CN108084863A - 一种合成革用水性聚氨酯表面处理剂的制备方法 - Google Patents

一种合成革用水性聚氨酯表面处理剂的制备方法 Download PDF

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CN108084863A
CN108084863A CN201711246547.XA CN201711246547A CN108084863A CN 108084863 A CN108084863 A CN 108084863A CN 201711246547 A CN201711246547 A CN 201711246547A CN 108084863 A CN108084863 A CN 108084863A
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蒋春霞
王文新
史玉玲
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Abstract

本发明涉及一种合成革用水性聚氨酯表面处理剂的制备方法,属于组合物技术领域。本发明以聚己二酸1,4‑丁二醇酯、蓖麻油、聚醚改性硅油、异佛尔酮二异氰酸酯为主要原料,以二羟甲基丙酸、改性多壁碳纳米管上的氨基协同小分子扩链剂为扩链剂,合成了改性水洗聚氨酯替代溶剂型合成革表面处理剂,本发明通过蓖麻油特有的支链赋予聚合物一定的交联网格状结构,在物理交联点的基础上增加了化学交联,从而使聚氨酯膜有较高的拉伸强度,且蓖麻油中长脂肪链可显著地提高水性聚氨酯漆膜的疏水性,同时将表面处理后的改性多壁碳纳米管镶嵌在聚氨酯链段上,形成微粗糙面,使改性多壁碳纳米管表面包覆了更厚的一层树脂,增加了体系的稳定性和耐干湿擦性能。

Description

一种合成革用水性聚氨酯表面处理剂的制备方法
技术领域
本发明涉及一种合成革用水性聚氨酯表面处理剂的制备方法,属于组合物技术领域。
背景技术
合成革工业的产品主要为人造革、合成革和超纤革。通常情况下,人造革主要以聚氯乙烯为成膜剂,以纺织布为基化通过层压复合的工艺进行加工。合成革主要以PU为成膜剂,以非织造布为基材,通过湿法涂层和干法移膜的工艺生产。
目前,很大部分合成革的生产企业,仍然采用着溶剂型的生产工艺,使用了大量有毒有害的有机溶剂,包括二甲基甲酰胺、甲苯、丁酮和丙酮等。目前,这些溶剂还不能被完全回收,废气的排放不仅严重污染环境,而且工人的身体健康因此受到了较大的损害。第二,由于使用了大量易燃易爆的有机溶剂,极大增加了合成革企业的生产风险。第三,在合成革产品中会残留一定量的有害溶剂,产品质量不易保证。要解决合成革行业存在的这些问题,开发生态合成革势在必行。生态合成革的环保性包含以下四个方面:首先,合成革制造过程中使用到的原材料必须没有毒害;第二,加工过程中工艺清洁环保,不会产生有害物质;第三,在使用过程中产品不会对人体造成危害,对环境不造成破坏;最后,产品在被废弃后能在自然环境中降解,且分解后的产物也不会对周围环境造成破坏。
由于个性、时尚、功能以及品种多样化的发展,合成革往往需要对其表层进行处理,以提高合成革的外观、手感,赋予合成革更多优异的性能,提高合成革的附加值。目前,对于大多数的合成革,表面处理剂、特殊树脂占生产成本的比例在20%,而对于一些高端PU革,这类助剂的成本己经占到整个生产成本的30%以上。目前合成革的表面后处理基本都采三版印刷的工艺,这是一个开放的生产体系。而目前表面处理剂基本以溶剂型聚氨酯为成膜剂,含有大量有害的有机溶剂。同时这些有机溶剂大多难溶于水,所以目前采用喷淋法的回收方法的效果比较差。合成革表面处理剂水性化的速度较慢是由多方面的原因造成的,但主要是因为合成革表面处理剂用水性树脂的缺乏。因此亟需开发一种合成革表面最顶层的表面处理剂,要求其耐水性、耐溶剂性、耐磨、耐刮性能优异。
发明内容
本发明所要解决的技术问题:针对合成革表面处理剂中,大量有机溶剂排放严重污染环境,而且会在成品总残留,具有难闻气味,危害身体健康的问题,提供了一种防雾霾氨基酸无硅油洗发香波的制备方法。
为解决上述技术问题,本发明采用的技术方案是:
(1)取多壁碳纳米管加入去离子水中超声分散30~40min,再加入硅烷偶联剂KH792搅拌反应,过滤水洗后干燥,得改性多壁碳纳米管;
(2)取聚己二酸1,4-丁二醇酯、蓖麻油、聚醚改性硅油、改性多壁碳纳米管,装入烧瓶中真空脱水1~2h,得反应液;
(3)将反应液降温至60~70℃,再加入异佛尔酮二异氰酸酯保温反应1~2h后加入二羟甲基丙酸,加热至70~80℃搅拌30~40min,得预聚物混合液;
(4)将预聚物混合液冷却至50~60℃,再加入三乙胺搅拌反应20~30min后降温至室温,再加入质量分数为1%小分子扩链剂水溶液,以1800~2000r/min搅拌1~2h,再加入流平剂、消泡剂继续搅拌20~30min,得合成革用水性聚氨酯表面处理剂。
步骤(1)所述硅烷偶联剂KH792用量为多壁碳纳米管质量的30~100%。
3.如权利要求1所述的一种合成革用水性聚氨酯表面处理剂的制备方法,其特征在于,步骤(1)所述搅拌反应过程为在40~60℃下以800~1000r/min搅拌反应4~6h。
步骤(2)所述聚己二酸1,4-丁二醇酯、蓖麻油、聚醚改性硅油、改性多壁碳纳米管的重量份为150~180份聚己二酸1,4-丁二醇酯,20~30份蓖麻油,10~15份聚醚改性硅油,3~5份改性多壁碳纳米管。
步骤(2)所述真空脱水过程为装入烧瓶中并加热至100~105℃真空脱水1~2h。
步骤(3)所述异佛尔酮二异氰酸酯用量为聚己二酸1,4-丁二醇酯质量的17.8~26.6%。
步骤(3)所述二羟甲基丙酸用量为聚己二酸1,4-丁二醇酯质量的5.6~8.0%。
步骤(4)所述三乙胺用量为聚己二酸1,4-丁二醇酯质量的3.3~5.3%,所述小分子扩链剂水溶液用量为聚己二酸1,4-丁二醇酯质量的22.2~33.3%。
步骤(4)所述小分子扩链剂为乙二胺、己二胺、丙二醇、1,4-丁二醇中的一种或多种。
步骤(5)所述流平剂为有机硅型流平剂或丙烯酸酯型流平剂,所述消泡剂选为有机硅类消泡剂、矿物油类消泡剂或聚醚类消泡剂中的一种或多种,所述流平剂、消泡剂与蓖麻油的质量比为(1~2):(1~2):(20~30)。
本发明与其他方法相比,有益技术效果是:
(1)本发明以聚己二酸1,4-丁二醇酯、蓖麻油、聚醚改性硅油、异佛尔酮二异氰酸酯为主要原料,以二羟甲基丙酸、改性多壁碳纳米管上的氨基协同小分子扩链剂为扩链剂,合成了改性水洗聚氨酯替代溶剂型合成革表面处理剂,以水为基本介质,制备具有不燃、气味小、不污染环境、对人体无害等优点的合成革用水性聚氨酯表面处理剂;
(2)本发明通过蓖麻油特有的支链赋予聚合物一定的交联网格状结构,在物理交联点的基础上增加了化学交联,从而使聚氨酯膜有较高的拉伸强度,且蓖麻油中长脂肪链可显著地提高水性聚氨酯漆膜的疏水性,同时将表面处理后的改性多壁碳纳米管镶嵌在聚氨酯链段上,在干燥成膜时,改性多壁碳纳米管被固定在体系中,失去了向上漂浮的能力,依靠改性多壁碳纳米管和聚氨酯树脂的收缩率和硬度的不同,形成的微粗糙面更是一种不规则的多面体,使改性多壁碳纳米管表面包覆了更厚的一层树脂,增加了体系的稳定性和耐干湿擦性能。
具体实施方式
取5~10g多壁碳纳米管,加入400~800mL去离子水中,以300W超声波超声分散30~40min,再加入3~5g硅烷偶联剂KH792,在40~60℃下以800~1000r/min搅拌反应4~6h,冷却至室温后过滤得滤渣,将滤渣用去离子水洗涤2~3次,并置于干燥箱中干燥,得改性多壁碳纳米管,取150~180g聚己二酸1,4-丁二醇酯,20~30g蓖麻油,10~15g聚醚改性硅油,3~5g改性多壁碳纳米管,装入烧瓶中并加热至100~105℃真空脱水1~2h,降温至60~70℃,再加入32~40g异佛尔酮二异氰酸酯,以300~400r/min保温搅拌1~2h后加入10~12g二羟甲基丙酸,加热至70~80℃搅拌30~40min,得预聚物混合液,将预聚物混合液冷却至50~60℃,再加入6~8g三乙胺,以300~400r/min搅拌反应20~30min后降温至室温,再加入40~50g质量分数为1%小分子扩链剂水溶液,以1800~2000r/min搅拌1~2h,再加入1~2g流平剂,1~2g消泡剂,继续搅拌20~30min,得合成革用水性聚氨酯表面处理剂。
实例1
取5g多壁碳纳米管,加入400mL去离子水中,以300W超声波超声分散30min,再加入3g硅烷偶联剂KH792,在40℃下以800r/min搅拌反应4h,冷却至室温后过滤得滤渣,将滤渣用去离子水洗涤2次,并置于干燥箱中干燥,得改性多壁碳纳米管,取150g聚己二酸1,4-丁二醇酯,20g蓖麻油,10g聚醚改性硅油,3g改性多壁碳纳米管,装入烧瓶中并加热至100℃真空脱水1h,降温至60℃,再加入32g异佛尔酮二异氰酸酯,以300r/min保温搅拌1h后加入10g二羟甲基丙酸,加热至70℃搅拌30min,得预聚物混合液,将预聚物混合液冷却至50℃,再加入6g三乙胺,以300r/min搅拌反应20min后降温至室温,再加入40g质量分数为1%小分子扩链剂水溶液,以1800r/min搅拌1h,再加入1g流平剂,1g消泡剂,继续搅拌20min,得合成革用水性聚氨酯表面处理剂。
实例2
取7g多壁碳纳米管,加入600mL去离子水中,以300W超声波超声分散35min,再加入4g硅烷偶联剂KH792,在50℃下以900r/min搅拌反应5h,冷却至室温后过滤得滤渣,将滤渣用去离子水洗涤2次,并置于干燥箱中干燥,得改性多壁碳纳米管,取165g聚己二酸1,4-丁二醇酯,25g蓖麻油,13g聚醚改性硅油,4g改性多壁碳纳米管,装入烧瓶中并加热至103℃真空脱水1h,降温至65℃,再加入36g异佛尔酮二异氰酸酯,以350r/min保温搅拌1h后加入11g二羟甲基丙酸,加热至75℃搅拌35min,得预聚物混合液,将预聚物混合液冷却至55℃,再加入7g三乙胺,以350r/min搅拌反应25min后降温至室温,再加入45g质量分数为1%小分子扩链剂水溶液,以1900r/min搅拌1h,再加入1g流平剂,1g消泡剂,继续搅拌25min,得合成革用水性聚氨酯表面处理剂。
实例3
取10g多壁碳纳米管,加入800mL去离子水中,以300W超声波超声分散40min,再加入5g硅烷偶联剂KH792,在60℃下以1000r/min搅拌反应6h,冷却至室温后过滤得滤渣,将滤渣用去离子水洗涤3次,并置于干燥箱中干燥,得改性多壁碳纳米管,取180g聚己二酸1,4-丁二醇酯,30g蓖麻油,15g聚醚改性硅油,5g改性多壁碳纳米管,装入烧瓶中并加热至105℃真空脱水2h,降温至70℃,再加入40g异佛尔酮二异氰酸酯,以400r/min保温搅拌2h后加入12g二羟甲基丙酸,加热至80℃搅拌40min,得预聚物混合液,将预聚物混合液冷却至60℃,再加入8g三乙胺,以400r/min搅拌反应30min后降温至室温,再加入50g质量分数为1%小分子扩链剂水溶液,以2000r/min搅拌2h,再加入2g流平剂,2g消泡剂,继续搅拌30min,得合成革用水性聚氨酯表面处理剂。
将本发明制备的合成革用水性聚氨酯表面处理剂及北京某公司生产的合成革表面处理剂进行检测,具体检测结果如下表表1:
表1合成革用水性聚氨酯表面处理剂性能表征
由表1可知本发明制备的合成革用水性聚氨酯表面处理剂,拉伸强度高,吸水率低,显著提高了成膜的疏水性,热稳定性能好,耐干湿擦性能优异。

Claims (10)

1.一种合成革用水性聚氨酯表面处理剂的制备方法,其特征在于,具体步骤为:
(1)取多壁碳纳米管加入去离子水中超声分散30~40min,再加入硅烷偶联剂KH792搅拌反应,过滤水洗后干燥,得改性多壁碳纳米管;
(2)取聚己二酸1,4-丁二醇酯、蓖麻油、聚醚改性硅油、改性多壁碳纳米管,装入烧瓶中真空脱水1~2h,得反应液;
(3)将反应液降温至60~70℃,再加入异佛尔酮二异氰酸酯保温反应1~2h后加入二羟甲基丙酸,加热至70~80℃搅拌30~40min,得预聚物混合液;
(4)将预聚物混合液冷却至50~60℃,再加入三乙胺搅拌反应20~30min后降温至室温,再加入质量分数为1%小分子扩链剂水溶液,以1800~2000r/min搅拌1~2h,再加入流平剂、消泡剂继续搅拌20~30min,得合成革用水性聚氨酯表面处理剂。
2.如权利要求1所述的一种合成革用水性聚氨酯表面处理剂的制备方法,其特征在于,步骤(1)所述硅烷偶联剂KH792用量为多壁碳纳米管质量的30~100%。
3.如权利要求1所述的一种合成革用水性聚氨酯表面处理剂的制备方法,其特征在于,步骤(1)所述搅拌反应过程为在40~60℃下以800~1000r/min搅拌反应4~6h。
4.如权利要求1所述的一种合成革用水性聚氨酯表面处理剂的制备方法,其特征在于,步骤(2)所述聚己二酸1,4-丁二醇酯、蓖麻油、聚醚改性硅油、改性多壁碳纳米管的重量份为150~180份聚己二酸1,4-丁二醇酯,20~30份蓖麻油,10~15份聚醚改性硅油,3~5份改性多壁碳纳米管。
5.如权利要求1所述的一种合成革用水性聚氨酯表面处理剂的制备方法,其特征在于,步骤(2)所述真空脱水过程为装入烧瓶中并加热至100~105℃真空脱水1~2h。
6.如权利要求1所述的一种合成革用水性聚氨酯表面处理剂的制备方法,其特征在于,步骤(3)所述异佛尔酮二异氰酸酯用量为聚己二酸1,4-丁二醇酯质量的17.8~26.6%。
7.如权利要求1所述的一种合成革用水性聚氨酯表面处理剂的制备方法,其特征在于,步骤(3)所述二羟甲基丙酸用量为聚己二酸1,4-丁二醇酯质量的5.6~8.0%。
8.如权利要求1所述的一种合成革用水性聚氨酯表面处理剂的制备方法,其特征在于,步骤(4)所述三乙胺用量为聚己二酸1,4-丁二醇酯质量的3.3~5.3%,所述小分子扩链剂水溶液用量为聚己二酸1,4-丁二醇酯质量的22.2~33.3%。
9.如权利要求1所述的一种合成革用水性聚氨酯表面处理剂的制备方法,其特征在于,步骤(4)所述小分子扩链剂为乙二胺、己二胺、丙二醇、1,4-丁二醇中的一种或多种。
10.如权利要求1所述的一种合成革用水性聚氨酯表面处理剂的制备方法,其特征在于,步骤(5)所述流平剂为有机硅型流平剂或丙烯酸酯型流平剂,所述消泡剂选为有机硅类消泡剂、矿物油类消泡剂或聚醚类消泡剂中的一种或多种,所述流平剂、消泡剂与蓖麻油的质量比为(1~2):(1~2):(20~30)。
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CN107400452A (zh) * 2017-06-30 2017-11-28 常州市日臣艺术装饰材料有限公司 一种水性聚氨酯皮革涂饰剂及其制备方法

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CN109023713A (zh) * 2018-08-29 2018-12-18 佛山朝鸿新材料科技有限公司 一种超细纤维合成革基布的制备方法
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