CN109337035B - 高耐甲苯性超细纤维合成革用聚氨酯树脂及其制备方法 - Google Patents

高耐甲苯性超细纤维合成革用聚氨酯树脂及其制备方法 Download PDF

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CN109337035B
CN109337035B CN201811179849.4A CN201811179849A CN109337035B CN 109337035 B CN109337035 B CN 109337035B CN 201811179849 A CN201811179849 A CN 201811179849A CN 109337035 B CN109337035 B CN 109337035B
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杨银龙
张其斌
孙向浩
杜明兵
张�浩
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Abstract

本发明公开了一种高耐甲苯性超细纤维合成革用聚氨酯树脂及其制备方法，所述聚氨酯树脂，由包含以下组分的原料制成：多元醇、扩链剂、三官能度化合物、二异氰酸酯、封端剂和溶剂。本发明采用芳香族二胺获得刚性更强的聚氨酯硬段，以及加入适量的可控的三官能度化合物，从而使得聚氨酯树脂有更低的甲苯溶胀率和甲苯抽出率。同时，本发明在制备聚氨酯树脂时引入热处理方法，可降低聚氨酯树脂的分子量分布，提高聚氨酯树脂的规整性，从而降低了聚氨酯树脂中小分子量的比例，进一步降低了聚氨酯树脂的甲苯溶胀率和甲苯抽出率。

Description

高耐甲苯性超细纤维合成革用聚氨酯树脂及其制备方法
技术领域
本发明涉及一种聚氨酯树脂及其制备方法，特别涉及一种超细纤维合成革用聚氨酯树脂及其制备方法。
背景技术
众所周知，超细纤维合成革常分为碱减量工艺和甲苯减量工艺。甲苯减量工艺是由海岛纤维无纺布经浸渍聚氨酯树脂后形成初级基布，然后将初级基布经85℃的热甲苯抽出纤维中的海组分而形成超细纤维合成革的一种工艺。常规的海组分为低密度聚乙烯或聚苯乙烯。由于整个抽出过程持续约4小时，故对聚氨酯的耐甲苯性提出了高要求。
超细纤维合成革用聚氨酯树脂的耐甲苯性包含两个指标，即甲苯溶胀率和甲苯抽出率。行业内人士常规地认为超细纤维合成革的手感是由聚氨酯树脂的100％定伸强度(即100％模量)决定，其忽略了聚氨酯树脂的甲苯溶胀率的影响。实际上，甲苯溶胀率越高，纤维离型效果越差，产品的手感就比较僵硬；反之，产品手感丰满有弹性。同时，甲苯溶胀率和甲苯抽出率也会对产品的折痕产生较大影响，而折痕是产品仿真性的关键指标之一。
研究聚氨酯树脂耐甲苯性的文献较少。中国专利申请CN106519159A公开了一种高耐水性、高耐甲苯性的柠檬烯基聚氨酯及其制备方法，其通过向聚氨酯主链中引入柠檬烯结构中的脂环族六元环，使得制备的聚氨酯具有优良的机械性能及耐溶剂性，其推荐用于涂料行业。该发明测试甲苯溶胀率为常温，且其甲苯溶胀率指标比较高。中国专利申请CN104710930A公开了一种浸涂用水性聚氨酯面漆，其首先通过制备含有双键的聚氨酯大单体，然后将其制备成PUA，实现同时达到漆膜硬度、耐水性、耐甲苯性等目的。文献《聚氨酯工业》，2017，32(2)，32-35公开了影响超细纤维合成革用聚氨酯树脂耐甲苯性的规律，阐述了扩链剂、多元醇、硬段含量等对聚氨酯树脂耐甲苯性的影响，但其制备的聚氨酯树脂结构简单，只有PU13同时满足甲苯溶胀率≤100％和甲苯抽出率≤1.0％，然而其测试方法是在25℃条件下测试，其在85℃仍然没有达到高耐甲苯性的要求。高耐甲苯性的要求是在85℃条件下测试，并能同时满足甲苯溶胀率≤100％和甲苯抽出率≤1.0％。
发明内容
本发明的目的在于提供一种高耐甲苯性超细纤维合成革用聚氨酯树脂及其制备方法，以解决现有的超细纤维合成革用聚氨酯树脂存在的技术不足。
本发明所述的高耐甲苯性超细纤维合成革用聚氨酯树脂，由包含以下组分的原料制成：多元醇、扩链剂、三官能度化合物、二异氰酸酯、封端剂、溶剂，其中：
(1)所述多元醇包含多元醇A和多元醇B，且多元醇A和多元醇B的摩尔数之比为1:2～2:1。
所述多元醇A选自聚四氢呋喃二醇，数均分子量1000～3000；
所述多元醇B选自聚碳酸酯二醇、聚己二酸己二醇酯二醇、聚己二酸丁二醇酯二醇、聚己二酸乙二醇酯二醇、聚己二酸丁二醇乙二醇共聚酯二醇、聚己二酸丁二醇新戊二醇共聚酯二醇、聚己二醇-3-甲基戊二醇酯二醇、聚己内酯二醇的至少一种，所述多元醇B的数均分子量为1000～3000；
(2)所述扩链剂包含双羟基扩链剂和双胺基扩链剂，且双胺基扩链剂的摩尔数与扩链剂总摩尔数的比值为0.3～0.5。
所述扩链剂总摩尔数与多元醇总摩尔数的比值为5～10。
所述双羟基扩链剂为乙二醇、丁二醇中的一种。
所述双胺基扩链剂为4,4’-二苯基甲烷二胺。
(3)所述三官能度化合物的摩尔数为扩链剂总摩尔数的0.1％～0.2％。
所述三官能度化合物为三羟基化合物，选自三羟基丙烷、三羟甲基乙烷、1,2,6-己三醇、甘油或三羟基聚醚中的一种或以上。
(4)所述二异氰酸酯的摩尔数为多元醇、扩链剂总摩尔数与1.5倍的三官能度化合物摩尔数之和，即
n(二异氰酸酯)＝n(多元醇)+n(扩链剂)+1.5n(三官能度化合物)。
所述二异氰酸酯为二苯基甲烷二异氰酸酯。
(5)所述封端剂的摩尔数为多元醇、扩链剂、三官能度化合物和二异氰酸酯总重量除以50000，即
Figure BDA0001824733100000031
所述封端剂选自单羟基化合物，如甲醇、乙醇等。
(6)所述溶剂的用量，为多元醇、扩链剂、三官能度化合物、二异氰酸酯封端剂和溶剂总重量的70％～80％。
所述溶剂选自二甲基甲酰胺、二甲基乙酰胺的至少一种。
所述的高耐甲苯性超细纤维合成革用聚氨酯树脂的制备方法，包括如下步骤：
(1)、将多元醇A、多元醇B、三官能度化合物、双羟基扩链剂、部分溶剂投入到反应釜，50～60℃搅拌均匀；
所述的部分溶剂指溶剂总重量的50％。
(2)、将二异氰酸酯一次性投入到反应釜，控制反应温度在70～85℃之间，常压反应，用二正丁胺滴定法跟踪检测异氰酸酯基团含量，保温至异氰酸酯基团含量恒定时，加入剩余溶剂并降温至60～65℃；
(3)、将双胺基扩链剂分批次投入到反应釜，60～65℃反应至粘度大于15万mPa·S(取样并在25℃条件下测试)后，开始升温至95～105℃。
(4)在95～105℃条件下热处理8小时以上。热处理后粘度会下降，跟踪粘度达到3～5万mPa·S(取样并在25℃条件下测试)后，降温至65～70℃。
(5)在65～70℃条件下加入封端剂，搅拌1～3小时，即可获得所述的高耐甲苯性超细纤维合成革用聚氨酯树脂。
与现有技术相比，本发明有以下有益效果：
本发明采用芳香族二胺获得刚性更强的聚氨酯硬段，以及加入适量的可控的三官能度化合物，从而使得聚氨酯树脂有更低的甲苯溶胀率和甲苯抽出率。同时，本发明在制备聚氨酯树脂时引入热处理方法，可降低聚氨酯树脂的分子量分布，提高聚氨酯树脂的规整性，从而降低了聚氨酯树脂中小分子量的比例，进一步降低了聚氨酯树脂的甲苯溶胀率和甲苯抽出率。
具体实施方式
下面结合具体实施例，进一步阐述本发明。应该理解，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。在实际应用中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。以下实施例所用原料均为市售。
实施例1
本实施例所用原料及重量表如表1
表1
重量(g) 摩尔数
聚四氢呋喃醚二醇(数分子量1000) 100 0.1
聚己二酸丁二醇酯二醇(数均分子量1000) 200 0.2
乙二醇 65.1 1.05
4,4’-二苯基甲烷二胺 89.1 0.45
三羟甲基丙烷 0.402 0.003
二苯基甲烷二异氰酸酯 451.13 1.8045
甲醇 0.58 0.0181
二甲基甲酰胺 2114.73
总量 3021.04
本实施例的高耐甲苯性超细纤维合成革用聚氨酯树脂的制备方法如下：
(1)、将100g聚四氢呋喃醚二醇、200g聚己二酸丁二醇酯二醇、65.1g乙二醇、0.402三羟甲基丙烷、1057.37g二甲基甲酰胺投入到反应釜，60℃搅拌均匀；
(2)、将451.13g二苯基甲烷二异氰酸酯一次性投入到反应釜，控制反应温度在85℃，常压反应，用二正丁胺滴定法跟踪检测异氰酸酯基团含量，保温至异氰酸酯基团含量恒定时，加入剩余1057.36g二甲基甲酰胺并降温至65℃；
(3)、将89.1g4,4’-二苯基甲烷二胺分批次投入到反应釜，65℃反应至粘度大于15万mPa·S(取样并在25℃条件下测试)后，升温至95℃；
(4)在95℃条件下热处理8小时以上。热处理后粘度会下降，跟踪粘度达到3万mPa·S(取样并在25℃条件下测试)后，降温至65℃。
(5)在65℃条件下加入0.58g甲醇，搅拌2小时，即可获得所述的高耐甲苯性超细纤维合成革用聚氨酯树脂。
实施例2
本实施例所用原料及重量表如表2
表2
重量(g) 摩尔数
聚四氢呋喃醚二醇(数分子量3000) 600 0.2
聚己二酸乙二醇酯二醇(数均分子量3000) 300 0.1
丁二醇 135 1.5
4,4’-二苯基甲烷二胺 297 1.5
三羟基聚醚(数均分子量480) 1.44 0.003
二苯基甲烷二异氰酸酯 826.13 3.3045
乙醇 1.99 0.0432
二甲基甲酰胺 8646.24
总量 10807.8
本实施例的高耐甲苯性超细纤维合成革用聚氨酯树脂的制备方法如下：
(1)、将600g聚四氢呋喃醚二醇、300g聚己二酸乙二醇酯二醇、135g丁二醇、1.44g三羟基聚醚、4323.12g二甲基甲酰胺投入到反应釜，50℃搅拌均匀；
(2)、将826.13g二苯基甲烷二异氰酸酯一次性投入到反应釜，控制反应温度在70℃，常压反应，用二正丁胺滴定法跟踪检测异氰酸酯基团含量，保温至异氰酸酯基团含量恒定时，加入剩余4323.12g二甲基甲酰胺并降温至60℃；
(3)、将297g4,4’-二苯基甲烷二胺分批次投入到反应釜，60℃反应至粘度大于15万mPa·S(取样并在25℃条件下测试)后，开始升温至105℃。
(4)在105℃条件下热处理8小时以上。热处理后粘度会下降，跟踪粘度达到5万mPa·S(取样并在25℃条件下测试)后，降温至70℃。
(5)在70℃条件下加入1.99g乙醇，搅拌2小时，即可获得所述的高耐甲苯性超细纤维合成革用聚氨酯树脂。
实施例3
本实施例所用原料及重量表如表3
表3
Figure BDA0001824733100000071
Figure BDA0001824733100000081
本实施例的高耐甲苯性超细纤维合成革用聚氨酯树脂的制备方法如下：
(1)、将200g聚四氢呋喃醚二醇、100g聚己二醇-3-甲基戊二醇酯二醇、100g聚己内酯二醇、86.4g丁二醇、0.22g甘油、1597.38g二甲基乙酰胺投入到反应釜，55℃搅拌均匀；
(2)、将450.9g二苯基甲烷二异氰酸酯一次性投入到反应釜，控制反应温度在75℃，常压反应，用二正丁胺滴定法跟踪检测异氰酸酯基团含量，保温至异氰酸酯基团含量恒定时，加入剩余1597.38g二甲基乙酰胺并降温至62℃；
(3)、将126.72g4,4’-二苯基甲烷二胺分批次投入到反应釜，62℃反应至粘度大于15万mPa·S(取样并在25℃条件下测试)后，开始升温至100℃。
(4)在100℃条件下热处理8小时以上。热处理后粘度会下降，跟踪粘度达到4万mPa·S(取样并在25℃条件下测试)后，降温至68℃。
(5)在68℃条件下加入0.68g甲醇，搅拌2小时，即可获得所述的高耐甲苯性超细纤维合成革用聚氨酯树脂。
为进一步说明本发明的技术创新，选取实施例一至三所得树脂、市售超细纤维合成革用聚氨酯树脂样本分别按0.15mm的厚度涂敷于镜面离型纸上，并于120℃条件下烘干，从离型纸上剥离得树脂膜。将树脂膜放置于25℃保干器中放置72小时，做耐甲苯性测试。耐甲苯性测试方法如下：将重量为m0的树脂膜放在85℃甲苯中浸泡4小时，拿出后放在自封袋中冷却至常温，然后取出将表面擦干，称重为m1，在120℃烘箱中烘至恒重m2。甲苯溶胀率计算式为[(m1－m0)/m0]×100％；甲苯抽出率计算式为[(m0－m2)/m0]×100％。分子量分布指数(d＝Mw/Mn)通过GPC方法测试。测试结果见表四。
其中所述的市售样本为浙江华峰合成树脂有限公司的牌号为TL4100和TL4210的产品。
表4
Figure BDA0001824733100000091
从表四可知，本发明制备的高耐甲苯性超细纤维合成革用聚氨酯树脂具有较低的甲苯溶胀率和甲苯抽出率，符合高耐甲苯性的要求。

Claims (6)

1.高耐甲苯性超细纤维合成革用聚氨酯树脂，其特征在于，由包含以下组分的原料制成：多元醇、扩链剂、三官能度化合物、二异氰酸酯、封端剂、溶剂，其中：
所述多元醇包含多元醇A和多元醇B；
所述多元醇A选自聚四氢呋喃二醇；
所述多元醇B选自聚碳酸酯二醇、聚己二酸己二醇酯二醇、聚己二酸丁二醇酯二醇、聚己二酸乙二醇酯二醇、聚己二酸丁二醇乙二醇共聚酯二醇、聚己二酸丁二醇新戊二醇共聚酯二醇、聚己二醇-3-甲基戊二醇酯二醇、聚己内酯二醇的至少一种；
所述的多元醇A和多元醇B的摩尔数之比为1:2～2:1；
所述扩链剂包含双羟基扩链剂和双胺基扩链剂，且双胺基扩链剂的摩尔数与扩链剂总摩尔数的比值为0.3～0.5，所述扩链剂总摩尔数与多元醇总摩尔数的比值为5～10，所述双羟基扩链剂为乙二醇，所述双胺基扩链剂为4,4’-二苯基甲烷二胺；
所述三官能度化合物的摩尔数为扩链剂总摩尔数的0.1％～0.2％，所述三官能度化合物为三羟基化合物，选自三羟基丙烷、三羟甲基乙烷、1,2,6-己三醇、甘油或三羟基聚醚中的一种或以上。
2.根据权利要求1所述的高耐甲苯性超细纤维合成革用聚氨酯树脂，其特征在于，所述多元醇A数均分子量为1000～3000，所述多元醇B的数均分子量为1000～3000。
3.根据权利要求1所述的高耐甲苯性超细纤维合成革用聚氨酯树脂，其特征在于，所述二异氰酸酯的摩尔数为多元醇、扩链剂总摩尔数与1.5倍的三官能度化合物摩尔数之和，所述二异氰酸酯为二苯基甲烷二异氰酸酯。
4.根据权利要求3所述的高耐甲苯性超细纤维合成革用聚氨酯树脂，其特征在于，所述封端剂的摩尔数为多元醇、扩链剂、三官能度化合物和二异氰酸酯总重量除以50000，所述封端剂选自单羟基化合物。
5.根据权利要求4所述的高耐甲苯性超细纤维合成革用聚氨酯树脂，其特征在于，所述溶剂的用量为多元醇、扩链剂、三官能度化合物、二异氰酸酯封端剂和溶剂总重量的70％～80％，所述溶剂选自二甲基甲酰胺、二甲基乙酰胺的至少一种。
6.根据权利要求1-5任一项所述的高耐甲苯性超细纤维合成革用聚氨酯树脂的制备方法，其特征在于，包括如下步骤：
(1)、将多元醇A、多元醇B、三官能度化合物、双羟基扩链剂、部分溶剂投入到反应釜，50～60℃搅拌均匀；
所述的部分溶剂指溶剂总重量的50％；
(2)、将二异氰酸酯一次性投入到反应釜，控制反应温度在70～85℃之间，常压反应，用二正丁胺滴定法跟踪检测异氰酸酯基团含量，保温至异氰酸酯基团含量恒定时，加入剩余溶剂并降温至60～65℃；
(3)、将双胺基扩链剂分批次投入到反应釜，60～65℃反应，取样并在25℃条件下测试，至粘度大于15万mPa·S后，开始升温至95～105℃；
(4)在95～105℃条件下热处理8小时以上；热处理后粘度会下降，跟踪粘度达到3～5万mPa·S后，降温至65～70℃；
(5)在65～70℃条件下加入封端剂，即可获得所述的高耐甲苯性超细纤维合成革用聚氨酯树脂。
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