CN114181353B - 一种改性水性聚氨酯组合物的合成及应用 - Google Patents
一种改性水性聚氨酯组合物的合成及应用 Download PDFInfo
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- CN114181353B CN114181353B CN202111458188.0A CN202111458188A CN114181353B CN 114181353 B CN114181353 B CN 114181353B CN 202111458188 A CN202111458188 A CN 202111458188A CN 114181353 B CN114181353 B CN 114181353B
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- diisocyanate
- isocyanate
- terminated prepolymer
- acrylate
- acid
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Abstract
本发明提供一种改性水性聚氨酯组合物的合成方法,包括如下步骤:合成异氰酸酯封端的预聚物,加入改性单体、多元胺扩链剂及乳化剂制得预改性乳液,再进行自由基聚合,最后脱除所有低沸点溶剂得改性水性聚氨酯组合物;其中,所述改性单体包括烯属不饱和单体中的至少一种。合成的树脂成本低廉,性能优异,满足单、双组分木器漆涂料应用需求,特别适用于有严苛活化期要求的双组份木器漆涂料应用。
Description
技术领域
本发明涉及一种改性水性聚氨酯组合物及制备方法和应用,特别涉及一种双组份水性木器漆涂料的应用领域。
背景技术
随着经济物质生活水平的提高,人们的健康环保意识逐渐增强。传统溶剂型木器漆虽然具有良好的丰满度、耐磨性、耐化学溶剂等优异性能,但其生产、施工中挥发的大量有机化合物VOC,对人体健康、生态环境带来严重的危害。国家环保法规日趋严格,溶剂型木器漆市场生存空间愈来愈受限制,推动木器漆涂料油改水已成行业的共识。
单组分水性木器漆具有施工便捷、干燥速度快、耐候性好和价格相对便宜等优点,在水性木器涂料中发展最为迅猛。但在某些对应用性能要求严苛的领域,单组分水性木器漆涂料存在丰满度、抗划伤、耐化学品性等方面的致命缺陷,无法满足于高端涂装要求,很难撼动溶剂型木器涂料的市场地位。涂膜物化性能与传统溶剂型双组份木器涂料相媲美的双组份水性木器涂料很快吸引了人们的目光,可以及时有效地弥补单组分水性木器涂料性能上的不足。
与单组分水性木器涂料不同的是,双组份水性木器涂料在成膜过程中产生化学交联反应,而多异氰酸酯是当前双组份水性木器涂料市场中综合性能最好的交联剂,常温就可以与树脂的羟基、水等发生反应生成氨基甲酸酯或脲;可预见的,有反应发生势必造成成品漆粘度的波动,并且随着漆品的放置,双组份水性木器涂料涂膜的物化性能也会受出现波动,如硬度、光泽度等。双组份木器涂料要想在家具生产中得到较好应用,就必须保证涂料在施工过程中物化性能有稳定的保障,也就是行业内所说的使用活化期稳定问题,这也是双组份水性木器涂料发展过程中亟需解决的问题。未来随着对水性木器涂料性能要求的不断提高,未来双组分涂装会逐渐成为行业主流,这就对乳液的双组分活化期稳定性提出了更高的要求,更稳定的粘度、更长的开放时间、涂膜物化性质稳定是产品品质的关键。
中国专利申请CN106609109A公开了一种木器用双组份改性水性聚氨酯涂料,由45-50%的聚醚多元醇、30-35%的环氧树脂、5-10%的异佛尔酮二异氰酸酯、5-10%的亲水扩链剂、2-5%的交联剂和5-15%的丙烯酸酯合成,其环氧改性稳定性较差,制备的水性聚氨酯乳液不通透,难满足木器涂料清透需求;另外低含量的丙烯酸酯改性其单双组分漆膜硬度还有较大提升空间。
美国专利US 5137961描述了一种不含表面活性剂的水性聚合物分散体,其包含阴离子水分散性聚氨酯和乙烯基聚合物,其中:聚氨酯与乙烯基聚合物的重量比为80∶20至30∶70,不含表面活性剂虽然对性能有一定提升,但乙烯基聚合物聚合过程中沉淀物生成较多,不利于生产。
中国专利申请CN108164650A中公开了一种端烯基非离子型水性聚氨酯改性丙烯酸酯乳液的合成方法,利用端烯基聚乙二醇合成含双键的非离子型水性聚氨酯单体,然后将丙烯酸酯类单体与所制备的端烯基聚氨酯通过乳液聚合方法聚合,得水性聚氨酯改性丙烯酸酯树脂,虽然利用丙烯酸酯和端烯基非离子水性聚氨酯进行接枝改性,在性能方面会有一定提升,但由于聚氨酯部分大的位阻效应其端烯基接枝效率很低,实际应用价值不大,并且以非离子基团做亲水主体,由于氢键作用体系粘度波动较大,对于双组份活化期有不利影响。
因此,如何开发一款满足单双组分性能需求、双组份活化期表现优异、性能佳的水性木器涂料,已成为本领域亟待解决的技术难点之一。
发明内容
本发明为弥补现有技术存在的不足,提供一种改性水性聚氨酯组合物的制备方法,本发明提供的制备方法简单可控,合成的树脂成本低廉,性能优异,满足单、双组分木器漆涂料应用需求,特别适用于有严苛活化期要求的双组份木器漆涂料应用。
本发明为达到其目的,采用的技术方案如下:
本发明第一方面提供一种改性水性聚氨酯组合物的制备方法,包括如下步骤:
(1)合成异氰酸酯封端的预聚物,
(2)加入低沸点有机溶剂,与异氰酸酯封端预聚物充分混合溶解,倒入溶有中和剂且高速剪切的水中,分散结束后加入多元胺扩链剂和乳化剂得预改性乳液,
其中,在步骤(1)和/或(2)中加入改性单体,
(3)加入引发剂进行自由基聚合,最后脱除低沸点有机溶剂。
其中,所述异氰酸酯封端预聚物为包含如下各组分的原料混合反应制得:多异氰酸酯、大分子多元醇、亲水扩链剂;不含小分子多元醇扩链剂;
其中,基于异氰酸酯封端的预聚物的质量(即多异氰酸酯、大分子多元醇、亲水扩链剂质量之和),各组分的用量分别为:
1)所述多异氰酸酯用量为异氰酸酯封端预聚物质量的25-50wt%;
2)所述大分子多元醇用量为异氰酸酯封端预聚物质量的45-70%;
3)所述亲水扩链剂用量为异氰酸酯封端预聚物质量的3-8wt%。
所述改性单体的用量为异氰酸酯封端预聚物质量的1.2-2.4倍,优选为1.4-2.0倍;
其中,步骤(2)中,改性单体添加方式可以是合成异氰酸酯封端预聚物过程中和/或合成异氰酸酯封端预聚物结束后和/或异氰酸酯封端预聚物分散后加入。
步骤(2)中,低沸点有机溶剂的加入量优选是异氰酸酯封端预聚物质量的0.7-1.2倍;
中和剂用量为异氰酸酯封端预聚物质量的2-6%;
多元胺扩链剂用量为异氰酸酯封端预聚物质量的4-8%;
乳化剂用量为异氰酸酯封端预聚物质量的0-10%,优选3-7%。
步骤(3)中,所述引发剂的用量为所述改性单体总质量的0.05-0.4%,优选为0.1-0.2%。
本发明的制备方法,所述多异氰酸酯可以是脂肪族、脂环族、芳香族或者其混合物,包括甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、异佛尔酮二异氰酸酯、六亚甲基二异氰酸酯、戊二异氰酸酯、六氢甲苯二异氰酸酯、三甲基己烷二异氰酸酯、苯二甲撑二异氰酸酯、1,4-环己烷二异氰酸酯、十二烷基二异氰酸酯、1,5-萘二异氰酸酯和二环己基甲烷二异氰酸酯等等中的一种或多种,优选二环己基甲烷二异氰酸酯。
本发明的制备方法,所述大分子多元醇包括数均分子量为400-4000,进一步优选数均分子量为600-2000的本领域已知的含异氰酸酯反应性基团的聚醚酯、和/或至少一种主链和/或侧链含有聚氧化乙烯链段的一元醇和/或二元醇;
优选的,所述本领域已知的含异氰酸酯反应性基团的聚醚酯,可以是聚醚多元醇、聚酯多元醇、聚碳酸酯多元醇,包括聚乙二醇、聚丙二醇、聚乙二醇-丙二醇、聚四氢呋喃醚二醇、二聚酸聚酯多元醇、聚烯烃多元醇、聚己内酯二元醇、聚碳酸酯二元醇、聚己二酸乙二醇酯二元醇、聚己二酸1,4-丁二醇酯二元醇、聚己二酸新戊二醇酯二元醇、聚己二酸1,6-己二醇酯二元醇和聚己二酸新戊二醇酯1,6-己二醇酯二元醇中的一种或多种,进一步数均分子量为1000道尔顿的聚丙二醇醚二元醇;
优选的,所述主链和/或侧链含有聚氧化乙烯链段的一元醇和/或二元醇,可以是含有聚氧化乙烯链段的聚合单元中含有90-100wt%的环氧乙烷,优选为Tego Chemie公司的D-3403、Perstrop公司的YmerTM N120和韩国乐天公司的MPEG520、MPEG1200、MPEG2200中的一种或多种,进一步优选为Perstrop公司的YmerTM N120和/或韩国乐天公司的MPEG1200。
本发明的制备方法,所述亲水扩链剂包括带有离子或潜在离子基团的可与异氰酸酯反应的化合物,包括二羟甲基丙酸、二羟甲基丁酸、氨基酸、氨基磺酸盐、酒石酸、N,N-二羟甲基马来酰胺酸、二氨基苯甲酸、二羟基丙磺酸钠等中的一种或多种,优选二羟甲基丙酸。
本发明的制备方法,所述中和剂包括氢氧化纳,氢氧化钾,三乙胺,N,N-二甲基乙醇胺,二甲基环己胺,三乙醇胺,甲基二乙醇胺,二异丙醇胺,乙基二异丙胺,二异丙基环己基胺,N-甲基吗啉,2-氨基-2-甲基-1-丙醇,氨水中的一种或多种。优选的中和剂是氢氧化钠、三乙胺和/或N,N-二甲基乙醇胺,进一步优选N,N-二甲基乙醇胺。
本发明的制备方法,所述多元胺扩链剂为至少含有两个活泼氢的有机或无机伯胺或仲胺官能的化合物,包括乙二胺、2-甲基1,5-戊二胺、异佛尔酮二胺、肼及其衍生物、羟乙基乙二胺、己二胺、二乙烯三胺、三乙烯四胺、环己烷二胺、苯二胺、甲苯二胺、二环己基甲烷二胺等及混合物,优选异佛尔酮二胺。
本发明的制备方法,所述乳化剂包括具有5000-9000数均分子量、20000-50000重均分子量的含有乳化基团或潜在乳化基团的离子或非离子型化合物,其拥有如下结构通式:
其中,n=8-22,m=8-44。
本发明的制备方法,所述改性单体为可发生自由基聚合的烯属不饱和单体,包括丙烯酸甲酯、丙烯酸磷酸酯、硅氧烷丙烯酸酯、甲基丙烯酸烯丙酯、丙烯酸乙酯、丙烯酸羟丙酯、丙烯酸丙酯、丙烯酸丁酯、甲基丙烯酸甲酯、甲基丙烯酸乙酯、三羟甲基丙烷三丙烯酸酯、季戊四醇三丙烯酸酯、甲基丙烯酸羟乙酯、甲基丙烯酸丁酯、四氢呋喃丙烯酸酯、苯乙烯、烯丙基甲基苯乙烯、丙烯酸异冰片酯和丙烯酸异辛酯等等烯属不饱和单体中的一种或多种,优选甲基丙烯酸甲酯。
本发明的制备方法,所述低沸点有机溶剂为沸点低于100℃的有机溶剂,包括丙酮、甲基乙基酮、环己烷、二氯甲烷、二氯乙烷、三氯乙烷、乙酸乙酯、戊烷、庚烷、己烷中的一种或多种,优选为丙酮。
本发明的制备方法,所述引发剂为氧化还原体系。优选的,所述氧化剂包括过硫酸氨、过硫酸钠、过硫酸钾过氧化二叔丁基、过氧化苯甲酰、过氧化氢、异丙苯过氧化氢和叔丁基过氧化氢中的一种或多种,进一步优选叔丁基过氧化氢;优选的,所述还原剂包括保险粉、N,N-二甲基苯胺、硫酸亚铁、硝酸银、硫醇、氯化亚铁、四乙烯亚胺、焦亚硫酸钠、吊白块、亚硫酸氢钠和异抗坏血酸中的一种或多种,进一步优选焦亚硫酸钠。
本发明的制备方法,制备所述异氰酸酯封端预聚物时所采用的反应温度优选为75-85℃;
优选的,所述改性单体与异氰酸酯封端预聚物混合溶解在20-70℃下进行;
优选的,所述预改性乳液引发聚合的引发温度为20-60℃。
本发明的制备方法,在所述引发聚合之后还包括如下步骤:通过减压蒸馏方式脱除引发聚合后所得改性水性聚氨酯组合物中的低沸点溶剂,方法为行业公知。
本发明制备的组合物,其平均粒子尺寸在50-150nm范围内,较佳方案中在70-120nm范围内。
本发明第二方面提供上述的制备方法制得的改性水性聚氨酯组合物的应用,优选适用于单、双组分木器漆涂料,特别优选适用于有严苛活化期要求的双组份木器漆涂料。
本发明第三方面还提供一种木器漆涂料,该木器漆涂料中包括上述的制备方法制得的改性水性聚氨酯组合物。
本发明提供的技术方案具有如下效益:
本发明改性水性聚氨酯组合物在合成过程中,通过配方设计,在合成阶段未引入除亲水扩链剂外的其他小分子多元醇扩链剂,设计聚氨酯拥有5000-9000的数均分子量、20000-50000的重均分子量,这样使得亲水基团均匀分布于聚氨酯链段之上并且形成类似于乳化剂的“Y”型结构,这种结构的益处在于,在制备水性木器涂料时,在不影响增稠剂对涂料增稠响应的前提下保证了整个浆料体系增稠的均一性,表现在最大程度保证了浆料粘度的稳定性。
本发明制得的改性水性聚氨酯组合物,令人惊讶的,通过添加本发明的乳化剂,使得在双组份木器涂料使用过程中优异的活化期不仅表现在拥有稳定的粘度,而且浆料开放时间更久、涂膜光泽和硬度不受影响;此乳化剂拥有与改性水性聚氨酯组合物中聚氨酯部分相似的数均和重均分子量,在制备改性水性聚氨酯组合物聚氨酯封端预聚物乳化完毕后加入,更有利于与聚氨酯分子链间的缠绕,以达到最佳乳化效果,并且在单体溶胀过程中促进单体向乳胶粒内部迁移,提高聚合稳定性,降低出渣量;在双组份涂料放置过程中,随着固化剂与水分子反应疏水性变强,体系增稠响应的提高,此乳化剂依靠这种分子量结构设计的羧酸根和聚氧化乙烯链段能起到很好的降粘作用,维持活化期的稳定;出人意料的,拥有此结构数均和重均分子量的乳化剂,在木器涂料应用过程中,不会影响单、双组分涂膜应用性能,与传统乳化剂相比其添加量范围也远超其他。
具体实施方式
为了更好的理解本发明的技术方案,下面结合实施例进一步阐述本发明的内容,但本发明的内容并不仅仅局限于以下实施例。
实施例或对比例中的“%”若未特别说明,均指“wt%”。
下面对实施例或对比例中所用到测试方法进行介绍:
粒径测试方法:采用马尔文粒径仪。
pH测试方法:采用瑞士万通pH计。
以下实施例或对比例制得的乳液在制备涂料时所用的配方见下表1:
表1
以下实施例或对比例制得的乳液在测试活化期时所用的配方见下表2:
表2
测试实施例与对比例的应用性能的方法介绍如下:
样板施工流程:基材—水性底擦色—水性头度底漆—水性Glaze—水性透明底漆—水性透明底漆—水性面修色—水性面漆。
耐醇测试:50%浓度乙醇溶液在成品样板上分别浸泡1h、24h,取下擦干后观察漆膜状态。
耐水测试:去离子水在成品样板上浸泡24h,取下擦干水渍后观察漆膜状态。
活化期测试方法:取现配好的双组份漆用涂四号杯调节粘度至60秒左右,放入预先调节好的35℃恒温烘箱内,计时每隔1小时取出测试漆样品粘度,记录每次粘度测试数据,观察粘度变化趋势,以前4小时内粘度变化最小者为最优。
光泽度测试方法:根据《漆膜光泽测定法》GB 1743-79,测试60°角光泽。
摆杆硬度测试方法:根据《漆膜硬度测定法摆杆阻尼试验》GB/T1730-1993,测试硬度。
下面对实施例或对比例中所使用的原料进行介绍:
HMDI(二环己基甲烷二异氰酸酯,NCO含量约为32.06%,万华化学集团股份有限公司);
PPG1000(聚环氧丙烷醚二元醇,羟值112mgKOH/g,数均分子量=1000,官能度为2,万华化学集团股份有限公司);
PNA1000(聚己二酸新戊二醇酯二元醇,羟值112mgKOH/g,数均分子量=1000,官能度为2,万华化学集团股份有限公司);
MPEG1200(甲氧基聚乙二醇醚,韩国乐天)
DMPA(二羟甲基丙酸,柏斯托);
BiCat8108(有机铋催化剂,美国领先)
DMEA(N,N-二甲基乙醇胺,德国BASF公司);
IPDA(异佛尔酮二胺,万华化学集团股份有限公司)
MMA(甲基丙烯酸甲酯,齐鲁石化);
St(苯乙烯,中石化)
LCN407(乳化剂,克莱恩)
焦亚硫酸钠(西陇化工股份有限公司)
TBHP(叔丁基过氧化氢,西陇化工股份有限公司)
268(异氰酸酯固化剂,万华化学集团股份有限公司)
U300(增稠剂,万华化学集团股份有限公司)
U604(增稠剂,万华化学集团股份有限公司)
U902(增稠剂,万华化学集团股份有限公司)
Tego 825(消泡剂,德国迪高公司)
Tego 902W(消泡剂,德国迪高公司)
Tego4100(润湿剂,德国迪高公司)
Tego410(手感剂,德国迪高公司)
BYK-7420ES(防沉剂,毕克化学)
Syloid ED-30(Grace,消光粉)
Neptune 5223NR(三叶,水性蜡粉)
Aquacer 539(蜡乳液,毕克化学)
DPM(成膜助剂,陶氏化学)
DPnB(成膜助剂,陶氏化学)
PMA(丙二醇甲醚醋酸酯,济南广宇化工有限公司)。
C501,乳化剂,由SMA树脂(苯乙烯与马来酸酐共聚物)与聚醚胺开环反应制得,其制备过程包括:将等摩尔量的SMA树脂和聚醚胺在80℃-140℃温度下开环反应6h,得C501乳化剂,分散溶解在溶有氨水的去离子水中。
对比例1:
向装有回流冷凝管、温度计和机械搅拌的四口烧瓶中加入78.6g HMDI(二环己基甲烷二异氰酸酯)、120gPPG1000(聚环氧丙烷醚二元醇)、2.4g MPEG1200、10.6g二羟甲基丙酸、0.1g BiCat8108,42g丙酮,升温至80℃反应直至理论NCO值,停止反应。降温至60℃以下,加入148g丙酮、211gMMA,搅拌均匀降温至40℃以下,分散杯中称取825g去离子水将7gDMEA溶解其中,在1500r/min的高速剪切条件下20分钟内倒入预聚体,分散完毕后加入四倍水稀释的12gIPDA和14gLCN407,得改性水性聚氨酯组合物预乳液。将此乳液转移至装有回流冷凝管、温度计和机械搅拌的四口烧瓶中,加入126gMMA,升温至32℃搅拌1h,依次加入0.35g叔丁基过氧化氢和0.35g焦亚硫酸钠引发自由基聚合,聚合完毕后将该乳液通过减压蒸馏方式除去其中的丙酮,得粒径86nm半透明泛蓝光的改性水性聚氨酯组合物。
对比例2:
向装有回流冷凝管、温度计和机械搅拌的四口烧瓶中加入78.6g HMDI(二环己基甲烷二异氰酸酯)、120gPPG1000(聚环氧丙烷醚二元醇)、2.4g MPEG1200、10.6g二羟甲基丙酸、0.1g BiCat8108,42g丙酮,升温至80℃反应直至理论NCO值,停止反应。降温至60℃以下,加入148g丙酮、211gMMA,搅拌均匀降温至40℃以下,分散杯中称取825g去离子水将7gDMEA溶解其中,在1500r/min的高速剪切条件下20分钟内倒入预聚体,分散完毕后加入四倍水稀释的12gIPDA,得改性水性聚氨酯组合物预乳液。将此乳液转移至装有回流冷凝管、温度计和机械搅拌的四口烧瓶中,加入126gMMA,升温至32℃搅拌1h,依次加入0.35g叔丁基过氧化氢和0.35g焦亚硫酸钠引发自由基聚合,聚合完毕后将该乳液通过减压蒸馏方式除去其中的丙酮,得粒径97nm半透明泛蓝光的改性水性聚氨酯组合物。
实施例1:
向装有回流冷凝管、温度计和机械搅拌的四口烧瓶中加入78.6g HMDI(二环己基甲烷二异氰酸酯)、120gPNA1000(聚己二酸新戊二醇酯二元醇)、2.4gMPEG1200、10.6g二羟甲基丙酸、0.1g BiCat8108、42g丙酮,升温至80℃反应直至理论NCO值,停止反应。
降温至60℃以下,加入148g丙酮、189gMMA,搅拌均匀降温至40℃以下,分散杯中称取825g去离子水将7gDMEA溶解其中,在1500r/min的高速剪切条件下20分钟内倒入预聚体,分散完毕后加入四倍水稀释的12gIPDA和20gC501,得改性水性聚氨酯组合物预乳液。
将此乳液转移至装有回流冷凝管、温度计和机械搅拌的四口烧瓶中,加入189gMMA,升温至32℃搅拌1h,依次加入0.38g叔丁基过氧化氢和0.38g焦亚硫酸钠引发自由基聚合,聚合完毕后将该乳液通过减压蒸馏方式除去其中的丙酮,得粒径80nm半透明泛蓝光的改性水性聚氨酯组合物。
实施例2:
向装有回流冷凝管、温度计和机械搅拌的四口烧瓶中加入74g IPDI(异佛尔酮二异氰酸酯)、132gPPG1000(聚环氧丙烷醚二元醇)、12g二羟甲基丙酸、0.1gBiCat8108、44g丙酮,升温至80℃反应直至理论NCO值,停止反应。
降温至60℃以下,加入154g丙酮、220gMMA,搅拌均匀降温至40℃以下,分散杯中称取825g去离子水将7.97gDMEA溶解其中,在1500r/min的高速剪切条件下20分钟内倒入预聚体,分散完毕后加入四倍水稀释的13.6gIPDA和8gC501,得改性水性聚氨酯组合物预乳液。将此乳液转移至装有回流冷凝管、温度计和机械搅拌的四口烧瓶中,加入132gMMA,升温至32℃搅拌1h,依次加入0.38g叔丁基过氧化氢和0.38g焦亚硫酸钠引发自由基聚合,聚合完毕后将该乳液通过减压蒸馏方式除去其中的丙酮,得粒径92nm半透明泛蓝光的改性水性聚氨酯组合物。
实施例3(优选)
向装有回流冷凝管、温度计和机械搅拌的四口烧瓶中加入78.6g HMDI(二环己基甲烷二异氰酸酯)、120gPPG1000(聚环氧丙烷醚二元醇)、2.4g MPEG1200、10.6g二羟甲基丙酸、0.1g BiCat8108、42g丙酮,升温至80℃反应直至理论NCO值,停止反应。
降温至60℃以下,加入148g丙酮、211gMMA,搅拌均匀降温至40℃以下,分散杯中称取825g去离子水将7gDMEA溶解其中,在1500r/min的高速剪切条件下20分钟内倒入预聚体,分散完毕后加入四倍水稀释的12gIPDA和14gC501,得改性水性聚氨酯组合物预乳液。将此乳液转移至装有回流冷凝管、温度计和机械搅拌的四口烧瓶中,加入126gMMA,升温至32℃搅拌1h,依次加入0.35g叔丁基过氧化氢和0.35g焦亚硫酸钠引发自由基聚合,聚合完毕后将该乳液通过减压蒸馏方式除去其中的丙酮,得粒径86nm半透明泛蓝光的改性水性聚氨酯组合物。
实施例4
向装有回流冷凝管、温度计和机械搅拌的四口烧瓶中加入61g HMDI(二环己基甲烷二异氰酸酯)、144gPPG2000(聚环氧丙烷醚二元醇)、2.4g MPEG1200、11g二羟甲基丙酸、0.11g BiCat8108,44g丙酮,升温至80℃反应直至理论NCO值,停止反应。
降温至60℃以下,加入152g丙酮、175gMMA、43gSt,搅拌均匀降温至40℃以下,分散杯中称取850g去离子水将7.3gDMEA溶解其中,在1500r/min的高速剪切条件下20分钟内倒入预聚体,分散完毕后加入四倍水稀释的9.6gIPDA和14.2gC501,得改性水性聚氨酯组合物预乳液。
将此乳液转移至装有回流冷凝管、温度计和机械搅拌的四口烧瓶中,加入132gMMA,升温至32℃搅拌1h,依次加入0.36g叔丁基过氧化氢和0.36g焦亚硫酸钠引发自由基聚合,聚合完毕后将该乳液通过减压蒸馏方式除去其中的丙酮,得粒径85nm半透明泛蓝光的改性水性聚氨酯组合物。
实施例5
向装有回流冷凝管、温度计和机械搅拌的四口烧瓶中加入72g HMDI(二环己基甲烷二异氰酸酯)、120gPPG1000(聚环氧丙烷醚二元醇)、2.4g MPEG1200、8.4g二羟甲基丙酸、0.1g BiCat8108,40g丙酮,升温至80℃反应直至理论NCO值,停止反应。
降温至60℃以下,加入142g丙酮、202gMMA,搅拌均匀降温至40℃以下,分散杯中称取790g去离子水将5.6gDMEA溶解其中,在1500r/min的高速剪切条件下20分钟内倒入预聚体,分散完毕后加入四倍水稀释的11.2gIPDA和13.2gC501,得改性水性聚氨酯组合物预乳液。将此乳液转移至装有回流冷凝管、温度计和机械搅拌的四口烧瓶中,加入122gMMA,升温至30℃搅拌1h,依次加入0.35g叔丁基过氧化氢和0.35g焦亚硫酸钠引发自由基聚合,聚合完毕后将该乳液通过减压蒸馏方式除去其中的丙酮,得粒径125nm泛蓝光的改性水性聚氨酯组合物。
实施例6
向装有回流冷凝管、温度计和机械搅拌的四口烧瓶中加入108g HMDI(二环己基甲烷二异氰酸酯)、120gPPG1000(聚环氧丙烷醚二元醇)、2.4g MPEG1200、20g二羟甲基丙酸、0.12g BiCat8108,50g丙酮,升温至80℃反应直至理论NCO值,停止反应。
降温至60℃以下,加入175g丙酮、251gMMA,搅拌均匀降温至40℃以下,分散杯中称取980g去离子水将13.68gDMEA溶解其中,在1500r/min的高速剪切条件下20分钟内倒入预聚体,分散完毕后加入四倍水稀释的17gIPDA和16.32gC501,得改性水性聚氨酯组合物预乳液。将此乳液转移至装有回流冷凝管、温度计和机械搅拌的四口烧瓶中,加入100gMMA,升温至32℃搅拌1h,依次加入0.35g叔丁基过氧化氢和0.35g焦亚硫酸钠引发自由基聚合,聚合完毕后将该乳液通过减压蒸馏方式除去其中的丙酮,得粒径60nm半透明泛蓝光的改性水性聚氨酯组合物。
将各实施例和对比例制得的组合物按照具体实施方式所列涂料配方制备双组份木器涂料,并进行性能测试。所得到的木器涂料的性能测试结果见下表:
从上表测试数据可已看出,本发明制得的改性聚氨酯组合物在双组份涂料活化期方面有好的表现,优选实施例3与对比例1相比添加C501与传统乳化剂相比,其活化期效果最好,并且不会对硬度及抗性产生不利影响;从对比例2可以看出不添加C501活化期表现较差,活化期时间短,光泽度下降较大。
从生产实践来看,本发明改性水性聚氨酯组合物的制备方法工艺简单可控,可以获得优异双组份性能,具有较大的实际使用价值。
本领域技术人员可以理解,在本说明书的教导之下,可对本发明做出一些修改或调整。这些修改或调整也应当在本发明权利要求所限定的范围之内。
Claims (16)
1.一种改性水性聚氨酯组合物的制备方法,包括如下步骤:
(1)合成异氰酸酯封端的预聚物;所述异氰酸酯封端的预聚物为包含如下各组分的原料混合反应制得:多异氰酸酯、大分子多元醇、亲水扩链剂,不含小分子多元醇扩链剂,所述大分子多元醇数均分子量为400-4000,选自聚醚酯、和/或至少一种主链和/或侧链含有聚氧化乙烯链段的一元醇和/或二元醇,
(2)加入低沸点有机溶剂,与异氰酸酯封端的预聚物充分混合溶解,与溶有中和剂的水混合分散,分散结束后加入多元胺扩链剂和乳化剂得预改性乳液;所述乳化剂具有5000-9000数均分子量、20000-50000重均分子量,其结构如下:其中,n=8-22,m=8-44;乳化剂用量为异氰酸酯封端的预聚物质量的3-10%,
其中,在步骤(1)和/或(2)中加入改性单体,
(3)加入引发剂进行自由基聚合,最后脱除低沸点有机溶剂。
2.根据权利要求1所述的制备方法,其特征在于,基于异氰酸酯封端的预聚物的质量,各组分的用量分别为:多异氰酸酯25-50wt%;大分子多元醇45-70%;亲水扩链剂3-8wt%。
3.根据权利要求1或2所述的制备方法,其特征在于,所述多异氰酸酯是脂肪族、脂环族、芳香族多异氰酸酯或者其混合物。
4.根据权利要求3所述的制备方法,其特征在于,所述多异氰酸酯选自甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、异佛尔酮二异氰酸酯、六亚甲基二异氰酸酯、戊二异氰酸酯、六氢甲苯二异氰酸酯、三甲基己烷二异氰酸酯、苯二甲撑二异氰酸酯、1,4-环己烷二异氰酸酯、十二烷基二异氰酸酯、1,5-萘二异氰酸酯和二环己基甲烷二异氰酸酯中的一种或多种。
5.根据权利要求1-2任一项所述的制备方法,其特征在于,所述聚醚酯选自聚醚多元醇、聚酯多元醇、聚碳酸酯多元醇中的一种或多种;
所述主链和/或侧链含有聚氧化乙烯链段的一元醇和/或二元醇,为含有聚氧化乙烯链段的聚合单元中含有90-100wt%的环氧乙烷。
6.根据权利要求5所述的制备方法,其特征在于,所述聚醚酯选自聚乙二醇、聚丙二醇、聚乙二醇-丙二醇、聚四氢呋喃醚二醇、二聚酸聚酯多元醇、聚烯烃多元醇、聚己内酯二元醇、聚碳酸酯二元醇、聚己二酸乙二醇酯二元醇、聚己二酸-1,4-丁二醇酯二元醇、聚己二酸新戊二醇酯二元醇、聚己二酸-1,6-己二醇酯二元醇和聚己二酸新戊二醇酯-1,6-己二醇酯二元醇中的一种或多种;
所述主链和/或侧链含有聚氧化乙烯链段的一元醇和/或二元醇,为Tego Chemie公司的D-3403、Perstrop公司的YmerTM N120和韩国乐天公司的MPEG520、MPEG1200、MPEG2200中的一种或多种。
7.根据权利要求1-2任一项所述的制备方法,其特征在于,所述亲水扩链剂包括带有离子或潜在离子基团的可与异氰酸酯反应的化合物。
8.根据权利要求7所述的制备方法,其特征在于,所述亲水扩链剂选自二羟甲基丙酸、二羟甲基丁酸、氨基酸、氨基磺酸盐、酒石酸、N,N-二羟甲基马来酰胺酸、二氨基苯甲酸、二羟基丙磺酸钠中的一种或多种。
9.根据权利要求1所述的制备方法,其特征在于,所述多元胺扩链剂为至少含有两个活泼氢的有机或无机伯胺或仲胺官能的化合物。
10.根据权利要求9所述的制备方法,其特征在于,所述多元胺扩链剂选自乙二胺、2-甲基1,5-戊二胺、异佛尔酮二胺、肼、羟乙基乙二胺、己二胺、二乙烯三胺、三乙烯四胺、环己烷二胺、苯二胺、甲苯二胺、二环己基甲烷二胺中的一种或多种。
11.根据权利要求9所述的制备方法,其特征在于,所述多元胺扩链剂用量为异氰酸酯封端预聚物质量的4-8%。
12.根据权利要求1所述的制备方法,其特征在于,所述乳化剂用量为异氰酸酯封端的预聚物质量的3-7%。
13.根据权利要求1所述的制备方法,其特征在于,所述改性单体选自丙烯酸甲酯、丙烯酸磷酸酯、硅氧烷丙烯酸酯、甲基丙烯酸烯丙酯、丙烯酸乙酯、丙烯酸羟丙酯、丙烯酸丙酯、丙烯酸丁酯、甲基丙烯酸甲酯、甲基丙烯酸乙酯、三羟甲基丙烷三丙烯酸酯、季戊四醇三丙烯酸酯、甲基丙烯酸羟乙酯、甲基丙烯酸丁酯、四氢呋喃丙烯酸酯、苯乙烯、烯丙基甲基苯乙烯、丙烯酸异冰片酯和丙烯酸异辛酯中的一种或多种。
14.根据权利要求13所述的制备方法,其特征在于,改性单体的用量为异氰酸酯封端预聚物质量的1.2-2.4倍。
15.根据权利要求1、13-14任一项所述的制备方法,其特征在于,所述引发剂引发体系为氧化还原体系;
其中,氧化剂包括过硫酸氨、过硫酸钠、过硫酸钾、过氧化二叔丁基、过氧化苯甲酰、过氧化氢、异丙苯过氧化氢和叔丁基过氧化氢中的一种或多种,
还原剂包括保险粉、N,N-二甲基苯胺、硫酸亚铁、硝酸银、硫醇、氯化亚铁、四乙烯亚胺、焦亚硫酸钠、吊白块、亚硫酸氢钠和异抗坏血酸中的一种或多种;
引发剂的用量为所述改性单体总质量的0.05-0.4%。
16.根据权利要求1-15任一项所述的制备方法制得的改性水性聚氨酯组合物在水性木器漆涂料中的应用。
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