CN106046307A - 一种用于鞋材的耐黄变的聚氨酯复合材料及其制备方法 - Google Patents
一种用于鞋材的耐黄变的聚氨酯复合材料及其制备方法 Download PDFInfo
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Abstract
本发明公开一种用于鞋材的耐黄变的聚氨酯复合材料,由以下重量份的原料组成:聚醚多元醇70‑90份,甲苯二异氰酸酯30‑45份,竹炭粉15‑25份,壳聚糖5‑6份,活性炭1‑3份,海藻酸钠1‑3份,明胶1‑3份,蔗糖脂肪酯10‑15份,3%氯化钙溶液5‑8份,金银花精油0.1‑0.3份,当归精油0.1‑0.3份,二月桂酸二丁基锡2‑4份,1,3‑丙二醇3‑5份,发泡剂0.5‑2份,乙酸溶液10‑20份,醋酸0.5‑1份,水适量,乙醇适量,纳米二氧化钛0.5‑1.5份,抗氧剂0.2‑0.6份,紫外线吸收剂0.3‑0.8份。本发明聚氨酯复合材料具有良好的透气性能和抗菌除臭功效,达到极好的耐黄变效果。
Description
技术领域
本发明涉及鞋材技术领域,具体涉及一种用于鞋材的耐黄变的聚氨酯复合材料及其制备方法。
背景技术
鞋类产品的穿用舒适性研究是现代制鞋领域的前沿课题之一,它是人们生活水平提高后的必然产物,具有重要的理论和现实意义。随着中国扩大内需、刺激消费政策的实施、中产阶层数量的扩大和城市化进程的加快,对质量较好、款式新颖的鞋类产品的消费和需求也将稳步增加。同时,高新技术日新月异,新技术、新产品层出不穷,从而推动新材料的不断发展和更新。新材料的成功应用将给制鞋业带来预想不到的成果,在这个过程中,鞋面材料的热湿传递性能,是影响舒适性的基本条件和重要因素。
聚氨酯弹性体具有缓冲性能好,质轻、耐磨、防滑等特点,加工性能好,已成为制鞋工业中一种重要的鞋用合成材料,可用于制造棒球鞋、高尔夫球、足球等的运功鞋、鞋底、鞋跟、鞋头,以及滑雪鞋、安全鞋、休闲鞋等。用于鞋材的聚氨酯材料有浇注型微孔弹性体及热塑性聚氨酯弹性体等,以微孔弹性体鞋底为主。聚氨酯微孔弹性体质轻,耐磨性又好,而且制品密度低,比传统的橡胶底和PVC鞋材要轻得多,而且设计可多样化,还可在注射成型中加入可热分解发泡剂,制成发泡TPU弹性鞋材。
黄国清等人在其发表的一种原位包埋微胶囊香精性质的研究一文中,利用原位聚合法制得香精含量为32.5%的微胶囊,它的粒径为1-4μm,此类制备过程中基本都需要加入甲醛生成预聚体,达不到环保的要求。另外王俊华等人在其发表的芳香保健微胶囊的研制及其在纺织品中的应用一文中,使用用界面聚合法制备了以聚氨酯为壁材、薰衣草为芯材的芳香整理剂,包载率达80%左右,3个月之后清香依旧。
受此启发,开发一种用于鞋材的透气性好、能够除臭的聚氨酯复合材料。
发明内容
本发明主要解决的技术问题是提供一种用于鞋材的耐黄变的聚氨酯复合材料及其制备方法。
本发明所要解决的技术问题,是通过以下技术方案实现的:
一种用于鞋材的耐黄变的聚氨酯复合材料,由以下重量份的原料组成:聚醚多元醇70-90份,甲苯二异氰酸酯30-45份,竹炭粉15-25份,壳聚糖5-6份,活性炭1-3份,海藻酸钠1-3份,明胶1-3份,蔗糖脂肪酯10-15份,3%氯化钙溶液5-8份,金银花精油0.1-0.3份,当归精油0.1-0.3份,二月桂酸二丁基锡2-4份,1,3-丙二醇3-5份,发泡剂CFA-A8 0.5-2份,乙酸溶液10-20份,醋酸0.5-1份,水适量,乙醇适量,纳米二氧化钛0.5-1.5份,抗氧剂1010 0.2-0.6份,紫外线吸收剂UV-327 0.3-0.8份。
具体步骤如下:
(1)室温下,取壳聚糖加入到乙酸溶液中,充分搅拌使壳聚糖完全溶解,然后加入竹炭粉、活性炭,充分搅拌2-3小时,调成糊状,放置12-20小时,然后在造粒机上制得球状颗粒,在干燥箱内烘干,备用;
(2)微胶囊的制备:
①、壁材的制备:将海藻酸钠溶液、明胶溶液加入容器中搅拌均匀,得到壁材溶液;
②、乳化:在壁材溶液中加入蔗糖脂肪酯,搅拌混合均匀,再加入芯材金银花精油、当归精油于10000-20000rmp高速剪切乳化5-15分钟;
③、微胶囊的固化:在不断搅拌的条件下,向乳化液中加入醋酸调节溶液的pH呈酸性,同时加入3%氯化钙溶液,置于冰水浴中搅拌50-80分钟后,静置,待微胶囊沉降;
④、后处理:倾去上清液,过滤,水洗至中性,再用无水乙醇洗涤,干燥即得金银花精油、当归精油微胶囊;
(3)将步骤(1)得到的球状颗粒与步骤(2)制备的微胶囊加入搅拌釜中,加入聚醚多元醇、纳米二氧化钛以及除去甲苯二异氰酸酯以外的剩余原料,以800-1500rpm的速度搅拌至混合均匀,得到混合料;
(4)将甲苯二异氰酸酯加入到步骤(3)得到的混合料,以2000-3000rpm的速度搅拌20-60秒,立即浇注注到事先涂有脱模剂并预热至40-50℃的模具中,将模具封闭后,30-50分钟后脱模,转入烘箱中60-90℃下熟化7-9小时出料,得到一种用于鞋材的耐黄变的聚氨酯复合材料。
其中,所述的步骤(2)微胶囊的制备中壁材溶液是浓度为1%-3%的海藻酸钠溶液,4%-7%的明胶溶液。
本发明的一种用于鞋材的耐黄变的聚氨酯复合材料,与现有技术相比具有如下优点:
(1)本发明利用微胶囊技术制备以中草药金银花、当归为芯材,海藻酸钠、明胶为壁材的清香除臭的微胶囊,既保持囊芯材料的清香除臭性质又能缓慢释放囊芯材料,延长作用时间,同时可提高与聚氨酯材料的相容性,使得聚氨酯复合材料的抗菌除臭功效显著;
(2)使用竹炭、活性炭与壳聚糖为原料,制备壳聚糖/竹炭-活性炭复合多孔吸附剂,壳聚糖可以较好的负载在竹炭、活性炭上,经混合结合后凹凸不平明显,蜂窝增强,使得聚氨酯复合材料具有良好的透气性能,同时达到除臭功效;
(3)纳米二氧化钛的电子结构,由充满电子的价电子带和没有电子的空轨道形成的导带结构存在禁止带间隙,当纳米二氧化钛受光照射,被禁止带间隙能量大的光吸收,价带的电子激发至导带,由于纳米二氧化钛的禁止带间隙约为2.3eV,相当于约410nm波长的光能,因此纳米二氧化钛的电子会受波长小于410nm的紫外光激发,从而形成很好的散射和吸收紫外光的能力;本发明采用加入纳米二氧化钛结合加入抗氧剂1010与紫外线吸收剂UV-327复合改性剂的方式改性聚氨酯材料,可以达到极好的耐黄变效果。 具体实施方式
一种用于鞋材的耐黄变的聚氨酯复合材料,由以下重量份(公斤)的原料组成:聚醚多元醇85,甲苯二异氰酸酯40,竹炭粉20,壳聚糖5,活性炭2,聚乙二醇1.5,海藻酸钠2,明胶1,蔗糖脂肪酯12,3%氯化钙溶液6,金银花精油0.2,当归精油0.2,二月桂酸二丁基锡3,1,3-丙二醇4,发泡剂CFA-A8 1,乙酸溶液15,醋酸1,纳米二氧化钛0.8,抗氧剂1010 0.3,紫外线吸收剂UV-327 0.5,水适量,乙醇适量。
具体步骤如下:
(1)室温下,取壳聚糖加入到乙酸溶液中,充分搅拌使壳聚糖完全溶解,然后加入竹炭粉、活性炭,充分搅拌3小时,调成糊状,放置15小时,然后在造粒机上制得球状颗粒,在干燥箱内烘干,备用;
(2)微胶囊的制备:
①、壁材的制备:将海藻酸钠溶液、明胶溶液加入容器中搅拌均匀,得到壁材溶液;
②、乳化:在壁材溶液中加入蔗糖脂肪酯,搅拌混合均匀,再加入芯材金银花精油、当归精油于15000rmp高速剪切乳化10分钟;
③、微胶囊的固化:在不断搅拌的条件下,向乳化液中加入醋酸调节溶液的pH呈酸性,同时加入3%氯化钙溶液,置于冰水浴中搅拌60分钟后,静置,待微胶囊沉降;
④、后处理:倾去上清液,过滤,水洗至中性,再用无水乙醇洗涤,干燥即得金银花精油、当归精油微胶囊;
(3)将步骤(1)得到的球状颗粒与步骤(2)制备的微胶囊加入搅拌釜中,加入聚醚多元醇、纳米二氧化钛以及除去甲苯二异氰酸酯以外的剩余原料,以800-1500rpm的速度搅拌至混合均匀,得到混合料;
(4)将甲苯二异氰酸酯加入到步骤(3)得到的混合料,以2500rpm的速度搅拌40秒,立即浇注注到事先涂有脱模剂并预热至45℃的模具中,将模具封闭后,40分钟后脱模,转入烘箱中80℃下熟化8小时出料,得到一种用于鞋材的耐黄变的聚氨酯复合材料。
其中,上述的步骤(2)微胶囊的制备中壁材溶液是浓度为2%的海藻酸钠溶液,5%的明胶溶液。
本发明产品检测数据:除臭性能优异,透气性良好,径向拉断强度/纬向拉断强度〉435N/3CM,径/纬向撕裂强度〉29N,老化试验不开裂。
Claims (3)
1.一种用于鞋材的耐黄变的聚氨酯复合材料,其特征在于,由以下重量份的原料组成:聚醚多元醇70-90份,甲苯二异氰酸酯30-45份,竹炭粉15-25份,壳聚糖5-6份,活性炭1-3份,海藻酸钠1-3份,明胶1-3份,蔗糖脂肪酯10-15份,3%氯化钙溶液5-8份,金银花精油0.1-0.3份,当归精油0.1-0.3份,二月桂酸二丁基锡2-4份,1,3-丙二醇3-5份,发泡剂CFA-A80.5-2份,乙酸溶液10-20份,醋酸0.5-1份,水适量,乙醇适量,纳米二氧化钛0.5-1.5份,抗氧剂1010 0.2-0.6份,紫外线吸收剂UV-327 0.3-0.8份。
2.根据权利要求书1所述的一种用于鞋材的耐黄变的聚氨酯复合材料的制备方法,其特征在于,具体步骤如下:
(1)室温下,取壳聚糖加入到乙酸溶液中,充分搅拌使壳聚糖完全溶解,然后加入竹炭粉、活性炭,充分搅拌2-3小时,调成糊状,放置12-20小时,然后在造粒机上制得球状颗粒,在干燥箱内烘干,备用;
(2)微胶囊的制备:
①、壁材的制备:将海藻酸钠溶液、明胶溶液加入容器中搅拌均匀,得到壁材溶液;
②、乳化:在壁材溶液中加入蔗糖脂肪酯,搅拌混合均匀,再加入芯材金银花精油、当归精油于10000-20000rmp高速剪切乳化5-15分钟;
③、微胶囊的固化:在不断搅拌的条件下,向乳化液中加入醋酸调节溶液的pH呈酸性,同时加入3%氯化钙溶液,置于冰水浴中搅拌50-80分钟后,静置,待微胶囊沉降;
④、后处理:倾去上清液,过滤,水洗至中性,再用无水乙醇洗涤,干燥即得金银花精油、当归精油微胶囊;
(3)将步骤(1)得到的球状颗粒与步骤(2)制备的微胶囊加入搅拌釜中,加入聚醚多元醇、纳米二氧化钛以及除去甲苯二异氰酸酯以外的剩余原料,以800-1500rpm的速度搅拌至混合均匀,得到混合料;
(4)将甲苯二异氰酸酯加入到步骤(3)得到的混合料,以2000-3000rpm的速度搅拌20-60秒,立即浇注注到事先涂有脱模剂并预热至40-50℃的模具中,将模具封闭后,30-50分钟后脱模,转入烘箱中60-90℃下熟化7-9小时出料,得到一种用于鞋材的耐黄变的聚氨酯复合材料。
3.根据权利要求书2所述的一种用于鞋材的耐黄变的聚氨酯复合材料的制备方法,其特征在于,步骤(2)微胶囊的制备中壁材溶液是浓度为1%-3%的海藻酸钠溶液,4%-7%的明胶溶液。
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