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CN106220817B - 一种无溶剂型汽车内饰革用中间层聚氨酯树脂及其制备方法 - Google Patents

一种无溶剂型汽车内饰革用中间层聚氨酯树脂及其制备方法 Download PDF

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CN106220817B
CN106220817B CN201610649714.4A CN201610649714A CN106220817B CN 106220817 B CN106220817 B CN 106220817B CN 201610649714 A CN201610649714 A CN 201610649714A CN 106220817 B CN106220817 B CN 106220817B
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dihydric alcohol
polyurethane resin
automobiles
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李晓飞
武春余
王海峰
孔为青
笪丽红
范培宏
吴文
胡俊
姚克俭
黄万里
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HEFEI ANLI POLYURETHANE NEW MATERIAL CO Ltd
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Abstract

本发明提供了一种无溶剂型汽车内饰革用中间层聚氨酯树脂及其制备方法，其由A组分和B组分按质量比2.5:1‑1:2.5进行混合而成；A组分由二异氰酸酯、低聚物二元醇、小分子二元醇、小分子三元醇、催化剂、光/热稳定剂、流平剂和无溶剂色浆组成；B组分由二异氰酸酯、三异氰酸酯、低聚物二元醇、小分子二元醇、小分子三元醇和抗氧剂组成。本发明制备的聚氨酯树脂可做为汽车内饰革的中间层使用，其满足汽车革产品耐水解性能的同时，可以有效保证汽车革的高温耐用性能及各项力学性能；制得的汽车革产品剥离强度高达145N/3cm，耐水解性能可达10周后剥离强度仍高达135N/3cm。

Description

一种无溶剂型汽车内饰革用中间层聚氨酯树脂及其制备方法
技术领域
本技术属于合成革领域，涉及一种无溶剂型汽车内饰革用中间层聚氨酯树脂，还涉及该树脂的制备方法。
背景技术
随着生活水平的不断提高，人们对乘用车的内部条件，尤其是对汽车内饰的功能性、美观性、舒适性及绿色环保性能等提出了越来越高的要求。目前市场上汽车内饰革主要由天然真皮和PVC人造革两大块组成，天然真皮由于要取材动物皮，对动物而言存在一定的伤害性，逐渐被动物保护组织抵制使用；而PVC人造革存在舒适性差、气味重、增塑剂易迁移等方面的不足，近些年也逐渐被高耐候性的聚氨酯(PU)合成革所取代。
溶剂型聚氨酯合成革产品具有透气、防水、柔软、耐磨、强度高、耐水解优异等特点，外观与性能均接近天然皮革。其加工主要由湿法工艺及干法工艺两部分组成，由成革加工工艺特点所决定，湿法成革加工及干法粘接加工工序的过程中所使用的有机溶剂N,N-二甲基甲酰胺(DMF)很难完全除尽，导致成品革中的DMF会有一定的残留；随着溶剂型聚氨酯合成革面临的环保压力的增加，开发更加绿色的聚氨酯合成革已迫在眉睫。
但是由于目前行业技术的局限性，完全使用水性聚氨酯树脂或无溶剂聚氨酯树脂加工全环保的汽车革，无论从成品物理性能上，还是从加工操作上而言，都存在一定的困难。另外，众所周知，聚氨酯合成革产品有机溶剂残留的主要影响工序在于湿法加工及干法粘接两个环节，因此，开发一款无溶剂型汽车革用中间层聚氨酯树脂，满足现有技术条件下加工生产的要求，同时可以不需要通过熟化工序来满足物理性能的要求，具有重要的技术和行业发展意义。
发明内容
本发明旨在提供一种无溶剂型汽车内饰革用中间层聚氨酯树脂及其制备方法，合成制得的无溶剂型汽车内饰革，其剥离强度及耐水解性能从性价比的角度 而言，均高于溶剂型汽车内饰革产品。
本发明提供了一种无溶剂型汽车内饰革用中间层聚氨酯树脂，其由A组分与B组分按质量比2.5：1～1：2.5进行混合而成：
所述的A组分由以下组分按质量份数制备而成：
所述B组由以下组分按质量份数制备而成：
进一步方案，所述二异氰酸酯为4,4’-二苯基甲烷二异氰酸酯(MDI-100)、2,4-二苯基甲烷二异氰酸酯与4,4’-二苯基甲烷二异氰酸酯的混合物(MDI-50)、二苯基甲烷二异氰酸酯与聚苯聚亚甲基多异氰酸酯的混合物(聚合MDI)中的一种或几种；
所述三异氰酸酯为HDI三聚体。
进一步方案，所述低聚物二元醇为分子量为1000-3000的聚四氢呋喃二元醇、聚碳酸酯二元醇、聚己内酯二元醇、聚酯二元醇中的一种或几种；
所述小分子二元醇为乙二醇、1,3-丙二醇、1,4-丁二醇、1,5-戊二醇、新戊二醇、一缩二乙二醇、3-甲基-1,5-戊二醇、1,6-己二醇、1,4-环己烷二甲醇氢醌双(2-羟乙基)醚中的一种或几种。
所述小分子三元醇为丙三醇、三羟甲基丙烷中的一种或两种。
进一步方案，所述催化剂为延迟型催化剂；所述光/热稳定剂为紫外线吸收剂、受阻胺类光稳定剂；所述流平剂为有机硅类流平剂；所述抗氧剂为抗氧剂245、抗氧剂1010、抗氧剂1035、抗氧剂1076、抗氧剂1098或抗氧剂3114。
进一步方案，所述延迟型催化剂为有机金属类催化剂；所述紫外线吸收剂为UV-1、UV-320、UV-1130、UV-P、UV-1164或UV-234；所述受阻胺类光稳定剂为292、622、770、944、5050、5060或5151；
所述有机硅类流平剂为BYK-322、BYK-333、BYK-345或BYK-361N。
本发明的另一个发明目的是提供上述一种无溶剂型汽车内饰革用中间层聚氨酯树脂的制备方法，其制备步骤如下：
(1)A组分的制备：向反应釜中投入低聚物二元醇，升温至100～120℃于真空条件下脱水2～4h；降温至30～40℃后加入小分子二元醇及异氰酸酯，于65～90℃下反应2～4h；然后再降温至30-40℃后依次加入小分子三元醇、催化剂、光/热稳定剂、流平剂及无溶剂色浆，升温至60～80℃搅拌2～4h后，制得A组分；
(2)B组分的制备：向反应釜内投入二异氰酸酯、三异氰酸酯及抗氧剂，再加入聚四氢呋喃二元醇、小分子二元醇及小分子三元醇，于60～90℃下搅拌反应2.5～4.5h，制得B组分；
(3)聚氨酯树脂的制备：在离型纸上涂覆脂肪族聚碳树脂浆料，烘干成型后获得脂肪族聚碳面层；将A组分与B组分按质量比2.5：1～1：2.5进行混合，在90-130℃预反应；然后将混合均匀的混合物浇注涂覆于上述烘干成型后的脂肪族聚碳面层，烘干即得无溶剂型汽车内饰革用中间层聚氨酯树脂。
进一步方案，所述步骤(1)中真空条件为-0.08MPa～-0.1MPa。
本发明制备的聚氨酯树脂在制备过程中没有添加溶剂，环保且对人体无害，可用于汽车内饰革，使用将其贴合基布，随后于110-150℃继续反应，使其交联固化成型；然后收卷并将离型纸剥离，即获得无溶剂型汽车革。
具体而言，与现有技术相比，本发明具有以下明显优点：
(1)本发明制备的聚氨酯树脂作为汽车内饰革的中间层使用，且同时还可起到粘接的作用，从而省去了成革加工过程中湿法和干法粘接工序环节有机溶剂的 使用，有效保证了汽车革的环保性。
(2)本发明中A组分通过引入适量二异氰酸酯进行预聚合成，一方面有效解决了A组分中低聚物二元醇和小分子多元醇之间的相容性问题；另一方面，可以有效调整A、B双组份物料之间的粘度、分子量等参数，从而保证生产加工时A/B料配比的稳定性。
(3)本发明树脂采用芳香族聚碳-聚酯-聚醚共聚体系，满足汽车革产品耐水解性能的同时，可以有效保证汽车革的高温耐用性能及各项力学性能；制得的汽车革产品剥离强度高达145N/3cm，耐水解性能可达10周后剥离强度仍高达135N/3cm。
(4)本发明树脂用于汽车革生产时，充分保证了连续生产操作性和反应性，通过一次加工即可成型，无需熟化工艺，有效缩短生产周期，降低能耗。
四、具体实施方式
下面通过具体的实施例对本发明做进一步的阐述，但是需要说明的是本发明的实施例中所描述的具体的物料配比、工艺条件及结果仅用于说明本发明，并不能以此限制本发明的保护范围，凡是根据本发明的精神实质所做的等效变化或修饰，都应该涵盖在本发明的保护范围之内。
实施例1：
一种无溶剂型汽车内饰革用中间层聚氨酯树脂，由组分A和组分B按质量比2.5:1进行混合组成：
所述的A组分按质量份数比例，构成如下：
所述B组分按质量份数比例，构成如下：
组分A中的Wannate MDI-100为烟台万华公司生产的纯二苯基亚甲基二异氰酸酯，T5652为日本旭化成化学品株式会社生产的数均分子量2000的聚碳酸酯二元醇，SP-2013为合肥安利聚氨酯新材料有限公司生产的数均分子量2000的聚酯二元醇，EG、甘油均为市售产品，MB20为美国空气化工产品公司生产的有机铋催化剂，Tinuvin 1130为德国BASF公司生产的紫外线吸收剂，Chisorb 292为中国台湾双键化工股份有限公司生产的光稳定剂，BYK-322为德国BYK公司生产有机硅类流平剂，BLPT-3751为浙江深蓝轻纺科技有限公司生产的无溶剂黑色浆；组分B中的N3300为德国拜耳公司生产的HDI三聚体，Poly THF 2000为德国BASF公司生产的数均分子量2000的聚四氢呋喃二醇，抗氧剂1010为中国台湾双键化工股份有限公司生产的抗氧剂。
上述无溶剂型汽车内饰革用中间层聚氨酯树脂的制备方法，该制备方法包括以下步骤：
(1)A组分的制备：向反应釜中投入低聚物二元醇，升温至120℃于-0.08MPa真空条件下脱水4h；降温至40℃后加入小分子二元醇及异氰酸酯，于90℃下反应2h；然后再降温至40℃后依次加入小分子三元醇、催化剂、光/热稳定剂、流平剂及无溶剂色浆，升温至60℃搅拌2h后，制得A组分；
(2)B组分的制备：向反应釜内投入二异氰酸酯、三异氰酸酯及抗氧剂，再加入聚四氢呋喃二元醇、小分子二元醇及小分子三元醇，于80℃下搅拌反应4.5h，制得B组分；
(3)聚氨酯树脂的制备：在离型纸上涂覆脂肪族聚碳树脂浆料，烘干成型后获得脂肪族聚碳面层；将A组分与B组分按质量比2.5：1进行混合，在120℃ 预反应；然后将混合均匀的混合物浇注涂覆于上述烘干成型后的脂肪族聚碳面层，烘干即得无溶剂型汽车内饰革用中间层聚氨酯树脂。
实施例2
一种无溶剂型汽车内饰革用中间层聚氨酯树脂，其由组分A和组分B按质量比1:2.5进行混合组成：
所述的A组分按质量份数比例，构成如下：
所述B组分按质量份数比例，构成如下：
组分A中的Wannate MDI-50为烟台万华公司生产的4,4’-MDI和2,4’-MDI的混合物，T5652为日本旭化成化学品株式会社生产的数均分子量2000的聚碳酸酯二元醇，SP-2313为合肥安利聚氨酯新材料有限公司生产的数均分子量2000的聚酯二元醇，1,4-BG和三羟甲基丙烷TMP均为市售产品，BiCAT 8108为美国领先化学品公司的有机铋催化剂，Chisorb P和Chisorb 944分别为中国台湾双键化工 有限公司的紫外线吸收剂和光稳定剂，BYK-345为德国BYK公司生产有机硅类流平剂，BLPT-3751为浙江深蓝轻纺科技有限公司生产的无溶剂黑色浆；组分B中的Wannate MDI-100为烟台万华公司生产的纯二苯基亚甲基二异氰酸酯，TPA-100为日本旭化成株式会社生产的HDI三聚体，Poly THF 2000为德国BASF公司生产的数均分子量2000的聚四氢呋喃二醇，抗氧剂1076为中国台湾双键化工股份有限公司生产的抗氧剂。
其制备方法如下：
(1)A组分的制备：向反应釜中投入低聚物二元醇，升温至100℃于-0.1MPa真空条件下脱水2h；降温至30℃后加入小分子二元醇及异氰酸酯，于65℃下反应4h；然后再降温至30℃后依次加入小分子三元醇、催化剂、光/热稳定剂、流平剂及无溶剂色浆，升温至80℃搅拌2h后，制得A组分；
(2)B组分的制备：向反应釜内投入二异氰酸酯、三异氰酸酯及抗氧剂，再加入聚四氢呋喃二元醇、小分子二元醇及小分子三元醇，于90℃下搅拌反应2.5h，制得B组分；
(3)聚氨酯树脂的制备：在离型纸上涂覆脂肪族聚碳树脂浆料，烘干成型后获得脂肪族聚碳面层；将A组分与B组分按质量比1：2.5进行混合，在130℃预反应；然后将混合均匀的混合物浇注涂覆于上述烘干成型后的脂肪族聚碳面层，烘干即得无溶剂型汽车内饰革用中间层聚氨酯树脂。
实施例3：
一种无溶剂型汽车内饰革用中间层聚氨酯树脂，其由组分A和组分B按质量比1:1进行混合组成：
所述的A组分按质量份数比例，构成如下：
所述B组分按质量份数比例，构成如下：
其中，所述A组分与B组分按质量比1:1进行混合。
组分A中的Wannate MDI-50为烟台万华公司生产的4,4’-MDI和2,4’-MDI的混合物，T5652为日本旭化成化学品株式会社生产的数均分子量2000的聚碳酸酯二元醇，220N为日本化学工业株式会社大赛璐的聚己内酯二元醇，1,3-PG为美国杜邦公司生产的1,3-丙二醇，三羟甲基丙烷TMP为市售产品，Borchi Kat 24为OMG Borchers公司生产的金属所酸盐催化剂，Chisorb 234为中国台湾双键化工有限公司的紫外线吸收剂，Tinuvin 5151为德国BASF公司生产的光稳定剂，BYK-361N为德国BYK公司生产有机硅类流平剂，BLPT-3751为浙江深蓝轻纺科技有限公司生产的无溶剂黑色浆；组分B中的Wannate MDI-100为烟台万华公司生产的纯二苯基亚甲基二异氰酸酯，Poly THF 2000为德国BASF公司生产的数均分子量2000的聚四氢呋喃二醇，抗氧剂3114为中国台湾双键化工股份有限公司生产的抗氧剂。
其制备方法如下：
(1)A组分的制备：向反应釜中投入低聚物二元醇，升温至110℃于-0.09MPa真空条件下脱水3h；降温至35℃后加入小分子二元醇及异氰酸酯，于80℃下反应3h；然后再降温至35℃后依次加入小分子三元醇、催化剂、光/热稳定剂、流平剂及无溶剂色浆，升温至70℃搅拌3h后，制得A组分；
(2)B组分的制备：向反应釜内投入二异氰酸酯、三异氰酸酯及抗氧剂，再加入聚四氢呋喃二元醇、小分子二元醇及小分子三元醇，于70℃下搅拌反应 3.5h，制得B组分；
(3)聚氨酯树脂的制备：在离型纸上涂覆脂肪族聚碳树脂浆料，烘干成型后获得脂肪族聚碳面层；将A组分与B组分按质量比1：1进行混合，在90℃预反应；然后将混合均匀的混合物浇注涂覆于上述烘干成型后的脂肪族聚碳面层，烘干即得无溶剂型汽车内饰革用中间层聚氨酯树脂。
实施例4：
将上述实施例1-3所制得的聚氨酯树脂贴合基布，随后于100-150℃继续反应，使其交联固化成型；固化成型后收卷并将离型纸剥离，即获得无溶剂型汽车内饰革。然后对无溶剂型汽车内饰革进行剥离强度(GB/T 8949)和耐水解性能(丛林测试)测试(QB/T 4671)，具体数据下表：
从上表数据可看出，本发明制备的聚氨酯树脂可做为汽车内饰革的中间层使用，其满足汽车革产品耐水解性能的同时，可以有效保证汽车革的高温耐用性能及各项力学性能；制得的汽车革产品剥离强度高达145N/3cm，耐水解性能可达10周后剥离强度仍高达135N/3cm。并且本发明制备的聚氨酯树脂用于汽车革生产时，充分保证了连续生产操作性和反应性，通过一次加工即可成型，无需熟化工艺，有效缩短生产周期，降低能耗。

Claims (7)

1.一种无溶剂型汽车内饰革用中间层聚氨酯树脂，其特征在于：由A组分与B组分按质量比2.5：1～1：2.5进行混合而成：
所述的A组分由以下组分按质量份数制备而成：
二异氰酸酯 5～15份
低聚物二元醇 70～80份
小分子二元醇 1～10份
小分子三元醇 0.5～5份
催化剂 0.01～0.5份
光/热稳定剂 0.5～2.5份
流平剂 0.02～0.5份
无溶剂色浆 0.2～2.0份；
所述B组由以下组分按质量份数制备而成：
二异氰酸酯 40～50份
三异氰酸酯 0～10份
聚四氢呋喃二元醇 35～50份
小分子二元醇 0.5～5份
小分子三元醇 0～2份
抗氧剂 0.5～1.0份，
所述催化剂为延迟型催化剂，所述延迟型催化剂为有机金属类催化剂。
2.根据权利要求1所述的一种无溶剂型汽车内饰革用中间层聚氨酯树脂，其特征在于：所述二异氰酸酯为4,4’-二苯基甲烷二异氰酸酯、2,4-二苯基甲烷二异氰酸酯与4,4’-二苯基甲烷二异氰酸酯的混合物、二苯基甲烷二异氰酸酯与聚苯聚亚甲基多异氰酸酯的混合物中的一种或几种；
所述三异氰酸酯为HDI三聚体。
3.根据权利要求1所述的一种无溶剂型汽车内饰革用中间层聚氨酯树脂，其特征在于：所述低聚物二元醇为分子量为1000-3000的聚四氢呋喃二元醇、聚碳酸酯二元醇、聚己内酯二元醇、聚酯二元醇中的一种或几种；
所述小分子二元醇为乙二醇、1,3-丙二醇、1,4-丁二醇、1,5-戊二醇、新戊二醇、一缩二乙二醇、3-甲基-1,5-戊二醇、1,6-己二醇、1,4-环己烷二甲醇氢醌双（2-羟乙基）醚中的一种或几种；
所述小分子三元醇为丙三醇、三羟甲基丙烷中的一种或两种。
4.根据权利要求1所述的一种无溶剂型汽车内饰革用中间层聚氨酯树脂，其特征在于：所述光/热稳定剂为紫外线吸收剂、受阻胺类光稳定剂；所述流平剂为有机硅类流平剂；所述抗氧剂为抗氧剂245、抗氧剂1010、抗氧剂1035、抗氧剂1076、抗氧剂1098或抗氧剂3114。
5.根据权利要求4所述的一种无溶剂型汽车内饰革用中间层聚氨酯树脂，其特征在于：所述紫外线吸收剂为UV-1、UV-320、UV-1130、UV-P、UV-1164或UV-234；所述受阻胺类光稳定剂为292、622、770、944、5050、5060或5151；
所述有机硅类流平剂为BYK-322、BYK-333、BYK-345或BYK-361N。
6.如权利要求1所述的一种无溶剂型汽车内饰革用中间层聚氨酯树脂的制备方法，其特征在于：制备步骤如下：
（1）A组分的制备：向反应釜中投入低聚物二元醇，升温至100～120℃于真空条件下脱水2～4h；降温至30～40℃后加入小分子二元醇及异氰酸酯，于65～90℃下反应2～4h；然后再降温至30-40℃后依次加入小分子三元醇、催化剂、光/热稳定剂、流平剂及无溶剂色浆，升温至60～80℃搅拌2～4h后，制得A组分；
（2）B组分的制备：向反应釜内投入二异氰酸酯、三异氰酸酯及抗氧剂，再加入聚四氢呋喃二元醇、小分子二元醇及小分子三元醇，于60～90℃下搅拌反应2.5～4.5h，制得B组分；
（3）聚氨酯树脂的制备：在离型纸上涂覆脂肪族聚碳树脂浆料，烘干成型后获得脂肪族聚碳面层；将A组分与B组分按质量比2.5：1～1：2.5进行混合，在90-130℃预反应；然后将混合均匀的混合物浇注涂覆于上述烘干成型后的脂肪族聚碳面层，烘干即得无溶剂型汽车内饰革用中间层聚氨酯树脂。
7.根据权利要求6所述的制备方法，其特征在于：所述步骤（1）中真空条件为-0.08MPa～-0.1MPa。
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