CN112538151B - 一种缓释香味凉感抗菌的聚氨酯海绵及其制备方法 - Google Patents
一种缓释香味凉感抗菌的聚氨酯海绵及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种缓释香味凉感抗菌的聚氨酯海绵及其制备方法。聚氨酯海绵由异氰酸酯和聚醚多元醇聚合形成,在聚氨酯海绵聚合过程中,加入β‑CD环糊精或β‑CD环糊精的包合物和壳聚糖微胶囊,β‑CD环糊精的包合物、壳聚糖微胶囊的囊芯为薄荷醇、木糖醇或薄荷醇与木糖醇的复合物。本发明的优点在于:将微胶囊和β‑CD或β‑CD包合物加入聚氨酯海绵聚合单体中,壳聚糖或β‑CD的活性基团参与聚氨酯的聚合反应,具有包合消臭的β‑CD环糊精能锚固在聚氨酯海绵中;聚合过程中部分从壳聚糖微胶囊中释放的薄荷醇或木糖醇,也可以重新被锚固在海绵上的β‑CD环糊精包合,制备的缓释香味凉感抗菌的海绵具有长效凉感和芳香消臭、抗菌优良性能。
Description
技术领域
本发明涉及家居海绵技术领域,具体涉及一种缓释香味凉感抗菌的聚氨酯海绵及其制备方法。
背景技术
聚氨酯海绵就是泡沫密度低于18kg/m3以下的低密度PU,记忆海绵就属于聚氨酯海绵的一种。目前生产聚氨酯海绵的主要技术有采用负压发泡技术、强制冷却技术和液态二氧化碳发泡技术。聚氨酯海绵除具备聚醚海绵的特性以外,还具备耐酸碱、耐潮、耐磨损、抗腐蚀、耐热、拉伸性好等独特特性,并且商品具有泡孔匀称、光泽度好、与纺织物复合型粘接率强等特性,广泛运用于高级车内饰,高端复合材料、植绒布、护肤品、打印机耗材、过滤等行业。
应用于家居领域的聚氨酯海绵,会具有蓄热的特性,因此在夏天温度持续上扬或者久坐久躺的环境之中,聚氨酯海绵垫会有闷热不适的感觉。另外,人体的汗味和体味对床品的微环境和睡眠质量也有重要影响,床品沾污的汗液、皮脂以及其他各种人体分泌物,这些不仅影响人们的使用,而且是微生物繁殖的良好环境,因此迫切需要开发具有舒适保健功能的聚氨酯海绵,以制成床垫、枕垫、坐垫等家居用品。
发明内容
本发明要解决的技术问题是提供一种缓释香味凉感抗菌的聚氨酯海绵及其制备方法,能够解决目前聚氨酯海绵家居用品使用时闷热不适、体味汗味等影响睡眠微环境的问题。
为解决上述技术问题,本发明的技术方案为:一种缓释香味凉感抗菌的聚氨酯海绵,由异氰酸酯和聚醚多元醇聚合形成聚氨酯海绵,在聚氨酯海绵聚合过程中,还加入壳聚糖微胶囊和β-CD环糊精或β-CD环糊精的包合物,所述β-CD环糊精的包合物的芯材、壳聚糖微胶囊的囊芯为薄荷醇、木糖醇或薄荷醇与木糖醇的复合物。
进一步地,聚氨酯海绵由以下重量份的组分组成:聚醚多元醇90-110份、MDI二苯基甲烷二异氰酸酯或TDI甲苯二异氰酸酯30-70份、链延长剂0-0.5份、高效泡沫稳定剂0.5-5份、高效复合催化剂0.1-1.0份、外发泡剂0-6份、水1-5份、β-CD环糊精或羟丙基β-CD环糊精、β-CD环糊精包合物、羟丙基β-CD环糊精包合物0.2-0.5份、壳聚糖微胶囊0.2-0.5份。
进一步地,所述薄荷醇和木糖醇的复合物的复合质量比为1:1-3。
进一步地,所述链延长剂为多元醇或二胺类低分子化合物,所述高效泡沫稳定剂为有机硅泡沫稳定剂或聚硅氧烷-聚氧化烯烃镶嵌共聚物,所述高效复合催化剂为锡类催化剂、胺类催化剂,所述外发泡剂为用于聚氨酯发泡的物理发泡剂,所述聚醚多元醇是用于聚氨酯发泡的聚醚。
进一步地,聚氨酯海绵的一种制备步骤如下:
S1、异氰酸酯和聚醚多元醇聚合时,在聚醚多元醇、MDI二苯基甲烷二异氰酸酯TDI甲苯二异氰酸酯、链延长剂、高效泡沫稳定剂、高效复合催化剂、外发泡剂、水中加入壳聚糖微胶囊、β-CD环糊精或羟丙基β-CD环糊精、β-CD环糊精包合物、羟丙基β-CD环糊精的包合物,制成原料进行聚合和发泡;
发泡为开放连续式低压平泡,将原料通过发泡喷嘴喷至发泡系统输送装置,边发泡边传送,同时对输送装置进行限位,控制聚氨酯海绵的宽度,聚氨酯海绵的厚度由原料的流量和输送速度控制,调节混合头的输出量满足泡沫的宽厚需求,并通过调节输送速度和降落板位置,控制泡沫顶部高度及弧度,获得所需的泡沫流型;
S2、大尺寸聚氨酯海绵发泡完成后,采用后续的切割技术进行异形切割。
进一步地,所述步骤S1中,发泡喷嘴喷射原料的流量控制在80-400kg/min,输送速度控制在2-6m/min,发泡时间为2-5min。
进一步地,聚氨酯海绵的另一种制备步骤如下:
S1、异氰酸酯和聚醚多元醇聚合形成聚氨酯海绵,聚合体系中还加入链延长剂、高效泡沫稳定剂、高效复合催化剂、外发泡剂、水;
S2、将聚氨酯海绵用壳聚糖微胶囊、β-CD环糊精或羟丙基β-CD环糊精、β-CD环糊精包合物、羟丙基β-CD环糊精包合物进行后处理,后处理的方式为超声浸渍或数码喷涂,热风烘干,浸渍或喷涂液的配方为:β-CD环糊精或羟丙基β-CD环糊精、β-CD环糊精包合物、羟丙基β-CD环糊精包合物40-100g/L,壳聚糖微胶囊30-50g/L,超声浸渍功率为100-150W,频率为40-80赫兹,温度为40-50℃,时间为30mim-60min,真空烘干的温度为40-50℃,压强为0.08-0.09Mpa,时间为10-12小时。
本发明的优点在于:
1、以植物来源作为凉感抗菌芳香芯材,以天然抗菌的壳聚糖和具有空腔雀巢包含消臭功能的淀粉分解物作为壁材,制备具有缓释性的微胶囊和雀巢包合物,并且将制备的微胶囊和β-CD环糊精或β-CD环糊精包合物加入聚氨酯海绵的聚合单体中,其中壳聚糖或β-CD环糊精的活性基团参与聚氨酯的聚合反应,制备得到缓释耐久的芳香包合消臭凉感抗菌功能的聚氨酯海绵;
2、由于薄荷醇和木糖醇具有清凉、芳香抗菌作用,在睡眠中由于人体的摩擦,聚氨酯海绵中β-CD环糊精包合物、壳聚糖微胶囊包覆的薄荷醇或木糖醇缓释,达到长效凉感和芳香消臭的效果;另外,在聚合过程中如果有部分从微胶囊中释放的薄荷醇或木糖醇的羟基也可以参与聚氨酯海绵的聚合反应,固着于聚氨酯海绵;
3、β-CD环糊精和羟丙基β-CD环糊精特定的空腔结构,具有包合消臭功能,其外表面具有多个羟基,也可以参与聚氨酯海绵的聚合反应,这样,具有包合消臭的β-CD环糊精就锚固在聚氨酯海绵中;另外,在聚合过程中如果有部分从壳聚糖微胶囊中释放的薄荷醇或木糖醇,也可以重新被锚固在海绵上的β-CD环糊精包合,达到缓释薄荷醇或木糖醇的作用。
具体实施方式
为了使本发明的目的、技术方案及优点更加清楚明白,以下结合具体实施方式,对本发明进行进一步详细说明。下面的实施例可以使本专业的技术人员更全面地理解本发明,但并不因此将本发明限制在所述的实施例范围之中。
一种缓释香味凉感抗菌的聚氨酯海绵的一种制备方法,具体制备步骤如下:
S1、异氰酸酯和聚醚多元醇聚合形成聚氨酯海绵,聚氨酯海绵由以下组分组成:聚醚多元醇、MDI二苯基甲烷二异氰酸酯或TDI甲苯二异氰酸酯、链延长剂、高效泡沫稳定剂、高效复合催化剂、外发泡剂、水、β-CD环糊精或羟丙基β-CD环糊精、β-CD环糊精包合物、羟丙基β-CD环糊精包合物、壳聚糖微胶囊,β-CD环糊精包合物或羟丙基β-CD环糊精包合物的芯材、壳聚糖微胶囊的囊芯为薄荷醇、木糖醇或薄荷醇与木糖醇的复合物,将以上组分制成原料进行聚合和发泡,链延长剂为多元醇或二胺类低分子化合物,高效泡沫稳定剂为有机硅泡沫稳定剂或聚硅氧烷-聚氧化烯烃镶嵌共聚物,高效复合催化剂为锡类催化剂、胺类催化剂,用于聚氨酯发泡的所有物理发泡剂都可作为外发泡剂,用于聚氨酯发泡的所有聚醚都可作为聚醚多元醇。
发泡为开放连续式低压平泡,将原料通过发泡喷嘴喷至发泡系统输送装置,边发泡边传送,同时对输送装置进行限位,控制聚氨酯海绵的宽度,聚氨酯海绵的厚度由原料的流量和输送速度控制,调节混合头的输出量满足泡沫的宽厚需求,并通过调节输送速度和降落板位置,控制泡沫顶部高度及弧度,获得所需的泡沫流型,发泡喷嘴喷射原料的流量控制在80-400kg/min,输送速度控制在2-6m/min,发泡时间为2-5min;
S2、大尺寸聚氨酯海绵发泡完成后,采用后续的切割技术进行异形切割。
实施例1
通过以上方法异氰酸酯和聚醚多元醇聚合制成普通绵,由以下重量份的组分组成:分子量为3000、羟值为56的聚醚70份,分子量为3000、羟值为28的聚醚30份,TDI 46份,有机硅泡沫稳定剂1.1份,锡复合催化剂0.18份,胺复合催化剂0.24份,二氯甲烷外发泡剂3.3份,水3.35份,β-CD环糊精或羟丙基β-CD环糊精或β-CD环糊精包合物或羟丙基β-CD环糊精包合物0.2份,壳聚糖微胶囊0.2份,β-CD环糊精包合物或羟丙基β-CD环糊精包合物的芯材、壳聚糖微胶囊的囊芯为薄荷醇、木糖醇或薄荷醇与木糖醇的复合物,薄荷醇和木糖醇的复合物的复合质量比为1:1。
实施例2
通过以上方法异氰酸酯和聚醚多元醇聚合制成慢回弹绵,由以下重量份的组分组成:分子量为3000、羟值为56的聚醚37份,分子量为3000、羟值为28的聚醚10份,分子量700、羟值为240的聚醚50份,分子量为5000、羟值为37的聚醚3份,TDI 36份,有机硅类泡沫稳定剂1.2份,锡复合催化剂0.7份,胺复合催化剂0.3份,水2份,β-CD环糊精或羟丙基β-CD环糊精或β-CD环糊精包合物或羟丙基β-CD环糊精包合物0.2份,壳聚糖微胶囊0.2份,β-CD环糊精包合物或羟丙基β-CD环糊精包合物的芯材、壳聚糖微胶囊的囊芯为薄荷醇、木糖醇或薄荷醇与木糖醇的复合物,薄荷醇和木糖醇的复合物的复合质量比为1:1。
实施例3
通过以上方法异氰酸酯和聚醚多元醇聚合制成气感绵,由以下重量份的组分组成:分子量为3000、羟值为28的聚醚13份,分子量为700、羟值为240的聚醚7份,分子量为5000、羟值为37的聚醚80份,MDI 59.4份,链延长剂0.23份,有机硅泡沫稳定剂3.1份,胺类催化剂0.33份,二氯甲烷外发泡剂5份,水3.33份以及β-CD环糊精或羟丙基β-CD环糊精或β-CD环糊精包合物或羟丙基β-CD环糊精包合物0.5份,壳聚糖微胶囊0.5份,β-CD环糊精包合物或羟丙基β-CD环糊精包合物的芯材、壳聚糖微胶囊的囊芯为薄荷醇、木糖醇或薄荷醇与木糖醇的复合物,薄荷醇和木糖醇的复合物的复合质量比为1:1。
对采用上述配方制得的一种缓释香味凉感抗菌的普通绵、慢回弹绵、气感绵进行相关性能测试,其测试结果见表1。
表1实施例1~3所制一种缓释香味凉感抗菌的普通绵、慢回弹绵、气感绵的性能测试结果
抑菌率根据GB/T 20944.3–2008《纺织品抗菌性能的评价第三部分:振荡法》测得;消(氨)臭率根据日本(1社)纤维评价技术协会SEK标志纤维制品认证基准21.消臭性试验(气体检知管法)测得,试验时间2h,臭气初始浓度:臭气100ppm;凉感Qmax依据GB/T35263-2017《纺织品接触瞬间凉感性能的检测和评价》测得,将聚氨酯海绵放置在冷板上,当热板温度达到设定温度(一般为35℃)时,△T=15℃,快速将热板置于聚氨酯海绵,记录显示屏上的值,即为Qmax值,其值越大,表示带走的热量越多,凉感效应越明显。
由上表可以看出,制备出的一种缓释香味凉感抗菌的普通绵、慢回弹绵、气感绵具有长效凉感和芳香消臭、抗菌优良性能。
一种缓释香味凉感抗菌的聚氨酯海绵的另一种制备方法,具体制备步骤如下:
S1、异氰酸酯和聚醚多元醇聚合形成聚氨酯海绵,聚合体系中还加入链延长剂、高效泡沫稳定剂、高效复合催化剂、外发泡剂、水;
S2、将聚氨酯海绵用壳聚糖微胶囊、羟丙基β-CD环糊精进行后处理,后处理的方式为超声浸渍,热风烘干,浸渍的组分为羟丙基β-CD环糊精和壳聚糖微胶囊,超声浸渍功率为100-150W,频率为40-80赫兹,温度为40-50℃,时间为30mim-60min,真空烘干的温度为40-50℃,压强为0.08-0.09Mpa,时间为10-12小时。
实施例4
聚氨酯海绵通过超声浸渍进行后处理的配方为:羟丙基β-CD环糊精40g/L,壳聚糖微胶囊30g/L。
实施例5
聚氨酯海绵通过超声浸渍进行后处理的配方为:羟丙基β-CD环糊精60g/L,壳聚糖微胶囊50g/L。
实施例6
聚氨酯海绵通过超声浸渍进行后处理的配方为:羟丙基β-CD环糊精50g/L,壳聚糖微胶囊40g/L。
表2实施例4-6中各组分的质量对比
为了比较采用上述配方制得的一种缓释香味凉感抗菌的聚氨酯海绵的性能,将其进行相关性能测试,其测试结果见表2。
表2实施例4-6所制一种缓释香味凉感抗菌的聚氨酯海绵的性能测试结果
由上表可以看出,制备出的一种缓释香味凉感抗菌的聚氨酯海绵具有长效凉感和芳香消臭、抗菌优良性能;此外,实施例4-6相互比较,可看出实施例5的各项性能均优于其他两个实施例,因而实施例5为最佳实施例。
以上显示和描述了本发明的基本原理和主要特征以及本发明的优点。本行业的技术人员应该了解,本发明不受上述实施例的限制,上述实施例和说明书中描述的只是说明本发明的原理,在不脱离本发明精神和范围的前提下,本发明还会有各种变化和改进,这些变化和改进都落入要求保护的本发明范围内。本发明要求保护范围由所附的权利要求书及其等效物界定。
Claims (5)
1.一种缓释香味凉感抗菌的聚氨酯海绵,由异氰酸酯和聚醚多元醇聚合形成聚氨酯海绵,其特征在于:聚氨酯海绵聚合过程中,加入壳聚糖微胶囊和β-CD环糊精,所述壳聚糖微胶囊的囊芯为薄荷醇、木糖醇或薄荷醇与木糖醇的复合物;
聚氨酯海绵由以下重量份的组分组成:聚醚多元醇90-110份、MDI二苯基甲烷二异氰酸酯或TDI甲苯二异氰酸酯30-70份、链延长剂0-0.5份、高效泡沫稳定剂0.5-5份、高效复合催化剂0.1-1.0份、外发泡剂0-6份、水1-5份、β-CD环糊精或羟丙基β-CD环糊精0.2-0.5份、壳聚糖微胶囊0.2-0.5份;
异氰酸酯和聚醚多元醇聚合时,在聚醚多元醇、MDI二苯基甲烷二异氰酸酯或TDI甲苯二异氰酸酯、链延长剂、高效泡沫稳定剂、高效复合催化剂、外发泡剂、水中加入壳聚糖微胶囊、β-CD环糊精或羟丙基β-CD环糊精,制成原料进行聚合和发泡。
2.根据权利要求1所述的一种缓释香味凉感抗菌的聚氨酯海绵,其特征在于:所述薄荷醇和木糖醇的复合物的复合质量比为1:1-3。
3.根据权利要求1所述的一种缓释香味凉感抗菌的聚氨酯海绵,其特征在于:所述链延长剂为多元醇或二胺类低分子化合物,所述高效泡沫稳定剂为有机硅泡沫稳定剂或聚硅氧烷-聚氧化烯烃镶嵌共聚物,所述高效复合催化剂为锡类催化剂、胺类催化剂,所述外发泡剂为用于聚氨酯发泡的物理发泡剂,所述聚醚多元醇是用于聚氨酯发泡的聚醚。
4.一种权利要求1所述的 缓释香味凉感抗菌的聚氨酯海绵的制备方法,其特征在于:聚氨酯海绵的制备步骤如下:
S1、异氰酸酯和聚醚多元醇聚合时,在聚醚多元醇、MDI二苯基甲烷二异氰酸酯或TDI甲苯二异氰酸酯、链延长剂、高效泡沫稳定剂、高效复合催化剂、外发泡剂、水中加入壳聚糖微胶囊、β-CD环糊精或羟丙基β-CD环糊精,制成原料进行聚合和发泡;
发泡为开放连续式低压平泡,将原料通过发泡喷嘴喷至发泡系统输送装置,边发泡边传送,同时对输送装置进行限位,控制聚氨酯海绵的宽度,聚氨酯海绵的厚度由原料的流量和输送速度控制,调节混合头的输出量满足泡沫的宽厚需求,并通过调节输送速度和降落板位置,控制泡沫顶部高度及弧度,获得所需的泡沫流型;
S2、大尺寸聚氨酯海绵发泡完成后,采用后续的切割技术进行异形切割。
5.根据权利要求4所述的一种缓释香味凉感抗菌的聚氨酯海绵的制备方法,其特征在于:所述步骤S1中,发泡喷嘴喷射原料的流量控制在80-400kg/min,输送速度控制在2-6m/min,发泡时间为2-5min。
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