CN105837774A - 一种高剥离耐水解聚氨酯树脂及其制备方法和应用 - Google Patents

一种高剥离耐水解聚氨酯树脂及其制备方法和应用 Download PDF

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CN105837774A
CN105837774A CN201610382049.7A CN201610382049A CN105837774A CN 105837774 A CN105837774 A CN 105837774A CN 201610382049 A CN201610382049 A CN 201610382049A CN 105837774 A CN105837774 A CN 105837774A
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polyurethane resin
parts
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CN105837774B (zh
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张勇
文远海
何俭辉
曾庆伟
齐佳圭
韩方平
韩帅
彭光伟
武星
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TAIZHOU HEXIN POLYMER NEW MATERIAL Co Ltd
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Abstract

本发明公开了一种高剥离耐水解聚氨酯树脂,其中:包括如下重量份数的组分:异氰酸酯6.5份‑8.0份、多元醇组合物12份‑15份、小分子扩链剂2.0份‑2.5份、N,N‑二甲基甲酰胺溶剂65份‑72份、封端剂0.03份‑0.1份、助剂1份‑2份,该聚氨酯树脂具有较高的剥离强度,从而在制作合成革时,能连接的更加牢固,同时公布了该聚氨酯树脂的制备方法和应用。

Description

一种高剥离耐水解聚氨酯树脂及其制备方法和应用
技术领域
本发明涉及聚氨酯树脂领域,特别涉及一种高剥离耐水解聚氨酯树脂及其制备方法和应用。
背景技术
聚氨酯树脂在合成革方面应用十分广泛,主要体现在服装、鞋、箱包、家具、汽车等多个领域。随着市场需求的日益扩大,革用聚氨酯树脂也迅速发展呈上升趋势,因此对技术的发展与更新也提出了更高的要求。
由于耐水解树脂的剥离强度很难跟普通聚氨酯树脂一样可以将剥离强度做到很高,这跟耐水解聚氨酯树脂所使用的原材料有一定的关联。但是随着合成革市场的不断发展,市场上对耐水解聚氨酯树脂的性能要求也进一步提高,要求跟普通聚氨酯树脂一样能有很高的剥离强度。
目前,公开号为CN103046376A的中国专利公开了一种耐黄变湿气固化聚氨酯镜面光油,其特征在于,由如下重量份数的原料制成:聚醚多元醇24-45%、异氰酸酯18-40%、三羟基多元醇2.9-10%、醋酸丁酸纤维素3.3-5.5%、抗氧剂0.02-0.06%、催化剂0.02-0.2%、30-42%的溶剂和0.001-0.01%的终止剂,但是这种聚氨酯镜面光油的聚醚多元醇含量较高,其耐剥离强度较差。
发明内容
本发明的第一发明目的是提供一种中低模量中高剥离耐水解的聚氨酯树脂。
本发明的上述技术目的是通过以下技术方案得以实现的:一种高剥离耐水解聚氨酯树脂,其中:包括如下重量份数的组分:
异氰酸酯 6.5份-8.0份
多元醇组合物 12份-15份
小分子扩链剂 2.0份-2.5份
N,N-二甲基甲酰胺溶剂 65份-72份
封端剂 0.03份-0.1份
助剂 1份-2份。
二苯基甲烷-4,4’-二异氰酸酯(MDI)具有对称的化学结构,可以形成结构规整且有序的相区,相应聚氨酯的强度、硬度和结晶度等都比较大,且具有很好的耐磨性。
作为优选方案,所述多元醇组合物包括聚醚多元醇和聚酯多元醇,其中聚醚多元醇与聚酯多元醇的质量比为10∶0-8∶2之间。
聚酯多元醇制备的聚氨酯产品强度和硬度较大,因为聚酯型聚氨酯分子内部一般含有强极性的酯基基团,内聚强度大,而且酯基易与N-H生成氢键,使分子链段的运动受到限制;而由聚醚多元醇制备的聚氨酯一般具有良好的弹性和延伸率,因为醚键的旋转比较容易,且其能使聚氨酯具有较好的耐低温性、疏水性和耐水解性。
聚酯多元醇与聚醚多元醇共聚降低反应结晶性,从而改善泡孔结构,使泡孔结构均匀细长直立。微观结构改变宏观性能,其均匀细长直立的泡孔结构能够具有高回弹性能,使得手感舒适。
由于合成革用聚氨酯树脂不仅需要满足较高的剥离强度外,还需要满足耐水解性能达到在碱溶液中浸泡后保持较高剥离强度,水洗速度要快。提高剥离强度不仅需要从原材料和工艺去调整,还需要调整聚氨酯树脂的微观结构。在同一工艺条件及原材料情况下,聚氨酯树脂微观泡孔结构越大,剥离强度相对较低。因此本发明采用不同分子量大小的多元醇调整泡孔结构,使得所制备的聚氨酯树脂的微观泡孔结构细小均匀直立,同时延缓预凝固速度。采用80%以上的聚醚多元醇以提高耐水解性能,采用聚醚多元醇和聚酯多元醇共聚的方法以提高产品的水洗速度,同时也降低反应结晶性。另外,结晶性的降低,对泡孔结构也有影响,使泡孔结构更细小。
作为优选方案,所述聚酯多元醇的分子量在500-2000之间,聚醚多元醇的分子量在1000-3000之间,所述聚酯多元醇为己二酸与二元醇反应得到的二醇系化合物,其中与己二酸反应的二元醇是乙二醇、二乙二醇、1,4-丁二醇中的一种或者两种混合物,所述聚醚多元醇化合物为环氧丙烷缩合物和聚四亚甲基醚二醇中的一种或两种。
作为优选方案,所述小分子扩链剂为乙二醇、二乙二醇、1,4-丁二醇、2,2-二甲基-1,3-丙二醇中的任意两种。
为调整凝固和水洗速度,使得凝固速度适中,水洗速度加快,选择混合扩链剂,通过调整混合扩链剂各组分的质量比,缓解树脂表面凝固速度,以达到本发明的目的。另外功能性改性助剂的加入不仅使得泡孔结构更细小,而且水洗速度也会提高,手感也变得舒适,具有真皮感。
作为优选方案,所述封端剂为甲醇和异丙醇中的一种或两种。
甲醇和异丁醇具有稳定的甲基和异丁基,醇基与反应链的端部反应将甲基和异丁基添加到相应位置,从而消除封端处的活性,终止分子链段的继续增长。
作为优选方案,所述助剂为松香、三羟甲基丙烷和有机硅助剂中的一种或多种。
松香是添加到聚氨酯树脂中,能提高聚氨酯树脂的剥离强度;三羟基甲基丙烷在反应过程中,将基团、链段交联,使得树脂内部结构强度更大,剥离强度提高;有机硅助剂既包含有机基团,又含有无机结构,因此兼具有机物的特性和无机物的功能,有机硅助剂的添加能增强聚氨酯合成革的手感,并且能增强聚氨酯树脂的交联性能,从而增强聚氨酯树脂的交联强度。
本发明中的聚氨酯树脂合成革在相同填充料的情况下,比强度较高,在添加较多填充料时也可以保持较高的剥离强度,因此可以增加填充料以降低合成革的成本。
本发明的第二发明目的在于提供一种高剥离耐水解聚氨酯树脂的制备方法。
本发明的上述技术目的是通过以下技术方案实现的:一种高剥离耐水解聚氨酯树脂的制备方法为:
步骤一:将多元醇组合物与部分异氰酸酯在溶剂DMF中进行预聚反应;
步骤二:将小分子扩链剂和溶剂与步骤一所得的预聚物充分反应,再加入剩余异氰酸酯,并在反应过程中加入溶剂DMF,调整树脂粘度在20000Mpa·s/25℃;
步骤三:加入封端剂终止反应,再加入助剂和少量溶剂DMF充分搅拌均匀。
该制备方法的优点在于:首先将部分异氰酸酯和多元醇组合物在溶剂中充分预聚反应,然后进行扩链,保证能生成足够链长的聚氨酯,避免多元醇的融入不充分,保证了多元醇组合物具良好的添加效果。
作为优选方案,在步骤一中的多元醇组合物的摩尔数与异氰酸酯的摩尔数的比例为1∶0.5-2。
该方案中,多元醇组合物与异氰酸酯的摩尔比为0.5到2之间,在保证多元醇能充分反应的情况下,异氰酸酯不过量,从而根据比例生成合适的预聚物进行下一步反应。
作为优选方案,在步骤一中反应温度为70℃到90℃之间,步骤二中反应温度控制在70℃到90℃之间。
本发明的第三发明目的在于提供一种高剥离耐水解聚氨酯树脂的应用。
本发明的上述技术目的是通过以下技术方案实现的:上述高剥离耐水解的聚氨酯树脂在合成革制备中的应用。
具体实施方式
实施例一:
一种高剥离耐水解聚氨酯树脂,配方为如下质量的物质(g):
其中聚酯多元醇的分子量:2000
环氧丙烷缩合物的分子量:1500。
本实施例的制备方法为:
步骤一:将环氧丙烷缩合物120g、聚酯多元醇30g与异氰酸酯55g在溶剂DMF中进行预聚反应,反应温度70℃;
步骤二:将小分子扩链剂和溶剂与步骤一所得的预聚物充分反应,再加入剩余异氰酸酯,并在反应过程中加入溶剂DMF,调整树脂粘度在20000Mpa·s/25℃,反应温度80℃;
步骤三:加入封端剂终止反应,再加入助剂和少量溶剂DMF充分搅拌均匀。
实施例二:
一种高剥离耐水解聚氨酯树脂,包括如下质量的物质(g):
其中聚酯多元醇的分子量:500
聚四亚甲基醚二醇的分子量:3000。
本实施例的制备方法为:
步骤一:将聚酯多元醇16g、环氧丙烷缩合物144g与异氰酸酯14g在溶剂DMF中进行预聚反应,反应温度80℃;
步骤二:将小分子扩链剂和溶剂与步骤一所得的预聚物充分反应,再加入剩余异氰酸酯,并在反应过程中加入溶剂DMF,调整树脂粘度在20000Mpa·s/25℃,反应温度75℃;
步骤三:加入封端剂终止反应,再加入助剂和少量溶剂DMF充分搅拌均匀。
实施例三:
一种高剥离耐水解聚氨酯树脂,包括如下质量的物质(g):
其中聚四亚甲基醚二醇和环氧丙烷缩合物的分子量:1000。
本实施例的制备方法为:
步骤一:将环氧丙烷缩合物60g、聚四亚甲基醚二醇60g与异氰酸酯60g在溶剂DMF中进行预聚反应,反应温度90℃;
步骤二:将小分子扩链剂和溶剂与步骤一所得的预聚物充分反应,再加入剩余异氰酸酯,并在反应过程中加入溶剂DMF,调整树脂粘度在20000Mpa·s/25℃,反应温度75℃;
步骤三:加入封端剂终止反应,再加入助剂和少量溶剂DMF充分搅拌均匀。
实施例四:
一种高剥离耐水解聚氨酯树脂,包括如下质量的物质(g):
其中聚酯多元醇的分子量:2000
聚四亚甲基醚二醇的分子量:2500。
本实施例的制备方法为:
步骤一:将聚酯多元醇115g、聚四亚甲基醚二醇25g与异氰酸酯41g在溶剂DMF中进行预聚反应,反应温度75℃;
步骤二:将小分子扩链剂和溶剂与步骤一所得的预聚物充分反应,再加入剩余异氰酸酯,并在反应过程中加入溶剂DMF,调整树脂粘度在20000Mpa·s/25℃,反应温度70℃;
步骤三:加入封端剂终止反应,再加入助剂和少量溶剂DMF充分搅拌均匀。
实施例五:
一种高剥离耐水解聚氨酯树脂,包括如下质量的物质(g):
其中聚酯多元醇的分子量:2000
聚四亚甲基醚二醇的分子量:2500。
本实施例的制备方法为:
步骤一:将聚酯多元醇22g、环氧丙烷缩合物110g与异氰酸酯20g在溶剂DMF中进行预聚反应,反应温度70℃;
步骤二:将小分子扩链剂和溶剂与步骤一所得的预聚物充分反应,再加入剩余异氰酸酯,并在反应过程中加入溶剂DMF,调整树脂粘度在20000Mpa·s/25℃,反应温度90℃;
步骤三:加入封端剂终止反应,再加入助剂和少量溶剂DMF充分搅拌均匀。
为了验证本发明的聚氨酯树脂具有能优异的耐水解性能,对上述实施例的产品进行分别实验,具体实验步骤如下:将上述5种实施例的产品与普通聚氨酯树脂按照合成革加工配方制作成Base样并分别裁取宽度30mm长度80mm的长条片状样品各三片,放置在10%的氢氧化钠水溶液中,在室温下放置12小时后,用清水洗净至PH为中性后80℃烘干,测试剥离强度,记录各个样品在放置10%的氢氧化钠水溶液中12小时前后的剥离强度,测试结果见下表1。
表1剥离强度测试结果表
从上述实验数据看出,本发明的聚氨酯树脂的耐水解性能大大增强,满足设计的耐碱后剥离强度保持率在90%以上的要求。
进一步再测试本发明样品的凝固速度和水洗速度,即DMF从聚氨酯溶液中萃取出来的速度:将普通合成革用聚氨酯树脂和本实施例中的产品按照合成革加工配方搅拌均匀后刮涂在革基布上,每隔一分钟观察凝固速度。待完全凝固后放入清水中浸泡,并每隔一分钟裁剪一条长约80mm,宽约15mm的样品测试其水洗情况,测试结果见下表2。
表2凝固速度和水洗速度试验结果记录表
样品 凝固速度(min) 水洗速度(mm)
普通合成革用聚氨酯树脂 7 7
实施例1样品 7 3
实施例2样品 7 4
实施例3样品 6 4
实施例4样品 6 3
实施例5样品 8 3
从上述试验数据可以看出本发明制备的聚氨酯树脂具有无泡孔或细小泡孔结构,水洗方便。
为了验证本发明的聚氨酯树脂具有中高模量,对上述实施例的产品进行分别实验,具体实验步骤如下:
将上述5种实施例所得的产品与普通聚氨酯树脂分别刮涂在镜面离型纸上,刮涂厚度0.25mm,恒温80℃烘干50min后室温下放置24小时,分别截取3条长40mm,宽6mm的样品,在拉伸试验机上进行拉伸试验,取平均值,其结果如下表3。
表3拉伸试验结果记录表:
从上述实验数据看出,本发明的聚氨酯树脂的100%模量在13-16MPa之间,且具有较高的断裂伸长率。
应当指出:对于本行业的技术人员来说,在不脱离本发明原理的前提下,还可以做出各种变化和改进,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同物界定。

Claims (10)

1.一种高剥离耐水解聚氨酯树脂,其特征在于:包括如下重量份数的组分:
异氰酸酯 6.5份-8.0份
多元醇组合物 12份-15份
小分子扩链剂 2.0份-2.5份
N,N-二甲基甲酰胺溶剂 65份-72份
封端剂 0.03份-0.1份
助剂 1份-2份。
2.根据权利要求1所述的一种高剥离耐水解聚氨酯树脂,其特征在于:所述多元醇组合物包括聚醚多元醇和聚酯多元醇,其中聚醚多元醇与聚酯多元醇的质量比为10:0-8:2之间。
3.根据权利要求2所述的一种高剥离耐水解聚氨酯树脂,其特征在于:聚酯多元醇的分子量在500-2000之间,聚醚多元醇的分子量在1000-3000之间,所述聚酯多元醇为己二酸与二元醇反应得到的二醇系化合物,其中与己二酸反应的二元醇是乙二醇、二乙二醇、1,4-丁二醇中的一种或者两种混合物,所述聚醚多元醇化合物为环氧丙烷缩合物和聚四亚甲基醚二醇中的一种或两种。
4.根据权利要求1所述的一种高剥离耐水解聚氨酯树脂,其特征在于:所述小分子扩链剂为乙二醇、二乙二醇、1,4-丁二醇、2,2-二甲基-1,3-丙二醇中的任意两种。
5.根据权利要求1所述的一种高剥离耐水解聚氨酯树脂,其特征在于:所述封端剂为甲醇、异丙醇中的一种或两种。
6.根据权利要求1所述的一种高剥离耐水解聚氨酯树脂,其特征在于:所述助剂为松香、三羟甲基丙烷和有机硅助剂中的一种或多种。
7.一种高剥离耐水解聚氨酯树脂的制备方法,其特征在于:
步骤一:将多元醇组合物与部分异氰酸酯在溶剂DMF中进行预聚反应;
步骤二:将小分子扩链剂和溶剂与步骤一所得的预聚物充分反应,再加入剩余异氰酸酯,并在反应过程中加入溶剂,调整树脂粘度在20000Mpa·s/25℃;
步骤三:加入封端剂终止反应,再加入助剂和少量溶剂DMF充分搅拌均匀。
8.根据权利要求7所述的一种高剥离耐水解聚氨酯树脂的制备方法,其特征在于:步骤一中的多元醇组合物的摩尔数与异氰酸酯的摩尔数的比例为1:0.5-2。
9.根据权利要求7所述的一种高剥离耐水解聚氨酯树脂的制备方法,其特征在于:步骤一中反应温度为70℃到90℃之间,步骤二中反应温度控制在70℃到90℃之间。
10.权利要求1-6任一所述的高剥离耐水解聚氨酯树脂在合成革的制备中的应用。
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