CN113501927A - 一种彩色水性聚氨酯及其制备方法 - Google Patents
一种彩色水性聚氨酯及其制备方法 Download PDFInfo
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- CN113501927A CN113501927A CN202110652450.9A CN202110652450A CN113501927A CN 113501927 A CN113501927 A CN 113501927A CN 202110652450 A CN202110652450 A CN 202110652450A CN 113501927 A CN113501927 A CN 113501927A
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- parts
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- waterborne polyurethane
- diisocyanate
- dye
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- Polyurethanes Or Polyureas (AREA)
Abstract
本发明公开了一种彩色水性聚氨酯，由以下重量份的原料制备而成：二异氰酸酯50‑200份，常规二元醇150‑350份，彩色聚酯多元醇50‑120分，小分子扩链剂1‑20份，亲水扩链剂10‑45份，去离子水400‑1200份；所述彩色聚酯多元醇由以下重量份的原料制备而成：二元酸20‑100份、小分子扩链剂30‑110份、含活性羟基的染料5‑20份、钛酸四丁酯0.1‑0.5份，其中羟基与羧基摩尔数为1.1‑1.3:1。本发明的彩色水性聚氨酯通过化学反应，将彩色基团原位合成到聚氨酯分子链中，染料与聚氨酯通过化学键结合，解决了色迁移、耐摩擦牢度和耐水性牢度低的弊病；同时，由于染料与聚氨酯在同一分子结构，属于一个体系，稳定性更强，无浮色现象。应用于超纤革，耐水洗色牢度、耐摩擦色牢度、耐色迁移等级更高。
Description
技术领域
本发明涉及高分子合成领域，具体涉及一种彩色水性聚氨酯及其制备方法。
背景技术
我国是世界上最大的纺织品生产和出口国，纺织品出口的持续稳定增长对保证我国外汇储备、国际收支平衡、人民币汇率稳定、解决社会就业及纺织业可持续发展至关重要。特别是近几年，我国PU合成革发展极为迅速，据统计， 2019年中国合成革产量为328.28万吨，同比增长9.6％。
水性聚氨酯由于特殊的分子结构及聚集状态结构具有成膜性能好、热、力学性能优良、耐水、耐寒、耐曲折等特点被广泛用于纺织印染、皮革加工等领域。
目前，聚氨酯合成革一般通过将水性聚氨酯和染料物理共混使用达到不同的颜色风格，现有的共混技术存在以下问题：染料与水性聚氨酯、织物通过氢键、范德华力等弱作用力结合在一起，导致颜色不牢固，易迁移；另外染料与水性聚氨酯共混后处于亚稳定状态，放置过程中会分层和浮色，制备出带色的水性聚氨酯是解决目前水性聚氨酯产品上述问题的有效途径。
CN104193952B公开了一种用于防水涂料的彩色聚氨酯乳液及其制备方法，其原理是在聚氨酯合成阶段引入显色扩链剂，将发色基团引入聚氨酯主链中；该方法需采用高反应活性的甲苯二异氰酸酯和阶段升温的方法(反应温度＜ 120℃)来提高与发色基团的反应效率，限制了应用范围的同时，仍然存在显色扩链剂利用率不高的问题。
CN104693403B公开了一种合成革用彩色聚氨酯树脂及其制备方法，其原理是采用含双羟基或者双伯氨基的染料在聚氨酯合成阶段将发色基团引入聚氨酯分子链中，解决色迁移的问题；制备过程中采用有机溶剂，造成污染的同时也存在安全隐患。
CN106496489B公开了一种水溶性彩色扩链剂、共聚型彩色聚氨酯乳液和彩色聚氨酯-丙烯酸酯共聚物乳液及制备方法，其通过改性将至少两个氨基引入水溶性染料中，然后在聚氨酯合成阶段将水溶性彩色扩链剂分子引入聚氨酯分子链中，从而解决色牢度问题；但是氨基与异氰酸酯基团反应剧烈并放出大量热，反应阶段容易导致凝胶现象，合成过程不易控制，存在安全隐患。
虽然以上各种方法都可以将发色基团引入聚氨酯分子链中但是仍然存在染料利用率低、反应不易控制的问题，限制了其在工业生产中的实际应用。
发明内容
本发明的目的在于提供一种彩色水性聚氨酯及其制备方法。本发明的彩色水性聚氨酯通过化学反应，将彩色基团原位合成到聚氨酯分子链中，染料与聚氨酯通过化学键结合，解决了色迁移、耐摩擦牢度和耐水性牢度低的弊病；同时，由于染料与聚氨酯在同一分子结构，属于一个体系，稳定性更强，无浮色现象。应用于超纤革，耐水洗色牢度、耐摩擦色牢度、耐色迁移等级更高。
为解决以上技术问题，本发明提供的技术方案是：
一种彩色水性聚氨酯，由以下重量份的原料制备而成：二异氰酸酯50-200 份，常规二元醇150-350份，彩色聚酯多元醇50-120分，小分子扩链剂1-20份，亲水扩链剂10-45份，去离子水400-1200份；
所述彩色聚酯多元醇由以下重量份的原料制备而成：二元酸20-100份、小分子扩链剂30-110份、含活性羟基的染料5-20份、钛酸四丁酯0.1-0.5份，其中羟基与羧基摩尔数为1.1-1.3:1。
优选的，所述的二元酸为己二酸、葵二酸和间苯二甲酸中的任意一种或多种。
优选的，所述的小分子扩链剂为乙二醇、1,2-丙二醇、1,3-丙二醇、1,4-丁二醇、1,5-戊二醇、1,6-己二醇和新戊二醇中的任意一种或多种。
根据权利要求1所述的彩色水性聚氨酯，其特征在于，所述的含活性羟基的染料为分散黄染料、酸性橙染料和湖蓝染料中的任意一种或多种。
优选的，所述的二异氰酸酯为六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯、甲苯二异氰酸酯、二环己基甲烷二异氰酸酯、苯亚甲基二异氰酸酯、1,5-奈二异氰酸酯、对苯二异氰酸酯中的任意一种或多种。
优选的，所述的二元醇为聚四氢呋喃二元醇、聚酯二元醇和聚丙二醇中的任意一种或多种。
优选的，所述的中和剂为三乙胺、二甲基乙醇胺、三乙醇胺和二乙醇胺中的任意一种或多种。
本发明还提供一种所述的彩色水性聚氨酯的制备方法，包括下列步骤：
步骤一：彩色聚酯多元醇的制备：
(1)将计量好的二元酸、小分子扩链剂、含活性羟基的染料、钛酸四丁酯称取至四口烧瓶中，升温至60-80℃，通过超声分散和搅拌，将物料搅拌均匀；
(2)逐步升温至240℃反应3-4小时；
(3)减压蒸馏出水分和残余单体，检测含水量、酸值、羟值至要求值，得到彩色聚酯多元醇。
步骤二：彩色水性聚氨酯的制备：
(1)将常规二元醇、彩色聚酯多元醇和二羟甲基丙酸于120℃真空脱水1 小时，降温至40-70℃，加入中和剂，将原材料搅拌至均匀透明，加入二异氰酸酯，在机械搅拌下，60-90℃反应1-3小时，投入小分子扩链剂，在70-85℃下反应2-4小时；
(2)在高速搅拌1500r/min下，将上述反应液分散在去离子水中，搅拌30 分钟，得到彩色水性聚氨酯。
本发明与现有技术相比，具有以下优点及有益效果：
本发明的彩色水性聚氨酯通过化学反应，将彩色基团原位合成到聚氨酯分子链中，染料与聚氨酯通过化学键结合，解决了色迁移、耐摩擦牢度和耐水性牢度低的弊病；同时，由于染料与聚氨酯在同一分子结构，属于一个体系，稳定性更强，无浮色现象。应用于超纤革，耐水洗色牢度、耐摩擦色牢度、耐色迁移等级更高。
具有以下优点：
本发明中彩色聚酯多元醇合成阶段可以高温反应(240℃)，远高于聚氨酯合成阶段最高温度120℃，明显提高了染料的反应效率和利用效率，减少了聚酯中的游离染料单体，节省了成本的同时，间接解决色牢度问题。
本发明在彩色聚酯多元醇合成阶段通过超声分散手段将染料与反应介质更好融合，进一步提高染料的利用效率。
本发明制备的彩色聚酯多元醇反应活性与常规二元醇活性接近，应用于聚氨酯合成阶段反应温和、易控制，可广泛用于工业生产。
本发明制备的彩色水性聚氨酯采用自制的彩色聚氨酯多元醇与常规多元醇的混合体系，可以采用常规的聚氨酯合成工艺将发色基团更高效率地接枝到聚氨酯主链，彻底解决染料反应活性低和色牢度差的问题。
具体实施方式
为了使本领域的技术人员更好地理解本发明的技术方案，下面结合具体实施例对本发明的优选实施方案进行描述，但是不能理解为对本专利的限制。
下述实施例中所述试验方法或测试方法，如无特殊说明，均为常规方法；所述试剂和材料，如无特殊说明，均从常规商业途径获得，或以常规方法制备。
所述分散黄染料、酸性橙染料和湖蓝染料的结构式分别如下：
一种彩色水性聚氨酯及其制备方法，包括以下组分，步骤一：彩色聚酯多元醇的制备，由以下重量份的原料制备而成：二元酸20-100份、小分子扩链剂 30-110份、含活性羟基的染料5-20份、钛酸四丁酯0.1-0.5份，其中羟基与羧基摩尔数为1.1-1.3:1；步骤二：彩色水性聚氨酯的制备，由以下重量份的原料制备而成：二异氰酸酯50-200份，常规二元醇150-350份，彩色聚酯二元醇50-120 分，小分子扩链剂1-20份，亲水扩链剂10-45份，去离子水400-1200份。
如上所述的一种彩色水性聚氨酯及其制备方法，所述的二元酸为己二酸、葵二酸、间苯二甲酸的任意一种或任意两种以上以任意比例混合的混合物。
如上所述的一种彩色水性聚氨酯及其制备方法，所述的小分子扩链剂为乙二醇、1,2-丙二醇、1,3-丙二醇、1,4-丁二醇、1,5-戊二醇、1,6-己二醇、新戊二醇的任意一种或任意两种以上以任意比例混合的混合物。
如上所述的一种彩色水性聚氨酯及其制备方法，所述的含活性羟基的染料为分散黄染料、酸性橙染料、湖蓝染料的任意一种或任意两种以上以任意比例混合的混合物。
如上所述的一种彩色水性聚氨酯及其制备方法，所述的二异氰酸酯为六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯、甲苯二异氰酸酯、二环己基甲烷二异氰酸酯、苯亚甲基二异氰酸酯、1,5-奈二异氰酸酯、对苯二异氰酸酯中的任意一种或任意两种以上以任意比例混合的混合物。
如上所述的一种彩色水性聚氨酯及其制备方法，所述的二元醇为聚四氢呋喃二元醇、聚酯二元醇、聚丙二醇中的任意一种或任意两种以上以任意比例混合的混合物。
如上所述的一种彩色水性聚氨酯及其制备方法，所述的中和剂为三乙胺、二甲基乙醇胺、三乙醇胺、二乙醇胺中的一种。
一种彩色水性聚氨酯及其制备方法，包括以下步骤：
步骤一：彩色聚酯多元醇的制备，(1)将计量好的二元酸、小分子扩链剂、含活性羟基的染料、钛酸四丁酯称取至四口烧瓶中，升温至60-80℃，通过超声分散和搅拌，将物料搅拌均匀；(2)逐步升温至240℃反应3-4小时；(3) 减压蒸馏出水分和残余单体，检测含水量、酸值、羟值至要求值，得到彩色聚酯多元醇。
步骤二：彩色水性聚氨酯的制备(1)将常规二元醇、彩色聚酯多元醇和二羟甲基丙酸于120℃真空脱水1小时，降温至40-70℃，加入中和剂，将原材料搅拌至均匀透明，加入二异氰酸酯，在机械搅拌下，60-90℃反应1-3小时，投入小分子扩链剂，在70-85℃下反应2-4小时；(2)在高速搅拌1500r/min下，将上述反应液分散在去离子水中，搅拌30分钟，得到彩色水性聚氨酯。
实施例1
步骤一：彩色聚酯多元醇的制备，(1)将计量好的己二酸100份、乙二醇51份、分散黄染料10份、钛酸四丁酯0.4份，称取至四口烧瓶中，升温至 80℃，通过超声分散和搅拌的方式，将物料搅拌均匀；(2)逐步升温至240℃反应4小时；(3)减压至-0.09Mpa蒸馏出水分和残余单体，检测含水量＜0.05％、酸值＜1mgKOH/g、羟值52-58mgKOH/g，得到彩色聚酯多元醇。
步骤二：彩色水性聚氨酯的制备(1)将300份聚四氢呋喃醚二醇(数均分子量为2000)、100份步骤一的彩色聚酯多元醇、25份二羟甲基丙酸于120℃真空脱水1小时，降温至50℃，加入23份三乙胺，将原材料搅拌至均匀透明，加入92份异氟尔酮二异氰酸酯，在机械搅拌下，90℃反应3小时，投入1.5份新戊二醇，在80℃下反应3小时；(2)在高速搅拌1500r/min下，将上述反应液分散在去750份离子水中，搅拌30分钟，得到彩色水性聚氨酯。
实施例2
步骤一：彩色聚酯多元醇的制备，(1)将计量好的己二酸60份、葵二酸 50份、1,4-丁二醇71份、含活性羟基的酸性橙染料13份、钛酸四丁酯0.3份，称取至四口烧瓶中，升温至80℃，通过超声分散和搅拌的方式，将物料搅拌均匀；(2)逐步升温至240℃反应4小时；(3)减压蒸馏出水分和残余单体，检测含水量＜0.05％、酸值＜1mgKOH/g、羟值52-58mgKOH/g，得到彩色聚酯多元醇。
步骤二：彩色水性聚氨酯的制备(1)将205份聚四氢呋喃二元醇(数均分子量为1000)、100份聚丙二醇(数均分子量为2000)、80份步骤一的彩色聚酯多元醇和30份二羟甲基丙酸于120℃真空脱水1小时，降温至50℃，加入27 份三乙胺，将原材料搅拌至均匀透明，加入215份二环己基甲烷二异氰酸酯，在机械搅拌下，90℃反应2小时，投入2份1,4-丁二醇，在75℃下反应3小时； (2)在高速搅拌1500r/min下，将上述反应液分散在792份去离子水中，搅拌 30分钟，得到彩色水性聚氨酯。
实施例3
步骤一：彩色聚酯多元醇的制备，(1)将计量好的己二酸120份、85份新戊二醇、20份含活性羟基的湖蓝染料、钛酸四丁酯0.3份称取至四口烧瓶中，升温至80℃，通过超声分散和搅拌的方式，将物料搅拌均匀；(2)逐步升温至 240℃反应4小时；(3)减压蒸馏出水分和残余单体，检测含水量＜0.05％、酸值＜1mgKOH/g、羟值52-58mgKOH/g，得到彩色聚酯多元醇。
步骤二：彩色水性聚氨酯的制备，(1)将210g聚四氢呋喃二元醇(数均分子量为2000)，100g步骤一的彩色聚酯多元醇、21份二羟甲基丙酸于120℃真空脱水1小时，降温至40℃，加入17份三乙胺，将原材料搅拌至均匀透明，加入115g甲苯二异氰酸酯，在机械搅拌下，80℃反应2小时，投入2g1,6-己二醇，在75℃下反应3小时；(2)在高速搅拌1500r/min下，将上述反应液分散在940去离子水中，搅拌30分钟，得到彩色水性聚氨酯。
对比例1
对比例1与实施例1的区别在于如下步骤：
步骤一：聚酯多元醇的制备，(1)将计量好的己二酸100份、乙二醇51 份、钛酸四丁酯0.4份，称取至四口烧瓶中，升温至80℃，通过超声分散和搅拌的方式，将物料搅拌均匀；(2)逐步升温至240℃反应4小时；(3)减压至 -0.09Mpa蒸馏出水分和残余单体，检测含水量＜0.05％、酸值＜1mgKOH/g、羟值52-58mgKOH/g，得到聚酯多元醇。
步骤二：彩色水性聚氨酯的制备(1)将300份聚四氢呋喃醚二醇(数均分子量为2000)、100份步骤一的聚酯多元醇、25份二羟甲基丙酸于120℃真空脱水1小时，降温至50℃，加入23份三乙胺，将原材料搅拌至均匀透明，加入92份异氟尔酮二异氰酸酯，在机械搅拌下，90℃反应3小时，投入1.5份新戊二醇，在80℃下反应3小时；(2)在高速搅拌1500r/min下，将上述反应液分散在去750份离子水中，搅拌30分钟，加入分散黄染料10份搅拌均匀后，得到彩色水性聚氨酯。
对比例2
对比例2与实施例2的区别在于如下步骤：
步骤一：聚酯多元醇的制备，(1)将计量好的己二酸60份、葵二酸50份、 1,4-丁二醇71份、钛酸四丁酯0.3份，称取至四口烧瓶中，升温至80℃，通过超声分散和搅拌的方式，将物料搅拌均匀；(2)逐步升温至240℃反应4小时； (3)减压蒸馏出水分和残余单体，检测含水量＜0.05％、酸值＜1mgKOH/g、羟值52-58mgKOH/g，得到聚酯多元醇。
步骤二：彩色水性聚氨酯的制备(1)将205份聚四氢呋喃二元醇(数均分子量为1000)、100份聚丙二醇(数均分子量为2000)、80份步骤一的聚酯多元醇和30份二羟甲基丙酸于120℃真空脱水1小时，降温至50℃，加入27份三乙胺，将原材料搅拌至均匀透明，加入215份二环己基甲烷二异氰酸酯，在机械搅拌下，90℃反应2小时，投入2份1,4-丁二醇，在75℃下反应3小时； (2)在高速搅拌1500r/min下，将上述反应液分散在792份去离子水中，搅拌 30分钟，然后加入含活性羟基的酸性橙染料13份，搅拌均匀，得到彩色水性聚氨酯。
对比例3
对比例3与实施例3的区别在于如下步骤：
步骤一：聚酯多元醇的制备，(1)将计量好的己二酸120份、85份新戊二醇、钛酸四丁酯0.3份称取至四口烧瓶中，升温至80℃，通过超声分散和搅拌的方式，将物料搅拌均匀；(2)逐步升温至240℃反应4小时；(3)减压蒸馏出水分和残余单体，检测含水量＜0.05％、酸值＜1mgKOH/g、羟值52-58 mgKOH/g，得到聚酯多元醇。
步骤二：彩色水性聚氨酯的制备，(1)将210份聚四氢呋喃二元醇(数均分子量为2000)，100份步骤一的聚酯多元醇、21份二羟甲基丙酸于120℃真空脱水1小时，降温至40℃，加入17份三乙胺，将原材料搅拌至均匀透明，加入115份甲苯二异氰酸酯，在机械搅拌下，80℃反应2小时，投入2份1,6-己二醇，在75℃下反应3小时；(2)在高速搅拌1500r/min下，将上述反应液分散在940份去离子水中，搅拌30分钟，然后加入20份含活性羟基的湖蓝染料，搅拌均匀后得到彩色水性聚氨酯。
对比例4
对比例4与实施例3的区别在于如下步骤：
步骤一：聚酯多元醇的制备，(1)将计量好的己二酸120份、85份新戊二醇、钛酸四丁酯0.3份称取至四口烧瓶中，升温至80℃，通过超声分散和搅拌的方式，将物料搅拌均匀；(2)逐步升温至240℃反应4小时；(3)减压蒸馏出水分和残余单体，检测含水量＜0.05％、酸值＜1mgKOH/g、羟值52-58 mgKOH/g，得到聚酯多元醇。
步骤二：彩色水性聚氨酯的制备，(1)将210份聚四氢呋喃二元醇(数均分子量为2000)，100份步骤一的聚酯多元醇、21份二羟甲基丙酸、20份含活性羟基的湖蓝染料于120℃真空脱水1小时，降温至40℃，加入17份三乙胺，将原材料搅拌至均匀透明，加入115份甲苯二异氰酸酯，在机械搅拌下，80℃反应2小时，投入2份1,6-己二醇，在75℃下反应3小时；(2)在高速搅拌1500r/min 下，将上述反应液分散在940份去离子水中，搅拌30分钟，得到彩色水性聚氨酯。
原材料选用相同的前提下，所制备的样品作为实施例1-3与对比例1-4进行检测。采用常规超纤革工艺，将实施例1-3和对比例1-4应用于超纤含浸工艺：首先将彩色水性聚氨酯含浸在超纤基布中，然后通过减量烘干后进行测试。耐色迁移、耐干湿擦牢度、耐水洗色牢度测试：按照GBT3920-2008。稳定性测试：量取50毫升彩色水性聚氨酯乳液进行离心测试，测试条件为15分钟，3000r/min，观察颜色均匀性。结果如表1所示：
表1
从上表可以看出，通过实施例与对比例测试结果对比，本发明生产的彩色水性聚氨酯具有更高的稳定性，应用于超纤革，耐水洗色牢度、耐摩擦色牢度、耐色迁移等级明显更高。
以上仅是本发明的优选实施方式，应当指出的是，上述优选实施方式不应视为对本发明的限制，本发明的保护范围应当以权利要求所限定的范围为准。对于本技术领域的普通技术人员来说，在不脱离本发明的精神和范围内，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。
Claims (8)
1.种彩色水性聚氨酯，其特征在于，由以下重量份的原料制备而成：二异氰酸酯50-200份，常规二元醇150-350份，彩色聚酯多元醇50-120分，小分子扩链剂1-20份，亲水扩链剂10-45份，去离子水400-1200份；
所述彩色聚酯多元醇由以下重量份的原料制备而成：二元酸20-100份、小分子扩链剂30-110份、含活性羟基的染料5-20份、钛酸四丁酯0.1-0.5份，其中羟基与羧基摩尔数为1.1-1.3:1。
2.根据权利要求1所述的彩色水性聚氨酯，其特征在于，所述的二元酸为己二酸、葵二酸和间苯二甲酸中的任意一种或多种。
3.根据权利要求1所述的彩色水性聚氨酯，其特征在于，所述的小分子扩链剂为乙二醇、1,2-丙二醇、1,3-丙二醇、1,4-丁二醇、1,5-戊二醇、1,6-己二醇和新戊二醇中的任意一种或多种。
4.根据权利要求1所述的彩色水性聚氨酯，其特征在于，所述的含活性羟基的染料为分散黄染料、酸性橙染料和湖蓝染料中的任意一种或多种。
5.根据权利要求1所述的彩色水性聚氨酯，其特征在于，所述的二异氰酸酯为六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯、甲苯二异氰酸酯、二环己基甲烷二异氰酸酯、苯亚甲基二异氰酸酯、1,5-奈二异氰酸酯、对苯二异氰酸酯中的任意一种或多种。
6.根据权利要求1所述的彩色水性聚氨酯，其特征在于，所述的二元醇为聚四氢呋喃二元醇、聚酯二元醇和聚丙二醇中的任意一种或多种。
7.根据权利要求1所述的彩色水性聚氨酯，其特征在于，所述的中和剂为三乙胺、二甲基乙醇胺、三乙醇胺和二乙醇胺中的任意一种或多种。
8.一种如权利要求1至7任一项所述的彩色水性聚氨酯的制备方法，其特征在于，包括下列步骤：
步骤一：彩色聚酯多元醇的制备：
(1)将计量好的二元酸、小分子扩链剂、含活性羟基的染料、钛酸四丁酯称取至四口烧瓶中，升温至60-80℃，通过超声分散和搅拌，将物料搅拌均匀；
(2)逐步升温至240℃反应3-4小时；
(3)减压蒸馏出水分和残余单体，检测含水量、酸值、羟值至要求值，得到彩色聚酯多元醇。
步骤二：彩色水性聚氨酯的制备：
(1)将常规二元醇、彩色聚酯多元醇和二羟甲基丙酸于120℃真空脱水1小时，降温至40-70℃，加入中和剂，将原材料搅拌至均匀透明，加入二异氰酸酯，在机械搅拌下，60-90℃反应1-3小时，投入小分子扩链剂，在70-85℃下反应2-4小时；
(2)在高速搅拌1500r/min下，将上述反应液分散在去离子水中，搅拌30分钟，得到彩色水性聚氨酯。
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