CN111072914A - 高固含聚氨酯树脂、浸渍浆料及其应用 - Google Patents

高固含聚氨酯树脂、浸渍浆料及其应用 Download PDF

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CN111072914A
CN111072914A CN201911169779.9A CN201911169779A CN111072914A CN 111072914 A CN111072914 A CN 111072914A CN 201911169779 A CN201911169779 A CN 201911169779A CN 111072914 A CN111072914 A CN 111072914A
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glycol
polyurethane resin
adipate
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胡海波
蒋红梅
卢亚伟
欧阳快华
唐劲松
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Shanghai Huafon New Material Research & Development Technology Co ltd
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Abstract

本发明公开了一种高固含聚氨酯树脂、浸渍浆料及其应用,所述的高固含聚氨酯树脂,包括如下质量百分比的组分:多元醇53~85%,扩链剂0.01~0.07%,二异氰酸酯8.0~25%,封闭剂1.5~21%,溶剂0~10%,得到的聚氨酯树脂固含量为90~100%。本发明还涉及一种浸渍浆料,包括如下质量份数的组分:所述的高固含聚氨酯树脂100份,无溶剂色浆0~20份,发泡粉0~5份,纸浆粉0~20份,轻钙0~20份,4,4’—二氨基二环己基甲烷3~15份。采用上述的浸渍浆料制备的超细纤维合成革,环保性能优越,剥离强度高、耐水解性能优异。

Description

高固含聚氨酯树脂、浸渍浆料及其应用
技术领域
本发明涉及超细纤维合成革制备方法。
背景技术
超细纤维合成革是由超细纤维和聚氨酯构成的复合材料,具有结构仿真性、透气性、柔软性等特点,是真皮的理想替代材料之一,广泛应用于沙发、汽车、箱包、制鞋、服装等领域。
目前,超细纤维合成革多由甲苯减量或者碱减量工艺制备而成,其典型步骤如下:1)通过海岛型无纺布浸渍聚氨酯的DMF溶液,并在DMF-H2O溶液中凝固形成聚氨酯微孔;2)通过热甲苯或者热碱液抽出纤维中的海相;3)通过干燥、上油、染色等处理工艺制成超细纤维合成革基布;4)通过贴面或磨皮等工艺制成成品革。该工艺的优点在于超细纤维合成革中的聚氨酯组分拥有大量的微孔结构,制成的合成革手感丰满、柔软、真皮感强;缺点在于过程中需要大量使用N,N-二甲基甲酰胺,不仅回收N,N-二甲基甲酰胺时需要消耗大量的能源,同时,N,N-二甲基甲酰胺的蒸汽和含有N,N-二甲基甲酰胺的废水对环境的污染和职员健康的危害也很严重。
发明内容
本发明的目的是提供一种高固含聚氨酯树脂、浸渍浆料及其应用,以解决传统溶剂型浸渍树脂带来的环保和健康问题。
所述的高固含聚氨酯树脂,是以包括如下质量百分比的组分为起始原料制备的:
多元醇 53~85%
扩链剂 0.01~0.07%
二异氰酸酯 8.0~25%
封闭剂 1.5~21%
溶剂 0~10%
重量固含量为90~100%;
所述的多元醇为聚醚多元醇和聚酯多元醇中的一种或其混合物;
所述的聚醚多元醇选自分子量为500-6000的聚环氧丙烷醚二元醇和分子量为500-2000的聚四氢呋喃醚二醇;
所述的聚酯多元醇选自分子量为800-3000的聚己二酸丁二醇酯二醇、聚己二酸新戊二醇酯二醇、聚己二酸新戊二醇乙二醇共聚酯二醇、聚己二酸新戊二醇丁二醇共聚酯二醇、聚己二酸新戊二醇己二醇共聚酯二醇、聚己二酸甲基丙二醇酯二醇、聚己二酸甲基丙二醇乙二醇共聚酯二醇、聚己二酸甲基丙二醇丁二醇共聚酯二醇、聚己二酸甲基丙二醇己二醇共聚酯二醇中的一种或几种;
优选的,所述的多元醇为:
数均分子量4000的聚环氧丙烷醚二醇和数均分子量2000的聚己二酸丁二醇酯二醇的混合物,重量比为:聚环氧丙烷醚二醇:聚己二酸丁二醇酯二醇=9-11:1;或者
数均分子量6000的聚环氧丙烷醚二醇和数均分子量1000的聚己二酸新戊二醇酯二醇的混合物,重量比为:聚环氧丙烷醚二醇:聚己二酸新戊二醇酯二醇=25-26:1;或者
数均分子量6000的聚环氧丙烷醚二醇和数均分子量1000的聚己二酸甲基丙二醇酯二醇的混合物,重量比为:聚环氧丙烷醚二醇:聚己二酸甲基丙二醇酯二醇=6-7:1;或者
数均分子量2000的聚环氧丙烷醚二醇和数均分子量2000的聚己二酸新戊二醇丁二醇共聚酯二醇的混合物,重量比为:聚环氧丙烷醚二醇:聚己二酸新戊二醇丁二醇共聚酯二醇=1.5-2:1;或者
数均分子量2000的聚环氧丙烷醚二醇和数均分子量2000的聚己二酸新戊二醇酯二醇的混合物,重量比为:聚环氧丙烷醚二醇:聚己二酸新戊二醇酯二醇=1:3-4;或者
数均分子量1000的聚环氧丙烷醚二醇,数均分子量2000的聚环氧丙烷醚二醇和数均分子量1000的聚己二酸甲基丙二醇丁二醇共聚酯二醇的混合物,重量比为:聚环氧丙烷醚二醇(数均分子量1000):聚环氧丙烷醚二醇(数均分子量2000):聚己二酸甲基丙二醇丁二醇共聚酯二醇=1-1.5:1-1.1:1。
所述的扩链剂选自1,4-丁二醇、一缩二乙二醇、1,3-丙二醇、2-甲基-1,3-丙二醇、新戊二醇中的一种或以上;
所述的二异氰酸酯选自甲苯二异氰酸酯、二苯基甲烷二异氰酸酯中的一种或以上;
所述的封闭剂包括选自二异丙胺、环氧丙醇、甲乙酮肟、丙酮肟、咪唑、2-硝基咪唑、吡唑、3,5-二甲基吡唑、丙二酸二乙酯、乙酰丙酮中的一种或以上;
所述的溶剂选自γ-丁内酯、γ-戊内酯、γ-己内酯、碳酸乙烯酯、碳酸丙烯酯、1,2-碳酸丁烯酯、丙二醇甲醚醋酸酯的一种或以上;
所述的高固含聚氨酯树脂的制备方法,包括以下步骤:
(1)将二异氰酸酯与多元醇、扩链剂和溶剂的混合物反应,65-80℃反应4-5h,检测NCO%含量,至NCO%含量到达理论值;
(2)降低反应温度至50-70℃,投入封闭剂,70-80℃反应至NCO%含量为0,即可制得所述的高固含聚氨酯树脂,树脂粘度在8000~40000mPa.S@25℃;
本发明还涉及一种浸渍浆料,包括如下质量份数的组分:
所述的高固含聚氨酯树脂 100份
无溶剂色浆 0~20份
发泡粉 0~5份
纸浆粉 0~20份
轻钙 0~20份
4,4’—二氨基二环己基甲烷 3~15份
优选的,所述高固含聚氨酯树脂浸渍浆料,由以下重量份的组分组成:
所述的高固含聚氨酯树脂 100份
无溶剂色浆 0~10份
发泡粉 0~2份
纸浆粉 0~10份
轻钙 0~10份
4,4’—二氨基二环己基甲烷 3~13份
所述的无溶剂色浆,采用市售的无溶剂色浆,如浙江深蓝新材料科技股份有限公司的BLPT3701,BLPT3713,BLPT3724、BLPT 3751等。
所述的发泡粉采用市售的膨胀微球等,如阿克苏诺贝尔公司的Expancel 051 DU 40,为一种粒径在9-15微米之间、发泡温度在106-147℃之间的物理发泡粉。
所述的纸浆粉采用市售的纸浆粉或者木质粉,如宜兴市圣德力合成革材料有限公司的高白度纸浆纤维粉;
所述的轻钙采用市售的轻钙,如永安跃发轻钙有限责任公司的轻质碳酸钙;
所述的4,4’—二氨基二环己基甲烷购自深圳业旭实业有限公司。
所述的高固含聚氨酯树脂浸渍浆料由常规的物理混合方法制成,浸渍浆料粘度在5000~20000mPa.S@25℃;
采用上述的浸渍浆料,制备超细纤维合成革的方法,包括如下步骤:
(1)采用干法刮涂工艺或者干法辊涂工艺,将高固含聚氨酯树脂浸渍精良均匀涂布在无纺布上,然后利用双辊挤压无纺布,压力控制在5-15kg,之后90-150℃烘干,得浸渍基布;或者将无纺布浸渍于所述的高固含聚氨酯树脂浸渍浆料中,控制含液率在50~100%,然后利用双辊挤压无纺布,压力控制在5-15kg,之后90-150℃烘干,得浸渍基布;
(2)将上述浸渍基布按照常规的减量(热甲苯减量或热碱液减量均可)、后处理等工艺进行处理,得到超细纤维合成革;
所述的减量、后处理等的方法为常规的,本领域的技术人员可以按照文献(如文献:曲建波.合成革工艺学[M] .化学工业出版社,2010 .)报道的方法进行原生基布的染色、上油、磨皮、磨绒等工艺处理得到超细纤维聚氨酯合成革基布,该基布可用于沙发革、手套革、汽车内饰革、鞋革等的生产,根据目标产品的不同,可选择不同100%模量和固含量的高固含聚氨酯树脂等来实现。
本发明的技术原理是:
利用所述高固含聚氨酯树脂的高固含低粘度的特点,可在不添加稀释溶剂的情况下,通过刮涂、辊涂或者常规含浸操作,均可有效实现高固含聚氨酯树脂浸渍浆料在无纺布中的均匀含浸;
利用所述高固含聚氨酯树脂的加热固化的特点,可直接通过加热的方式实现聚氨酯树脂的固化,通过发泡粉或填料的添加,可模拟常规超细纤维合成革中聚氨酯组份的泡孔结构,实现超细纤维合成革丰富的手感。
与现有技术相比,本发明有以下有益效果:
(1)本发明所得聚氨酯树脂固含量在≥90%,使用时被回收和排放的环保型溶剂不超过10%,传统溶剂型聚氨酯树脂使用时固含量≤20%,使用时超过80%的溶剂被回收和排放,故本发明环保性能优越。
(2)本发明使用高固含聚氨酯树脂制备超细纤维合成革,工艺流程依次包括:
挤压含浸、烘干成型、减量烘干、后整理,相比于传统溶剂型聚氨酯树脂制备超纤纤维合成革的挤压含浸、DMF-H2O凝固成型、水洗烘干、减量、后整理工艺,本发明省去了“DMF-H2O凝固”和“水洗烘干”两道工序,在简化生产工艺、节省设备投入的同时,不再使用DMF,且无含DMF的废水产生,极大降低了环境污染,并大幅节省了DMF回收和废水处理所需的费用和能耗。
(3)本发明使用高固含聚氨酯树脂制得的超细纤维合成革的剥离强度高、耐水解性能优异。
具体实施方式
下面结合具体实施例,进一步阐述本发明。需要说明的是,这些实施例仅用于说明本发明,而不用于限定本发明的保护范围。在实际应用技术人员根据本发明做出的改进和调整,仍属于本发明的保护范围。以下实施例中所用原料均为市售。
实施例1
本实施例中,制备高固含聚氨酯树脂所用原料及质量如表1.1。
表1.1
Figure DEST_PATH_IMAGE002
本实施例的高固含聚氨酯树脂的制备步骤如下:
(1)将称好的聚环氧丙烷醚二醇(数均分子量4000)、聚己二酸丁二醇酯二醇(数均分子量2000)、1,4-丁二醇和γ-己内酯投入到反应釜中,升温至40℃,搅拌均匀;
(2)将称好的二苯基甲烷二异氰酸酯投入到反应釜中,升温至75℃,于此温度下反应6小时后检测NCO%含量,直至NCO%含量达到理论值(NCO%理论值为1.07%);
(3)降温至60℃,投入称好的环氧丙醇,升温至60℃反应1小时,即得到高固含聚氨酯树脂A,树脂粘度为30000mPa.S@25℃,固含量为90%。
本实施例应用高固含聚氨酯树脂制备超纤纤维合成革的步骤如下:
(1)配置高固含聚氨酯树脂浸渍浆料,所用原料及配比如表1.2:
表1.2
原料名称 质量(单位:kg)
高固含聚氨酯树脂A(固含量90%) 100
BLPT 3701(无溶剂色膏) 2
纸浆纤维粉 5
4,4’—二氨基二环己基甲烷 3
将表1.2中原料混合均匀,制得粘度为约20000mPa.S@25℃的高固含聚氨酯树脂浸渍浆料。
(2)原生基布的制备:
将上述高固含聚氨酯树脂浸渍浆料均匀涂布在无纺布上,然后利用双辊挤压无纺布,压力控制在10kg,之后90℃烘干,制得浸渍基布;将浸渍基布投入到减量工序中,用75℃甲苯减量3小时,并将减量完成的基布在130℃扩幅干燥设备上烘干,制得原生基布。
将原生基布按照文献报道的方法经过染色、上油、磨皮、贴面,即可获得所述的超细纤维合成革A。
实施例2
本实施例中制备高固含聚氨酯树脂所用原料及质量如表2.1。
表2.1
Figure DEST_PATH_IMAGE004
本实施例的高固含聚氨酯树脂的制备步骤如下:
(1)将称好的聚环氧丙烷醚二醇(数均分子量6000)、聚己二酸新戊二醇酯二醇(数均分子量1000)和新戊二醇投入到反应釜中,升温至40℃,搅拌均匀;
(2)将称好的二苯基甲烷二异氰酸酯投入到反应釜中,升温至75℃,于此温度下反应6小时后检测NCO%含量,直至NCO%含量达到理论值(NCO%理论值为2.68%);
(3)降温至60℃,投入称好的咪唑,升温至70摄氏度反应1小时,即得到高固含聚氨酯树脂B,树脂粘度为35000mPa.S@25℃,固含量为100%。
本实施例应用高固含聚氨酯树脂制备超纤纤维合成革的步骤如下:
(1)配置高固含聚氨酯树脂浸渍浆料,所用原料及配比如表2.2:
表2.2
原料名称 质量(单位:kg)
高固含聚氨酯树脂B(固含量100%) 100
Expancel 051 DU 40 0.5
轻质碳酸钙 10
4,4’—二氨基二环己基甲烷 6
将表2.2中原料混合均匀,制得粘度为约18000mPa.S@25℃的高固含聚氨酯树脂浸渍浆料。
(2)原生基布的制备:
将上述高固含聚氨酯树脂浸渍浆料均匀涂布在无纺布上,然后利用双辊挤压无纺布,压力控制在6kg,之后150℃烘干,制得浸渍基布;将浸渍基布投入到减量工序中,用75℃甲苯减量3小时,并将减量完成的基布在130℃扩幅干燥设备上烘干,制得原生基布。
将原生基布按照文献报道的方法经过染色、上油、磨皮、贴面,即可获得所述的超细纤维合成革B。
实施例3
实施例中制备高固含聚氨酯树脂所用原料及质量如表3.1。
表3.1
Figure 4
本实施例的高固含聚氨酯树脂的制备步骤如下:
(1)将称好的聚环氧丙烷醚二醇(数均分子量6000)、聚己二酸甲基丙二醇酯二醇(数均分子量1000)和2-甲基-1,3-丙二醇投入到反应釜中,升温至30℃,搅拌均匀;
(2)将称好的甲苯二异氰酸酯和二苯基甲烷二异氰酸酯投入到反应釜中,升温至70℃,于此温度下反应6小时后检测NCO%含量,直至NCO%含量达到理论值(NCO%理论值为3.52%);
(3)降温至50℃,投入称好的甲乙酮肟,升温至60摄氏度反应1小时,即得到高固含聚氨酯树脂C,树脂粘度为32000mPa.S@25℃,固含量为100%。
本实施例应用高固含聚氨酯树脂制备超纤纤维合成革的步骤如下:
(1)配置高固含聚氨酯树脂浸渍浆料,所用原料及配比如表3.2:
表3.2
原料名称 质量(单位:kg)
高固含聚氨酯树脂C(固含量100%) 100
BLPT 3701 3
Expancel 051 DU 40 1
纸浆纤维粉 5
轻质碳酸钙 5
4,4’—二氨基二环己基甲烷 8
将表3.2中原料混合均匀,制得粘度为约12000mPa.S@25℃的高固含聚氨酯树脂浸渍浆料。
(2)原生基布的制备:
将上述高固含聚氨酯树脂浸渍浆料均匀涂布在无纺布上,然后利用双辊挤压无纺布,压力控制在5kg,之后90℃烘干,制得浸渍基布;将浸渍基布投入到减量工序中,用1.5%的NaOH水溶液80℃碱减量2小时,并将减量完成的基布在130℃扩幅干燥设备上烘干,制得原生基布。
将原生基布按照文献报道的方法经过染色、上油、磨皮、贴面,即可获得所述的超细纤维合成革C。
实施例4
实施例中制备高固含聚氨酯树脂所用原料及质量如表4.1。
表4.1
Figure 5
本实施例的高固含聚氨酯树脂的制备步骤如下:
(1)将称好的聚环氧丙烷醚二醇(数均分子量2000)、聚己二酸新戊二醇丁二醇共聚酯二醇(数均分子量2000)、新戊二醇和γ-戊内酯投入到反应釜中,升温至40℃,搅拌均匀;
(2)将称好的甲苯二异氰酸酯和二苯基甲烷二异氰酸酯投入到反应釜中,升温至75℃,于此温度下反应6小时后检测NCO%含量,直至NCO%含量达到理论值(NCO%理论值为4.71%);
(3)降温至60℃,投入称好的3,5-二甲基吡唑,升温至60-70摄氏度反应1小时,即得到高固含聚氨酯树脂D,树脂粘度为25000mPa.S@25℃,固含量为91%。
本实施例应用高固含聚氨酯树脂制备超纤纤维合成革的步骤如下:
(1)配置高固含聚氨酯树脂浸渍浆料,所用原料及配比如表4.2:
表4.2
原料名称 质量(单位:kg)
高固含聚氨酯树脂D(固含量91%) 100
BLPT 3751 5
Expancel 051 DU 40 1.5
纸浆纤维粉 10
4,4’—二氨基二环己基甲烷 11
将表3.2中原料混合均匀,制得粘度为约10000mPa.S@25℃的高固含聚氨酯树脂浸渍浆料。
(2)原生基布的制备:
将上述高固含聚氨酯树脂浸渍浆料均匀涂布在无纺布上,然后利用双辊挤压无纺布,压力控制在5—8kg,之后90-150℃烘干,制得浸渍基布;将浸渍基布投入到减量工序中,用75℃甲苯减量3小时,并将减量完成的基布在130℃扩幅干燥设备上烘干,制得原生基布。
将原生基布按照文献报道的方法经过染色、上油、磨皮、贴面,即可获得所述的超细纤维合成革D。
实施例5
实施例中制备高固含聚氨酯树脂所用原料及质量如表5.1。
表5.1
Figure 6
本实施例的高固含聚氨酯树脂的制备步骤如下:
(1)将称好的聚环氧丙烷醚二醇(数均分子量2000)、聚己二酸新戊二醇酯二醇(数均分子量2000)、新戊二醇和碳酸丙烯酯投入到反应釜中,升温至35℃,搅拌均匀;
(2)将称好的甲苯二异氰酸酯投入到反应釜中,升温至73℃,于此温度下反应6小时后检测NCO%含量,直至NCO%含量达到理论值(NCO%理论值为5.57%);
(3)降温至55℃,投入称好的二异丙胺,升温至65摄氏度反应1小时,即得到高固含聚氨酯树脂E,树脂粘度为15000mPa.S@25℃,固含量为90.4%。
本实施例应用高固含聚氨酯树脂制备超纤纤维合成革的步骤如下:
(1)配置高固含聚氨酯树脂浸渍浆料,所用原料及配比如表5.2:
表5.2
原料名称 质量(单位:kg)
高固含聚氨酯树脂E(固含量90.4%) 100
BLPT 3724 8
Expancel 051 DU 40 2
纸浆纤维粉 8
4,4’—二氨基二环己基甲烷 12
将表3.2中原料混合均匀,制得粘度为约8000mPa.S@25℃的高固含聚氨酯树脂浸渍浆料。
(2)原生基布的制备:
将无纺布浸渍于上述的高固含聚氨酯树脂浸渍浆料中,控制含液率在90%,然后利用双辊挤压无纺布,压力控制在8kg,之后150℃烘干,制得浸渍基布;将浸渍基布投入到减量工序中,用75℃甲苯减量3小时,并将减量完成的基布在130℃扩幅干燥设备上烘干,制得原生基布。
将原生基布按照文献报道的方法经过染色、上油、磨皮、贴面,即可获得所述的超细纤维合成革E。
实施例6
实施例中制备高固含聚氨酯树脂所用原料及质量如表6.1。
表6.1
Figure DEST_PATH_IMAGE012
本实施例的高固含聚氨酯树脂的制备步骤如下:
(1)将称好的聚环氧丙烷醚二醇(数均分子量1000)、聚环氧丙烷醚二醇(数均分子量2000)、聚己二酸甲基丙二醇丁二醇共聚酯二醇(数均分子量1000)、1,4-丁二醇和γ-丁内酯投入到反应釜中,升温至40℃,搅拌均匀;
(2)将称好的甲苯二异氰酸酯和二苯基甲烷二异氰酸酯投入到反应釜中,升温至70℃,于此温度下反应6小时后检测NCO%含量,直至NCO%含量达到理论值(NCO%理论值为6.54%);
(3)降温至50-60℃,投入称好的丙二酸二乙酯,升温至60-70摄氏度反应1小时,即得到高固含聚氨酯树脂F,树脂粘度为10000mPa.S@25℃,固含量为95.5%。
本实施例应用高固含聚氨酯树脂制备超纤纤维合成革的步骤如下:
(1)配置高固含聚氨酯树脂浸渍浆料,所用原料及配比如表6.2:
表6.2
原料名称 质量(单位:kg)
高固含聚氨酯树脂F(固含量95.5%) 100
BLPT 3713 5
Expancel 051 DU 40 1.5
纸浆纤维粉 5
轻质碳酸钙 5
4,4’—二氨基二环己基甲烷 13
将表3.2中原料混合均匀,制得粘度为约6000mPa.S@25℃的高固含聚氨酯树脂浸渍浆料。
(2)原生基布的制备:
将无纺布浸渍于上述的高固含聚氨酯树脂浸渍浆料中,控制含液率在100%,然后利用双辊挤压无纺布,压力控制在7kg,之后100℃烘干,制得浸渍基布;将浸渍基布投入到减量工序中,用1.5%的NaOH水溶液80℃碱减量2小时,并将减量完成的基布在130℃扩幅干燥设备上烘干,制得原生基布。
将原生基布按照文献报道的方法经过染色、上油、磨皮、贴面,即可获得所述的超细纤维合成革F。
将上述六组超细纤维合成革按照ISO 12219-2:2012(筛分法测定汽车内饰件材料中挥发性有机化合物排放--袋式法)标准进行DMF和甲苯含量的测试,同时和市售溶剂型超细纤维合成革对比,结果见表7。
表7
Figure DEST_PATH_IMAGE014
注:N.D.=Not Detected,表示未检出或者小于检测限。
从表7可知,实施例1至6制得的超细纤维合成革中的DMF含量均<10ppm,对比市售超细纤维合成革,DMF含量明显要低很多,说明用本发明生产的超细纤维合成革DMF残留很少或没有,环保性能优异。
将上述六组超细纤维合成革根据QB/T2888-2007标准测试其剥离强度。将上述六组超细纤维合成革按照QB/T2888-2007标准的附录A耐水解性试验的A.1试验方法1进行丛林耐候试验,70℃、95%湿度条件下放置5周,测试丛林后的剥离强度,同时和市售溶剂型超细纤维合成革对比,结果见表8.1;按照QB/T2888-2007标准的附录A耐水解性试验的A.2试验方法2进行耐碱性试验,于10%的NaOH水溶液中浸泡24h,测试泡碱后的剥离强度,同时和市售溶剂型超细纤维合成革对比,结果见表8.2。
表8.1
Figure DEST_PATH_IMAGE016
表8.2
Figure DEST_PATH_IMAGE018
从表8.1和8.2可知,实施例1至6制得的超细纤维合成革耐水解性能优异,且水解后剥离衰减<10%,满足绝大多数应用需求。其中实施例3至6制得的超细纤维合成革水解后剥离力在100N/3cm以上,符合高剥离合成革的要求。同时,和市售常规超细纤维合成革对比,本发明制得的超细纤维合成革在剥离强度和耐水解性能上明显优于市售溶剂型超细纤维合成革,说明用本发明生产的超细纤维合成革性能优异,剥离强度高,耐水解性能好。

Claims (10)

1. 高固含聚氨酯树脂,其特征在于,是以包括如下质量百分比的组分为起始原料制备的:
多元醇 53~85%
扩链剂 0.01~0.07%
二异氰酸酯 8.0~25%
封闭剂 1.5~21%
溶剂 0~10%。
2.根据权利要求1所述的高固含聚氨酯树脂,其特征在于,所述的多元醇为聚醚多元醇和聚酯多元醇中的一种或其混合物;
所述的聚醚多元醇选自分子量为500-6000的聚环氧丙烷醚二元醇和分子量为500-2000的聚四氢呋喃醚二醇;
所述的聚酯多元醇选自分子量为800-3000的聚己二酸丁二醇酯二醇、聚己二酸新戊二醇酯二醇、聚己二酸新戊二醇乙二醇共聚酯二醇、聚己二酸新戊二醇丁二醇共聚酯二醇、聚己二酸新戊二醇己二醇共聚酯二醇、聚己二酸甲基丙二醇酯二醇、聚己二酸甲基丙二醇乙二醇共聚酯二醇、聚己二酸甲基丙二醇丁二醇共聚酯二醇、聚己二酸甲基丙二醇己二醇共聚酯二醇中的一种或几种;
所述的扩链剂选自1,4-丁二醇、一缩二乙二醇、1,3-丙二醇、2-甲基-1,3-丙二醇、新戊二醇中的一种或以上;
所述的二异氰酸酯选自甲苯二异氰酸酯、二苯基甲烷二异氰酸酯中的一种或以上;
所述的封闭剂包括选自二异丙胺、环氧丙醇、甲乙酮肟、丙酮肟、咪唑、2-硝基咪唑、吡唑、3,5-二甲基吡唑、丙二酸二乙酯、乙酰丙酮中的一种或以上。
3. 根据权利要求2所述的高固含聚氨酯树脂,其特征在于,所述的多元醇为:
数均分子量4000的聚环氧丙烷醚二醇和数均分子量2000的聚己二酸丁二醇酯二醇的混合物,重量比为:聚环氧丙烷醚二醇:聚己二酸丁二醇酯二醇=9-11:1;或者
数均分子量6000的聚环氧丙烷醚二醇和数均分子量1000的聚己二酸新戊二醇酯二醇的混合物,重量比为:聚环氧丙烷醚二醇:聚己二酸新戊二醇酯二醇=25-26:1;或者
数均分子量6000的聚环氧丙烷醚二醇和数均分子量1000的聚己二酸甲基丙二醇酯二醇的混合物,重量比为:聚环氧丙烷醚二醇:聚己二酸甲基丙二醇酯二醇=6-7:1;或者:
数均分子量2000的聚环氧丙烷醚二醇和数均分子量2000的聚己二酸新戊二醇丁二醇共聚酯二醇的混合物,重量比为:聚环氧丙烷醚二醇:聚己二酸新戊二醇丁二醇共聚酯二醇=1.5-2:1;或者
数均分子量2000的聚环氧丙烷醚二醇和数均分子量2000的聚己二酸新戊二醇酯二醇的混合物,重量比为:聚环氧丙烷醚二醇:聚己二酸新戊二醇酯二醇=1:3-4;或者
数均分子量1000的聚环氧丙烷醚二醇,数均分子量2000的聚环氧丙烷醚二醇和数均分子量1000的聚己二酸甲基丙二醇丁二醇共聚酯二醇的混合物,重量比为:聚环氧丙烷醚二醇(数均分子量1000):聚环氧丙烷醚二醇(数均分子量2000):聚己二酸甲基丙二醇丁二醇共聚酯二醇=1-1.5:1-1.1:1。
4.根据权利要求2所述的高固含聚氨酯树脂,其特征在于,所述的溶剂选自γ-丁内酯、γ-戊内酯、γ-己内酯、碳酸乙烯酯、碳酸丙烯酯、1,2-碳酸丁烯酯、丙二醇甲醚醋酸酯的一种或以上。
5.根据权利要求1~4任一项所述的高固含聚氨酯树脂,其特征在于,制备方法,包括以下步骤:
(1)将二异氰酸酯与多元醇、扩链剂和溶剂的混合物反应,65-80℃反应4-5h;
(2)降低反应温度至50-70℃,投入封闭剂,70-80℃反应至NCO%含量为0,即可制得所述的高固含聚氨酯树脂。
6. 浸渍浆料,其特征在于,包括如下质量份数的组分:
权利要求1~5任一项所述的高固含聚氨酯树脂 100份
无溶剂色浆 0~20份
发泡粉 0~5份
纸浆粉 0~20份
轻钙 0~20份
4,4’—二氨基二环己基甲烷 3~15份。
7. 根据权利要求6所述的浸渍浆料,其特征在于,由以下重量份的组分组成:
权利要求1~5任一项所述的高固含聚氨酯树脂 100份
无溶剂色浆 0~10份
发泡粉 0~2份
纸浆粉 0~10份
轻钙 0~10份
4,4’—二氨基二环己基甲烷 3~13份。
8.根据权利要求6或7所述的浸渍浆料,其特征在于,所述的发泡粉为一种粒径在9-15微米之间、发泡温度在106-147℃之间的物理发泡粉。
9.权利要求6~8任一项所述的浸渍浆料的应用,其特征在于,用于制备超细纤维合成革。
10.根据权利要求9所述的应用,其特征在于,应用方法,包括如下步骤:
(1)采用干法刮涂工艺或者干法辊涂工艺,将高固含聚氨酯树脂浸渍精良均匀涂布在无纺布上,然后利用双辊挤压无纺布,压力控制在5-15kg,之后90-150℃烘干,得浸渍基布;或者将无纺布浸渍于所述的高固含聚氨酯树脂浸渍浆料中,控制含液率在50~100%,然后利用双辊挤压无纺布,压力控制在5-15kg,之后90-150℃烘干,得浸渍基布;
(2)将上述浸渍基布减量、后处理等工艺进行处理,得到超细纤维合成革。
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