CN111454420B - 一种高固含羧酸型水性聚氨酯的制备方法 - Google Patents

一种高固含羧酸型水性聚氨酯的制备方法 Download PDF

Info

Publication number
CN111454420B
CN111454420B CN202010286203.7A CN202010286203A CN111454420B CN 111454420 B CN111454420 B CN 111454420B CN 202010286203 A CN202010286203 A CN 202010286203A CN 111454420 B CN111454420 B CN 111454420B
Authority
CN
China
Prior art keywords
solvent
chain extender
dmpa
waterborne polyurethane
mass ratio
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202010286203.7A
Other languages
English (en)
Other versions
CN111454420A (zh
Inventor
曲建波
王建勇
张志浩
张海涛
张维栋
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Anhui Huada Chemicals Co ltd
Original Assignee
Qilu University of Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Qilu University of Technology filed Critical Qilu University of Technology
Priority to CN202010286203.7A priority Critical patent/CN111454420B/zh
Publication of CN111454420A publication Critical patent/CN111454420A/zh
Application granted granted Critical
Publication of CN111454420B publication Critical patent/CN111454420B/zh
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • C08G18/6677—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203 having at least three hydroxy groups
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3206—Polyhydroxy compounds aliphatic
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
    • C08G18/348—Hydroxycarboxylic acids
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/6692—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/34

Abstract

本发明提供一种高固含羧酸型水性聚氨酯的制备方法，所述水性聚氨酯固含量≥40%；断裂伸长率≥780%，吸水率≤33%。本发明制备的水性聚氨酯乳液，外观为乳白色液体，乳液粒径为195‑200 nm，外观为乳白色液体，拉伸强度为6.1‑6.3MPa，断裂伸长率为780‑786.1%；吸水率为30‑33%。

Description

一种高固含羧酸型水性聚氨酯的制备方法
技术领域
本发明涉及合成革化学品技术领域，尤其涉及一种高固含羧酸型水性聚氨酯的制备方法。
背景技术
水性聚氨酯（WPU）乳液因其乳液连续相为水相，安全易储存，使用方便成本低，越来越收到了世界各国的重视，但是在早期勘探中，WPU的固体含量仅为25％-40％，以蒸发潜热高的水为介质导致干燥的速度比较慢，使得干燥成本和运输成本比较高。而高固含量的WPU成为了一个特殊而重要的研究方向。
目前市场上所销售的水性聚氨酯固含量大多为20％-40％，虽然其环保安全但是干燥过程中，水的蒸发潜热比有机溶剂的蒸发潜热高，相同固含量下，水性聚氨酯干燥时间比溶剂型的要长，且运输费用较高，提高乳液固含量是重要的研究方向，如果乳液固含量达到45％以上，在40~60℃干燥温度下其干燥速率可与普通溶剂型聚氨酯树脂在室温的干燥速率相近。
但是固含量高的水性聚氨酯乳液，容易导致稳定性差；
现有技术中采用DMPA作为扩链剂，制备的水性聚氨酯的吸水率较高。
发明内容
针对以上技术问题，本发明提供一种高固含羧酸型水性聚氨酯及其制备方法，并达到以下发明目的：制备高固含水性聚氨酯的同时，使得聚氨酯乳液具有很好的稳定性；降低吸水率。
为达到以上发明目的，本发明采用以下技术方案：
一种高固含羧酸型水性聚氨酯的制备方法，所述水性聚氨酯固含量≥40%；断裂伸长率≥780%，吸水率≤33%。
所述制备方法，包括聚合反应、加入扩链剂和溶剂、加入中和剂；所述扩链剂，为DMPA和丁二醇，质量比例为5-5.2:0.12-0.14。
所述聚合反应，调节反应温度至85-90℃，以重量份计，加入异氰酸酯20-25份、多元醇45-55份、小分子扩链剂0.1-0.3份，反应0.5-1h后加入催化剂0.1-0.3份，继续反应1-1.5h。
所述小分子扩链剂为三羟甲基丙烷；所述多元醇为聚四氢呋喃二元醇；
所述异氰酸酯为甲苯二异氰酸酯；所述的催化剂为辛酸亚锡。
所述加入扩链剂和溶剂，加入DMPA、丁二醇和溶剂，80-88℃反应1.5-3h；
所述的溶剂为N-甲基吡咯烷酮。
所述DMPA与异氰酸酯的质量比为5-5.2: 20-25；所述DMPA与N-甲基吡咯烷酮的质量比为5-5.2:6-8。
所述加入中和剂，降温至45-60℃，加入溶剂和中和剂TEA，中和成盐0.5h，得到端NCO基封端的聚氨酯预聚体。
所述中和剂与DMPA的质量比为3.4-3.6：5-5.2；
所述的溶剂为丁酮；所述的中和剂为三乙胺； 所述溶剂与中和剂的质量比为5-7：3.4-3.6。
所述制备方法，还包括后处理，所述后处理，将上述聚氨酯预聚体在剪切速度1200-1800r/min状态下分散到去离子水中，减压蒸馏脱除溶剂，随后将其在室温下放置不做处理让其自然熟化2-4天得到水性聚氨酯乳液。
所述去离子水与聚氨酯预聚体的质量比为1:1。
与现有技术相比，本发明具有以下有益效果：
本发明制备的水性聚氨酯乳液，乳液粒径为195-200 nm，外观为乳白色液体，拉伸强度为6.1-6.3MPa，断裂伸长率为780-786.1%；吸水率为30-33%。
具体实施方式
以下实例对本发明做进一步说明，并非限制本发明的范围。
实施例1：一种高固含羧酸型水性聚氨酯的制备方法，包括以下步骤：
步骤1、聚合反应
将多元醇在80℃下、0.08Mpa真空脱水3h，调节反应温度至88℃，按照配比加入异氰酸酯（20份）、多元醇（50份）、小分子扩链剂（0.3份）；反应0.5h后加入催化剂0.1份， 继续反应1.2h。
所述的小分子扩链剂为三羟甲基丙烷；
所述多元醇为聚四氢呋喃二元醇；
所述异氰酸酯为甲苯二异氰酸酯；
所述的催化剂为辛酸亚锡。
步骤2、加入扩链剂和溶剂
加入5.1质量份亲水扩链剂、0.13质量份丁二醇（BG）和6质量份溶剂，85℃反应2h；
所述的溶剂选用N-甲基吡咯烷酮；
所述亲水扩链剂为2,2-二羟甲基丙酸（DMPA）。
步骤3、加入中和剂
在上述反应基础上，关闭加热装置，降温至50℃，加入6质量份溶剂和3.5质量份中和剂TEA，中和成盐0.5h，得到端NCO基封端的聚氨酯预聚体；
所述的溶剂为丁酮；
所述的中和剂为三乙胺。
步骤4、后处理
将上述预聚体在剪切速度1500r/min状态下分散到去离子水中，减压蒸馏脱除溶剂，随后将其在室温下放置不做处理让其自然熟化3天得到固含量为41.5%的水性聚氨酯乳液。
所述去离子水与步骤3制备的聚氨酯预聚体的质量比为1:1。
实施例1制备的水性聚氨酯乳液，乳液粒径为198.2 nm，外观为乳白色液体，拉伸强度为6.2MPa，断裂伸长率为786.1%；吸水率为33%。
实施例2
在实施例1基础上，对比例1-5更改的因素为：
对比例1-4为改变步骤2中扩链剂的种类、用量，具体改变之处见表1-3，其余条件同实施例1，对比例5除了改变步骤2中扩链剂的用量，还改变了步骤3中和剂的加入方式，改变为将中和剂加入水中，然后将预聚体分散到水中进行中和反应，其余条件同实施例1；
制备的水性聚氨酯，效果指标如下表1-3：
表1
Figure DEST_PATH_IMAGE001
通过表1可见，对比例1-3的步骤2，只采用DMPA作为扩链剂时，制备的水性聚氨酯，固含量相对较低，对比例4-5的固含量有所提高，但是对比例5的粒径显著增大，不利于乳液的稳定性，对比例4的断裂伸长率和吸水率指标不理想（具体见表2和表3）。
实施例3：
表2
Figure 566647DEST_PATH_IMAGE002
速度、宽度、厚度、标距是指拉伸强度、断裂伸长率测量是所用模具尺寸以及水性聚氨酯薄膜的厚度。
表2可见，实施例1在保证拉伸强度的同时，可以明显提高断裂伸长率。
实施例4：
表3
Figure DEST_PATH_IMAGE003
W0是指薄膜原有的质量， W1是指将薄膜浸泡在蒸馏水48h后取出后称量的质量。
表3可见，实施例1可以明显降低水性聚氨酯的吸水率。
除非特殊说明，本发明采用的比例均为质量比例，采用的百分比，均为质量百分比。

Claims (1)

1.一种高固含羧酸型水性聚氨酯的制备方法，其特征在于：所述水性聚氨酯固含量≥40%；断裂伸长率≥780%，吸水率≤33%；
所述制备方法，包括聚合反应、加入扩链剂和溶剂、加入中和剂；所述扩链剂，为DMPA和丁二醇，质量比例为5.10:0.13；
所述聚合反应，调节反应温度至85-90℃，以重量份计，加入异氰酸酯20-25份、多元醇45-55份、小分子扩链剂0.1-0.3份，反应0.5-1h后加入催化剂0.1-0.3份，继续反应1-1.5h；
所述小分子扩链剂为三羟甲基丙烷；所述多元醇为聚四氢呋喃二元醇；
所述异氰酸酯为甲苯二异氰酸酯；所述的催化剂为辛酸亚锡；
所述加入扩链剂和溶剂，加入DMPA、丁二醇和溶剂，80-88℃反应1.5-3h；
所述的溶剂为N-甲基吡咯烷酮；
所述DMPA与异氰酸酯的质量比为5.10:（20-25）；所述DMPA与N-甲基吡咯烷酮的质量比为5.10:（6-8）；
所述加入中和剂，降温至45-60℃，加入溶剂和中和剂TEA，中和成盐0.5h，得到端NCO基封端的聚氨酯预聚体；
所述中和剂与DMPA的质量比为（3.4-3.6）：5.10；所述的溶剂为丁酮；所述的中和剂为三乙胺；所述溶剂与中和剂的质量比为（5-7）：（3.4-3.6）。
CN202010286203.7A 2020-04-13 2020-04-13 一种高固含羧酸型水性聚氨酯的制备方法 Active CN111454420B (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010286203.7A CN111454420B (zh) 2020-04-13 2020-04-13 一种高固含羧酸型水性聚氨酯的制备方法

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010286203.7A CN111454420B (zh) 2020-04-13 2020-04-13 一种高固含羧酸型水性聚氨酯的制备方法

Publications (2)

Publication Number Publication Date
CN111454420A CN111454420A (zh) 2020-07-28
CN111454420B true CN111454420B (zh) 2022-03-29

Family

ID=71675450

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010286203.7A Active CN111454420B (zh) 2020-04-13 2020-04-13 一种高固含羧酸型水性聚氨酯的制备方法

Country Status (1)

Country Link
CN (1) CN111454420B (zh)

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19849702B9 (de) * 1998-10-28 2004-09-09 Degussa Construction Chemicals Gmbh Verfahren zur Herstellung einer Polyurethan-Polymer-Hybrid-Dispersion mit hoher Filmhärte sowie deren Verwendung
DE19858554A1 (de) * 1998-12-18 2000-06-21 Sueddeutsche Kalkstickstoff Selbstvernetzende Polyurethan-Polymer-Hybrid-Dispersion
CN101348703B (zh) * 2008-06-20 2012-06-06 中山大学 一种水性聚氨酯胶粘剂及其制备方法
CN101906192B (zh) * 2010-08-04 2012-05-09 中山大学 一种水性聚氨酯-丙烯酸酯复合乳液的制备方法
CN102219886B (zh) * 2011-05-23 2012-08-29 福州大学 一种高固含量水性聚氨酯乳液的制备方法
CN102746784B (zh) * 2012-07-30 2014-11-19 江苏瑞丰科技实业有限公司 一种节能保温阻燃防水防腐功能涂料及其制备方法
CN103450438A (zh) * 2013-09-03 2013-12-18 山东天庆科技发展有限公司 一种高固含量水性聚氨酯树脂及其合成方法
CN107057027B (zh) * 2017-01-16 2019-08-20 北京理工大学 一种高固含量低粘度水性聚氨酯的制备方法
CN110128615B (zh) * 2019-05-10 2022-04-15 江苏奥斯佳材料科技股份有限公司 一种水性聚氨酯及其制备方法和应用
CN110272530A (zh) * 2019-05-24 2019-09-24 合肥科天水性科技有限责任公司 一种多粒径羧酸型水性聚氨酯的制备方法及应用

Also Published As

Publication number Publication date
CN111454420A (zh) 2020-07-28

Similar Documents

Publication Publication Date Title
CN103981716A (zh) 一种皮革用有机硅改性水性聚氨酯的制备方法及制品
CN109456459B (zh) 一种提高水性聚氨酯耐水或耐溶剂性的方法
CN101429417A (zh) 高粘结性水性聚氨酯胶粘剂及其制备方法
CN103524708A (zh) 封闭水性聚氨酯改性pae湿强剂的制备方法
CN102964559A (zh) 一种用于uv固化水性聚氨酯涂料的高支化度聚酯多元醇的制备和应用方法
CN108264621B (zh) 一种水性聚氨酯非均相扩链合成方法
CN104695231A (zh) 一种防水透湿水性聚氨酯织物涂层材料及其制备方法
CN110845775A (zh) 一种耐磨抗压的高性能橡胶及其制备方法
CN111454420B (zh) 一种高固含羧酸型水性聚氨酯的制备方法
CN108299613A (zh) 一种抗菌型阴离子水性聚氨酯树脂及其制备方法
CN113444221A (zh) 一种环氧树脂改性水性聚氨酯的制备方法
CN110218396B (zh) 一种uv印刷胶辊及其制备方法
CN109942785B (zh) 一种羧基化氧化石墨烯改性羧酸型水性聚氨酯的制备方法
CN110105553B (zh) 超支化聚酯改性衣康酸基水性光固化树脂及其制备方法
CN108727931B (zh) 一种适用于头层牛皮的底层涂饰剂的制备方法
CN111057210A (zh) 一种水性聚氨酯涂层剂及其制备方法和应用
CN113527624B (zh) 透明聚氨酯弹性体及其制备方法
CN110606920A (zh) 一种水性丙烯酸改性聚氨酯树脂的制备方法
CN112898520B (zh) 一种水性聚氨酯分散体及其合成方法
CN111303370A (zh) 一种采用后扩链剂制备水性聚氨酯的方法
CN103526326A (zh) 一种抗蠕变聚酯的高模低缩型活化工业丝及其制备方法
CN102978943A (zh) 一种无助剂的棉织物整理剂及其制备方法
CN114316202A (zh) 一种紫外光固化水性聚氨酯丙烯酸酯乳液及其制备方法
CN103526327A (zh) 一种抗蠕变聚酯的高模低缩工业丝及其制备方法
CN114045024B (zh) 一种强韧耐磨磷酸钙寡聚物-水性聚氨酯材料及制备方法

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
TR01 Transfer of patent right
TR01 Transfer of patent right

Effective date of registration: 20230912

Address after: 235200 YONGGU Light Chemical Industrial Park, Xiaoxian County, Suzhou City, Anhui Province

Patentee after: ANHUI HUADA CHEMICALS Co.,Ltd.

Address before: 250353 University Road, Changqing District, Ji'nan, Shandong Province, No. 3501

Patentee before: Qilu University of Technology