CN105131243A - 环氧改性磺酸型水性聚氨酯乳液及其制备方法和应用 - Google Patents

环氧改性磺酸型水性聚氨酯乳液及其制备方法和应用 Download PDF

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CN105131243A
CN105131243A CN201510545483.8A CN201510545483A CN105131243A CN 105131243 A CN105131243 A CN 105131243A CN 201510545483 A CN201510545483 A CN 201510545483A CN 105131243 A CN105131243 A CN 105131243A
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杨芳
李有刚
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Ke Litai Macromolecular Material Limited-Liability Co In Chongqing
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Abstract

本发明公开了环氧改性磺酸型水性聚氨酯乳液及其制备方法和应用，磺酸型水性聚氨酯乳液按重量份包括如下组分，多元醇70-80份，二异氰酸酯10-15份，小分子醇扩链剂1-2份，有机铋类和/或有机锡类催化剂0.01-0.05份，亲水扩链剂2.5-3.5份和环氧树脂5-15份，配方简单，混配稳定性好，并且提高了水性聚氨酯粘胶的耐水解性，可以用于制备3D家具免漆吸塑胶，具有使用温度低，粘接强度高，耐高温性能好等优点。

Description

环氧改性磺酸型水性聚氨酯乳液及其制备方法和应用
技术领域
本发明属于材料领域，具体涉及一种环氧改性磺酸型水性聚氨酯吸塑液，还涉及该磺酸型水性聚氨酯吸塑胶的制备方法和应用。
背景技术
目前市场上免漆3D家具的制造主要是以密度板和PVC膜作为粘接基材，大多数采用吸塑工艺。由于PVC膜耐高温能力差，高温高压条件下烘烤、保压吸塑会导致PVC膜表面的花纹发生变形甚至膜破坏，同时较高的操作温度能耗高，并存在一定的危险性，所以活化温度低的3D家具免漆吸塑胶亟待开发。
目前研究报道的低活化温度的水性聚氨酯吸塑胶主要是羧酸型的，存在的问题是混配稳定性差，即与EVA乳液混配时容易发生凝胶。一般在混配前需要加入pH调节剂来调节乳液的酸碱度，一方面增加了操作的复杂性，另一方面pH调节剂是一种小分子物质，对乳液的性能有一定的影响。因此，急需一种混配稳定性更好的水性聚氨酯，并且具有出色的粘接能力、高膜量、高强度和良好的耐化学性。
发明内容
有鉴于此，本发明的目的之一在于提供环氧改性磺酸型水性聚氨酯乳液；本发明的目的之二在于提供环氧改性磺酸型水性聚氨酯乳液的制备方法；本发明的目的之三在于提供环氧改性磺酸型水性聚氨酯乳液的应用；本发明的目的之四在于提供含有环氧改性磺酸型水性聚氨酯乳液的3D家具免漆吸塑胶；本发明的目的之五在于提供3D家具免漆吸塑胶的制备方法。
为实现上述发明目的，本发明提供如下技术方案：
1、环氧改性磺酸型水性聚氨酯乳液，所述磺酸型水性聚氨酯乳液按重量份包括如下组分，多元醇70-80份，二异氰酸酯10-15份，小分子醇扩链剂1-2份，有机铋类和/或有机锡类催化剂0.01-0.05份，亲水扩链剂2.5-3.5份和环氧树脂5-15份。
优选的，所述多元醇为聚酯多元醇和/或聚醚多元醇。
优选的，所述多元醇为己二酸型聚酯多元醇、苯酐聚酯多元醇、聚己内酯多元醇，聚碳酸酯多元醇中的一种或多种；所述二异氰酸酯为甲苯二异氰酸酯、1,6-六亚甲基二异氰酸酯、异氟尔酮二异氰酸酯、二苯基甲烷二异氰酸酯、苯二亚甲基二异氰酸酯、萘-1,5-二异氰酸酯、四甲基苯二亚甲基二异氰酸酯中的一种或多种；所述小分子醇扩链剂为乙二醇、丙二醇、新戊二醇、1,6己二醇，1,4-环己烷二甲醇、二乙二醇、二丙二醇、3-甲基-1,5-戊二醇，1,3-丁二醇、1,4-丁二醇、一缩二乙二醇中的一种或多种；所述亲水扩链剂为乙二胺基乙磺酸钠、1,2-二羟基-3-丙磺酸钠、二胺基丁磺酸和二胺基苯磺酸钠中的一种或多种；所述环氧树脂为双酚A型、双酚S型或酚醛型。
优选的，所述多元醇为己二酸型聚酯多元醇；所述二异氰酸酯为甲苯二异氰酸酯；所述小分子醇扩链剂为二乙二醇；所述亲水扩链剂为乙二胺基乙磺酸钠；所述催化剂为二月桂酸有机锡；所述环氧树脂为双酚A型。
2、所述环氧改性磺酸型水性聚氨酯乳液的制备方法，包括如下步骤，将多元醇在110～130℃真空脱水，在干燥惰性气体保护下，将脱水的多元醇降温至70～75℃，加入二异氰酸酯反应1～1.5h，期间加入相当于多元醇质量2-3倍的丙酮调节黏度，然后向预聚体中加入小分子醇扩链剂、环氧树脂和有机铋类和/或有机锡类催化剂，于75～80℃保温反应4.5～5h，再降温至35～45℃，加入亲水扩链剂保温反应10～15min，得到离聚物，按照固含量40％的比例加水乳化，匀速搅拌，脱除丙酮即得环氧改性磺酸型水性聚氨酯乳液。
3、所述环氧改性磺酸型水性聚氨酯乳液在制备3D家具免漆吸塑胶中的应用。
4、含有所述环氧改性磺酸型水性聚氨酯乳液的3D家具免漆吸塑胶。
优选的，所述3D家具免漆吸塑胶按重量份包括如下组分，环氧改性的磺酸型水性聚氨酯乳液30-70份，水性聚氨酯乳液10-30份，乙酸乙烯酯-乙烯共聚乳液30-50份和增稠剂0.1-1.5份。
优选的，所述水性聚氨酯乳液为活化温度在35-45℃的水性聚氨酯乳液；所述增稠剂为缔合型水性聚氨酯增稠剂；所述增强剂为聚碳化二亚胺、水性聚多异氰酸酯和有机硅偶联剂中的一种或多种。
上述方案中，所述的水性聚氨酯乳液为高固含水性聚氨酯乳液，本发明中所采用的水性聚氨酯乳液有如U54、U53、U2710，由拜耳(中国)有限公司上海聚合物科研开发中心购得；水性聚氨酯乳液8601，由广东东方树脂有限公司购得，水性聚氨酯乳液AC-309W，由诠达化学股份有限公司购得。
上述方案中，所述的乙酸乙烯酯-乙烯共聚乳液(EVA乳液)采用的有DA-102、CW40-701、CW40-707、CW40-600、VINNAPAS707K、VINNAPASEP706K和CP143中的一种或多种，所述的DA-102，由大连化工(南京)公司购得；CW40-701、CW40-707、CW40-600，由中国石化集团四川维尼纶厂购得；VINNAPAS707K、VINNAPASEP706K，由瓦克化学(中国)有限公司购得；CP143，由塞拉尼斯(中国)有限公司购得。
上述方案中，所述的增稠剂的型号为BYK420和BYK425的增稠剂，可由毕克化学技术咨询(上海)有限公司；BorchiGel0625和BorchiGelL75N，可由上海松尾贸易有限公司购得。
上述方案中，使用的聚碳化二亚胺为DESMODURXP2802，可由拜耳(中国)有限公司上海聚合物科研开发中心购得；水性聚多异氰酸酯为TKA-100和TPA-100，可由旭化成精细化工(南通)有限公司购得；有机硅偶联剂为KH602和KH550，可由广州市聚成兆业有机硅原料有限公司购得，作为优选的，所述的增强剂选用TKA-100。
5、所述3D家具免漆吸塑胶的制备方法，包括如下步骤：将乙酸乙烯酯-乙烯共聚乳液以转速300-600转/min搅拌，加入环氧改性的磺酸型水性聚氨酯乳液、水性聚氨酯乳液，搅拌30-60min，混合均匀，然后在混合体系中滴加增稠剂，搅拌30-60min，过滤得到3D家具免漆吸塑胶；
或将乙酸乙烯酯-乙烯共聚乳液以转速300-600转/min搅拌，加入环氧改性的磺酸型水性聚氨酯乳液、水性聚氨酯乳液，搅拌30-60min，混合均匀，然后在混合体系中滴加增稠剂，搅拌30-60min，过滤得到3D家具免漆吸塑胶，喷涂前加入增强剂。
本发明的有益效果在于：本发明公开了环氧改性磺酸型水性聚氨酯乳液，由于在磺酸型水性聚氨酯引入环氧进行接枝改性，利用交联结构改性的方法，提高水性聚氨酯胶粘剂的耐水解性，同时由于环氧树脂具有出色的粘接能力、高模量、高强度、良好的耐化学性，将其引入有望提高水性聚氨酯胶粘剂的综合性能，并在一定程度上降低成本，具有现实研究和实际应用意义，将其制成3D家具免漆吸塑胶后使用温度低，粘接强度高，尤其是耐高温性能好，50℃烘烤4h后60℃烘烤4h，接着65℃烘烤4h，75℃继续烘烤4h，免漆3D家具吸塑样件侧边缩边小于3mm，凹槽不反弹，完全能保证免漆3D家具在运输过程中及使用过程中的产品质量，并且还具有如下优点：
1)本发明的3D家具免漆吸塑胶用低活化温度的环氧改性的磺酸型水性聚氨酯吸塑胶实现了零VOC排放，满足了人们对家居环境不断提高的标准。另外，使用时，该乳液可与多种增强剂配合，满足不同的粘接强度的需求，保障了免漆3D家具吸塑成型后的耐温性。
2)本发明的3D家具免漆吸塑胶用低活化温度的环氧改性的磺酸型水性聚氨酯吸塑胶采用增稠剂调整胶液的黏度，保证胶液具有良好的流挂性，施工方便，减少了胶液的损耗，大大降低了成本，同时可以根据不同地域的温度差异，调整黏度，操控性更强。
3)本发明的3D家具免漆吸塑胶用低活化温度的环氧改性的磺酸型水性聚氨酯吸塑胶相对于没有经过环氧改性的磺酸型水性聚氨酯吸塑胶而言耐水解性明显提高，具有更好的储存稳定性。
具体实施方式
下面将对本发明的优选实施例进行详细的描述。实施例中未注明具体条件的实验方法，通常按照常规条件或按照制造厂商所建议的条件。
实施例1、环氧改性磺酸型水性聚氨酯乳液的制备
环氧改性磺酸型水性聚氨酯乳液，按重量份计包括如下组分：
配方1：聚己二酸丁二醇多元醇(CMA-44)56份；聚己二酸己二醇多元醇(4020D)14份；1,6-六亚甲基二异氰酸酯(HDI)15份；二乙二醇(DEG)2份；二月桂酸有机锡(T12)0.01份，乙二胺基磺酸钠3份和双酚A型5份。
配方2：聚己二酸丁二醇多元醇(CMA-44)43份；聚己二酸己二醇多元醇(4020D)37份；甲苯二异氰酸酯10份；1,4-丁二醇0.5份，乙二醇0.5份；二月桂酸有机锡(T12)0.05份，1,2-二羟基-3-丙磺酸钠2.5份和双酚S型15份。
配方3：苯酐聚酯多元醇75份；二苯基甲烷二异氰酸酯12份；1,3-丁二醇1.5份；二月桂酸有机锡(T12)0.03份，乙二胺基磺酸钠3.5份和酚醛型10份。
其制备方法为：将多元醇在110-130℃真空脱水，在干燥惰性气体保护下，将脱水的多元醇降温至70-75℃，加入二异氰酸酯反应1-1.5h，期间加入相当于多元醇质量2-3倍的丙酮调节黏度，然后向预聚体中加入小分子醇扩链剂、环氧树脂和二月桂酸有机锡，于75-80℃保温反应4.5-5h，直至NCO含量达到理论值，预聚结束，降温至35-45℃，加入亲水扩链剂保温反应10-15min，得到离聚物，按照固含量40％的比例加去离子水乳化，匀速搅拌30min后，减压蒸馏脱除丙酮即得环氧改性磺酸型水性聚氨酯乳液。
实施例2、3D家具免漆吸塑胶的制备(不含增强剂)
3D家具免漆吸塑胶，按重量份计包括如下组分：环氧改性的磺酸型水性聚氨酯乳液70份；水性聚氨酯乳液(U54)10份；乙酸乙烯酯-乙烯共聚乳液(DA-102)50份和增稠剂(缔合型水性聚氨酯增稠剂BYK420)0.1份。
其制备方法为：在室温下，将乙酸乙烯酯-乙烯共聚乳液以转速300-600转/min搅拌，加入环氧改性的磺酸型水性聚氨酯乳液、高固含的水性聚氨酯乳液，搅拌30-60min，混合均匀，在所制备的混合体系中缓慢滴加增稠剂，搅拌30-60min，过滤得到3D家具免漆吸塑胶，即低活化温度的环氧改性的磺酸型水性聚氨酯乳液吸塑胶。
实施例3、3D家具免漆吸塑胶的制备(含增强剂)
3D家具免漆吸塑胶，按重量份计包括如下组分：环氧改性的磺酸型水性聚氨酯乳液30份；水性聚氨酯乳液(AC-309W)30份；乙酸乙烯酯-乙烯共聚乳液(CW40-701)30份，增稠剂(缔合型水性聚氨酯增稠剂BYK425)1.5份和增强剂(聚碳化二亚胺DESMODURXP2802)5份。
其制备方法为：在室温下，将乙酸乙烯酯-乙烯共聚乳液以转速300-600转/min搅拌，加入环氧改性的磺酸型水性聚氨酯乳液、水性聚氨酯乳液，搅拌30-60min，混合均匀，在所制备的混合体系中缓慢滴加增稠剂，搅拌30-60min，过滤得3D家具免漆吸塑胶，即低活化温度的环氧改性的磺酸型水性聚氨酯乳液吸塑胶，吸塑胶喷涂前加入增强剂混合均匀，3-4小时内使用，否则增强剂失效。
实施例4、测试方法
1)活化温度测试：按照GB/T2791-1995标准进行制样，以密度板和PVC膜作为基材，胶液喷涂于密度板上进行单面上胶的方式，室温下晾干，再与PVC膜贴合，在KT520-01T气动热压机上进行热压粘接，模压压力为0.3MPa，时间60s，模压温度可调，热压后用手逆向(180°剥离)扯PVC膜，密度板与PVC膜完全粘合并造成密度板表层木屑被撕破视为胶层活化，此时的模压温度即为活化温度，结果如表1所示。
2)耐温性测试：按照GB/T2791-1995标准进行制样，以密度板和PVC膜作为基材，胶液喷涂于密度板上进行单面上胶的方式，室温下晾干，再与PVC膜贴合，在KT520-01T气动热压机上进行热压粘接，模压压力为0.3MPa，时间60s，模压温度设定为53℃热压后，将粘接好的基材在80℃条件下预热20min，挂1Kg钩码进行测试，采用180°剥离方式，结果如表1所示。
3)耐水解性测试：取一定质量的乳液，置于干燥洁净的玻璃瓶中，密封后放进60℃的水浴锅中，放置6天6夜后，观察乳液结皮及沉淀情况并测试耐温性(测试方法同上)，结果如表1所示。
4)吸塑耐温测试：以免漆3D家具和PVC膜作为基材，胶液喷涂于免漆3D家具上进行单面上胶的方式，室温下晾干，再与PVC膜真空吸塑贴合，温度180℃，真空度-0.08～-0.09MPa，预热时间：30s，出台时间180s，保压时间200s。吸塑完成后，将吸塑样品放于烘箱中进行烘烤，分别进行50、60、65、70、75℃连续烘烤4h后观测吸塑样件侧边有无缩边、正面有无爆口现象，结果如表2所示。
表1、乳液及胶液的基本性能
项目 活化温度 耐温性 耐水解性
环氧改性磺酸型水性聚氨酯乳液 36℃ 7925s/cm 1405s/cm
3D家具免漆吸塑胶液 37℃ 5680s/cm 551s/cm
表2、吸塑耐温测试结果
项目 50℃-4h 60℃-4h 65℃-4h 75℃-4h
1# 0 0.3 1.5 2
2# 0 0.2 0.3 1
3# 0 0.5 1 1.5
4# 0 0 0 0
备注：1#：未加固化剂胶液吸塑30丝PVC膜；2#：加固化剂(TKA-100)胶液吸塑30丝PVC膜；3#：未加固化剂胶液吸塑15丝PVC膜；4#：加固化剂(TKA-100)胶液吸塑15丝PVC膜；表中数据表示相应温度下烘烤后板材侧边沿缩边的距离(单位：mm)
最后说明的是，以上优选实施例仅用以说明本发明的技术方案而非限制，尽管通过上述优选实施例已经对本发明进行了详细的描述，但本领域技术人员应当理解，可以在形式上和细节上对其作出各种各样的改变，而不偏离本发明权利要求书所限定的范围。

Claims (10)

1.环氧改性磺酸型水性聚氨酯乳液，其特征在于：所述磺酸型水性聚氨酯乳液按重量份包括如下组分，多元醇70-80份，二异氰酸酯10-15份，小分子醇扩链剂1-2份，有机铋类和/或有机锡类催化剂0.01-0.05份，亲水扩链剂2.5-3.5份和环氧树脂5-15份。
2.根据权利要求1所述环氧改性磺酸型水性聚氨酯乳液，其特征在于：所述多元醇为聚酯多元醇和/或聚醚多元醇。
3.根据权利要求1所述环氧改性磺酸型水性聚氨酯乳液，其特征在于：所述多元醇为己二酸型聚酯多元醇、苯酐聚酯多元醇、聚己内酯多元醇，聚碳酸酯多元醇中的一种或多种；所述二异氰酸酯为甲苯二异氰酸酯、1,6-六亚甲基二异氰酸酯、异氟尔酮二异氰酸酯、二苯基甲烷二异氰酸酯、苯二亚甲基二异氰酸酯、萘-1,5-二异氰酸酯、四甲基苯二亚甲基二异氰酸酯中的一种或多种；所述小分子醇扩链剂为乙二醇、丙二醇、新戊二醇、1,6己二醇，1,4-环己烷二甲醇、二乙二醇、二丙二醇、3-甲基-1,5-戊二醇，1,3-丁二醇、1,4-丁二醇、一缩二乙二醇中的一种或多种；所述亲水扩链剂为乙二胺基乙磺酸钠、1,2-二羟基-3-丙磺酸钠、二胺基丁磺酸和二胺基苯磺酸钠中的一种或多种；所述环氧树脂为双酚A型、双酚S型或酚醛型。
4.根据权利要求3所述环氧改性磺酸型水性聚氨酯乳液，其特征在于：所述多元醇为己二酸型聚酯多元醇；所述二异氰酸酯为甲苯二异氰酸酯；所述小分子醇扩链剂为二乙二醇；所述亲水扩链剂为乙二胺基乙磺酸钠；所述催化剂为二月桂酸有机锡；所述环氧树脂为双酚A型。
5.权利要求1～4任一项所述环氧改性磺酸型水性聚氨酯乳液的制备方法，其特征在于：包括如下步骤，将多元醇在110～130℃真空脱水，在干燥惰性气体保护下，将脱水的多元醇降温至70～75℃，加入二异氰酸酯反应1～1.5h，期间加入相当于多元醇质量2-3倍的丙酮调节黏度，然后向预聚体中加入小分子醇扩链剂、环氧树脂和有机铋类和/或有机锡类催化剂，于75～80℃保温反应4.5～5h，再降温至35～45℃，加入亲水扩链剂保温反应10～15min，得到离聚物，按照固含量40％的比例加水乳化，匀速搅拌，脱除丙酮即得环氧改性磺酸型水性聚氨酯乳液。
6.权利要求1～4任一项所述环氧改性磺酸型水性聚氨酯乳液在制备3D家具免漆吸塑胶中的应用。
7.含有权利要求1～4任一项所述环氧改性磺酸型水性聚氨酯乳液的3D家具免漆吸塑胶。
8.根据权利要求7所述的3D家具免漆吸塑胶，其特征在于：所述3D家具免漆吸塑胶按重量份包括如下组分，环氧改性的磺酸型水性聚氨酯乳液30-70份，水性聚氨酯乳液10-30份，乙酸乙烯酯-乙烯共聚乳液30-50份，增稠剂0.1-1.5份和增强剂0-5份。
9.根据权利要求8所述的3D家具免漆吸塑胶，其特征在于：所述水性聚氨酯乳液为活化温度在35-45℃的水性聚氨酯乳液；所述增稠剂为缔合型水性聚氨酯增稠剂；所述增强剂为聚碳化二亚胺、水性聚多异氰酸酯和有机硅偶联剂中的一种或多种。
10.权利要求8或9所述3D家具免漆吸塑胶的制备方法，其特征在于，包括如下步骤：将乙酸乙烯酯-乙烯共聚乳液以转速300-600转/min搅拌，加入环氧改性的磺酸型水性聚氨酯乳液、水性聚氨酯乳液，搅拌30-60min，混合均匀，然后在混合体系中滴加增稠剂，搅拌30-60min，过滤得到3D家具免漆吸塑胶；
或将乙酸乙烯酯-乙烯共聚乳液以转速300-600转/min搅拌，加入环氧改性的磺酸型水性聚氨酯乳液、水性聚氨酯乳液，搅拌30-60min，混合均匀，然后在混合体系中滴加增稠剂，搅拌30-60min，过滤得到3D家具免漆吸塑胶，喷涂前加入增强剂。
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CN106590392A (zh) * 2016-11-25 2017-04-26 重庆中科力泰高分子材料股份有限公司 用于医药包装的水性op保护剂及其制备方法
CN107353394A (zh) * 2017-08-23 2017-11-17 黄山联固新材料科技有限公司 一种涂料、聚氨酯及其制备方法
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CN106590392A (zh) * 2016-11-25 2017-04-26 重庆中科力泰高分子材料股份有限公司 用于医药包装的水性op保护剂及其制备方法
CN107353394A (zh) * 2017-08-23 2017-11-17 黄山联固新材料科技有限公司 一种涂料、聚氨酯及其制备方法
CN110105541A (zh) * 2019-05-10 2019-08-09 杨婷婷 一种水性环氧树脂的制备方法
CN112341918A (zh) * 2020-10-23 2021-02-09 杭州海维特化工科技有限公司 一种耐增塑剂迁移pvc薄膜水性背涂剂及其制备方法
CN112778492A (zh) * 2020-12-30 2021-05-11 广东工业大学 一种aas型环氧改性水性聚氨酯乳液及其制备方法
CN114801389A (zh) * 2022-05-20 2022-07-29 江苏大亚新型包装材料有限公司 烟用包装胚膜的制备方法及其胚膜以及烟用包装盒的制备
CN114801389B (zh) * 2022-05-20 2024-03-26 江苏大亚新型包装材料有限公司 烟用包装胚膜的制备方法及其胚膜以及烟用包装盒的制备

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