CN113322044A - 一种合成革用水性改性粘合剂及其制备方法 - Google Patents
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Abstract
一种合成革用水性改性粘合剂及其制备方法，包括如下重量份数的物质：封端剂封端的水性聚氨酯乳液60‑80份，去离子水20‑40份，消泡剂0.01‑0.05份，润湿剂0.1‑1份，流平剂0.01‑0.1份，增稠剂0.05‑0.5份。本发明所提供的亚硫酸氢钠封端的水性聚氨酯乳液，控制合适的封端比例，得到的乳液稳定，成膜有较高的拉伸强度和断裂伸长率，在高温下解封的特性，在用于合成革的粘合剂时，除了较高初粘性，优异的流平性和铺展性外，更有较长时间的半干状态，易于工业化生产控制。
Description
技术领域
本发明属于水性改性粘合剂制备领域，具体地说是一种合成革用水性改性粘合剂及其制备方法。
背景技术
合成革工业是我国具有综合优势的传统轻工产业，传统的合成革工业多用油性树脂做粘合层，油性树脂做粘合层有其本身的优势：弹性好，可操作空间大。然而，近年来，随着VOCs的严格限制以及欧盟REACH法规的颁布使得我国传统溶剂型合成革失去市场竞争力。从国内外发展现状和趋势来看，涂层材料朝着水性化方向发展，合成革制造朝着绿色、生态化、高值化的方向发展。目前，采用水性聚氨酯生产合成革，是解决传统合成革生产过程中产生溶剂污染问题的主要方向。
水性聚氨酯相比于油性聚氨酯，除了环保无污染外，树脂具有更强的附着力和卓越的耐候性，耐油污、易清洗。水性合成革转移涂层工艺为：
但是作为合成革用的水性粘合剂，是将基布与水性发泡层之间紧密贴合，湿料贴合会使粘合剂渗入基布中造成成革手感硬，褶痕纹路不细致等弊端，目前市面上的半干贴烘干程度不易控制，易出现脱模现象，剥离强度不稳定。
发明内容
本发明提供一种合成革用水性改性粘合剂，用以解决现有技术中的缺陷。
本发明通过以下技术方案予以实现：
一种合成革用水性改性粘合剂，包括如下重量份数的物质：
封端剂封端的水性聚氨酯乳液60-80份，去离子水20-40份，消泡剂0.01-0.05份，润湿剂0.1-1份，流平剂0.01-0.1份，增稠剂0.05-0.5份。
如上所述的一种合成革用水性改性粘合剂，所述的封端剂封端的水性聚氨酯乳液包括如下重量份数的物质：
聚醚多元醇60-80份，二异氰酸酯14-30份，催化剂0.01-0.05份，小分子扩链剂0.5-1.5份，亲水性扩链剂3.3-4.5份，中和剂2.1-3.1份，封端剂1-2份，胺类扩链剂0.05-7份。
如上所述的一种合成革用水性改性粘合剂，所述的聚醚多元醇为聚四氢呋喃醚二醇。
如上所述的一种合成革用水性改性粘合剂，所述的聚四氢呋喃二醇的分子量为3000，羟值为38±1mg KOH/g，-OH官能度为2。
如上所述的一种合成革用水性改性粘合剂，所述的二异氰酸酯为异佛二酮二异氰酸酯、六亚甲基二异氰酸酯其中的任意一种。
如上所述的一种合成革用水性改性粘合剂，所述的催化剂为二丁基二月硅酸锡或辛酸亚锡其中的任意一种。
如上所述的一种合成革用水性改性粘合剂，所述的小分子扩链剂为1,4-丁二醇或1,6-己二醇其中的任意一种或两种以任意比例混合的混合物。
如上所述的一种合成革用水性改性粘合剂，所述的亲水性扩链剂为二羟甲基丙酸。
如上所述的一种合成革用水性改性粘合剂，所述的封端剂为亚硫酸氢钠。
如上所述的一种合成革用水性改性粘合剂，所述的碱性中和剂为三乙胺或N,N-二甲基乙醇胺其中的任意一种。
如上所述的一种合成革用水性改性粘合剂，所述的胺类扩链剂为水合肼、乙二胺、异佛二酮二胺其中的任意一种。
如上所述的一种合成革用水性改性粘合剂，所述的消泡剂为有机硅氧烷类消泡剂。
如上所述的一种合成革用水性改性粘合剂，所述的润湿剂为烷酚聚氧乙烯醚非离子润湿剂。
如上所述的一种合成革用水性改性粘合剂，所述的流平剂为有机硅流平剂。
如上所述的一种合成革用水性改性粘合剂，所述的增稠剂为水性聚氨酯增稠剂。
一种合成革用水性改性粘合剂的制备方法，包括以下步骤：
步骤一：按照配比称取聚醚多元醇，磺酸型聚酯多元醇，二异氰酸酯，催化剂，小分子扩链剂，亲水性扩链剂，碱性中和剂，胺类扩链剂；
步骤二：向反应器中加入聚醚多元醇和磺酸型聚酯多元醇，在氮气的保护下，加入二异氰酸酯和催化剂的，反应温度80-90℃，反应1-2h，得预聚体；
步骤三：将步骤三得到的预聚体的温度降至50-70℃，加入小分子扩链剂和亲水性扩链剂，混合反应2-3h，制得含羧基的聚氨酯预聚体；
步骤四：将步骤三所得的羧基的聚氨酯预聚体降至20-30℃，加入封端剂，继续搅拌反应1h，
步骤五：将步骤三所得的被封端剂封端的含亲水基和羧基的聚氨酯预聚体导入乳化釜中，加入中和剂，在20-25℃的温度下，在800-1300r/min的转速下加入体积是被封端剂封端的含亲水基和羧基的聚氨酯预聚体1.1-1.5倍的去离子水乳化，乳化3-5min，加入胺类扩链剂，胺类扩链剂添加时间为3-5min，加完后继续搅拌分散10-30min，真空脱除有机溶剂，即制得封端剂封端的水性聚氨酯乳液；
步骤六：按照配比称量封端剂封端的水性聚氨酯乳液，消泡剂，润湿剂，流平剂，增稠剂；
步骤七：将封端剂封端的水性聚氨酯乳液放入反应器中在搅拌条件下加入消泡剂、润湿剂、流平剂，在转速200-400r/min的搅拌条件下，搅拌20-40min，助剂分散均后实时监测粘度，当达到指定粘度后既得至预定粘度即得水性改性粘合剂。
本发明的优点是：本发明所提供的亚硫酸氢钠封端的水性聚氨酯乳液，控制合适的封端比例，得到的乳液稳定，成膜有较高的拉伸强度和断裂伸长率，在高温下解封的特性，在用于合成革的粘合剂时，除了较高初粘性，优异的流平性和铺展性外，更有较长时间的半干状态，易于工业化生产控制。
具体实施方式
为使本发明实施例的目的、技术方案和优点更加清楚，下面将结合本发明实施例，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
实施例1
将300g聚四氢呋喃醚二醇加入到装有搅拌器，温度计的四口烧瓶中，加热至110℃，抽真空脱水，真空度显示-0.08Mpa，1.5h后降温至75℃以下，降真空管口换为冷凝回流管，投入58.00g IPDI，加二丁基二月硅酸锡0.06g，混匀后升温至85-90℃，反应2小时；降低所得到的预聚体的温度至60℃，加入3.00g 1,6-己二醇和12.6g二羟甲基丙酸，同时加入丙酮控制反应体系粘度，在70-75℃条件下，进行扩链反应，时间为3小时，将预聚体冷却至20-25℃，加入亚硫酸氢钠5.6g,继续搅拌1小时，制得预聚体。将预聚体转入乳化釜中，加入9.20g三乙胺，高速剪切下加水乳化，水温为20-25℃，最后加入水合肼10％水溶液28.3g分散均匀，真空脱除丙酮，即制得亚硫酸氢钠封端的水性聚氨酯乳液。所得乳液的固含量为35％，粘度为80mPa.s，pH值：7.36。
实施例2
将300g聚四氢呋喃醚二醇加入到装有搅拌器，温度计的四口烧瓶中，加热至120℃，抽真空脱水，真空度显示-0.09Mpa，1.5h后降温至75℃以下，降真空管口换为冷凝回流管，投入46.00g IPDI，17.00g HDI，加辛酸亚锡0.09g，混匀后升温至85-90℃，反应2小时；降低所得到的预聚体的温度至60℃，加入2.00g 1,4-丁二醇、1.00g 1，6-己二醇和13.50g二羟甲基丙酸，同时加入丙酮控制反应体系粘度，在70-75℃条件下，进行扩链反应，时间为3小时，将预聚体冷却至20-25℃，加入亚硫酸氢钠3.86g,继续搅拌1小时，制得预聚体。将预聚体转入乳化釜中，加入9.16g三乙胺，高速剪切下加水乳化，水温为20-25℃，最后加入乙二胺10％水溶液19.12g分散均匀，真空脱除丙酮，即制得亚硫酸氢钠封端的水性聚氨酯乳液。所得乳液的固含量为36％，粘度为120mPa.s，pH值：7.22。
合成革用粘合剂的原料组分：水性聚氨酯乳液60份，去离子水40份，消泡剂0.01份，润湿剂0.3份，流平剂0.1份，增稠剂0.1份。
将水性聚氨酯乳液200g，低速搅拌的条件下，缓慢加入消泡剂0.02g，润湿剂0.6g，流平剂0.2g，增稠剂0.2g，所制得的粘合剂pH值：7.12，粘度：1800mPa.s。无间隙刮涂，80℃烘干3分钟，胶膜仍能够100％贴合，无空隙，无渗料。
实施例3
将250g聚四氢呋喃醚二醇加入到装有搅拌器，温度计的四口烧瓶中，加热至120℃，抽真空脱水，真空度显示-0.08Mpa，1.5h后降温至75℃以下，降真空管口换为冷凝回流管，投入63.00g IPDI，加辛酸亚锡0.15g，混匀后升温至80-85℃，反应1.5小时；降低所得到的预聚体的温度至60℃，加入5.01g 1,6-己二醇和11.20g二羟甲基丙酸，同时加入丙酮控制反应体系粘度，在70-75℃条件下，进行扩链反应，时间为2.5小时，将预聚体冷却至25-30℃，加入亚硫酸氢钠5.5g,继续搅拌1小时，制得预聚体。将预聚体转入乳化釜中，加入7.22g二甲基乙醇胺，高速剪切下加水乳化，水温为20-25℃，最后加入异佛二酮二胺10％水溶液22.31g分散均匀，真空脱除丙酮，即制得亚硫酸氢钠封端的水性聚氨酯乳液。所得乳液的固含量为38％，粘度为90mPa.s，pH值：7.37。
合成革用粘合剂的原料组分：水性聚氨酯乳液70份，去离子水30份，消泡剂0.05份，润湿剂0.6份，流平剂0.03份，增稠剂0.3份。
将水性聚氨酯乳液300g，低速搅拌的条件下，缓慢加入消泡剂0.15g，润湿剂1.8g，流平剂0.09g，增稠剂0.9g，所制得的粘合剂pH值：7.21，粘度：2100mPa.s。无间隙刮涂，80℃烘干3分钟，胶膜仍能够100％贴合，无空隙，无渗料。
实施例4
将600g聚四氢呋喃醚二醇加入到装有搅拌器，温度计的四口烧瓶中，加热至120℃，抽真空脱水，真空度显示-0.08Mpa，1.5h后降温至75℃以下，降真空管口换为冷凝回流管，投入93.00g IPDI，25.00g HDI，加二丁基二月硅酸锡0.32g，混匀后升温至90-95℃，反应2小时；降低所得到的预聚体的温度至60℃，加入5.02g 1,4-丁二醇和24.89g二羟甲基丙酸，同时加入丙酮控制反应体系粘度，在70-75℃条件下，进行扩链反应，时间为3小时，将预聚体冷却至25-30℃，加入亚硫酸氢钠8.55g,继续搅拌1小时，制得预聚体。将预聚体转入乳化釜中，加入16.94g三乙胺，高速剪切下加水乳化，水温为20-25℃，最后加入乙二胺10％水溶液38.93g分散均匀，真空脱除丙酮，即制得亚硫酸氢钠封端的水性聚氨酯乳液。所得乳液的固含量为35％，粘度为60mPa.s，pH值：7.22。
合成革用粘合剂的原料组分：水性聚氨酯乳液80份，去离子水20份，消泡剂0.3份，润湿剂0.4份，流平剂0.06份，增稠剂0.3份。
将水性聚氨酯乳液600g，低速搅拌的条件下，缓慢加入消泡剂1.8g，润湿剂2.4g，流平剂0.36g，增稠剂1.8g，所制得的粘合剂pH值：7.11，粘度：2000mPa.s。无间隙刮涂，80℃烘干3分钟，胶膜仍能够100％贴合，无空隙，无渗料。
将实施例1-4所得的水性高固聚氨酯乳液进行制膜操作，选择现有技术制备的聚氨酯乳液也采用相同方法进行制膜操作，并对其拉伸强度和断裂伸长率进行检测；将实施例2-4制得的水性改性粘合剂，与现有的市售水性粘合剂作为对照例对比了粘结强度、耐热温度和半干状态时间，其结果如表一所示。
表一
最后应说明的是：以上实施例仅用以说明本发明的技术方案，而非对其限制；尽管参照前述实施例对本发明进行了详细的说明，本领域的普通技术人员应当理解：其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分技术特征进行等同替换；而这些修改或者替换，并不使相应技术方案的本质脱离本发明各实施例技术方案的精神和范围。
Claims (9)
1.一种合成革用水性改性粘合剂，其特征在于：包括如下重量份数的物质：
封端剂封端的水性聚氨酯乳液60-80份，去离子水20-40份，消泡剂0.01-0.05份，润湿剂0.1-1份，流平剂0.01-0.1份，增稠剂0.05-0.5份。
2.根据权利要求1所述的一种合成革用水性改性粘合剂，其特征在于：所述的封端剂封端的水性聚氨酯乳液包括如下重量份数的物质：
聚醚多元醇60-80份，二异氰酸酯14-30份，催化剂0.01-0.05份，小分子扩链剂0.5-1.5份，亲水性扩链剂3.3-4.5份，中和剂2.1-3.1份，封端剂1-2份，胺类扩链剂0.05-7份。
3.根据权利要求1所述的一种合成革用水性改性粘合剂，其特征在于：
所述的聚醚多元醇为聚四氢呋喃醚二醇；
所述的聚四氢呋喃二醇的分子量为3000，羟值为38±1mg KOH/g，-OH官能度为2。
4.根据权利要求1所述的一种合成革用水性改性粘合剂，其特征在于：
所述的二异氰酸酯为异佛二酮二异氰酸酯、六亚甲基二异氰酸酯其中的任意一种；
所述的催化剂为二丁基二月硅酸锡或辛酸亚锡其中的任意一种；
所述的小分子扩链剂为1,4-丁二醇或1,6-己二醇其中的任意一种或两种以任意比例混合的混合物；
所述的亲水性扩链剂为二羟甲基丙酸；
所述的封端剂为亚硫酸氢钠；
所述的碱性中和剂为三乙胺或N,N-二甲基乙醇胺其中的任意一种；
所述的胺类扩链剂为水合肼、乙二胺、异佛二酮二胺其中的任意一种。
5.根据权利要求1所述的一种合成革用水性改性粘合剂，其特征在于：所述的消泡剂为有机硅氧烷类消泡剂。
6.根据权利要求1所述的一种合成革用水性改性粘合剂，其特征在于：所述的润湿剂为烷酚聚氧乙烯醚非离子润湿剂。
7.根据权利要求1所述的一种合成革用水性改性粘合剂，其特征在于：所述的流平剂为有机硅流平剂。
8.根据权利要求1所述的一种合成革用水性改性粘合剂，其特征在于：所述的增稠剂为水性聚氨酯增稠剂。
9.一种合成革用水性改性粘合剂的制备方法，其特征在于：包括以下步骤：
步骤一：按照配比称取聚醚多元醇，磺酸型聚酯多元醇，二异氰酸酯，催化剂，小分子扩链剂，亲水性扩链剂，碱性中和剂，胺类扩链剂；
步骤二：向反应器中加入聚醚多元醇和磺酸型聚酯多元醇，在氮气的保护下，加入二异氰酸酯和催化剂的，反应温度80-90℃，反应1-2h，得预聚体；
步骤三：将步骤三得到的预聚体的温度降至50-70℃，加入小分子扩链剂和亲水性扩链剂，混合反应2-3h，制得含羧基的聚氨酯预聚体；
步骤四：将步骤三所得的羧基的聚氨酯预聚体降至20-30℃，加入封端剂，继续搅拌反应1h，
步骤五：将步骤三所得的被封端剂封端的含亲水基和羧基的聚氨酯预聚体导入乳化釜中，加入中和剂，在20-25℃的温度下，在800-1300r/min的转速下加入体积是被封端剂封端的含亲水基和羧基的聚氨酯预聚体1.1-1.7倍的去离子水乳化，乳化3-5min，加入胺类扩链剂，胺类扩链剂添加时间为3-5min，加完后继续搅拌分散10-30min，真空脱除有机溶剂，即制得封端剂封端的水性聚氨酯乳液；
步骤六：按照配比称量封端剂封端的水性聚氨酯乳液，消泡剂，润湿剂，流平剂，增稠剂；
步骤七：将封端剂封端的水性聚氨酯乳液放入反应器中在搅拌条件下加入消泡剂、润湿剂、流平剂，在转速200-400r/min的搅拌条件下，搅拌20-40min，助剂分散均后实时监测粘度，当达到指定粘度后既得至预定粘度即得水性改性粘合剂。
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103173179A (zh) * | 2013-03-07 | 2013-06-26 | 常州大学 | 一种层压复合织物用水性聚氨酯胶粘剂的制备方法 |
| CN104877538A (zh) * | 2015-05-19 | 2015-09-02 | 上海化工研究院 | 一种水性可剥离聚氨酯涂料及其制备方法 |
| CN108179001A (zh) * | 2017-12-21 | 2018-06-19 | 台州圣腾胶业有限公司 | 一种水性环保聚氨酯胶粘剂及其制造工艺和应用 |
| US20180271191A1 (en) * | 2017-03-27 | 2018-09-27 | Shujun Sang | High-elasticity polyurethane material |
-
2021
- 2021-02-05 CN CN202110160049.3A patent/CN113322044A/zh active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103173179A (zh) * | 2013-03-07 | 2013-06-26 | 常州大学 | 一种层压复合织物用水性聚氨酯胶粘剂的制备方法 |
| CN104877538A (zh) * | 2015-05-19 | 2015-09-02 | 上海化工研究院 | 一种水性可剥离聚氨酯涂料及其制备方法 |
| US20180271191A1 (en) * | 2017-03-27 | 2018-09-27 | Shujun Sang | High-elasticity polyurethane material |
| CN108179001A (zh) * | 2017-12-21 | 2018-06-19 | 台州圣腾胶业有限公司 | 一种水性环保聚氨酯胶粘剂及其制造工艺和应用 |
Non-Patent Citations (3)
| Title |
|---|
| 刘程等: "《表面活性剂应用手册》", 31 August 1995, 化学工业出版社 * |
| 强涛涛: "《合成革化学品》", 31 July 2016, 中国轻工业出版社 * |
| 李子东等: "《胶黏剂助剂》", 30 June 2009, 化学工业出版社 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114752341A (zh) * | 2022-05-17 | 2022-07-15 | 河北邦泰氨纶科技有限公司 | 一种封端型水性聚氨酯真空吸塑胶及其制备方法 |
| CN114752341B (zh) * | 2022-05-17 | 2024-01-30 | 河北邦泰氨纶科技有限公司 | 一种封端型水性聚氨酯真空吸塑胶及其制备方法 |
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