CN115232285A - 一种合成革用无溶剂聚氨酯树脂及其制备方法 - Google Patents
一种合成革用无溶剂聚氨酯树脂及其制备方法 Download PDFInfo
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- CN115232285A CN115232285A CN202210987237.8A CN202210987237A CN115232285A CN 115232285 A CN115232285 A CN 115232285A CN 202210987237 A CN202210987237 A CN 202210987237A CN 115232285 A CN115232285 A CN 115232285A
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- solvent
- polyurethane resin
- polyester polyol
- polyol
- free polyurethane
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
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- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
- C08G18/4241—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols from dicarboxylic acids and dialcohols in combination with polycarboxylic acids and/or polyhydroxy compounds which are at least trifunctional
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
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- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4825—Polyethers containing two hydroxy groups
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6603—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6607—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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Abstract
本发明涉及一种合成革用无溶剂聚氨酯树脂及其制备方法,由异氰酸酯基组分、羟基组分和催化剂组分构成,异氰酸酯基组分的原料包括聚酯多元醇A、聚醚多元醇、阻聚剂和异氰酸酯,羟基组分的原料包括聚酯多元醇B和助剂,聚酯多元醇A、聚酯多元醇B分别是采用小分子多元醇和小分子多元酸进行聚合制得羟值25‑140mgKOH/g的聚酯多元醇,聚酯多元醇B中的小分子多元醇为二官能度和三官能度以上的小分子多元醇的组合。本发明的树脂由异氰酸酯基组分、羟基组分和催化剂组分构成,配合羟基组分中的特定聚酯多元醇的使用,使得本发明能够达到聚碳酸酯体系的无溶剂聚氨酯树脂基本同等水平的剥离强度、耐水解性及低温性,而成本低于聚碳酸酯体系的无溶剂聚氨酯树脂。
Description
技术领域
本发明属于无溶剂合成革技术领域,具体涉及一种合成革用环保型无溶剂聚氨酯树脂及其制备方法。
背景技术
无溶剂合成革是近年发展的一种新型清洁化生产工艺,其是以液体为原料,将其输送、计量、冲击混合、快速反应和成型同时进行为特征的新型环保工艺。在原料使用和加工过程中都不会用到任何溶剂,不会出现易燃易爆情况,因此不会对生态环境造成污染、伤害工人的身体健康,大大降低了合成革企业生产的危险系数。无溶剂聚氨酯合成革具有溶剂型聚氨酯产品的力学强度高、耐磨、耐老化、弹性好、可再加工性强等优良性能。
无溶剂合成革的基本原理是物料混合涂布后的在线快速反应成型。通过两种或两种以上的物料,以设定比例分别加注到混合头,经混合均匀后注射、涂布到基布或离型纸上。进入干燥箱后,混合的物料开始反应,逐步形成高分子网络聚合物,并在后续过程中熟化成型。
无溶剂合成革成型过程是一个化学反应的过程,其中包括异氰酸酯基与羟基的链增长、交联反应,还包括异氰酸酯与水的反应过程。化学发泡是形成泡孔的主要原因,利用异氰酸酯与水反应生成的胺基化合物和CO2气体,在革层形成细小的发泡微孔,增加了合成革的透气性。过多的水会影响泡孔结构和分子空间网状交联结构的形成,一定要控制好工艺,控制好环境温度湿度,保证产品的质量稳定。良好的泡孔结构赋予合成革软弹的手感和细腻的仿真皮感。
目前,市场上的无溶剂合成革树脂主要是采用聚醚和聚碳酸酯体系,主要原因是耐水解较好,耐水解可以达到5年以上,甚至10年的测试要求,但聚醚体系存在剥离强度低和物理性能差,而聚碳酸酯价格高,使得聚碳酸酯体系的无溶剂聚氨酯树脂成本高。
已有专利中采用聚酯和聚醚联合使用制备的合成革用无溶剂聚氨酯树脂,如中国专利CN 110066373 A公开的一种合成革用无溶剂聚氨酯树脂,由组分A和组分B混合反应而成,其中A组分包括多元醇,B组分包括多元醇、异氰酸酯和二羟甲基丙酸,其中采用的多元醇包括聚醚多元醇和聚酯多元醇,并且通过采用二羟甲基丙酸的加入提高其剥离强度。该合成革用无溶剂聚氨酯树脂虽然具有较高的剥离强度,但其耐低温性仍然不好,并且没有涉及聚氨酯树脂的耐水解性。
发明内容
本发明的目的是为了解决现有技术的不足,提供一种低成本同时还具有优异的剥离强度、低温性和耐水解性的合成革用无溶剂聚氨酯树脂及其制备方法。
为达到上述目的,本发明采用如下技术方案:
一种合成革用无溶剂聚氨酯树脂,由异氰酸酯基组分、羟基组分和催化剂组分构成,所述异氰酸酯基组分的原料包括聚酯多元醇A、聚醚多元醇、阻聚剂和异氰酸酯,所述羟基组分的原料包括聚酯多元醇B和助剂,所述聚酯多元醇A、聚酯多元醇B分别是采用小分子多元醇和小分子多元酸进行聚合制备得到的羟值为25-140mgKOH/g的聚酯多元醇,其中,所述聚酯多元醇B中的小分子多元醇为二官能度的小分子多元醇和三官能度以上的小分子多元醇的组合,其中,所述三官能度以上的小分子多元醇的质量占所述聚酯多元醇B的总质量的0.5~1.0%。
根据本发明的一些实施方式,所述三官能度以上的小分子多元醇为三羟甲基丙烷、季戊四醇、丙三醇中的一种或多种的组合。
根据本发明的一些实施方式,所述小分子多元酸为间苯二甲酸、邻苯二甲酸、苯酐、对苯二甲酸、己二酸、丁二酸、癸二酸、月桂二酸、1,4环己烷二甲酸、偏苯三酸酐、壬二酸中的一种或多种的组合。
根据本发明的一些实施方式,所述二官能度的小分子多元醇为乙二醇、一缩二乙二醇、二缩三乙二醇、1,4-丁二醇、1,4-环己烷二甲醇、乙基丁基丙二醇,2,2,4-三甲基1,3-戊二醇,1,3-丁二醇、甲基丙二醇、1,6-己二醇、新戊二醇中的一种或多种的组合。
根据本发明的一些实施方式,所述聚酯多元醇A中的小分子多元醇为二官能度的小分子多元醇和三官能度以上的小分子多元醇的组合,其中,所述三官能度以上的小分子多元醇的质量占所述聚酯多元醇A的总质量的0.5~1.0%。
优选地,所述聚酯多元醇A与聚酯多元醇B相同。
根据本发明的一些实施方式,所述聚酯多元醇B通过包括以下步骤的方法制备得到:
在惰性气体气氛中,使所述小分子多元醇和小分子多元酸在反应釜内、在150~230℃下脱水2~7h,然后加入催化剂,升温至230~240℃,脱醇反应2~6h,制得羟值为25~140mgKOH/g、酸值小于等于1mgKOH/g的聚酯多元醇B。
所述聚酯多元醇B制备中使用的所述催化剂包括但不限于有机配体或络合配体的钛酸酯、钛酸盐、有机锡化合物、铋化合物、胺类物质、吗啉衍生物中的一种或多种的组合。
所述聚酯多元醇B的制备中,所述小分子多元醇与小分子多元酸的摩尔比为1.1~1.4:1。
在一些具体实施方式中,制备所述聚酯多元醇B的具体实施方式为:在氮气气氛中,将所述小分子多元醇、小分子多元酸加入带蒸馏塔的反应釜中,升温至150~220℃,有水生成,控制蒸馏塔塔顶温度在98~102℃,恒温0.5~1.5h,然后在150-230℃下,反应2-5h出水结束;加入催化剂,升温至230~240℃,抽真空脱醇2~6h,制得所述聚酯多元醇B。
根据本发明的一些实施方式,所述聚醚多元醇为聚环氧乙烷多元醇、聚环氧丙烷多元醇、聚四氢呋喃多元醇中的一种或多种的组合。
进一步地,所述聚醚多元醇的数均分子量为800~2500。
根据本发明的一些实施方式,所述异氰酸酯为甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、1,5-萘二异氰酸酯、六亚甲基二异氰酸酯、甲基环己基二异氰酸酯、4,4’-二环己基甲烷二异氰酸酯、异佛尔酮二异氰酸酯、对苯二异氰酸酯、对苯二亚甲基二异氰酸酯、四甲基二亚甲基二异氰酸酯,以及这类化合物的多聚体、改性产物中的一种或多种的组合。
进一步地,所述异氰酸酯为二苯基甲烷二异氰酸酯和/或异佛尔酮二异氰酸酯。优选地,所述异氰酸酯为二苯基甲烷二异氰酸酯。
根据本发明的一些实施方式,所述催化剂为有机金属催化剂和胺类催化剂按质量比为1:20~30的组合。
进一步地,所述有机金属催化剂为有机铋、二月桂酸二丁基锡中的一种或多种的组合。
进一步地,所述胺类催化剂为三乙烯二胺、四甲基二亚乙基三胺、1,8-二氮杂二环十一碳-7-烯、2,2-二吗啉基二乙基醚中的一种或多种的组合。
根据本发明的一些实施方式,所述助剂包括扩链剂、匀泡剂中的一种或多种的组合。
进一步地,所述扩链剂为乙二醇、丙二醇、1,4-丁二醇中的一种或多种的组合。
进一步地,所述匀泡剂为有机硅氧烷,具体如DC-3042、DC-3043。
进一步地,所述阻聚剂为能够提供活泼氢的酸性物质,其包括但不限于磷酸、次磷酸、对苯二酚、芥酸、苯甲酸、柠檬酸,上述阻聚剂可以单独或组合使用。
在一些优选且具体实施方式中,所述异氰酸酯基组分中,所述聚酯多元醇A与聚醚多元醇的质量比为1.5~2.5:1。
在一些优选且具体实施方式中,按重量份计,所述异氰酸酯基组分的原料包括300~400份聚酯多元醇A、150~200份聚醚多元醇、0.01~0.05份阻聚剂和300~500份异氰酸酯。
在一些优选且具体实施方式中,按重量份计,所述羟基组分的原料包括100份聚酯多元醇B、0.1~1份匀泡剂和1.5~10份扩链剂。
根据本发明的一些实施方式,所述羟基组分、异氰酸酯基组分、催化剂组分的质量比为100:40-120:0.3-1.0。
本发明采取的第二技术方案为:一种如上述所述的合成革用无溶剂聚氨酯树脂的制备方法,包括以下步骤:
(1)异氰酸酯基的制备
使异氰酸酯和阻聚剂在45~55℃下进行混合,然后加入聚酯多元醇A和聚醚多元醇在70~80℃下进行反应,得到所述异氰酸酯基组分;
(2)羟基组分的制备
使聚酯多元醇B进行脱水直至含水量低于0.05%,然后加入助剂进行混合,得到所述羟基组分。
进一步地,步骤(1)的具体实施方式为:将异氰酸酯和阻聚剂在反应釜内,在45~55℃下搅拌5~30min,然后加入聚酯多元醇A和聚醚多元醇,在70~75℃下反应2~4h,得到所述异氰酸酯基组分。
本发明采取的第三技术方案:上述所述合成革用无溶剂聚氨酯树脂在合成革的面层、中间层的用途。
当所述无溶剂聚氨酯树脂用于合成革的面层时,将所述羟基组分、异氰酸酯基组分和催化剂组分按质量比100:40-120:0.3-1.0进行混合,在然后按涂布量18丝~22丝涂布在离型纸上,然后在100-130℃烘箱进行烘干熟化,将半干的树脂贴合基布,熟化后再将离型纸剥离即得到无溶剂聚氨酯合成革。
当所述无溶剂聚氨酯树脂用于合成革的中间层时,可以不发泡,也可以发泡后使用。
由于上述技术方案运用,本发明与现有技术相比具有下列优点:
本发明的合成革用无溶剂聚氨酯树脂由异氰酸酯基组分、羟基组分和催化剂组分构成,配合羟基组分中的特定聚酯多元醇的使用,使得本发明的无溶剂聚氨酯树脂能够达到聚碳酸酯体系的无溶剂聚氨酯树脂基本同等水平的剥离强度、耐水解性及低温性,而成本确低于聚碳酸酯体系的无溶剂聚氨酯树脂。
具体实施方式
下面结合具体实施例对本发明的具体实施作进一步详细说明,但本发明的实施和保护范围不限于此。
实施例1
本实施例的合成革用无溶剂聚氨酯树脂,其由以下方法制备得到:
(1)聚酯多元醇B1的制备
在氮气气氛中,将乙二醇152.2kg、丁二醇220.9kg、三羟甲基丙烷8.5kg和己二酸618.4kg,加入到反应釜中,升温至150℃-190℃,开始有水生成,要控制出水速度,保证塔顶温度在98-102℃,恒温1h后继续升温;在150-220℃下继续反应,反应4h出水结束,加入30g催化剂继续升温反应,温度升至230℃反应1h,采用真空状态下,逐步降低真空度的方法,脱醇反应在3.5h,得到羟值为55.8mgKOH/g,酸值为0.4mgKOH/g的聚酯多元醇B1,其数均分子量为2000。
(2)异氰酸酯基组分的制备
将400kg的MDI-100加入到反应釜中,开启搅拌,控制反应釜温度为52℃,将磷酸0.04Kg加入反应釜中,搅拌15min;将180kg聚醚多元醇PPG-2000和340kg的聚酯多元醇B1,分批依次加入反应釜,最后加入8kg液化MDI,控制反应釜温度为72℃,反应3h后,测试NCO=13.6%,降温至45℃出料,即得异氰酸酯基组分;
(3)羟基组分的制备
将100kg聚酯多元醇B1以及2.0kg扩链剂乙二醇、0.4kg DC-3042和0.2Kg DC-3043,在105℃下真空干燥2h,使其含水量低于0.05%,搅拌均匀并降温至40~50℃,即得羟基组分;
(4)催化剂组分的制备
将1kg的有机铋和25kg的胺类催化剂DABCO EG在小反应釜中搅拌混合均匀即可,包装而成催化剂组分。
用于合成革时,将羟基组分、异氰酸酯基组分、催化剂组分按质量比100:60:0.5混合。
实施例2
本实施例的合成革用无溶剂聚氨酯树脂,其由以下方法制备得到:
(1)聚酯多元醇B2的制备
在氮气气氛中,将乙二醇125.1kg、丁二醇145.3kg、二甘醇128.4kg、丙三醇7.4kg、己二酸560.3kg和对苯二甲酸33.5kg加入到反应釜中,升温至155-190℃,开始有水生成,要控制出水速度,保证塔顶温度在98-102℃,出水稳定后继续升温;在155-210℃下继续反应,反应3h出水结束,加入催化剂0.04kg继续升温反应,温度升至240℃反应1h,采用真空状态下,逐步降低真空度的方法,脱醇反应在3h,得到羟值为76.1mgKOH/g,酸值为0.3mgKOH/g的聚酯多元醇B2,其数均分子量为1500。
(2)异氰酸酯基组分的制备
将370kg的MDI-100加入到反应釜中,开启搅拌,控制反应釜温度为55℃,将磷酸0.04kg加入反应釜中,搅拌15min;将170kg PTMEG-2000和390kg聚酯多元醇B2,分批依次加入反应釜,最后加入70kg液化MDI,控制反应釜温度为75℃,反应3h后,测试NCO=11.6%,降温至43℃出料,即得异氰酸酯基组分。
(3)羟基组分的制备
将100kg聚酯多元醇B2以及5.0kg扩链剂丁二醇、0.4kg DC3042和0.2kg DC3043,在110℃下真空干燥2h,使其含水量低于0.05%,搅拌均匀并降温至42℃,即得羟基组分;
(4)催化剂组分的制备
将1kg的有机铋和22kg的胺类催化剂DABCO EG在小反应釜中搅拌混合均匀即可,包装而成催化剂组分。
用于合成革时,将羟基组分、异氰酸酯基组分、催化剂组分按100:100:0.4进行混合。
实施例3
本实施例的合成革用无溶剂聚氨酯树脂,其由以下方法制备得到:
(1)聚酯多元醇B3的制备
在氮气气氛中,将乙二醇97.7kg、新戊二醇205.1kg、己二醇116.2kg、季戊四醇5.4kg和己二酸575.6kg,加入到反应釜中,升温至150-190℃,开始有水生成,要控制出水速度,保证塔顶温度在98-102℃,恒温1h后继续升温;在150-210℃下继续反应,反应5h出水结束,加入催化剂0.03kg继续升温反应,温度升至240℃反应2.5h,采用真空状态下,逐步降低真空度的方法,脱醇反应在4h,得到羟值为44.5mgKOH/g,酸值为0.5mgKOH/g的聚酯多元醇B3,其数均分子量为2500。
(2)异氰酸酯基组分的制备
将330kg的IPDI加入到反应釜中,开启搅拌,控制反应釜温度为56℃,将磷酸0.04g加入反应釜中,搅拌15min;将190kg聚醚多元醇PPG-1000和330kg的聚酯多元醇B3,分批依次加入反应釜,控制反应釜温度为74℃,反应3h后,测试NCO=14.8%,降温至41℃出料,即得异氰酸酯基组分B3。
(3)羟基组分的制备
将100kg聚酯多元醇B3以及9kg丙二醇、0.4kg DC3042和0.2kg DC3043,在112℃下真空干燥2h,使其含水量低于0.05%,搅拌均匀并降温至45℃出料,即得羟基组分。
(4)催化剂组分的制备
将1kg的有机铋和28kg的胺类催化剂DABCO EG在小反应釜中搅拌混合均匀即可,包装而成催化剂组分。
用于合成革时,将羟基组分、异氰酸酯基组分、催化剂组分按100:100:0.7进行混合。
实施例4
本实施例的合成革用无溶剂聚氨酯树脂,与实施例1的不同之处在于:采用CMA-244代替步骤(2)中的聚酯多元醇B1。其他同实施例1。
对比例1
本对比例的合成革用无溶剂聚氨酯树脂,与实施例1的不同之处在于:采用华大化学集团的CMA-244代替步骤(2)和步骤(3)中的聚酯多元醇B1。其他同实施例1。
对比例2
本对比例的合成革用无溶剂聚氨酯树脂,与实施例2的不同之处在于:使用华大化学集团的MX-706代替步骤(2)和步骤(3)中的聚酯多元醇B2。其他同实施例2。
对比例3
本对比例的合成革用无溶剂聚氨酯树脂,与实施例1的不同之处在于:采用聚碳酸酯多元醇PCDL-2000代替步骤(2)和步骤(3)中的聚酯多元醇B1。其他同实施例1。
对比例4
本对比例的合成革用无溶剂聚氨酯树脂,与实施例1的不同之处在于:步骤(1)中,三羟甲基丙烷的用量为15kg。
其他同实施例1。
对比例5
本对比例的合成革用无溶剂聚氨酯树脂,与实施例1的不同之处在于:步骤(2)中,采“260kg PTMEG-2000和300kg聚酯多元醇B2”代替“170kg PTMEG-2000和390kg聚酯多元醇B2”。其他同实施例1。
将实施例1-4和对比例1-5按照配比进行混合后,在离型纸上进行涂布(涂布量为20丝),然后在100-130℃烘箱进行烘干熟化5-10min,将半干的树脂贴合基布(Tc布,材质为涤纶和棉混纺,厚度为0.65mm),熟化后再将离型纸剥离即得到无溶剂聚氨酯合成革。将上述制备好的合成革测试其剥离强度,耐水解性能,在低温箱进行低温耐折测试,在高温烘箱进行耐温性测试,测试结果如下表1。
表1为采用实施例1~4和对比例1~5的树脂制备的合成革的测试结果
注:剥离强度按照GB/T 8949-2008标准进行测试;
耐温性测试为120℃*500h,将合成革置于120℃环境下500h,观察合成革表面,若表面无异常,则通过测试(即Pass),否则不通过(即No);
低温耐折测试为-25℃*10万次曲挠不开裂;
耐水解测试标准为QB/T 4671-2014。
虽然实施例1和对比例3,在性能测试结果上不相上下,但是实施例1的无溶剂聚氨酯树脂的成本比对比例3的无溶剂聚氨酯树脂低约10元/kg。
上述实施例制备的合成革用无溶剂聚氨酯树脂环境保护适应性好,生产过程中没有溶剂排放,不会影响生产工人的身体健康,不会对周边环境产生污染,有利于清洁化生产。
上述实施例采用特定的聚酯多元醇搭配聚醚多元醇制备的合成革用无溶剂聚氨酯树脂,产品熟化速度快,生产工艺容易控制,物理机械性能优异,耐水解也可以达到10年以上测试技术标准(70℃*95%湿度条件),耐折测试可以达到-25℃*10万次无异常,耐温性符合120℃*500h收缩率小于3%的技术要求。
上述实施例的无溶剂聚氨酯树脂用于合成革的面层,在其他实施例中,也可以用于合成革的中间层,作为中间层时也可以对其进行发泡。
上述实施例只为说明本发明的技术构思及特点,其目的在于让熟悉此项技术的人士能够了解本发明的内容并据以实施,并不能以此限制本发明的保护范围。凡根据本发明精神实质所作的等效变化或修饰,都应涵盖在本发明的保护范围之内。
在本文中所披露的范围的端点和任何值都不限于该精确的范围或值,这些范围或值应当理解为包含接近这些范围或值的值。对于数值范围来说,各个范围的端点值之间、各个范围的端点值和单独的点值之间,以及单独的点值之间可以彼此组合而得到一个或多个新的数值范围,这些数值范围应被视为在本文中具体公开。
Claims (10)
1.一种合成革用无溶剂聚氨酯树脂,由异氰酸酯基组分、羟基组分和催化剂组分构成,所述异氰酸酯基组分的原料包括聚酯多元醇A、聚醚多元醇、阻聚剂和异氰酸酯,其特征在于:所述羟基组分的原料包括聚酯多元醇B和助剂,所述聚酯多元醇A、聚酯多元醇B分别是采用小分子多元醇和小分子多元酸进行聚合制备得到的羟值为25-140mgKOH/g的聚酯多元醇,其中,所述聚酯多元醇B中的小分子多元醇为二官能度的小分子多元醇和三官能度以上的小分子多元醇的组合,其中,所述三官能度以上的小分子多元醇的质量占所述聚酯多元醇B的总质量的0.5~1.0%。
2.根据权利要求1所述的合成革用无溶剂聚氨酯树脂,其特征在于:所述三官能度以上的小分子多元醇为三羟甲基丙烷、季戊四醇、丙三醇中的一种或多种的组合。
3.根据权利要求1所述的合成革用无溶剂聚氨酯树脂,其特征在于:所述小分子多元酸为间苯二甲酸、邻苯二甲酸、苯酐、对苯二甲酸、己二酸、丁二酸、癸二酸、月桂二酸、1,4环己烷二甲酸、偏苯三酸酐、壬二酸中的一种或多种的组合;和/或,所述二官能度的小分子多元醇为乙二醇、一缩二乙二醇、二缩三乙二醇、1,4-丁二醇、1,4-环己烷二甲醇、乙基丁基丙二醇,2,2,4-三甲基1,3-戊二醇,1,3-丁二醇、甲基丙二醇、1,6-己二醇、新戊二醇中的一种或多种的组合。
4.根据权利要求1或2或3所述的合成革用无溶剂聚氨酯树脂,其特征在于:所述聚酯多元醇A中的小分子多元醇为二官能度的小分子多元醇和三官能度以上的小分子多元醇的组合,其中,所述三官能度以上的小分子多元醇的质量占所述聚酯多元醇A的总质量的0.5~1.0%。
5.根据权利要求1~3中任一项所述的合成革用无溶剂聚氨酯树脂,其特征在于:所述聚醚多元醇为聚环氧乙烷多元醇、聚环氧丙烷多元醇、聚四氢呋喃多元醇中的一种或多种的组合;和/或,所述异氰酸酯为甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、1,5-萘二异氰酸酯、六亚甲基二异氰酸酯、甲基环己基二异氰酸酯、4,4’-二环己基甲烷二异氰酸酯、异佛尔酮二异氰酸酯、对苯二异氰酸酯、对苯二亚甲基二异氰酸酯、四甲基二亚甲基二异氰酸酯中的一种或多种的组合;和/或,所述催化剂为有机金属催化剂和胺类催化剂按质量比为1:20~30的组合;和/或,所述助剂包括扩链剂、匀泡剂、偶联剂中的一种或多种的组合。
6.根据权利要求5所述的合成革用无溶剂聚氨酯树脂,其特征在于:所述聚醚多元醇的数均分子量为800~2500;和/或,所述异氰酸酯为二苯基甲烷二异氰酸酯和/或异佛尔酮二异氰酸酯;和/或,所述有机金属催化剂为有机铋、二月桂酸二丁基锡中的一种或多种的组合;和/或,所述胺类催化剂为三乙烯二胺、四甲基二亚乙基三胺、1,8-二氮杂二环十一碳-7-烯、2,2-二吗啉基二乙基醚中的一种或多种的组合。
7.根据权利要求1所述的合成革用无溶剂聚氨酯树脂,其特征在于:所述异氰酸酯基组分中,所述聚酯多元醇A与聚醚多元醇的质量比为1.5~2.5:1。
8.根据权利要求1所述的合成革用无溶剂聚氨酯树脂,其特征在于:按重量份计,所述异氰酸酯基组分的原料包括300~400份聚酯多元醇A、150~200份聚醚多元醇、0.01~0.05份阻聚剂和300~500份异氰酸酯;和/或,
按重量份计,所述羟基组分的原料包括100份聚酯多元醇B、0.1~1份匀泡剂和1.5~10份扩链剂。
9.根据权利要求1~4、8中任一项所述的合成革用无溶剂聚氨酯树脂,其特征在于:所述羟基组分、异氰酸酯基组分、催化剂组分的质量比为100:40-120:0.3-1.0。
10.一种如权利要求1~9中任一项所述的合成革用无溶剂聚氨酯树脂的制备方法,其特征在于,所述制备方法包括以下步骤:
(1)异氰酸酯基的制备
使异氰酸酯和阻聚剂在45~55℃下进行混合,然后加入聚酯多元醇A和聚醚多元醇在70~80℃下进行反应,得到所述异氰酸酯基组分;
(2)羟基组分的制备
使聚酯多元醇B进行脱水直至含水量低于0.05%,然后加入助剂进行混合,得到所述羟基组分。
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