CN113773467A - 一种超绵软细折痕特殊湿法革用树脂及其制备方法 - Google Patents
一种超绵软细折痕特殊湿法革用树脂及其制备方法 Download PDFInfo
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Abstract
本发明属于树脂材料领域,具体涉及一种超绵软细折痕特殊湿法革用树脂及其制备方法,包括以下重量百分比的原料:聚酯多元醇20‑40%,线性羟基硅油0.5‑2%,二苯基甲烷4.4’二异氰酸酯3‑5%,二醇小分子扩链剂0.5‑0.8%,N‑N二甲基甲酰胺68‑72%,湿法绵感助剂0.5‑1.5%。本发明采用聚酯多元醇跟羟基硅油共聚,采用聚酯多元醇当主链,跟混合聚醚当主链相比,具有泡孔结构细密化、凝固速度和渗透性适中、脱DMF速度快、剥离强度高的同时,兼具手感超绵软、细折痕的特点,适用于鞋革、服装、箱包、沙发等领域的应用。
Description
技术领域
本发明属于树脂材料领域,具体涉及一种超绵软细折痕特殊湿法革用树脂及其制备方法。
背景技术
目前,天然皮革由于价格昂贵和动物保护组织的要求,已经限制使用。聚氨酯PU革得到蓬勃发展,而且PU革由于具有可着色性强,耐磨好性、价格低廉、容易保养以及优越的低温柔韧性,在鞋类、家具、汽车座椅、服装及箱包等领域受到广泛的应用。PU革用树脂是生产PU革的主要原材料。随着人民生活水平的提高,近些年蛋白质PU革和超绵软PU革得到大力发展。无论是蛋白质PU革和超绵软PU革都容易出折痕,并且折痕比较粗,同时也是PU革的泡孔结构比较大的原因。而且尚未有良好的解决方案,因此,开发出一种超绵软折痕细的特殊湿法革用树脂就显得有现实意义。
发明内容
本发明的目的是针对现有技术中的不足,提供一种超绵软细折痕特殊湿法革用树脂的制备方法。本发明采用聚酯多元醇跟线性羟基硅油共聚,具有泡孔结构细密化、凝固速度和渗透性适中,脱DMF速度快,手感超绵软,细折痕特点,可以解决市面上PU革出现的折痕问题。
为实现上述目的,本发明解决其技术问题所采用的技术方案是:
一种超绵软细折痕特殊湿法革用树脂,包括以下重量百分比的原料:聚酯多元醇20-40%,线性羟基硅油0.5-2%,二苯基甲烷4.4’二异氰酸酯3-5%,二醇小分子扩链剂0.5-0.8%,N-N二甲基甲酰胺68-72%,湿法绵感助剂0.5-1.5%。
优选的,所述聚酯多元醇为己二酸系聚酯多元醇;所述的己二酸系聚酯多元醇为聚己二酸二乙二醇二元醇、聚己二酸乙二醇二乙二醇二元醇、聚己二酸1,4-丁二醇二元醇、聚己二酸乙二醇1,4-丁二醇二元醇的一种或多种;
所述聚己二酸二乙二醇二元醇的羟值为37-112mgKOH/g、聚己二酸乙二醇二乙二醇二元醇的羟值为37-112mgKOH/g、聚己二酸1,4-丁二醇二元醇的羟值为37-112mgKOH/g、聚己二酸乙二醇1,4-丁二醇二元醇的羟值为24-112mgKOH/g。
优选的,所述二醇小分子扩链剂为乙二醇、1,4-丁二醇、二甘醇中的一种或多种。
优选的,所述线性羟基硅油的重量百分比为0.5-1%,具体选用道康宁公司的SF-8427和/或OFX-3667。
优选的,所述湿法绵感助剂为上海日多高分子材料有限公司的PR-69。
本发明还提供一种超绵软细折痕特殊湿法革用树脂的制备方法,具体包括如下步骤:
(1)将各原材料按上述重量百分比称重,各原材料的重量百分比之和为1;
首先将N-N二甲基甲酰胺分为A、B两份,其中A份为总原材料重量的30-40%,余下记为B份;在混合聚醚多元醇中投入抗氧化剂、线性羟基硅油、二醇小分子扩链剂和A份的N-N二甲基甲酰胺混合均匀,得到初步混合物料;
(2)将二苯基甲烷-4,4’-二异氰酸酯按照重量分为C、D两份,其中C份为其重量的70-80%,余下记为D份;
在步骤(1)得到的初步混合物料中先加入C份的二苯基甲烷-4,4’-二异氰酸酯,在一定温度条件下反应后,再加入D份的二苯基甲烷-4,4’-二异氰酸酯进行补加增粘,然后加入B份的N-N二甲基甲酰胺,加入甲醇终止反应,终止反应后,最后再加入湿法绵感助剂(0.5-1.5%),混合均匀,降温出料得到最终树脂产品。
优选的,步骤(1)中所述抗氧化剂为2、6一二叔丁基对甲酚、亚磷酸三苯酯中的一种或多种混合;所述抗氧化剂用量为聚酯多元醇重量的0~0.1%。
优选的,步骤(2)中所述一定温度条件为75-80℃,反应时间为80-90分钟。
优选的,步骤(2)中所述甲醇的加入量为总原材料重量的0.015%~0.02%。
优选的,步骤(2)中所述初步混合物料中还可以加入催化剂,所述催化剂选自二丁基二月桂酸锡,辛酸亚锡或者有机铋催化剂中的一种或多种,添加量为聚酯多元醇重量的0~0.1%。
优选的,步骤(2)中所述最终树脂产品的粘度在160000CPS-260000CPS(25℃),固含量为28-32%。
本发明具有如下的有益效果:
(1)本发明的优点在于采用聚酯多元醇与线性羟基硅油共聚;因为纯聚酯产品中聚酯分子间的凝集力往往比较强,有利于树脂的凝固发泡,而发泡的泡孔比较大,但线性羟基硅油分子间的凝集力比聚酯多元醇小,从而实现凝固速率适中,也有利于泡孔结构密且小,同时线性羟基硅油的疏水性比聚酯多元醇更利于实现脱DMF速度快。本发明的优化,线性羟基硅油的含量为0.5-1.0,线性羟基硅油的含量至关重要,用量过少起不到作用,用量过多,反而会导致泡孔结构小而散或者无泡孔结构,同时造成产品折痕比较粗、手感和水洗情况较差的问题。
(2)本发明采用上海日多高分子材料有限公司的绵感助剂PR-69使手感更绵软,从而实现整体性能的优化。
(3)本发明通过配方设计,兼顾综合性能,解决了工艺复杂问题的同时,制备综合性能优异的树脂;采用聚酯多元醇当主链,跟混合聚醚当主链相比,在具有泡孔结构细密化、凝固速度和渗透性适中、脱DMF速度快、剥离强度高的同时,兼具手感超绵软、细折痕的特点。
具体实施方式
以下实施例进一步说明本发明的内容,但不应理解为对本发明的限制。在不背离本发明精神和实质的情况下,对本发明方法、步骤或条件所作的修改和替换,均属于本发明的范围。若未特别指明,实施例中所用的技术手段为本领域技术人员所熟知的常规手段。
下述实例以革用聚氨酯树脂的工业化生产流程为依据,具体步骤详见实施例。下述实施例中,由行内的公知技术:DMF指代N、N—二甲基甲酰胺,MDI为二苯基甲烷—4,4’—二异氰酸酯。
首先将N-N二甲基甲酰胺分为A、B两份,其中A份为4000kg,B份为3000kg;将二苯基甲烷-4,4’-二异氰酸酯按照重量分为C、D两份,其中C份为600kg,D份为200kg;
线性羟基硅油具体选用道康宁公司的SF-8427和OFX-3667,两者无比例要求,下述实施例中总量控制在60-150kg
实施例1:
(1)将2kg抗氧剂和2100kg聚酯多元醇、60kg线性羟基硅油、70kg二醇小分子扩链剂A和A份4000kgDMF混合搅拌均匀,得到初步混合物料;
(2)在初步混合物料中投入C份600kgMDI升温至80℃保温90分钟后,再投入D份的200kgMDI补加增粘,分批加入B份3000kgDMF,加入2kg甲醇终止后,最后再加入100kg湿法绵感助剂,降温得到最终树脂产品,记为产品1。
实施例2:
(1)将2kg抗氧剂和2200kg聚酯多元醇、90kg线性羟基硅油、70kg二醇小分子扩链剂A和A份4000kgDMF混合搅拌均匀,得到初步混合物料;
(2)在初步混合物料中投入C份600kgMDI升温至80℃保温90分钟,再投入D份的200kgMDI,补加增粘,分批加入B份3000kgDMF,加入2kg甲醇终止后,加入100kg湿法绵感助剂,降温得到最终树脂产品,记为产品2。
实施例3:
(1)将2kg抗氧剂和2300kg聚酯多元醇、120kg线性羟基硅油、70kg二醇小分子扩链剂A和A份4000kgDMF混合搅拌均匀,得到初步混合物料;
(2)在初步混合物料中投入C份600kgMDI升温至80℃保温90分钟,再投入D份的200kgMDI补加增粘,分批加入B份3000kgDMF,加入2kg甲醇终止后,加入100kg湿法绵感助剂,降温得到最终树脂产品,记为产品3。
实施例4:
(1)将2kg抗氧剂和2400kg聚酯多元醇、150kg线性羟基硅油、70kg二醇小分子扩链剂A和A份4000kgDMF混合搅拌均匀,得到初步混合物料;
(2)在初步混合物料中投入C份600kgMDI升温至80℃保温90分钟,再投入D份的200kgMDI,补加增粘,分批加入B份3000kgDMF,加入2kg甲醇终止后,加入100kg湿法绵感助剂,降温得到最终树脂产品,记为产品4。
检测试验与结论
为验证本发明所述的超绵软细折痕特殊湿法革用树脂具有手感超绵软、折痕细等特点,将上述实施例1-4制备的树脂按合成革行业常规的制革配方(树脂:100份,DMF:110,木质粉:35,轻质碳酸钙:20)配置成涂刮液,以1.5mm的刀距涂覆在已处理好的仿棉绒布(0.65mm)上,经凝固、水洗、烘干,得到湿法贝斯。
每张湿法贝斯样品平行3张,分别进行手感感官判断、100倍显微镜观察检测。手感判断为专业合成革工程师用手触摸感官,泡孔结构采用MG10085-1A100X读数显微镜观察。
表1各实施例产品物性对比
产品 | 产品1 | 产品2 | 产品3 | 产品4 |
手感 | 超绵软 | 超绵软 | 绵软 | 僵硬 |
固含量% | 29.6 | 29.9 | 30.3 | 30.1 |
水洗情况 | 好 | 好 | 慢 | 慢 |
厚度(mm) | 1.24 | 1.23 | 1.2 | 1.19 |
泡孔结构 | 大而散 | 密而小 | 小而散 | 无泡孔 |
从表1数据中,实施例2中为最佳实施方案,其优点明显好于其他实施例产品。从技术角度也能很好说明情况,聚氨酯的湿法凝固速率跟发泡效率随着线性羟基硅油的用量增大而逐步变小。作为本发明的优化,线性羟基硅油的含量为0.5-1.0%;线性羟基硅油的含量至关重要,用量过少起不到作用,用量过多,反而会导致泡孔结构小而散或者无泡孔结构,同时造成产品手感和水洗情况较差。
本发明通过配方设计,兼顾综合性能,解决了工艺复杂问题的同时,制备综合性能优异的树脂;采用聚酯多元醇当主链,跟混合聚醚当主链相比,在具有泡孔结构细密化、凝固速度和渗透性适中、脱DMF速度快、剥离强度高的同时,兼具手感超绵软、细折痕的特点。
说明:以上实施例仅用以说明本发明而并非限制本发明所描述的技术方案;因此,尽管本说明书参照上述的各个实施例对本发明已进行了详细的说明,但是本领域的普通技术人员应当理解,仍然可以对本发明进行修改或等同替换;而一切不脱离本发明的精神和范围的技术方案及其改进,其均应涵盖在本发明的权利要求范围内。
Claims (10)
1.一种超绵软细折痕特殊湿法革用树脂,其特征在于,包括以下重量百分比的原料:聚酯多元醇20-40%,线性羟基硅油0.5-2%,二苯基甲烷4.4’二异氰酸酯3-5%,二醇小分子扩链剂0.5-0.8%,N-N二甲基甲酰胺68-72%,湿法绵感助剂0.5-1.5%。
2.根据权利要求1所述的一种超绵软细折痕特殊湿法革用树脂,其特征在于,所述聚酯多元醇为己二酸系聚酯多元醇;所述的己二酸系聚酯多元醇为聚己二酸二乙二醇二元醇、聚己二酸乙二醇二乙二醇二元醇、聚己二酸1,4-丁二醇二元醇、聚己二酸乙二醇1,4-丁二醇二元醇的一种或多种;
所述聚己二酸二乙二醇二元醇的羟值为37-112mgKOH/g、聚己二酸乙二醇二乙二醇二元醇的羟值为37-112mgKOH/g、聚己二酸1,4-丁二醇二元醇的羟值为37-112mgKOH/g、聚己二酸乙二醇1,4-丁二醇二元醇的羟值为24-112mgKOH/g。
3.根据权利要求1所述的一种超绵软细折痕特殊湿法革用树脂,其特征在于,所述二醇小分子扩链剂为乙二醇、1,4-丁二醇、二甘醇中的一种或多种。
4.根据权利要求1所述的一种超绵软细折痕特殊湿法革用树脂,其特征在于,所述线性羟基硅油的重量百分比为0.5-1%,具体选用道康宁公司的SF-8427和/或OFX-3667。
5.根据权利要求1所述的一种超绵软细折痕特殊湿法革用树脂,其特征在于,所述湿法绵感助剂为上海日多高分子材料有限公司的PR-69。
6.根据权利要求1~5任意一项所述的超绵软细折痕特殊湿法革用树脂的制备方法,其特征在于,具体步骤如下:
(1)将各原材料按上述重量百分比称重,各原材料的重量百分比之和为1;首先将N-N二甲基甲酰胺分为A、B两份,其中A份为总原材料重量的30-40%,余下记为B份;在混合聚醚多元醇中投入抗氧化剂、线性羟基硅油、二醇小分子扩链剂和A份的N-N二甲基甲酰胺混合均匀,得到初步混合物料;
(2)将二苯基甲烷-4,4’-二异氰酸酯按照重量分为C、D两份,其中C份为其重量的70-80%,余下记为D份;
在步骤(1)得到的初步混合物料中先加入C份的二苯基甲烷-4,4’-二异氰酸酯,在一定温度条件下反应后,再加入D份的二苯基甲烷-4,4’-二异氰酸酯进行补加增粘,然后加入B份的N-N二甲基甲酰胺,加入甲醇终止反应,终止反应后,最后再加入湿法绵感助剂,混合均匀,降温出料得到最终树脂产品。
7.根据权利要求6所述的超绵软细折痕特殊湿法革用树脂的制备方法,其特征在于,步骤(1)中所述抗氧化剂为2、6一二叔丁基对甲酚、亚磷酸三苯酯中的一种或多种混合;所述抗氧化剂用量为聚酯多元醇重量的0~0.1%。
8.根据权利要求6所述的超绵软细折痕特殊湿法革用树脂的制备方法,其特征在于,步骤(2)中所述一定温度条件为75-80℃,反应时间为80-90分钟;所述甲醇的加入量为总原材料重量的0.015%~0.02%;所述初步混合物料中还可以加入催化剂,所述催化剂选自二丁基二月桂酸锡、辛酸亚锡或者有机铋催化剂中的一种或多种,添加量为聚酯多元醇重量的0~0.1%。
9.根据权利要求6所述的超绵软细折痕特殊湿法革用树脂的制备方法,其特征在于,步骤(2)中所述最终树脂产品的粘度为160000CPS-260000CPS,固含量为28-32%。
10.根据权利要求1所述的超绵软细折痕特殊湿法革用树脂应用于鞋革、箱包或服装领域。
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