应造成预聚体粘度大。CN203943790 U公布了一种石墨烯安全套的制备方法，石墨烯作为夹层配置在聚合物层之间或石墨烯与聚合物混合物直接制备单层安全套结构，但石墨烯做夹层分散性差，直接与聚合物混合相容性差。
因此，对于制备石墨烯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。
发明内容
为解决上述现有技术中存在的缺陷，本发明提供一种石墨烯水性聚氨酯安全套用水性聚氨酯乳液、及其制备方法和应用。
本发明提供的石墨烯水性聚氨酯安全套用水性聚氨酯乳液的制备方法，包括下述步骤，各成分以质量分数计：
1）预聚体制备：将15~18%的大分子二元醇投入反应釜，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40℃，投入2.5~4.5%的二异氰酸酯，搅拌升温至80~90℃，保温反应2~3小时，降温至50℃，投入0.7~0.8%的亲水扩链剂和4~4.5%的溶剂，搅拌升温至80℃反应3~4小时，降温至50℃，投入0.2~0.8%的小分子扩链剂和6~6.5%溶剂，搅拌升温至70~75℃反应2~3小时，然后降温至10~20℃，加入0.6~0.65%的成盐剂和10~11 %的溶剂，搅拌30 min，获得预聚体；
2）乳化过程：将预聚体导入分散釜，加入预聚体的质量的1~3%的封闭型石墨烯，400 r/min搅拌0.5小时，调整转盘转速至1200~1400r/min，匀速向预聚体中加入预聚体的质量的54~56%的去离子水，预聚体打开后继续高速搅拌1 min，然后降低转速至400 r/min搅拌3小时；
3）脱溶过程：将上述过程2）获得的乳液升温至30~35℃，-0.09MPa条件下脱去乳液中的溶剂，制得石墨烯水性聚氨酯安全套用水性聚氨酯乳液。
其中，以质量分数计，所述封闭型石墨烯是如下制成：将25~40 %的功能化石墨烯、25~40 %的溶剂和15~30 %的二异氰酸酯投入反应釜，搅拌升温至60~90℃，保温反应4小时，降温至40℃，投入5~25%的封闭剂，升温至60℃反应3小时，降温至20℃导出，密封保存。
其中，所述功能化石墨烯为羟基化石墨烯或氨基化石墨烯中的一种或几种，羟基或氨基含量为4~12%，石墨烯厚度为0.8~1.2 nm；所述溶剂为丙酮。
此外，在1）预聚体制备中，所述二异氰酸酯为氰酸酯为甲苯二异氰酸酯（TDI）、二苯基甲烷二异氰酸酯（MDI）、异佛尔酮二异氰酸酯IPDI或六亚甲基二异氰酸酯HDI中一种或几种；所述溶剂为丙酮。
此外，所述大分子二元醇为聚环氧丙烷（PPG）或聚四氢呋喃醚二醇（PTMEG）中的一种或几种，大分子二元醇分子量为1500~4000；所述亲水扩链剂为二羟甲基丙酸（DMPA）；所述小分子扩链剂为1,4-丁二醇（BDO）、1,6-己二醇（HDO）、甲基丙二醇（MPD）或环己二甲醇（CHDM）中的一种或几种；所述成盐剂为三乙胺。
此外，所述二异氰酸酯为脂肪族二异氰酸酯；所述封闭剂为环己酮肟、甲乙酮肟、丙酮肟或乙酰苯胺中的一种或几种。
此外，所述脂肪族二异氰酸酯为六亚甲基二异氰酸酯（HDI）或异佛尔酮二异氰酸酯（IPDI）中的一种或几种。
作为优选技术方案，在封闭型石墨烯的制备过程中，所述二异氰酸酯为脂肪族二异氰酸酯，优选的，使用六亚甲基二异氰酸酯（HDI）或异佛尔酮二异氰酸酯（IPDI）中的一种或几种；在石墨烯表面接上异氰酸酯基团，根据相似相容原理，有利于提高石墨烯在水性聚氨酯预聚体分散性和相容性。
作为优选技术方案，在封闭型石墨烯的制备过程中，所述封闭剂为环己酮肟、甲乙酮肟、丙酮肟或乙酰苯胺中的一种或几种；封闭剂封端异氰酸根基团，所述封闭剂解封温度在80~130℃，解封温度低。
作为优选技术方案，本发明所述水性聚氨酯乳液为端羟基水性聚氨酯乳液，若制备端异氰酸根的水性聚氨酯乳液，在高温成膜过程中无法与解封的功能化石墨烯表面的异氰酸根反应；
本发明还提供一种石墨烯水性聚氨酯安全套用水性聚氨酯乳液，其是如上所述制备方法制得的石墨烯水性聚氨酯安全套用水性聚氨酯乳液，该石墨烯水性聚氨酯安全套用水性聚氨酯乳液为端羟基水性聚氨酯乳液。
本发明还提供一种如上所述的石墨烯水性聚氨酯安全套用水性聚氨酯乳液的应用，其用于制备安全套。
本发明还提供一种安全套，其是由如上所述的石墨烯水性聚氨酯安全套用水性聚氨酯乳液制备而成。
本发明的有益效果在于：
（1）本发明制备的石墨烯水性聚氨酯安全套用水性聚氨酯乳液解决了石墨烯在水性聚氨酯预聚体中分散性和相容性不好的问题；
（2）本发明制备的石墨烯水性聚氨酯安全套用水性聚氨酯乳液为常温单组份水性聚氨酯，高温成膜时，封闭型石墨烯端基封闭剂解封释放出异氰酸根，此时端异氰酸根的石墨烯可视为交联剂与水性聚氨酯分子链端基的羟基反应，石墨烯作为交联点，提高水性聚氨酯胶膜的强度、回弹性、耐化学性、耐穿刺性、耐磨性和导热性，同时不影响水性聚氨酯胶膜的手感和透明度。
具体实施方式
以下，结合实施例进一步详述本发明的技术方案，但本发明并不限定于这些实施例。
实施例1
封闭型石墨烯的制备，以质量分数计：
将25kg的羟基化石墨烯（羟基含量4 %）、40kg的丙酮和15 kg的HDI投入反应釜，搅拌升温至80 ℃，保温反应4小时，降温至40 ℃，投入20kg的环己酮肟封闭剂，升温至60℃反应3小时，降温至20℃导出，密封保存；
石墨烯水性聚氨酯安全套用水性聚氨酯乳液的制备工艺，以质量分数计：
1）预聚体制备：将16.7 kg的PPG 1500投入反应釜，搅拌加热至100℃，-0.1 MPa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40 ℃，投入2.22 kg的IPDI和0.95 kg的TDI，搅拌升温至85℃，保温反应2小时，降温至50℃，投入0.75kg的DMPA和4.2 kg的丙酮，搅拌升温至80℃反应3小时，降温至50℃，投入0.27 kg的BDO和6.4 kg丙酮，搅拌升温至75℃反应3小时，然后降温至10℃，加入0.56kg的三乙胺和10.5kg的丙酮，搅拌30 min，获得预聚体；
2）乳化过程：将预聚体导入分散釜，加入上述制备的2.15kg的封闭型石墨烯，400r/min搅拌0.5 小时，调整转盘转速至1200 r/min，匀速向预聚体中加入55.3kg的去离子水，预聚体打开后继续高速搅拌1 min，然后降低转速至400 r/min搅拌3小时；
3）脱溶过程：将上述过程2）获得的乳液升温至35℃，-0.09 MPa条件下脱去乳液中的丙酮，制得石墨烯水性聚氨酯安全套用水性聚氨酯乳液。
实施例2
封闭型石墨烯的制备，以质量分数计：
将40 kg的氨基化石墨烯（氨基含量8%）、40 kg的丙酮和15kg的IPDI投入反应釜，搅拌升温至60 ℃，保温反应4小时，降温至40 ℃，投入5 kg的甲乙酮肟封闭剂，升温至60℃反应3小时，降温至20℃导出，密封保存；
石墨烯水性聚氨酯安全套用水性聚氨酯乳液的制备工艺，以质量分数计：
1）预聚体制备：将15.03 kg的PPG 3000投入反应釜，搅拌加热至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40 ℃，投入2.59kg的IPDI和1.1kg的MDI，搅拌升温至80℃，保温反应3小时，降温至50℃，投入0.8 kg的DMPA和4.0 kg的丙酮，搅拌升温至80℃反应4小时，降温至50℃，投入0.8 kg的HDO和6.42kg丙酮，搅拌升温至70 ℃反应3小时，然后降温至20℃，加入0.6 kg的三乙胺和10.0 kg的丙酮，搅拌30 min，获得预聚体；
2）乳化过程：将预聚体导入分散釜，加入上述制备的2.66 kg的封闭型石墨烯，400r/min搅拌0.5 小时，调整转盘转速至1400 r/min，匀速向预聚体中加入56.0 kg的去离子水，预聚体打开后继续高速搅拌1 min，然后降低转速至400 r/min搅拌3小时；
3）脱溶过程：将上述过程2）获得的乳液升温至30℃，-0.09 MPa条件下脱去乳液中的丙酮，制得石墨烯水性聚氨酯安全套用水性聚氨酯乳液。
实施例3
封闭型石墨烯的制备，以质量分数计：
将32.0 kg的羟基化石墨烯（羟基含量12 %）、25.0kg的丙酮和18.0 kg的HDI投入反应釜，搅拌升温至90℃，保温反应4小时，降温至40 ℃，投入25.0 kg的乙酰苯胺封闭剂，升温至60℃反应3小时，降温至20℃导出，密封保存；
石墨烯水性聚氨酯安全套用水性聚氨酯乳液的制备工艺，以质量分数计：
1）预聚体制备：将18.0kg的PTMEG 3000投入反应釜，搅拌加热至105℃，-0.1 MPa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40 ℃，投入2.07 kg的IPDI和2.43kg的HDI，搅拌升温至90 ℃，保温反应2小时，降温至50 ℃，投入0.7 kg的DMPA和4.3 kg的丙酮，搅拌升温至80 ℃反应4小时，降温至50 ℃，投入0.52 kg的CHDM和6.5kg丙酮，搅拌升温至75 ℃反应3小时，然后降温至20 ℃，加入0.58 kg的三乙胺和9.88 kg的丙酮，搅拌30 min，获得预聚体；
2）乳化过程：将预聚体导入分散釜，加入上述制备的1.02 kg的封闭型石墨烯，400r/min搅拌0.5 小时，调整转盘转速至1300 r/min，匀速向预聚体中加入54.0kg的去离子水，预聚体打开后继续高速搅拌1 min，然后降低转速至400 r/min搅拌3小时；
3）脱溶过程：将上述过程2）获得的乳液升温至35 ℃，-0.09 MPa条件下脱去乳液中的丙酮，制得石墨烯水性聚氨酯安全套用水性聚氨酯乳液。
实施例4
封闭型石墨烯的制备，以质量分数计：
将27.5 kg的氨基化石墨烯（氨基含量8 %）、27.5 kg的丙酮和30.1 kg的IPDI投入反应釜，搅拌升温至80 ℃，保温反应4小时，降温至40 ℃，投入15kg的丙酮肟封闭剂，升温至60℃反应3小时，降温至20℃导出，密封保存；
石墨烯改性水性聚氨酯乳液的制备工艺，以质量分数计：
1）预聚体制备：将16.37kg的PTMEG 4000投入反应釜，搅拌加热至105℃，-0.1 MPa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40 ℃，投入2.5 kg的MDI，搅拌升温至85℃，保温反应2小时，降温至50 ℃，投入0.78 kg的DMPA和4.5kg的丙酮，搅拌升温至80 ℃反应4小时，降温至50 ℃，投入0.2 kg的MPD和6.0kg丙酮，搅拌升温至75 ℃反应3小时，然后降温至20 ℃，加入0.65kg的三乙胺和11.0kg的丙酮，搅拌30 min，获得预聚体；
2）乳化过程：将预聚体导入分散釜，加入3.0kg的封闭型石墨烯，400 r/min搅拌0.5 小时，调整转盘转速至1200 r/min，匀速向预聚体中加入55.0kg的去离子水，预聚体打开后继续高速搅拌1 min，然后降低转速至400 r/min搅拌3小时；
3）脱溶过程：将上述过程2）获得的乳液升温至30℃，-0.09 MPa条件下脱去乳液中的丙酮，制得石墨烯水性聚氨酯安全套用水性聚氨酯乳液。
使用以上各实施例所制备的石墨烯水性聚氨酯安全套用水性聚氨酯乳液按直浸法制备聚氨酯安全套，对上述实施案例获得乳液固含量和pH值依据GB/T11175-2002进行检测，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：
表1 各实施案例性能测试结果
Figure DEST_PATH_IMAGE002
由此可见，以本发明的石墨烯水性聚氨酯安全套用水性聚氨酯乳液按照直浸法制备方法制备的水性聚氨酯安全套单层厚度薄至30 μm以下，膜的断裂伸长率在900 %以上，断裂强度30 MPa以上，100 %模量2.2 MPa以下，安全套爆破压力大于3.0 kPa，爆破体积8 L以上。

Claims (5)

1.一种石墨烯水性聚氨酯安全套用水性聚氨酯乳液的制备方法，其特征在于，包括下述步骤，各成分以质量分数计：
1）预聚体制备：将15~18%的大分子二元醇投入反应釜，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40℃，投入2.5~4.5%的二异氰酸酯，搅拌升温至80~90℃，保温反应2~3小时，降温至50℃，投入0.7~0.8 %的亲水扩链剂和4~4.5%的溶剂，搅拌升温至80℃反应3~4小时，降温至50℃，投入0.2~0.8%的小分子扩链剂和6~6.5%溶剂，搅拌升温至70~75℃反应2~3小时，然后降温至10~20℃，加入0.6~0.65%的成盐剂和10~11 %的溶剂，搅拌30 min，获得预聚体；
2）乳化过程：将预聚体导入分散釜，加入1~3%的封闭型石墨烯，400 r/ min搅拌0.5小时，调整转盘转速至1200~1400r/min，匀速向预聚体中加入54~56%的去离子水，预聚体打开后继续高速搅拌1 min，然后降低转速至400 r/min搅拌3小 时；
3）脱溶过程：将上述乳化过程获得的乳液升温至30~35℃，-0.09MPa条件下脱去乳液中的 溶剂，制得石墨烯水性聚氨酯安全套用水性聚氨酯乳液；
以质量分数计，所述封闭型石墨烯由如下方法制成：将25~40 %的功能化石墨烯、25~40%的溶剂和15~30%的二异氰酸酯投入反应釜， 搅拌升温至60~90℃，保温反应4小时，降温至40℃，投入5~25%的封闭剂，升温至60℃反应3 小时，降温至20℃导出，密封保存；
所述功能化石墨烯为羟基化石墨烯或 氨基化石墨烯中的一种或几种，羟基或氨基含量为4~12%，石墨烯厚度为0.8~1.2 nm；所述封闭型石墨烯制备过程中，所述溶剂为丙酮，所述二异氰酸酯为脂肪族二异氰酸 酯；所述封闭剂为环己酮肟、甲乙酮肟、丙酮肟或乙酰苯胺中的一种或几种；所述脂肪族二异氰酸酯为六亚甲基二 异氰酸酯（HDI）或异佛尔酮二异氰酸酯（IPDI）中的一种或几种。
2.根据权利要求1所述的制备方法，其特征在于，在1）预聚体制备中，所述二异氰酸酯为甲苯二异氰酸酯（TDI）、二苯基甲烷二异氰酸酯（MDI）、异佛尔酮二异氰酸酯 IPDI或六亚甲基二异氰酸酯HDI中一种或几种；所述溶剂为丙酮。
3.根据权利要求1所述的制备方法，其特征在于，所述大分子二元醇为聚环氧丙烷（PPG）或聚四氢呋喃醚二醇（PTMEG）中的一种或几种，大分子二元醇分子量为1500~4000；所述亲水扩链剂为二羟甲基丙酸（DMPA）；所述小分子扩链剂为1,4-丁二醇（BDO）、1,6-己二醇（HDO）、甲基丙二醇（MPD）或环己二甲醇（CHDM）中的一种或几种；所述成盐剂为三乙胺。
4.一种石墨烯水性聚氨酯安全套用水性聚氨酯乳液，其特征在于，该石墨烯水性聚氨酯安全套用水性聚氨酯乳液是根据权利要求1-3中任意一项所述制备方法制得的石墨烯水性聚氨酯安全套用水性聚氨酯乳液，该石墨烯水性聚氨酯安全套用水性聚氨酯乳液为端羟基水性聚氨酯乳液。
5.一种根据权利要求4所述的石墨烯水性聚氨酯安全套用水性聚氨酯乳液的应用，其特征在于，用于制备安全套。
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