CN113605109A - 一种负离子水性聚氨酯合成革及其制备方法 - Google Patents
一种负离子水性聚氨酯合成革及其制备方法 Download PDFInfo
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Abstract
本发明属于合成革技术领域,公开了一种负离子水性聚氨酯合成革及其制备方法,包括以下步骤:S1.将10‑60 wt%碳酸钙、30‑80 wt%电气石矿物和5‑20 wt%丙烯酸树脂按比例加入到球磨机中,研磨10min;S2.向S1中加入20‑100份丙烯酸改性的水性聚氨酯树脂中,同时加入1‑6份自由基引发剂,搅拌混合均匀,经压缩空气发泡。通过利用丙烯酸树脂改性碳酸钙和电气石,不但可以有效提升粉体与树脂间的相容性,而且让矿物粉体与丙烯酸改性的水性聚氨酯乳液通过共价键连接,赋予该发泡层一定的机械强度,提升合成革的机械性能;使用有机硅和磷酸酯双改性的水性聚氨酯乳液作为面层原料,赋予制备出来的合成革表面具有耐污渍性能,同时还兼具阻燃性。
Description
技术领域
本发明涉及合成革技术领域,具体涉及的是一种负离子水性聚氨酯合成革及其制备方法。
背景技术
聚氨酯以其软硬度可调范围广、耐低温、柔韧性好、附着力强等优点被广泛应用于皮革涂饰、涂料、胶黏剂等领域。然而随着各国环境安全法律法规的出台,许多国家已限制了溶剂型聚氨酯的应用。
水性聚氨酯由于其连续相为水,安全易于保存和储存,且使用方便成本低,较完整的保留了溶剂型聚氨酯的特性,另外由于水性聚氨酯分子链中存在库仑力和氢键的作用,使其在某些性能上优于溶剂型聚氨酯,因此水性聚氨酯的研制与生产受到世界各国的重视,而且都取得了长足的发展。在水性聚氨酯的制备中,为了获得稳定的聚氨酯乳液,需在聚氨酯的预聚体分子中引入亲水基团,使其在水中乳化。
自苏联学者报道空气中的负离子可以消除病菌的研究成果以来,国内外掀起了负离子的研究热潮。目前市场中已经有不少负离子的相关产品,如负离子地板、负离子内墙涂料、负离子装饰纸、负离子家装生态板等,但以上述产品都是用于家居环境,很难做成易于人们携带的产品,限制了负离子领域技术发展。另鲜有报道水性聚氨酯与负离子结合的相关技术研究。因此,我们提出了一种负离子水性聚氨酯合成革及其制备方法。
发明内容
本发明的目的是提供一种负离子水性聚氨酯合成革及其制备方法,以用于进一步加工成服装、鞋子、箱包等方便人们随身携带的产品,甚至进一步用于汽车内饰,为人们提供更好的负离子环境,保障大家的健康,可以有效解决背景技术中提出的问题。
为实现上述目的,本发明采取的技术方案为:
一种负离子水性聚氨酯合成革及其制备方法,包括以下步骤:
S1.将10-60 wt%碳酸钙、30-80 wt%电气石矿物和5-20 wt%丙烯酸树脂按比例加入到球磨机中,研磨10min;
S2.向S1中加入20-100份丙烯酸改性的水性聚氨酯树脂中,同时加入1-6份自由基引发剂,搅拌混合均匀,经压缩空气发泡;
S3.将S2发泡后的浆料通过二辊压延机涂覆于基布表面,并于110-130℃烘箱中烘干后,再在其表面贴合5-20 μm水性聚氨酯面层,得到负离子水性聚氨酯合成革。
进一步地,所述电气石矿物粒度≥200目。
优选地,所述丙烯酸树脂为2-丙烯酸、2-呋喃丙烯酸、丙烯酸 2-羧乙酯、2-(三氟甲基)丙烯酸、4-吡啶丙烯酸、2-苄基丙烯酸、3,3-二甲基丙烯酸中的任一种。
进一步地,所述自由基引发剂为偶氮二异丁腈、偶氮二异庚腈和偶氮二异丁酸二甲酯中的任一种。
优选地,所述水性聚氨酯面层原料为有机硅和磷酸酯双改性的水性聚氨酯乳液。
与现有技术相比,本发明具有如下有益效果:
一、通过利用丙烯酸树脂改性碳酸钙和电气石,不但可以有效提升粉体与树脂间的相容性,而且让矿物粉体与丙烯酸改性的水性聚氨酯乳液通过共价键连接,赋予该发泡层一定的机械强度,提升合成革的机械性能;;
二、使用有机硅和磷酸酯双改性的水性聚氨酯乳液作为面层原料,赋予制备出来的合成革表面具有耐污渍性能,同时还兼具阻燃性;
三、利用矿物粉体的稳泡作用,避免了化学稳泡剂的使用;
四、采用有机硅和磷酸酯双改性的水性聚氨酯乳液作为面层原料、通过在发泡层中添加大量的碳酸钙和电气石等阻燃材料,使得该合成革具有一定的阻燃性能;
五、采用球磨技术不但让碳酸钙和电气石矿物粉体研磨的更细,而且利用了球磨过程中产生的升温增压作用,更好的实现丙烯酸树脂对粉体的表面改性。
具体实施方式
为使本发明实现的技术手段、创作特征、达成目的与功效易于明白了解,下面结合具体实施方式,进一步阐述本发明。
以下实施例涉及到的丙烯酸改性的水性聚氨酯树脂乳液、有机硅和磷酸酯双改性的水性聚氨酯乳液的制备方法如下:丙烯酸改性的水性聚氨酯树脂
在装配有机械搅拌桨、回流冷凝器和温度计的三口圆底烧瓶中,异佛尔酮二异氰酸酯(IPDI,32%)、聚醚多元醇(PPG2000,5%)和聚四氢呋喃多元醇(PTMG2000,40%),室温搅拌均匀后,将反应温度调至(80±1)℃,滴加催化剂二月桂酸二丁基锡(DBTDL,0.6%),搅拌反应2小时;然后将反应温度调至(60±1)℃,加入一定量的丙烯酸改性剂(2-羟乙基)甲基丙烯酸酯(HMA,6.4%),搅拌反应1小时,加入一定量1,4-丁二醇(BDO,4%),搅拌反应0.5小时,随后加入计量的2,2-二羟甲基丙酸(DMPA,5.5%),继续反应1小时;期间加入适量丙酮稀释。随后降温至室温,加入适量丙酮和计量三乙胺(TEA,4.5%)进行中和反应,中和结束后,在高速搅拌下,再加入计量的乙二胺(EDA,2%) 进行扩链,并往体系中加入水进行乳化,最后减压蒸馏除去丙酮,得到丙烯酸改性的水性聚氨酯乳液(MAWPU)。
有机硅和磷酸酯双改性的水性聚氨酯乳液
在装配有机械搅拌桨、回流冷凝器和温度计的三口圆底烧瓶中,加入计量的异佛尔酮二异氰酸酯(IPDI,12%)、六亚甲基二异氰酸酯(HDI,20%)、聚四氢呋喃多元醇(PTMG2000,25%)、双羟基封端聚硅氧烷(羟基硅油,羟基含量8-10%,15%)和有机磷酸酯二醇(OP550,10%),室温搅拌均匀后,将反应温度调至(80±1)℃,滴加催化剂二月桂酸二丁基锡(DBTDL,1%),搅拌反应2小时,加入一定量1,4-丁二醇(BDO,4%),搅拌反应1小时,随后加入计量的2,2-二羟甲基丙酸(DMPA,5%),继续反应1小时;期间加入适量丙酮稀释。随后降温至室温,加入适量丙酮和计量三乙胺(TEA,5%)进行中和反应,中和结束后,在高速搅拌下,再加入计量的乙二胺(EDA,3%) 进行扩链,并往体系中加入水进行乳化,最后减压蒸馏除去丙酮,得到有机聚硅氧烷和磷酸酯原位双改性的水性聚氨酯乳液;
实施例1
将碳酸钙(60 wt%)、电气石矿物(30 wt%)和丙烯酸树脂(10 wt%)加入到球磨机中,研磨10min后,取一定量(60份)加入到乙烯基改性的水性聚氨酯树脂(100份)中,同时加入一定量的自由基引发剂(3份),搅拌混合均匀,经压缩空气发泡后,将该浆料通过二辊压延机涂覆于基布表面,并于120℃烘箱中烘干后,再在其表面贴合一层水性聚氨酯面层,得到负离子水性聚氨酯合成革。
实施例2
将碳酸钙(40 wt%)、电气石矿物(40 wt%)和丙烯酸树脂(20 wt%)加入到球磨机中,研磨10min后,取一定量(100份)加入到乙烯基改性的水性聚氨酯树脂(100份)中,同时加入一定量的自由基引发剂(6份),搅拌混合均匀,经压缩空气发泡后,将该浆料通过二辊压延机涂覆于基布表面,并于120℃烘箱中烘干后,再在其表面贴合一层水性聚氨酯面层,得到负离子水性聚氨酯合成革。
实施例3
将碳酸钙(15 wt%)、电气石矿物(80 wt%)和丙烯酸树脂(5 wt%)加入到球磨机中,研磨10min后,取一定量(20份)加入到乙烯基改性的水性聚氨酯树脂(100份)中,同时加入一定量的自由基引发剂(1份),搅拌混合均匀,经压缩空气发泡后,将该浆料通过二辊压延机涂覆于基布表面,并于120℃烘箱中烘干后,再在其表面贴合一层水性聚氨酯面层,得到负离子水性聚氨酯合成革。
对比例1
将木粉(20份)、发泡剂(4份)、水性色浆(1份)、增稠剂(1份)加入到阴离子型水性聚氨酯树脂(100份)中,搅拌混合均匀后,将该浆料通过发泡机发泡至1.5倍率后,刮涂在经2%草酸溶液处理烘干后的基布表面,并于120℃烘箱中烘干后,再在其表面贴合一层水性聚氨酯面层,得到水性聚氨酯合成革。
对实施例1-3、对比例制得的合成革进行性能检测,具体检测结果参见下表1。
表1不同合成革样品的性能测试结果
以上显示和描述了本发明的基本原理和主要特征和本发明的优点。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)
1.一种负离子水性聚氨酯合成革及其制备方法,其特征在于:包括以下步骤:
S1. 将10-60 wt%碳酸钙、30-80 wt%电气石矿物和5-20 wt%丙烯酸树脂按比例加入到球磨机中,研磨10min;
S2. 向S1中加入20-100份丙烯酸改性的水性聚氨酯树脂中,同时加入1-6份自由基引发剂,搅拌混合均匀,经压缩空气发泡;
S3. 将S2发泡后的浆料通过二辊压延机涂覆于基布表面,并于110-130℃烘箱中烘干后,再在其表面贴合5-20 μm水性聚氨酯面层,得到负离子水性聚氨酯合成革。
2.根据权利要求1所述的一种负离子水性聚氨酯合成革及其制备方法,其特征在于:所述电气石矿物粒度≥200目。
3.根据权利要求1所述的一种负离子水性聚氨酯合成革及其制备方法,其特征在于:所述丙烯酸树脂为2-丙烯酸、2-呋喃丙烯酸、丙烯酸 2-羧乙酯、2-(三氟甲基)丙烯酸、4-吡啶丙烯酸、2-苄基丙烯酸、3,3-二甲基丙烯酸中的任一种。
4.根据权利要求1所述的一种负离子水性聚氨酯合成革及其制备方法,其特征在于:所述自由基引发剂为偶氮二异丁腈、偶氮二异庚腈和偶氮二异丁酸二甲酯中的任一种。
5.根据权利要求1所述的一种负离子水性聚氨酯合成革及其制备方法,其特征在于:所述水性聚氨酯面层原料为有机硅和磷酸酯双改性的水性聚氨酯乳液。
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