CN106947097A - 石墨烯贴合纳米氮化硼复合乳胶制备夹层无敏隔绝避孕套的方法 - Google Patents
石墨烯贴合纳米氮化硼复合乳胶制备夹层无敏隔绝避孕套的方法 Download PDFInfo
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Abstract
本发明涉及复合材料及医疗器械领域，具体为一种石墨烯贴合纳米氮化硼复合乳胶制备夹层无敏、高隔绝避孕套的方法。首先将电场处理的石墨烯与改性的六方纳米片层氮化硼按5％～2000％的固体质量比例，贴合复合。然后以固体质量比例0.05‰～10‰复合到胶乳中，制备的复合乳胶液是第二次浸渍时使用。在第一次和第三次浸渍时均为正常的胶乳材料浸渍，最终制成含三明治结构的无敏，高隔绝避孕套。本发明制备的避孕套具有很稳定的透明色泽，不易出现改性石墨烯变质而发灰发暗、皮肤接触过敏、耐候稳定性差等缺陷。石墨烯与具有“白色石墨烯”之称的纳米片层氮化硼复合后，可增强胶乳拉伸强度、韧性、导热，有效阻隔病毒液体的渗透。
Description
技术领域
本发明涉及复合材料及医疗器械领域，具体为一种石墨烯贴合纳米氮化硼复合乳胶制备夹层无敏、高隔绝避孕套的方法。
背景技术
避孕套绝大部分材质是天然胶乳，它的优点很多，缺点也有一些，如：胶乳天然的形成直径从几百到几千纳米的微孔[1]，一些艾滋病(最大直径：120nm)、乙肝(最大直径42nm)、人体乳头瘤(最大直径55nm)等可能有透过微孔传播的几率。
石墨烯和六方纳米片层氮化硼均为二维纳米材料，具有极高的片径/厚度比，有很好的韧性和不可透过性[2]。但是所有改性石墨烯、氧化石墨烯及还原石墨烯都会久置后变为灰黑色，即便是CVD的本征态石墨烯团聚后也会呈现灰色。所以，单纯由石墨烯复合胶乳避孕套不可避免发生色泽不稳定，影响使用观感和性能耐候性。如下图为盖茨基金资助的曼彻斯特大学的石墨烯避孕套项目的研发产品。由图可看出添加的石墨烯越多，避孕套越灰越暗[3]。
对比国际专利申请：PCT/IN2014/000711，公布号:WO/2015/068174，标题：GRAPHENE BASED POLYMER COMPOSITES FOR PRODUCING CONDOMS WITH HIGH HEATTRANSFER,IMPROVED SENSITIVITY AND CAPACITY FOR DRUG DELIVERY(一种石墨烯基聚合物复合材料生产高导热、低过敏、可药物输送的避孕套)，文中也是使用单纯的石墨烯或衍生物来复合胶乳等聚合物制造避孕套，同样也会极大概率的遇到耐候差，色泽加深的问题。
参考文献：
[1]Kerr L.,Chaput M.,Boyd S.,Galevi E.,Millward P.,Characterizationand creation of defects in condoms,Journal of testing and evaluation,2001,29,214；
[2]Y.Su,V.G.Kravets,S.L.Wong,J.Waters,A.K.Geim,R.R.Nair,Impermeablebarrier films and protective coatings based on reduced graphene oxide.NatureCommunications 2014,5,4843；
[3]MariaIliuta,Claudio Silvaa,b,Scott Herrickc,Mark McGlothlinc,Aravind Vijayaraghavana,Graphene and water-based elastomers thin-filmcomposites by dip-moulding.Carbon,106,2016,228-232。
发明内容
本发明的目的在于提供一种石墨烯贴合纳米氮化硼复合乳胶制备夹层无敏、高隔绝避孕套的方法，所得避孕套比纯石墨烯复合避孕套比，具有更稳定的色泽和透光度，惰性不过敏，同时也可有效增强阻隔性、力学性能、导热性。
为了实现上述目的，本发明采用以下技术方案：
一种石墨烯贴合纳米氮化硼复合乳胶制备夹层无敏隔绝避孕套的方法，首先将电场处理的石墨烯与改性的六方纳米片层氮化硼按5％～2000％的固体质量比例，贴合复合；然后以固体质量比例0.05‰～10‰复合到胶乳中，制备成石墨烯贴合纳米氮化硼/胶乳复合乳胶液；采用三次浸渍工艺成型，第一次和第三次浸渍时为常规胶乳浸渍，第二次浸渍时，浸渍液为石墨烯贴合纳米氮化硼/胶乳复合胶乳液，最终制成最内表面和最外表面为常规胶乳膜、中间是石墨烯贴合六方纳米片层氮化硼复合乳胶的避孕套。
所述的石墨烯贴合纳米氮化硼复合乳胶制备夹层无敏隔绝避孕套的方法，在制备贴合体分散液时，贴合体石墨烯和六方纳米片层氮化硼的固体份质量比例为：5％～2000％；贴合体的分散体系是pH在4.5～8的水系分散液，根据石墨烯的尺寸种类和比例调节。
所述的石墨烯贴合纳米氮化硼复合乳胶制备夹层无敏隔绝避孕套的方法，在制备贴合体分散液时，贴合体填料与胶乳的固体份质量比例为0.05‰～10‰。
所述的石墨烯贴合纳米氮化硼复合乳胶制备夹层无敏隔绝避孕套的方法，所用六方纳米片层氮化硼是各种方法制备的六方氮化硼单层结构或少层结构，氮化硼的层数为1～30层，即厚度为10nm以下，六方氮化硼各层间距为0.335nm；所用六方纳米片层氮化硼用表面活性剂改性，获得与要贴合的石墨烯片表面相反的电荷；表面活性剂是非离子型表面活性剂、阴离子表面活性剂、阳离子表面活性剂的一种类型或复配类型。
所述的石墨烯贴合纳米氮化硼复合乳胶制备夹层无敏隔绝避孕套的方法，贴合氮化硼的石墨烯是电场处理的石墨烯，处理方法是简单正负电极板对石墨烯溶液施加电场，从而负载石墨烯表面电荷；或者，用电渗析设备完成石墨烯胶体的荷电目的。
所述的石墨烯贴合纳米氮化硼复合乳胶制备夹层无敏隔绝避孕套的方法，电场处理的石墨烯是高度亲水、高透光率的石墨烯，石墨烯的氧含量大于20wt％，层数小于三层。
本发明的设计思想是：
六方氮化硼BN与石墨都是等电子体层状结构，有白色石墨之称，单层氮化硼称为“白色石墨烯”透明无色，具有良好的润滑性，导热性和物化惰性，与生物细胞不会有过敏排异效应。由于氮化硼纳米片本身无色透明，即便纳米堆叠也不会有什么颜色变化。结合两个方面，通过本发明技术角度和手段，将六方纳米片层氮化硼与石墨烯通过静电吸引的软团聚，形成贴合体，然后再和胶乳复合制造避孕套。既减少石墨烯在胶乳中的含量，保持高透明度，又增强避孕套的导热性能，还不降低避孕套的力学性质。同时为了避免极少数人群对添加物石墨烯的过敏，特意设计复合增强填料为夹层，避免与使用者的肌肤接触，引发皮肤或黏膜的不适(本身对纯胶乳制品也过敏的使用者除外)。
因此，石墨烯贴合纳米氮化硼复合乳胶制备夹层无敏、高隔绝避孕套是一种很有市场潜力的创新工艺思路。
与现有技术相比，本发明的优点及有益效果是：
1、本发明将电场处理的石墨烯与改性的六方纳米片层氮化硼按5％～2000％的固体比例，贴合复合。然后以固体质量比例0.05‰～10‰复合到胶乳中，制备的复合乳胶液是第二次浸渍时使用。在第一次和第三次浸渍时均为正常的胶乳材料浸渍，最终制成含三明治结构的无敏，高隔绝避孕套。不同于一般石墨烯避孕套，本发明制备的避孕套具有很稳定的透明色泽，不易出现改性石墨烯变质而发灰发暗、皮肤接触过敏、耐候稳定性差等缺陷。石墨烯与具有“白色石墨烯”之称的纳米片层氮化硼复合后，可增强胶乳拉伸强度、韧性、导热，有效阻隔病毒液体的渗透。
2、本发明具有原理科学、惰性无毒、耐候性好的特点，可制造出超薄、高导热、高隔绝的避孕套。
附图说明
图1.石墨烯贴合纳米氮化硼复合乳胶制备夹层无敏、高隔绝避孕套的方法流程图。
图2.石墨烯贴合纳米氮化硼复合乳胶制备夹层无敏、高隔绝避孕套的材料微观结构示意图。图中，1避孕套；2贴合体强化隔绝层；3乳胶橡胶层；4橡胶粒子；5石墨烯和氮化硼片层贴合体。
具体实施方式
如图1所示，本发明石墨烯贴合纳米氮化硼复合乳胶制备夹层无敏、高隔绝避孕套的方法流程如下：带负电/正电荷的石墨烯胶体和氮化硼胶体，通过静电吸引贴合，形成石墨烯/氮化硼纳米片层贴合体，加入胶乳液后，制成石墨烯贴合氮化硼/胶乳夹层避孕套。
如图2所示，石墨烯贴合纳米氮化硼复合乳胶制备夹层无敏、高隔绝避孕套的材料微观结构如下：避孕套1的壁厚方向分三层，中间夹层为贴合体强化隔绝层2，贴合体强化隔绝层2的两侧分别为乳胶橡胶层3。其中，贴合体强化隔绝层2为橡胶粒子4、石墨烯和氮化硼片层贴合体5组成。
在具体实施过程中，本发明首先制备石墨烯/六方纳米片层氮化硼贴合体溶液：0.05wt‰～10wt‰(优选范围为：0.5wt‰～2wt‰)浓度的石墨烯水溶液经过电场荷电后带上负电荷，在搅拌的条件下，将0.05wt‰～10wt‰(优选范围为：1wt‰～4wt‰)浓度的六方氮化硼纳米片层材料的溶液用表面活性剂改性。然后将二者混合搅拌、使之发生静电吸附贴合，通过控制溶液中氧化石墨烯或盐酸在水里的比例来调节pH值，使之在4.5～8范围，如亲水氧化石墨烯或稀盐酸提供基础的酸性，用水的含量、其它种类的改性石墨烯及改性的六方纳米片层氮化硼综合一起调节最终的pH值。然后超声，使贴合体分散均匀。贴合体分散液中，石墨烯固体质量与氮化硼质量比为：5wt％～2000wt％(优选范围为：40wt％～80wt％)。贴合体的分散液与胶乳液混合均匀，制成复合的胶乳液，贴合体溶液固含量与胶乳中的固体份质量比例为0.05wt‰～10wt‰(优选范围为：0.2wt‰～0.5wt‰)。采用三次浸渍工艺成型，第一次和第三次浸渍时为常规胶乳浸渍，第二次浸渍时，浸渍液为石墨烯贴合纳米氮化硼/胶乳复合胶乳液，最终制成最内表面和最外表面为常规胶乳膜，中间是石墨烯贴合六方纳米片层氮化硼复合乳胶的避孕套。
其中，所用六方纳米片层氮化硼可以是1～30层左右，即厚度为10nm以下(六方氮化硼各层间距为0.335nm)。所用六方纳米片层氮化硼可以用表面活性剂改性，获得与要贴合的石墨烯片表面相反的电荷。表面活性剂可以是非离子型表面活性剂、阴离子表面活性剂、阳离子表面活性剂的一种类型或一定比例的复配类型。电场处理的石墨烯是高度亲水、高透光率的石墨烯，石墨烯的氧含量大于20wt％，层数小于三层，电性与要复合的六方纳米片层氮化硼溶液胶体相反。
为了方便调节贴合体的分散体系pH值，可选择水氧化石墨烯及改性的六方纳米片层氮化硼体系，或其它非氧化石墨烯与稀盐酸与改性的六方纳米片层氮化硼体系，通过调节水中浓度、及其相互剥离，获得需要的pH值。贴合氮化硼的石墨烯是电场处理的石墨烯，处理方法可以是简单正负电极板对石墨烯溶液施加电场，从而负载石墨烯表面电荷，或用电渗析设备完成石墨烯胶体的荷电目的，然后采用三次浸渍，做成夹层形式。
下面，通过实施例及测试结果对本发明进一步详细说明。
实施例1
本实施例中，石墨烯贴合纳米氮化硼复合乳胶制备夹层无敏隔绝避孕套的方法如下：
石墨烯/六方纳米片层氮化硼贴合体溶液制备：1㎏浓度为2wt‰的氧化石墨烯水溶液经过电场荷电后带上负电荷。将含0.1wt‰六方氮化硼纳米片层材料的水溶液1㎏用0.1wt‰的聚乙烯吡咯烷酮改性。然后将二者混合搅拌超声，使之分散均匀。然后在干净的混料桶中加入10Kg浓度为60wt％的天然胶乳，在搅拌条件下逐步加入前面配好的2Kg浓度为2.1wt‰的石墨烯/六方纳米片层氮化硼贴合体溶液，加入完毕后，可适量加入0.1wt‰分散稳定剂平平加O(烷基聚氧乙烯醚)，持续搅拌1个小时使其混合均匀。此时调节粘度为15mPa·s左右。将复合后的胶液静置24小时左右，使其充分熟化，然后加入浸渍机中采用三次浸渍，做成夹层形式。
为了验证本发明所制备新材料及避孕套产品的性能优势，发明人依据国家标准GB7544-2009《天然乳胶橡胶避孕套技术要求和实验方法》，对实施例1所制备的批量的石墨烯/乳胶复合避孕套进行抽检测试，作为对比，试验中同时抽检测试利用实施例1相同工艺过程制备的纯天然乳胶避孕套，以及某市售品牌天然乳胶避孕套的相关性能指标，结果对比如表1所示：
表1：本例批量抽检复合避孕套的性能指标及对比
由表实检数据可得出结论：在对比的产品尺寸基本一致的情况下，石墨烯/氮化硼夹层避孕套的各项检测指标都优于市售某品牌胶乳避孕套。同时也不比纯石墨烯避孕套的性能差的情况下，外观透明度更优于后者。
实施例2
本实施例中，石墨烯贴合纳米氮化硼复合乳胶制备夹层无敏隔绝避孕套的方法如下：
石墨烯/六方纳米片层氮化硼贴合体溶液制备：1㎏浓度为1wt‰的氧化石墨烯和浓度为1wt‰氨基化石墨烯水溶液经过电渗析荷电后带上负电荷。将含0.1wt‰六方氮化硼纳米片层材料的水溶液1㎏用0.1wt‰的十二烷基磺酸钠改性。然后将二者混合搅拌超声，使之分散均匀。然后在干净的混料桶中加入10Kg浓度为60wt％的天然胶乳，在搅拌条件下逐步加入前面配好的2Kg浓度为2.1wt‰的石墨烯/六方纳米片层氮化硼贴合体溶液，加入完毕后，可适量加入0.1wt‰分散稳定剂聚乙烯吡咯烷酮，持续搅拌1个小时使其混合均匀。此时调节粘度为20mPa·s左右。将复合后的胶液静置24小时左右，使其充分熟化，然后加入浸渍机中采用三次浸渍，做成夹层形式。
实施例结果表明，将本发明制备的石墨烯贴合纳米氮化硼复合乳胶制备夹层无敏隔绝避孕套浸泡到水合肼等还原性液体中，均不发生变色，避孕套内外膜电阻率也没有变化，说明橡胶粒子、石墨烯和氮化硼片层贴合体组成的贴合体强化隔绝层作为避孕套增强的中间夹层是很稳定很安全的。本发明所制备的石墨烯贴合纳米氮化硼复合乳胶制备夹层无敏隔绝避孕套产品具有极佳的阻隔性能和优异的力学性能，正确使用这种安全套产品，可有效阻隔小尺寸病毒及微生物的性传播。
上面所述的实施例仅仅是对本发明的优选实施方式进行描述，并非对本发明的范围进行限定，在不脱离本发明创造设计的精神前提下，本领域普通工程技术人员对本发明技术方案做出的各种变形和改进，均应落入本发明的权利要求书确定的保护范围内。
Claims (6)
1.一种石墨烯贴合纳米氮化硼复合乳胶制备夹层无敏隔绝避孕套的方法，其特征在于，首先将电场处理的石墨烯与改性的六方纳米片层氮化硼按5％～2000％的固体质量比例，贴合复合；然后以固体质量比例0.05‰～10‰复合到胶乳中，制备成石墨烯贴合纳米氮化硼/胶乳复合乳胶液；采用三次浸渍工艺成型，第一次和第三次浸渍时为常规胶乳浸渍，第二次浸渍时，浸渍液为石墨烯贴合纳米氮化硼/胶乳复合胶乳液，最终制成最内表面和最外表面为常规胶乳膜、中间是石墨烯贴合六方纳米片层氮化硼复合乳胶的避孕套。
2.按照权利要求1所述的石墨烯贴合纳米氮化硼复合乳胶制备夹层无敏隔绝避孕套的方法，其特征在于，在制备贴合体分散液时，贴合体石墨烯和六方纳米片层氮化硼的固体份质量比例为：5％～2000％；贴合体的分散体系是pH在4.5～8的水系分散液，根据石墨烯的尺寸种类和比例调节。
3.按照权利要求2所述的石墨烯贴合纳米氮化硼复合乳胶制备夹层无敏隔绝避孕套的方法，其特征在于，在制备贴合体分散液时，贴合体填料与胶乳的固体份质量比例为0.05‰～10‰。
4.按照权利要求1所述的石墨烯贴合纳米氮化硼复合乳胶制备夹层无敏隔绝避孕套的方法，其特征在于，所用六方纳米片层氮化硼是各种方法制备的六方氮化硼单层结构或少层结构，氮化硼的层数为1～30层，即厚度为10nm以下，六方氮化硼各层间距为0.335nm；所用六方纳米片层氮化硼用表面活性剂改性，获得与要贴合的石墨烯片表面相反的电荷；表面活性剂是非离子型表面活性剂、阴离子表面活性剂、阳离子表面活性剂的一种类型或复配类型。
5.按照权利要求1所述的石墨烯贴合纳米氮化硼复合乳胶制备夹层无敏隔绝避孕套的方法，其特征在于，贴合氮化硼的石墨烯是电场处理的石墨烯，处理方法是简单正负电极板对石墨烯溶液施加电场，从而负载石墨烯表面电荷；或者，用电渗析设备完成石墨烯胶体的荷电目的。
6.按照权利要求1所述的石墨烯贴合纳米氮化硼复合乳胶制备夹层无敏隔绝避孕套的方法，其特征在于，电场处理的石墨烯是高度亲水、高透光率的石墨烯，石墨烯的氧含量大于20wt％，层数小于三层。
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| CN113121892A (zh) * | 2021-04-15 | 2021-07-16 | 桂林恒保健康防护有限公司 | 一种导热碳分子复合胶乳制备导热超薄避孕套的方法 |
| CN116836418A (zh) * | 2023-08-31 | 2023-10-03 | 广州双一乳胶制品有限公司 | 一种抗老化的避孕套及其制备方法 |
| CN116836418B (zh) * | 2023-08-31 | 2023-11-28 | 广州双一乳胶制品有限公司 | 一种抗老化的避孕套及其制备方法 |
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