CN104892893B - 一种具有抗菌功能的聚氨酯坐垫材料及其制备方法与应用 - Google Patents
一种具有抗菌功能的聚氨酯坐垫材料及其制备方法与应用 Download PDFInfo
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Abstract
本发明公开了一种具有抗菌功能的聚氨酯坐垫材料及其制备方法与应用。该材料的结构式如式I所示。本发明以聚醚多元醇组合物和异氰酸酯为基本原料,加入喹诺酮类抗菌剂参与缩聚反应,得到该具有抗菌功能的聚氨酯坐垫材料。该材料将喹诺酮类抗菌剂固定于聚氨酯材料,具有持久抗菌、安全无害、高效的效果;且该材料的硬度、透气性和弹性性能优良。因此,可将其制备聚氨酯坐垫。
Description
技术领域
本发明属于高分子材料领域,特别涉及一种具有抗菌功能的聚氨酯坐垫材料及其制备方法与应用。
背景技术
众所周知,软质聚氨酯是通过多元醇组合物和异氰酸酯在发泡剂存在的情况下通过缩聚反应得到的。而软质聚氨酯泡沫因其具有优异的柔软性、回弹性、机械性能和独特的耐油、抗溶剂性能而被广泛应用于座椅座垫的制备中。
随着聚氨酯工艺的成熟,越来越多的聚氨酯材料被应用于公共座椅上,出于对柔软感、透气性能等要求,对于应用于座垫的聚氨酯材料的要求也越来越高。鉴于座椅的高使用频率、潮湿的天气影响以及缺乏及时的清洁,长时间下座垫上会滋生大量的微生物(细菌、真菌),并且在公共场所容易传播疾病,对于人体的健康产生非常大的威胁。
因此,希望能开发出一种具有持久抗菌能力的聚氨酯座垫材料,在能够高效地抑制细菌、真菌等微生物在座垫上繁衍的同时,能够保持其杀菌性能的稳定性,且加入的杀菌材料对人体无害,安全。
发明内容
本发明的首要目的在于克服现有技术的缺点与不足,提供一种具有抗菌功能的聚氨酯坐垫材料。
本发明的另一目的在于提供所述具有抗菌功能的聚氨酯坐垫材料的制备方法。
本发明的再一目的在于提供所述具有抗菌功能的聚氨酯坐垫材料的应用。
本发明的目的通过下述技术方案实现:一种具有抗菌功能的聚氨酯坐垫材料,结构式如式I所示:
其中,R1为R2为R3为
所述的n为214~500。
所述的m为1~308。
所述具有抗菌功能的聚氨酯坐垫材料的制备方法,是以聚醚多元醇组合物和异氰酸酯为基本原料,加入喹诺酮类抗菌剂参与缩聚反应,得到该具有抗菌功能的聚氨酯坐垫材料;优选包括如下步骤:
(1)将聚醚多元醇组合物和异氰酸酯为原料进行加成反应,生成末端带-NCO基的预聚体;
(2)将喹诺酮类抗菌剂与预聚体为原料进行缩聚反应,得到具有抗菌功能的聚氨酯坐垫材料,反应过程如下:
其中,R1为R2为
R3-COOH为喹诺酮类抗菌剂,R3为
所述具有抗菌功能的聚氨酯坐垫材料的制备方法,更优选为包含如下步骤:
①按照聚醚多元醇组合物、喹诺酮类抗菌剂、催化剂、发泡剂、泡沫稳定剂、扩链剂的加料顺序,将各原料逐步添加到反应容器中,边加料,边搅拌;
②搅拌均匀后加入异氰酸酯,得到混合液体;
③将混合液体于50~60℃反应,得到具有抗菌功能的聚氨酯坐垫材料;其中,各原料的用量按质量份计,如下:聚醚多元醇组合物100份、异氰酸酯40~50份、喹诺酮类抗菌剂0.3~0.5份、催化剂0.5~1份、发泡剂6.5~17份、泡沫稳定剂0.2~0.5份、扩链剂6~10份。
所述的聚醚多元醇组合物对于聚氨酯泡沫的发泡性、透气性与强度等性质都具有重要的影响。本发明通过合理的选择和搭配,聚醚多元醇组合物具有如下特征时,性能更优异:所述的聚醚多元醇组合物由聚醚多元醇和聚合物多元醇组成;优选由聚醚多元醇和聚合物多元醇按质量比4:1配比。
所述的聚醚多元醇优选为平均官能团数为2~3,羟值为33~37mgKOH/g、平均相对分子质量在2000~6500的聚醚多元醇。
所述的聚合物多元醇优选为平均官能团数为2~3,羟值为22~26mgKOH/g、平均相对分子质量在5000~6500的聚合物多元醇。
所述的聚醚多元醇组合物优选为具有如式II所示的聚醚多元醇组合物:
其中,n为214~500。
所述的异氰酸酯优选为结构式如式III所示的4,4’-二苯基甲烷二异氰酸酯,NCO值为22~28%;
所述的异氰酸酯的用量优选为46~47质量份,更优选为46质量份。
所述的喹诺酮类抗菌剂优选为如式IV所示的恩氟奎林羧酸、如式V所示的萘啶酸和如式VI所示的氟哌酸中的至少一种;
所述的喹诺酮类抗菌剂的用量优选为0.3~0.4质量份,更优选为0.3质量份。
所述的催化剂为三亚乙基二胺、延迟催化剂和二甲基乙醇胺(DMEA)中的至少一种。
所述的三亚乙基二胺优选为溶剂为DPG、三亚乙基二胺的含量为33%(w/v)的三亚乙基二胺。
所述的延迟催化剂优选为双(二甲基胺基乙基)醚。
所述的双(二甲基胺基乙基)醚优选为溶剂为DPG、双(二甲基胺基乙基)醚含量为70%(w/v)的双(二甲基胺基乙基)醚。
所述的催化剂的用量优选为0.6~1质量份;更优选为0.6质量份。
所述的发泡剂为环戊烷、一氟二氯乙烷(HCFC-141b)和一氟三氯甲烷(CFC-11)中的至少一种。
所述的发泡剂的用量优选为7质量份。
所述的泡沫稳定剂为PU-1253硅油和PU-1231硅油中的一种或两种。
所述的泡沫稳定剂的用量优选为0.3~0.4质量份,更优选为0.3质量份。
所述的扩链剂为乙二醇、1,4-丁二醇和一缩二乙二醇中的至少一种。
所述的扩链剂的用量优选为6~7质量份,更优选为7质量份。
所述的具有抗菌功能的聚氨酯坐垫材料在制备聚氨酯坐垫中的应用。
一种具有抗菌功能的聚氨酯坐垫,由上述具有抗菌功能的聚氨酯坐垫材料制备得到。
所述的具有抗菌功能的聚氨酯坐垫的制备方法,包括如下步骤:
①按照聚醚多元醇组合物、喹诺酮类抗菌剂、催化剂、发泡剂、泡沫稳定剂、扩链剂的加料顺序,将各原料逐步添加到反应容器中,边加料,边搅拌;
②搅拌均匀后加入异氰酸酯,得到混合液体;
③将混合液体的温度维持在50~60℃;将发泡模板预热到50℃,然后将混合液体注入发泡模具的型腔中,随即开始发泡,再打开模具,得到聚氨酯座垫。
步骤②中所述的搅拌的时间优选为5min。
步骤③中所述的发泡的时间优选为4min。
本发明相对于现有技术具有如下的优点及效果:
本发明中,由于加入的抗菌剂具有基团-COOH,其羧基中的活泼氢在缩聚反应中能够与异氰酸根反应而以共价键的形式结合,使得抗菌剂固定于聚氨酯材料中,不以游离的形式存在,从而抗菌剂不会流失而抗菌功效不会随着时间的推移而减弱,且抗菌剂与异氰酸酯反应生成CO2有助于发泡。本发明所选择的喹诺酮类抗菌剂具有长效抗菌效果,对人体无害。因此本发明具有持久抗菌、安全无害、高效的效果。
具体实施方式
下面结合实施例对本发明作进一步详细的描述,但本发明的实施方式不限于此。
实施例1~4及对比例1
一、按照表1的发泡原液成分配比,配料准备原料,然后按照多元醇聚合物、抗菌剂、催化剂、发泡剂、泡沫稳定剂、扩链剂的加料顺序,将各原料逐步添加到混合容器中,边加料,边搅拌,搅拌5分钟后再加入4,4’-二苯基甲烷二异氰酸酯。待混合液体维持温度在50℃;将发泡模板预热到50℃,然后将混合液体注入发泡模具的型腔中,随即开始发泡,待4min后打开模具便可得到聚氨酯座垫。
表1
A-1(聚醚多元醇):环氧乙烷-环氧丙烷嵌段共聚物,官能度为2-3,羟值为33-37mgKOH/g(上海高桥,牌号为330n聚醚多元醇)。
A-2(聚合物多元醇):乙烯基聚合物接枝聚醚多元醇,官能度为2-3,羟值为22-26mgKOH/g(上海高桥,牌号为3630聚合物多元醇)。
B(异氰酸酯):4,4’-二苯基甲烷二异氰酸酯,NCO值为22-28%。
C-1(催化剂):三乙烯二胺的33%DPG溶液,即溶剂为DPG,三乙烯二胺的浓度为质量体积比33%。
C-2(催化剂):双(2-二甲基胺基乙基)醚的70%DPG溶液,即溶剂为DPG,双(2-二甲基胺基乙基)醚的浓度为质量体积比70%。
C-3(催化剂):二甲基乙醇胺(DMEA)。
D-1(发泡剂):环戊烷。
D-2(发泡剂):HCFC-141b。
D-3(发泡剂):CFC-11。
E1(泡沫稳定剂):PU-1253硅油。
E2(泡沫稳定剂):PU-1231硅油。
F1(扩链剂):乙二醇。
F2(扩链剂):1,4-丁二醇。
F3(扩链剂):一缩二乙二醇。
G-1(抗菌剂):恩氟奎林羧酸抗菌剂。
G-2(抗菌剂):萘啶酸抗菌剂。
G-3(抗菌剂):氟哌酸抗菌剂。
H-1(抗菌剂):季铵盐(商业编号为“FRESCHE 3851ANTIMICROBIAL”,澳大利亚Fresche Bioscience公司)。
硬度通过硬度测试仪器(上海自九具有限公司硬度计)检测。
抗菌实验采用QB/T 4341-2012附录D抑菌圈方法,测试细菌种为大肠杆菌ATCC8739(上海宝录生物科技有限公司)和金黄色葡萄球菌ATCC 6538p(上海复祥生物科技有限公司),真菌种为青霉菌BGWWW23218(南京便诊生物科技有限公司)。
二、空白实验对比
分别将0.1g季铵盐抗菌剂和0.1g恩氟奎林羧酸抗菌剂滴在两片大小相同的滤纸上,分别测试两者对大肠杆菌的抗菌效果,数据如下表2所示:
表2
样品名 | 抑菌圈直径(cm) |
季铵盐抗菌剂 | 1.8 |
奎诺酮抗菌剂 | 2 |
上述实验结果表明,市面上所销售的应用于抗菌聚氨酯材料中的季铵盐抗菌剂的用量为本发明所用抗菌剂的十倍,但是抑菌圈小于本发明所用抗菌剂得到的抑菌圈。可见,将奎诺酮抗菌剂用于制备聚氨酯坐垫材料,具有优异的抗菌效果。
上述实施例为本发明较佳的实施方式,但本发明的实施方式并不受上述实施例的限制,其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化,均应为等效的置换方式,都包含在本发明的保护范围之内。
Claims (8)
1.一种具有抗菌功能的聚氨酯坐垫材料,其特征在于其结构式如式I所示:
其中,R1为R2为R3为
n为214~500;
m为1~308;
该具有抗菌功能的聚氨酯坐垫材料通过如下步骤得到:是以聚醚多元醇组合物和异氰酸酯为基本原料,加入喹诺酮类抗菌剂参与缩聚反应,得到该具有抗菌功能的聚氨酯坐垫材料;
所述的异氰酸酯为4,4’-二苯基甲烷二异氰酸酯;
所述的喹诺酮类抗菌剂为恩氟奎林羧酸或萘啶酸。
2.权利要求1所述的具有抗菌功能的聚氨酯坐垫材料的制备方法,其特征在于步骤如下:是以聚醚多元醇组合物和异氰酸酯为基本原料,加入喹诺酮类抗菌剂参与缩聚反应,得到该具有抗菌功能的聚氨酯坐垫材料;
所述的异氰酸酯为4,4’-二苯基甲烷二异氰酸酯;
所述的喹诺酮类抗菌剂为恩氟奎林羧酸或萘啶酸。
3.根据权利要求2所述的具有抗菌功能的聚氨酯坐垫材料的制备方法,其特征在于包括如下步骤:
①按照聚醚多元醇组合物、喹诺酮类抗菌剂、催化剂、发泡剂、泡沫稳定剂、扩链剂的加料顺序,将各原料逐步添加到反应容器中,边加料,边搅拌;
②搅拌均匀后加入异氰酸酯,得到混合液体;
③将混合液体于50~60℃反应,得到具有抗菌功能的聚氨酯坐垫材料;
其中,各原料的用量按质量份计,如下:聚醚多元醇组合物100份、异氰酸酯40~50份、喹诺酮类抗菌剂0.3~0.5份、催化剂0.5~1份、发泡剂6.5~17份、泡沫稳定剂0.2~0.5份、扩链剂6~10份。
4.根据权利要求3所述的具有抗菌功能的聚氨酯坐垫材料的制备方法,其特征在于:
所述的异氰酸酯为4,4’-二苯基甲烷二异氰酸酯,NCO值为22~28%;
所述的催化剂为三亚乙基二胺、延迟催化剂和二甲基乙醇胺中的至少一种;
所述的发泡剂为环戊烷、一氟二氯乙烷和一氟三氯甲烷中的至少一种;
所述的泡沫稳定剂为PU-1253硅油和PU-1231硅油中的一种或两种;
所述的扩链剂为乙二醇、1,4-丁二醇和一缩二乙二醇中的至少一种。
5.根据权利要求4所述的具有抗菌功能的聚氨酯坐垫材料的制备方法,其特征在于:
所述的异氰酸酯的用量为46~47质量份;
所述的喹诺酮类抗菌剂的用量为0.3~0.4质量份;
所述的催化剂的用量为0.6~1质量份;
所述的泡沫稳定剂的用量为0.3~0.4质量份;
所述的扩链剂的用量为6~7质量份。
6.权利要求1所述的具有抗菌功能的聚氨酯坐垫材料在制备聚氨酯坐垫中的应用。
7.一种具有抗菌功能的聚氨酯坐垫,其特征在于:由权利要求1所述具有抗菌功能的聚氨酯坐垫材料制备得到。
8.权利要求7所述的具有抗菌功能的聚氨酯坐垫的制备方法,其特征在于包括如下步骤:
①按照聚醚多元醇组合物、喹诺酮类抗菌剂、催化剂、发泡剂、泡沫稳定剂、扩链剂的加料顺序,将各原料逐步添加到反应容器中,边加料,边搅拌;
②搅拌均匀后加入异氰酸酯,得到混合液体;
③将混合液体的温度维持在50~60℃;将发泡模板预热到50℃,然后将混合液体注入发泡模具的型腔中,随即开始发泡,再打开模具,得到聚氨酯座垫。
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