CN104211899A - 聚醛改性羧酸‐非离子型聚氨酯水分散体及其制备方法与在涂料中的应用 - Google Patents
聚醛改性羧酸‐非离子型聚氨酯水分散体及其制备方法与在涂料中的应用 Download PDFInfo
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- CN104211899A CN104211899A CN201410422012.3A CN201410422012A CN104211899A CN 104211899 A CN104211899 A CN 104211899A CN 201410422012 A CN201410422012 A CN 201410422012A CN 104211899 A CN104211899 A CN 104211899A
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- polyacetals
- modification
- chain extender
- preparation
- water dispersion
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Classifications
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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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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- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
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- 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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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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Abstract
本发明公开了聚醛改性羧酸-非离子型聚氨酯水分散体及其制备方法与在涂料中的应用。制备时,以质量份数计,加入30~60份聚合物二元醇、1~10份聚醛树脂和1‐5份羧酸型亲水扩链剂,升温至45℃‐55℃,加入中和剂,待反应体系透明后加入23~60份二异氰酸酯单体,升温;加入1‐10份小分子二元醇扩链剂和2‐10份非离子亲水扩链剂,反应后调节反应物粘度,降温,得到聚氨酯预聚体;加入去离子水中乳化,加入胺类扩链剂,蒸馏脱除溶剂并调节pH值。该水分散体采用含羧酸的亲水扩链剂与非离子型亲水扩链剂结合制备的,具有高固体含量;采用聚醛树脂对其进行改性,其涂膜的交联密度高,涂膜硬度高,耐水性和耐化学品性能优异。
Description
技术领域
本发明涉及一种聚氨酯水分散体,特别是涉及一种聚醛改性羧酸‐非离子型聚氨酯水分散体及其制备方法与在涂料中的应用,属于有机高分子化合物领域的用异氰酸酯的高分子化合物。
背景技术
聚氨酯水分散体(PUD)以水为分散介质,具有无毒、不燃、不污染环境、节能等优点,广泛应用于涂料、胶黏剂、皮革涂饰剂和油墨等领域。采用羧基(‐COOH)或磺酸基(‐SO3‐)等亲水组份通过自乳化的方法制备的PUD,其涂膜的耐水性和耐化学品性不好;通常羧酸型PUD的固体含量不高,磺酸型亲水扩链剂来源困难,含胺基的磺酸盐制备PUD工艺较复杂,大规模工业化生产较困难。制备非离子聚氧乙烯醚型PUD时,非离子亲水组分添加量大,致使PUD成本高,涂膜硬度低、耐水和耐化学品性能差。因此,单独使用羧酸、磺酸和非离子等亲水化合物制备PUD,致使PUD固体含量较低、涂膜耐水、耐化学品性差而限制了PUD在水性涂料中的推广应用。采用氮丙啶、聚碳化二亚胺和多环氧化合物等外交联剂对PUD进行后交联改性,可提高PUD涂膜的耐化学品性和耐寒性,这些外交联改性使PUD制品施工时间受限,且其涂膜的耐醇性仍有待提高。在提高PUD涂膜硬度方面,通常采用环氧树脂对PUD进行改性,如许戈文等(二乙醇胺开环环氧树脂改性水性聚氨酯的合成及性能研究,涂料工业,2014,44(2):32‐38)和瞿金清等(环氧改‐眭水性聚氨酯涂料的合成与性能研究,高校化工学报,2002,16(5):570‐574)采用环氧树脂改性PUD可提高涂膜硬度,但该方法使涂膜的耐黄变性能下降,而且制备工艺复杂,合成控制困难。
发明内容
本发明要解决的技术问题是提供一种聚醛改性羧酸‐非离子型聚氨酯水分散体及其制备方法,该聚氨酯水分散体具有固体含量高、涂膜硬度高和耐化学品性优异的优点。
本发明另一个要解决的技术问题是提供所述聚醛改性羧酸‐非离子型聚氨酯水分散体在水性涂料中的应用。
为解决上述技术问题,本发明采用的技术方案是:
一种聚醛改性羧酸‐非离子型聚氨酯水分散体的制备方法,包括如下步骤:
1)聚氨酯预聚体的制备:以质量份数计,在反应釜中,加入30~60份聚合物二元醇、1~10份聚醛树脂和1‐5份羧酸型亲水扩链剂,升温至45℃‐55℃,加入中和剂中和,待反应体系透明后加入23~60份二异氰酸酯单体,升温至60℃~100℃,保温1.0小时~2.0小时;加入1‐10份小分子二元醇扩链剂和2‐10份非离子亲水扩链剂,在50~70℃下反应至NCO基含量低于5%;调节反应物粘度为300-3000cps,降温,得到聚氨酯预聚体;
2)乳化和扩链:将聚氨酯预聚体加入去离子水中乳化,随后加入胺类扩链剂,反应至NCO含量低于0.5%;
3)蒸馏脱除溶剂并调节pH值至6‐8,得到所述的聚醛改性羧酸‐非离子型聚氨酯水分散体;
所述的中和剂为N,N‐二甲基乙醇胺、氨水、三乙胺其中一种或两种以上的混合物;
所述聚合物二元醇的数均分子质量为300-10000,羟值为30-200mgKOH/g;
所述的二异氰酸酯单体为甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、已二异氰酸酯、异佛尔酮二异氰酸酯、四甲基间苯二亚甲基二异氰酸酯(m-TMXDI)、苯二亚甲基二异氰酸酯一种或多种;
所述的小分子扩链剂为乙二醇、丙二醇、1,4-丁二醇,1,6-己二醇,1,4-环己二醇、二乙二醇、二甘醇其中一种或多种;
所述的羧酸型亲水扩链剂为二羟甲基丙酸、二羟甲基丁酸和二羟甲基戊酸其中一种或多种;
所述的非离子型亲水扩链剂为聚氧乙烯醚YmerTMN120、聚乙二醇和聚乙二醇单甲醚其中一种或多种;
所述的胺类扩链剂为肼、乙二胺、己二胺、异佛尔酮二胺、二乙烯三胺何三乙烯四胺中的一种或多种。
所述中和剂的用量为羧酸型亲水单体重量的80‐120%。
所述调节反应物粘度为300-3000cps为通过加入丙酮调节。
所述降温为降温至50℃以下。
所述胺类扩链剂的用量为聚氨酯预聚体质量的0.1%~0.2%。
所述去离子水的加入量为聚氨酯预聚体重量的1~10倍。
所述聚合物二元醇为山东东大公司的CMA-1044聚酯二元醇、赫斯公司的T-1136聚酯二元醇、N210聚醚多元醇、N220聚醚多元醇、Diol1000聚醚多元醇、Diol2000聚醚多元醇、聚碳酸酯二元醇、聚四氢呋喃二元醇、聚丙烯酸酯二元醇、聚丁二烯二元醇和聚己内酯二元醇一种或一种以上的混合物。
所述蒸馏脱除溶剂是在温度为50~120℃和真空度为0.02~0.1Mpa的条件下进行。本发明蒸馏方法是本领域常用的蒸馏方法,可以是常用蒸馏,还可以是减压蒸馏,优选蒸馏方法为减压蒸馏。减压蒸馏优选在温度为50‐120℃和真空度为0.02‐0.1Mpa的条件下进行。
一种聚醛改性羧酸‐非离子型聚氨酯水分散体,由上述制备方法制得。其固含量为45~60%,粘度为50~2000CP,乳胶粒径为50~500纳米。
所述聚醛改性羧酸‐非离子型聚氨酯水分散体在水性涂料中的应用,该涂料含有30~90%聚醛改性羧酸‐非离子型聚氨酯水分散体。该水性涂料还可以含有助剂,颜料或者填料。本领域的技术人员可以依据本领域的知识确定助剂、颜料、填料的种类和用量。
本发明制备方法乳化过程中可以加入消泡剂。所用的消泡剂是本领域常用的消泡剂,例如TEGO‐810、TEGO‐805、TEGO‐825、TEGO‐845其中一种或两种以上混合物。
本发明的聚氨酯水分散体具有高固体含量可提高水性聚氨酯涂料的成膜性能,改善涂膜的丰满度,提高涂膜的光泽和装饰性能;该分散体耐电解质(钙离子)稳定性优异和对各种成膜助剂(各类高沸点有机溶剂)的容忍度高,不含低分子乳化剂,亲水羧酸盐的浓度低,涂膜的交联密度高、硬度高、耐化学介质性能好、热稳定性好、干燥速度快和易打磨等性能,无毒,不易燃。既可用于水性木器涂料,也可以用于水性皮革涂饰剂、水性粘合剂、水性油墨及水性金属涂料。
与现有技术相比,本发明具有以下优点:
(1)采用含羧酸的亲水扩链剂与非离子型亲水扩链剂结合制备PUD,可提高PUD的固体含量至60%,具有良好的贮存稳定性。同时羧酸盐与非离子组成的复合亲水扩链剂制备的PUD可降低采用单一亲水扩链剂制备PUD的添加量,可以调整两者比率调控聚氨酯水分散体的固体含量和性能。羧酸盐和非离子的浓度低,涂膜具有优异的耐水性、耐擦洗性和耐沾污性。
(2)采用聚醛树脂对水性聚氨酯进行改性,由于聚醛树脂含有大量的刚性环和羟基,通过羟基与NCO基的反应将聚醛树脂引入到PU链上,一方面提高PUD涂膜硬度,另一方面提高PUD涂膜的交联密度,提高涂膜的耐水性和耐化学品性能。聚醛树脂的结构如下:
3)该分散体具有高固体含量,可降低聚氨酯水分散体的施工成本,提高涂膜的光泽和装饰性能。
(4)本发明先将羧酸型亲水扩链剂用胺类中和剂中和成盐,能溶于聚合物二醇,有利于后续与二异氰酸酯反应。该工艺避免使用高沸点有毒溶剂如二甲基吡咯烷酮和二甲基甲酰胺溶解羧酸型亲水扩链剂如二羟基丙酸,还可避免使用有毒的有机锡类催化剂,因季铵盐类如三乙胺等中和剂是NCO基与OH基反应的催化剂。因此,该技术使得制备的PUD不含有毒的高沸点溶剂和有机锡催化剂。
(5)本技术制备的聚氨酯水分散体无毒,不易燃。没有人为的添加卤代烃、苯、甲苯、二甲苯、甲醛及其聚合物以及重金属铅、镉铬、汞的化合物。产品中总挥发性有机化合物的含量(TVOC)小于50g/L。完全满足环境标志产品认证技术要求水性涂料HJ/T201‐2005标准,属于绿色环保产品。
具体实施方式
为更好地理解本发明,下面结合实施例对本发明作进一步的描述,但是需要说明的是,实施例不构成对比本发明保护范围的限定。
实施例中,高固体含量的聚氨酯水分散体用如下方法进行表征:分散体的粒径和分布采用纳米粒度分析仪(ZS Nano S)测定。
实施例中,聚氨酯水分散体的水性涂料的涂膜性能用如下方法表征:乳胶膜交联密度通过MEK(甲基乙基酮)加热回流萃取的方法测定;涂膜的摆杆硬度按GB/T1730‐93测定;附着力按GB/T9286‐88十字划格法测定;耐化学溶剂性(MEK)的测试是用被MEK饱和的无纺纸往返擦洗涂膜表面,记录涂膜刚被擦破的擦洗次数。
实施例1
(1)聚氨酯预聚体各组分的原料用量和制备:
表1
在装有搅拌浆、温度计和冷凝器的反应釜中,按照表1的原料配方,加入聚碳酸酯二元醇(PCDL‐2000)、聚醛树脂A81和二羟甲基丁酸,升温至50℃,加入中和剂N,N‐二甲基乙二醇胺中和,待反应体系透明后加入甲苯二异氰酸酯(TDI),升温至100℃,保温1.0小时;加入聚乙二醇,在60℃下反应至NCO基含量低于5%;用丙酮调节反应物粘度为300cps,降温至50℃以下,得到聚氨酯预聚体。
(2)聚醛改性羧酸‐非离子型聚氨酯水分散体的制备
(a)将100g步骤1获得的聚氨酯加入1000g去离子水,高速乳化;
(b)加入0.2g肼(胺类扩链剂),50℃下反应2小时,直到NCO基团含量低于0.5%;
(c)然后在温度为120℃和真空度为0.02Mpa的条件下减压蒸馏脱除溶剂,调整固含量为45%。
(d)调节pH值至8,得聚醛改性羧酸‐非离子型聚氨酯水分散体。
(3)聚醛改性羧酸‐非离子型聚氨酯水分散体的性能:经检测,固含量:45%;粘度:300cps;分散体平均粒径(Dp)=92nm;常温贮存稳定性1年;
(4)聚醛改性羧酸‐非离子型聚氨酯水分散体涂料
(a)配方
(b)配制方法和使用
依据上述配方,将聚醛改性羧酸‐非离子型聚氨酯水分散体、润湿剂TEGO245、消泡剂TEGO810、增稠剂SN612、水、pH值调节剂AMP‐95和成膜助剂二丙二醇丁醚,在800转/min下分散15分钟,得到水性聚氨酯涂料。将获得的聚醛改性羧酸‐非离子型聚氨酯水分散体涂料在常温下固化干燥7天。
(c)上述聚醛改性羧酸‐非离子型聚氨酯水分散体涂料性能如表所示:
表2 聚醛改性羧酸‐非离子型聚氨酯水分散体木器涂料的综合性能
通常单独使用羧酸型亲水扩链剂制备的PUD的固体含量不高,羧酸型亲水扩链剂添加量较大,导致其涂膜的耐水性和耐化学品性不好;单独使用非离子聚氧乙烯醚型制备PUD时,非离子亲水组分添加量大(一般超过10%),致使PUD成本高,涂膜硬度低、耐水和耐化学品性能也差。研究表明羧酸型PUD是靠扩散双电层和溶剂化作用使之在水中稳定存在,非离子型PUD稳定性是依赖胶粒表面的空间位阻;本实施例据羧酸型PUD和非离子型PUD的稳定机理的互补性规律,将羧酸型亲水单体与非离子亲水单体聚乙二醇相结合,能形成多级粒径分布的PUD,非离子单体能在PU胶粒表面形成空间位阻是羧酸型PUD更稳定,制备高固体含量(45%‐60%)的PUD,克服单独使用羧酸型亲水扩链剂的聚氨酯水分散体的固体含量低的缺点(一般35%左右)。
发明人发现,亲水扩链剂与非亲水扩链剂相结合在水中使PUD稳定,降低羧酸型亲水单体和非离子亲水单体的添加量,制备涂膜的耐水性和耐醇性明显优于单独采用羧酸型亲水单体和非离子型亲水单体制备的PUD涂料。
虽然采用硬树脂如环氧树脂、酚醛树脂等改性PUD现有技术已有报道,但都会影响涂膜的耐黄变性能;发明人发现,由于A81单位链节中含有1个六元环及2个羟基,聚合物端基为羟基和醛基,其羟基可与异氰酸酯基(‐NCO)反应将A81引入到PUD链上,A81链上的多个羟基可赋予PUD具有适当的交联结构,提高涂膜的耐水和耐化学品性。同时,A81的玻璃转化温度较高(约85℃),分子结构中含有大量刚性结构六元环,可进一步提高PUD涂膜硬度,改善涂膜的耐醇性。从表2可知,通过聚醛A81链上的羟基与异氰酸酯基反应,将聚醛A81化学键合到水性聚氨酯链上,提高涂膜硬度至0.76,高于常规水性聚氨酯的涂膜硬度(0.55)。因此,本发明改性方法使得制备的聚氨酯水分散体具有高固体含量,涂膜硬度高和具有优异的耐化学品性。
实施例2
(1)聚氨酯预聚体各组分的用量和制备:
表3
在装有搅拌浆、温度计和冷凝器的反应釜中,加入T‐1136聚酯二元醇、Diol1000聚醚多元醇、聚醛A81树脂和羧酸型亲水扩链剂二羟甲基戊酸,升温至50℃左右,加入90%的亲水单体重量的中和剂三乙胺中和,待反应体系透明后加入二异氰酸酯单体己二异氰酸酯和异佛尔酮二异氰酸酯,升温至95℃,保温1.5小时;加入小分子二元醇扩链剂乙二醇和非离子亲水扩链剂聚乙二醇和聚氧乙烯醚YmerTMN120,在55℃下反应至NCO基含量低于5%;用丙酮调节反应物粘度为400cps,降温至50℃以下,得到聚氨酯预聚体。
(2)聚醛改性羧酸‐非离子型聚氨酯水分散体的制备:
(a)将100g步骤1获得的聚氨酯加入800g去离子水,高速乳化;
(b)加入0.1g异氟尔酮二胺胺类扩链剂,50℃下反应2小时,直到NCO基团含量低于0.5%;
(c)然后在温度为100℃和真空度为0.03Mpa的条件下减压蒸馏脱除溶剂,调整固含量为48%。
(d)调节pH值至7,得聚醛改性羧酸‐非离子型聚氨酯水分散体。
(3)聚醛改性羧酸‐非离子型聚氨酯水分散体的性能:固含量:48%;粘度:500cps;分散体平均粒径(Dp)=104nm;常温贮存稳定性1年;
(4)聚醛改性羧酸‐非离子型聚氨酯水分散体涂料
(a)配方
(b)配制方法和使用
依据上述配方,将聚氨酯分散体、消泡剂、水、成膜助剂等,在适当分散机转速下分散15分钟,得到水性聚氨酯涂料。将获得的聚醛改性羧酸‐非离子型聚氨酯水分散体涂料在常温下固化干燥7天。
(c)聚醛改性羧酸‐非离子型聚氨酯水分散体涂料性能如表所示:
表4 聚醛改性羧酸‐非离子型聚氨酯水分散体木器涂料的综合性能
实施例3
(1)聚氨酯预聚体各组分的用量:
表5
在装有搅拌浆、温度计和冷凝器的反应釜中,加入聚合物二元醇N220、聚丁二烯二元醇、聚醛树脂A81和羧酸型亲水扩链剂二羟甲基丙酸和二羟甲基丁酸,升温至50℃左右,加入95%的亲水单体重量的中和剂三乙胺中和,待反应体系透明后加入二异氰酸酯单体四甲基间苯二亚甲基二异氰酸酯,升温至90℃,保温2小时;加入小分子二元醇扩链剂己二醇,在70℃下反应至NCO基团含量为9%;加入非离子亲水扩链剂聚氧乙烯醚YmerTMN120,在60℃下反应至NCO基含量低于5%;用丙酮调节反应物粘度为500cps,降温至50℃以下,得到聚氨酯预聚体。
(2)聚醛改性羧酸‐非离子型聚氨酯水分散体的制备:
(a)将100g步骤1获得的聚氨酯加入600g去离子水,高速乳化;
(b)加入0.2g异氟尔酮二胺胺类扩链剂,50℃下反应2小时,直到NCO基团含量低于0.5%;
(c)然后在温度为90℃和真空度为0.04Mpa的条件下减压蒸馏脱除溶剂,调整固含量为50%。
(d)调节pH值至7,得聚醛改性羧酸‐非离子型聚氨酯水分散体。
(3)聚醛改性羧酸‐非离子型聚氨酯水分散体的性能:固含量:50%;粘度:700cps;分散体平均粒径(Dp)=117nm;常温贮存稳定性1年;耐钙离子稳定性优异;对成膜助剂容忍度优异;
(4)聚醛改性羧酸‐非离子型聚氨酯水分散体涂料
(a)配方
(b)配制方法和使用
依据上述配方,将聚氨酯分散体、消泡剂、水、成膜助剂等,在适当分散机转速下分散15分钟,得到水性聚氨酯涂料。将获得的聚醛改性羧酸‐非离子型聚氨酯水分散体涂料在常温下固化干燥7天。
(c)聚醛改性羧酸‐非离子型聚氨酯水分散体涂料性能如表所示:
表6 聚醛改性羧酸‐非离子型聚氨酯水分散体木器涂料的综合性能
实施例4
(1)聚氨酯预聚体各组分的用量:
表7
在装有搅拌浆、温度计和冷凝器的反应釜中,加入聚合物二元醇N220和聚四氢呋喃二元醇、聚醛树脂A81和羧酸型亲水扩链剂二羟甲基丙酸和二羟甲基丁酸,升温至50℃,加入中和剂三乙胺1.4g中和(100%的羧酸型亲水单体重量),待反应体系透明后加入二异氰酸酯单体异氟尔酮二异氰酸酯,升温至85℃,保温1小时;加入小分子二元醇扩链剂环己二醇,在80℃下反应至NCO基团含量为10%;加入非离子亲水扩链剂聚乙二醇,在65℃下反应至NCO基含量低于5%;用丙酮调节反应物粘度为1000cps,降温至50℃以下,得到聚氨酯预聚体。
(2)聚醛改性羧酸‐非离子型聚氨酯水分散体的制备:
(a)将100g步骤1获得的聚氨酯加入400g去离子水,高速乳化;
(b)加入0.1g乙二胺胺类扩链剂,50℃下反应2小时,直到NCO基团含量低于0.5%;
(c)然后在温度为80℃和真空度为0.04Mpa的条件下减压蒸馏脱除溶剂,调整固含量为52%。
(d)调节pH值至8,得聚醛改性羧酸‐非离子型聚氨酯水分散体。
(3)聚醛改性羧酸‐非离子型聚氨酯水分散体的性能:固含量:52%;粘度:800cps;分散体平均粒径(Dp)=137nm;常温贮存稳定性1年;耐钙离子稳定性优异;对成膜助剂容忍度优异;
(4)聚醛改性羧酸‐非离子型聚氨酯水分散体
(a)配方
(b)配制方法和使用
依据上述配方,将聚氨酯分散体、消泡剂、水、成膜助剂等,在适当分散机转速下分散15分钟,得到水性聚氨酯涂料。将获得的聚醛改性羧酸‐非离子型聚氨酯水分散体涂料在常温下固化干燥7天。
(c)聚醛改性羧酸‐非离子型聚氨酯水分散体涂料性能如表所示:
表8 聚醛改性羧酸‐非离子型聚氨酯水分散体木器涂料的综合性能
实施例5
(1)聚氨酯预聚体各组分的用量:
表9
在装有搅拌浆、温度计和冷凝器的反应釜中,加入CMA‐1044聚酯二元醇、聚醛树脂A81和羧酸型亲水扩链剂二羟甲基丙酸,升温至50℃左右,加入100%的亲水单体重量的中和剂三乙胺中和,待反应体系透明后加入二异氰酸酯单体二苯基甲烷二异氰酸酯,升温至80℃,保温1.5小时;加入小分子二元醇扩链剂丙二醇和非离子亲水扩链剂聚乙二醇单甲醚,在60℃下反应至NCO基含量低于5%;用丙酮调节反应物粘度为2000cps,降温至50℃以下,得到聚氨酯预聚体。
(2)聚醛改性羧酸‐非离子型聚氨酯水分散体的制备:
(a)将100g步骤1获得的聚氨酯加入200g去离子水,高速乳化;
(b)加入0.1g己二胺胺类扩链剂,50℃下反应2小时,直到NCO基团含量低于0.5%;
(c)然后在温度为80℃和真空度为0.06Mpa的条件下减压蒸馏脱除溶剂,调整固含量为54%。
(d)调节pH值至7,得聚醛改性羧酸‐非离子型聚氨酯水分散体。
(3)聚醛改性羧酸‐非离子型聚氨酯水分散体的性能:固含量:54%;粘度:1000cps;分散体平均粒径(Dp)=126nm;常温贮存稳定性1年;
(4)高固含量聚氨酯水性涂料
(a)配方
(b)配制方法和使用
依据上述配方,将聚氨酯分散体、消泡剂、水、成膜助剂等,在适当分散机转速下分散15分钟,得到水性聚氨酯涂料。将获得的聚醛改性羧酸‐非离子型聚氨酯水分散体涂料在常温下固化干燥7天。
(c)聚醛改性羧酸‐非离子型聚氨酯水分散体涂料性能如表所示:
表10 聚醛改性羧酸‐非离子型聚氨酯水分散体木器涂料的综合性能
实施例6
(1)聚氨酯预聚体各组分的用量:
表11
在装有搅拌浆、温度计和冷凝器的反应釜中,加入聚合物二元醇N210和聚己内酯二元醇PCL‐1000、聚醛树脂A81和羧酸型亲水扩链剂二羟甲基丙酸和二羟甲基戊酸,升温至50℃左右,待反应体系透明后加入二异氰酸酯单体,升温至70℃,保温2小时;加入小分子二元醇扩链剂二乙二醇和非离子亲水扩链剂聚氧乙烯醚YmerTMN120,在70℃下反应至NCO基含量低于5%;加入中和剂中和,用丙酮调节反应物粘度为3000cps,降温至50℃以下,得到聚氨酯预聚体。
(2)聚醛改性羧酸‐非离子型聚氨酯水分散体制备:
(a)将100g步骤1获得的聚氨酯加入400g去离子水,高速乳化;
(b)加入0.2g乙二胺胺类扩链剂,50℃下反应2小时,直到NCO基团含量低于0.5%;
(c)然后在温度为70℃和真空度为0.07Mpa的条件下减压蒸馏脱除溶剂,调整固含量为54%。
(d)调节pH值至6,得聚醛改性羧酸‐非离子型聚氨酯水分散体。
(3)聚醛改性羧酸‐非离子型聚氨酯水分散体的性能:固含量:54%;粘度:1270cps;分散体平均粒径(Dp)=143nm;常温贮存稳定性1年;
(4)聚醛改性羧酸‐非离子型聚氨酯水分散体水性涂料
(a)配方
(b)配制方法和使用
依据上述配方,将聚氨酯分散体、消泡剂、水、成膜助剂等,在适当分散机转速下分散15分钟,得到水性聚氨酯涂料。将获得的聚醛改性羧酸‐非离子型聚氨酯水分散体涂料在常温下固化干燥7天。
(c)聚醛改性羧酸‐非离子型聚氨酯水分散体涂料性能如表所示:
表12 聚醛改性羧酸‐非离子型聚氨酯水分散体木器涂料的综合性能
实施例7
(1)聚氨酯预聚体各组分的用量:
表13
在装有搅拌浆、温度计和冷凝器的反应釜中,加入聚合物二元醇聚丙烯酸酯二元醇PA‐4000、聚醛树脂A81和羧酸型亲水扩链剂二羟甲基丙酸,升温至50℃左右,加入115%的亲水单体重量的中和剂三乙胺中和,待反应体系透明后加入二异氰酸酯单体苯二亚甲基二异氰酸酯,升温至75℃,保温1.5小时;加入小分子二元醇扩链剂二甘醇和非离子亲水扩链剂聚乙二醇单甲醚,在60℃下反应至NCO基含量低于5%;用丙酮调节反应物粘度为800cps,降温至50℃以下,得到聚氨酯预聚体。
(2)聚醛改性羧酸‐非离子型聚氨酯水分散体的制备:
(a)将100g步骤1获得的聚氨酯加入500g去离子水,高速乳化;
(b)加入0.2g三乙烯四胺胺类扩链剂,50℃下反应2小时,直到NCO基团含量低于0.5%;
(c)然后在温度为60℃和真空度为0.08Mpa的条件下减压蒸馏脱除溶剂,调整固含量为56%。
(d)调节pH值至7,得聚醛改性羧酸‐非离子型聚氨酯水分散体。
(3)聚醛改性羧酸‐非离子型聚氨酯水分散体的性能:固含量:56%;粘度:1460cps;分散体平均粒径(Dp)=149nm;常温贮存稳定性1年;耐钙离子稳定性优异;对成膜助剂容忍度优异;
(4)聚醛改性羧酸‐非离子型聚氨酯水分散体水性涂料
(a)配方
(b)配制方法和使用
依据上述配方,将聚氨酯分散体、消泡剂、水、成膜助剂等,在适当分散机转速下分散15分钟,得到水性聚氨酯涂料。将获得的聚醛改性羧酸‐非离子型聚氨酯水分散体涂料在常温下固化干燥7天。
(c)聚醛改性羧酸‐非离子型聚氨酯水分散体涂料性能如表所示:
表14 聚醛改性羧酸‐非离子型聚氨酯水分散体木器涂料的综合性能
实施例8
(1)聚氨酯预聚体各组分的用量:
表15
在装有搅拌浆、温度计和冷凝器的反应釜中,加入聚合物二元醇Diol2000聚醚多元醇、
聚醛树脂A81和羧酸型亲水扩链剂二羟甲基丙酸,升温至50℃左右,加入120%的亲水单体重量的中和剂中和,待反应体系透明后加入二异氰酸酯单体异佛尔酮二异氰酸酯,升温至60℃,保温2.0小时;加入小分子二元醇扩链剂1,4‐丁二醇和非离子亲水扩链剂聚氧乙烯醚YmerTMN120,在70℃下反应至NCO基含量低于5%;用丙酮调节反应物粘度为1000cps,降温至50℃以下,得到聚氨酯预聚体。
(2)聚醛改性羧酸‐非离子型聚氨酯水分散体的制备:
(a)将100g步骤1获得的聚氨酯加入100g去离子水,高速乳化;
(b)加入0.1g乙二胺胺类扩链剂,50℃下反应2小时,直到NCO基团含量低于0.5%;
(c)然后在温度为50℃和真空度为0.1Mpa的条件下减压蒸馏脱除溶剂,调整固含量为60%。
(d)调节pH值至6,得聚醛改性羧酸‐非离子型聚氨酯水分散体。
(3)聚醛改性羧酸‐非离子型聚氨酯水分散体的性能:固含量:60%;粘度:1680cps;分散体平均粒径(Dp)=500nm;常温贮存稳定性1年;
(4)聚醛改性羧酸‐非离子型聚氨酯水分散体涂料
(a)配方
(b)配制方法和使用
依据上述配方,将聚氨酯分散体、消泡剂、水、成膜助剂等,在适当分散机转速下分散15分钟,得到水性聚氨酯涂料。将获得的聚醛改性羧酸‐非离子型聚氨酯水分散体涂料在常温下固化干燥7天。
(c)聚醛改性羧酸‐非离子型聚氨酯水分散体涂料性能如表所示:
表16 聚醛改性羧酸‐非离子型聚氨酯水分散体涂料的综合性能
Claims (10)
1.聚醛改性羧酸‐非离子型聚氨酯水分散体的制备方法,其特征在于包括如下步骤:
1)聚氨酯预聚体的制备:以质量份数计,在反应釜中,加入30~60份聚合物二元醇、1~10份聚醛树脂和1‐5份羧酸型亲水扩链剂,升温至45℃‐55℃,加入中和剂中和,待反应体系透明后加入23~60份二异氰酸酯单体,升温至60℃~100℃,保温1.0小时~2.0小时;加入1‐10份小分子二元醇扩链剂和2‐10份非离子亲水扩链剂,在50~70℃下反应至NCO基含量低于5%;调节反应物粘度为300-3000cps,降温,得到聚氨酯预聚体;
2)乳化和扩链:将聚氨酯预聚体加入去离子水中乳化,随后加入胺类扩链剂,反应至NCO含量低于0.5%;
3)蒸馏脱除溶剂并调节pH值至6‐8,得到所述的聚醛改性羧酸‐非离子型聚氨酯水分散体;
所述的中和剂为N,N‐二甲基乙醇胺、氨水、三乙胺其中一种或两种以上的混合物;
所述聚合物二元醇的数均分子质量为300-10000,羟值为30-200mgKOH/g;
所述的二异氰酸酯单体为甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、已二异氰酸酯、异佛尔酮二异氰酸酯、四甲基间苯二亚甲基二异氰酸酯(m-TMXDI)、苯二亚甲基二异氰酸酯一种或多种;
所述的小分子扩链剂为乙二醇、丙二醇、1,4-丁二醇,1,6-己二醇,1,4-环己二醇、二乙二醇、二甘醇其中一种或多种;
所述的羧酸型亲水扩链剂为二羟甲基丙酸、二羟甲基丁酸和二羟甲基戊酸其中一种或多种;
所述的非离子型亲水扩链剂为聚氧乙烯醚YmerTMN120、聚乙二醇和聚乙二醇单甲醚其中一种或多种;
所述的胺类扩链剂为肼、乙二胺、己二胺、异佛尔酮二胺、二乙烯三胺何三乙烯四胺中的一种或多种。
2.根据权利要求1所述的聚醛改性羧酸‐非离子型聚氨酯水分散体的制备方法,其特征在于,所述中和剂的用量为羧酸型亲水单体重量的80‐120%。
3.根据权利要求1所述的聚醛改性羧酸‐非离子型聚氨酯水分散体的制备方法,其特征在于,所述调节反应物粘度为300-3000cps为通过加入丙酮调节。
4.根据权利要求1所述的聚醛改性羧酸‐非离子型聚氨酯水分散体的制备方法,其特征在于,所述降温为降温至50℃以下。
5.根据权利要求1所述的聚醛改性羧酸‐非离子型聚氨酯水分散体的制备方法,其特征在于,所述胺类扩链剂的用量为聚氨酯预聚体质量的0.1%~0.2%。
6.根据权利要求1所述的聚醛改性羧酸‐非离子型聚氨酯水分散体的制备方法,其特征在于,所述去离子水的加入量为聚氨酯预聚体重量的1~10倍。
7.根据权利要求1所述的聚醛改性羧酸‐非离子型聚氨酯水分散体的制备方法,其特征在于,所述聚合物二元醇的CMA-1044聚酯二元醇、T-1136聚酯二元醇、N210聚醚多元醇、N220聚醚多元醇、Diol1000聚醚多元醇、Diol2000聚醚多元醇、聚碳酸酯二元醇、聚四氢呋喃二元醇、聚丙烯酸酯二元醇、聚丁二烯二元醇和聚己内酯二元醇一种或多种。
8.根据权利要求1所述的聚醛改性羧酸‐非离子型聚氨酯水分散体的制备方法,其特征在于,所述蒸馏脱除溶剂是在温度为50~120℃和真空度为0.02~0.1Mpa的条件下进行。
9.一种聚醛改性羧酸‐非离子型聚氨酯水分散体,其特征在于其由权利要求1‐8任一项所述制备方法制得,其固含量为45~60%,粘度为50~2000CP,乳胶粒径为50~500纳米。
10.权利要求9所述聚醛改性羧酸‐非离子型聚氨酯水分散体在水性涂料中的应用,其特征在于,该涂料含有30~90%聚醛改性羧酸‐非离子型聚氨酯水分散体。
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Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105062341A (zh) * | 2015-07-31 | 2015-11-18 | 华南理工大学 | 具有助成膜功能的聚醛改性水性聚氨酯及其制备方法与应用 |
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Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6362273B1 (en) * | 1997-09-26 | 2002-03-26 | Avecia Bv | Aqueous polymer dispersions |
CN1344285A (zh) * | 1999-03-17 | 2002-04-10 | 纳幕尔杜邦公司 | 高固体含量的环氧化物、蜜胺和异氰酸酯组合物 |
CN1483777A (zh) * | 2003-07-21 | 2004-03-24 | 深圳市飞扬实业有限公司 | 高丰满度高清晰度环保型聚氨酯哑光清漆 |
CN102775898A (zh) * | 2012-08-16 | 2012-11-14 | 广州立邦涂料有限公司 | 无溶剂型聚氨酯自流平地坪漆及其制备方法 |
-
2014
- 2014-08-25 CN CN201410422012.3A patent/CN104211899B/zh not_active Expired - Fee Related
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6362273B1 (en) * | 1997-09-26 | 2002-03-26 | Avecia Bv | Aqueous polymer dispersions |
CN1344285A (zh) * | 1999-03-17 | 2002-04-10 | 纳幕尔杜邦公司 | 高固体含量的环氧化物、蜜胺和异氰酸酯组合物 |
CN1483777A (zh) * | 2003-07-21 | 2004-03-24 | 深圳市飞扬实业有限公司 | 高丰满度高清晰度环保型聚氨酯哑光清漆 |
CN102775898A (zh) * | 2012-08-16 | 2012-11-14 | 广州立邦涂料有限公司 | 无溶剂型聚氨酯自流平地坪漆及其制备方法 |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105062341A (zh) * | 2015-07-31 | 2015-11-18 | 华南理工大学 | 具有助成膜功能的聚醛改性水性聚氨酯及其制备方法与应用 |
CN105062341B (zh) * | 2015-07-31 | 2018-06-29 | 华南理工大学 | 具有助成膜功能的聚醛改性水性聚氨酯及其制备方法与应用 |
CN107090066A (zh) * | 2017-05-27 | 2017-08-25 | 岳阳市英泰材料科技有限公司 | 自乳化水性脲‑异丁醛‑甲醛树脂及其制备方法 |
CN107522839A (zh) * | 2017-08-30 | 2017-12-29 | 广东德美精细化工集团股份有限公司 | 一种无溶剂具备阴离子和非离子特性的水性聚氨酯树脂制备方法 |
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