CN105601884A - 一种聚氨酯合成革水性表处用交联剂的制备方法 - Google Patents
一种聚氨酯合成革水性表处用交联剂的制备方法 Download PDFInfo
- Publication number
- CN105601884A CN105601884A CN201610141365.5A CN201610141365A CN105601884A CN 105601884 A CN105601884 A CN 105601884A CN 201610141365 A CN201610141365 A CN 201610141365A CN 105601884 A CN105601884 A CN 105601884A
- Authority
- CN
- China
- Prior art keywords
- synthetic leather
- preparation
- catalyst
- crosslinking agent
- place
- 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.)
- Pending
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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
- C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
- C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
-
- 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
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3855—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur
-
- 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
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3855—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur
- C08G18/3857—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur having nitrogen in addition to sulfur
-
- 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
- C08G18/4833—Polyethers containing oxyethylene units
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Treatment And Processing Of Natural Fur Or Leather (AREA)
- Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
Abstract
本发明涉及一种聚氨酯合成革水性表处用交联剂的制备方法,首先将各原料按重量份数多异氰酸酯100~140份、亲水改性剂1.5~2份、催化剂0.005~0.01份催化剂为脂肪胺类催化剂或金属有机物类催化剂、有机溶剂10~50份混合后进行加热,加热至50~130℃反应3~4h,真空减压脱除溶剂,制备得到聚氨酯合成革水性表处用交联剂。本发明制备方法简单,步骤易于操作,制备得到的交联剂稳定性较好,且在水性聚氨酯表处剂中分散性好,交联效果好。
Description
技术领域
本发明涉及一种聚氨酯合成革水性表处用交联剂的制备方法,属于交联剂制备技术领域。
背景技术
交联剂能够增加聚氨酯分子链间的交联结构,从而提高合成革水性聚氨酯表处剂成膜后的物化性能,是合成革水性聚氨酯表处剂的重要助剂,其中多异氰酸酯类交联剂具有交联效率高,交联温度低,成本低廉且毒性较低等优点。然而传统的多异氰酸酯交联剂主要为疏水的结构,难以在环保性的水性聚氨酯表处剂中进行应用。
发明内容
本发明的目的是为了解决传统的多异氰酸酯交联剂无法在水性聚氨酯表处剂中分散性差交联效果不佳的问题,提供了一种制备方法简单,步骤易于操作的聚氨酯合成革水性表处用交联剂的制备方法,制备得到的交联剂稳定性较好,且在水性聚氨酯表处剂中分散性好,交联效果好。
本发明采用如下技术方案:一种聚氨酯合成革水性表处用交联剂的制备方法,包括如下步骤:
(1)将原料一种或两种多异氰酸酯、亲水改性剂、催化剂和有机溶剂依次添加到装有冷凝回流装置的密闭三口烧瓶中,通入氮气保护,加热至50~130℃反应,其中各原料按重量份数计分别为:多异氰酸酯100~140份、亲水改性剂1.5~2份、催化剂0.005~0.01份、有机溶剂10~50份,所述催化剂为脂肪胺类催化剂或金属有机物类催化剂;
(2)反应3~4h后,每隔半小时检测一次异氰酸根(-NCO)含量,直至-NCO含量达到加入量的10-25%后,真空减压脱出溶剂,制备得到聚氨酯合成革水性表处用交联剂产品;
(3)待溶剂脱除完毕后,停止加热,冷却至室温,取少量产品分散于水中,观察分散情况,若均匀分散于水中,无油状小液滴和沉淀产生,将产品封装于充有氮气保护的密封玻璃瓶中。
进一步的,所述多异氰酸酯为六亚甲基二异氰酸酯、异氟尔酮二异氰酸酯、甲苯二异氰酸酯、二苯基甲烷二异氰酸酯的三聚体或二苯基甲烷二异氰酸酯的二聚体。
进一步的,所述亲水改性剂为聚乙二醇单甲醚或含有端羟基/端氨基/亚胺基的磺酸盐混合物。
进一步的,所述脂肪胺类催化剂为三乙胺、三乙烯二胺、四甲基丁二胺。
进一步的,所述金属有机物类催化剂为二丁基二月桂酸锡、辛酸亚锡、环烷酸锌或有机Ag金属盐催化剂中的一种。
进一步的,所述有机溶剂为丙酮、丁酮、乙酸乙酯、乙酸丁酯、甲苯、N,N-二甲基甲酰胺、N-甲基吡咯烷酮中的一种。
进一步的,所述有机溶剂在使用前需浸泡在活化后的3A或4A分子筛中20~24小时。
本发明制备方法简单,步骤易于操作,制备得到的交联剂稳定性较好,且在水性聚氨酯表处剂中分散性好,交联效果好,能够提高合成革水性聚氨酯表处剂胶膜的抗拉强度,降低合成革水性聚氨酯表处剂胶膜的吸水率和溶胀率。
具体实施方式
下面将结合具体实施例对本发明作进一步的说明。
实施例一:
首先按重量份数分别加入140份的HDI三聚体、2份亲水改性剂(MPEG350与氨乙基磺酸,质量比3:5)、0.006份三乙胺和20份丁酮加入到装有冷凝回流装置的密闭三口烧瓶中,通入氮气保护,室温搅拌15min后,升温至80℃反应3h后每隔半小时检测一次-NCO含量,直至-NCO含量达到加入量的10%后,减压脱除丁酮,待反应器冷却至室温后,检测产品水分散性,若均匀分散于水中,无油状小液滴和沉淀产生则合格,合格后倒入玻璃瓶中密闭保存。
实施例二:
在干燥的装有冷凝回流装置和150℃量程温度计的250ml三口烧瓶中按重量份数分别加入100份HDI三聚体/HDI二聚体混合物(质量比5:1)、2份亲水改性剂(MPEG350与环己氨基乙磺酸,质量比3:5)、0.01份三乙胺和10份丁酮加入到装有冷凝回流装置的密闭三口烧瓶中,通入氮气保护,室温搅拌15min后,升温至100℃反应3h后每隔半小时检测一次-NCO含量,直至-NCO含量达到加入量的20%后,减压脱除丁酮,待反应器冷却至室温后,检测产品水分散性,若均匀分散于水中,无油状小液滴和沉淀产生则合格,合格后倒入玻璃瓶中密闭保存。
实施例三:
在干燥的装有冷凝回流装置和150℃量程温度计的250ml三口烧瓶中按重量份数分别加入100份HDI三聚体和HDI二聚体混合物,其中HDI三聚体和HDI二聚体的质量比5:1、1.5份亲水改性剂(MPEG500与羟乙基磺酸钠,质量比2:6)、0.005份DBTDL和23份N-甲基吡咯烷酮加入到装有冷凝回流装置的密闭三口烧瓶中,通入氮气保护,室温搅拌15min后,升温至100℃反应4h后每隔半小时检测一次-NCO含量,直至-NCO含量达到加入量的25%后,减压脱除N-甲基吡咯烷酮,待反应器冷却至室温后,检测产品水分散性,若均匀分散于水中,无油状小液滴和沉淀产生则合格,合格后倒入玻璃瓶中密闭保存。
对实施例一制备得到的聚氨酯合成革水性表处用交联剂进行性能检测,结果如表1:
表1
对加入本发明制备的交联剂和未加入交联剂的合成革水性聚氨酯表处剂成膜进行性能检测,结果如表2。
表2
性能 | 未加交联剂 | 加入本发明交联剂 |
60°光泽度 | 49 | 72 |
柔软度/mm | 6.65 | 4.75 |
吸水率/% | 32.3 | 12.4 |
溶胀率/% | 33.8 | 14.9 |
抗拉强度/MPa | 2.4 | 10.2 |
断裂伸长率/% | 476 | 285 |
Tg/℃ | -53 | -45.9 |
10%失重温度/℃ | 330.9 | 338.3 |
由表2可知,加入本发明的交联剂后,合成革水性聚氨酯表处剂胶膜的光泽度提高,吸水率和溶胀率都得到了一定程度的降低,合成革水性聚氨酯表处剂胶膜的抗拉强度由2.4MPa提高至10.2MPa,断裂伸长率降低至285%。
Claims (7)
1.一种聚氨酯合成革水性表处用交联剂的制备方法,其特征在于:包括如下步骤:
(1)将原料一种或两种多异氰酸酯、亲水改性剂、催化剂和有机溶剂依次添加到装有冷凝回流装置的密闭三口烧瓶中,通入氮气保护,加热至50~130℃反应,其中各原料按重量份数计分别为:多异氰酸酯100~140份、亲水改性剂1.5~2份、催化剂0.005~0.01份、有机溶剂10~50份,所述催化剂为脂肪胺类催化剂或金属有机物类催化剂;
(2)反应3~4h后,每隔半小时检测一次异氰酸根(-NCO)含量,直至-NCO含量达到加入量的10-25%后,真空减压脱出溶剂,制备得到聚氨酯合成革水性表处用交联剂产品;
(3)待溶剂脱除完毕后,停止加热,冷却至室温,取少量产品分散于水中,观察分散情况,若均匀分散于水中,无油状小液滴和沉淀产生,将产品封装于充有氮气保护的密封玻璃瓶中。
2.如权利要求1所述的聚氨酯合成革水性表处用交联剂的制备方法,其特征在于:所述多异氰酸酯为六亚甲基二异氰酸酯、异氟尔酮二异氰酸酯、甲苯二异氰酸酯、二苯基甲烷二异氰酸酯的三聚体或二苯基甲烷二异氰酸酯的二聚体。
3.如权利要求1所述的聚氨酯合成革水性表处用交联剂的制备方法,其特征在于:所述亲水改性剂为聚乙二醇单甲醚或含有端羟基/端氨基/亚胺基的磺酸盐混合物。
4.如权利要求1所述的聚氨酯合成革水性表处用交联剂的制备方法,其特征在于:所述脂肪胺类催化剂为三乙胺、三乙烯二胺或四甲基丁二胺。
5.如权利要求1所述的聚氨酯合成革水性表处用交联剂的制备方法,其特征在于:所述金属有机物类催化剂为二丁基二月桂酸锡、辛酸亚锡、环烷酸锌或有机Ag金属盐催化剂中的一种。
6.如权利要求1所述的聚氨酯合成革水性表处用交联剂的制备方法,其特征在于:所述有机溶剂为丙酮、丁酮、乙酸乙酯、乙酸丁酯、甲苯、N,N-二甲基甲酰胺、N-甲基吡咯烷酮中的一种。
7.如权利要求1所述的聚氨酯合成革水性表处用交联剂的制备方法,其特征在于:所述有机溶剂在使用前需浸泡在活化后的3A或4A分子筛中20~24小时。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201610141365.5A CN105601884A (zh) | 2016-03-11 | 2016-03-11 | 一种聚氨酯合成革水性表处用交联剂的制备方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201610141365.5A CN105601884A (zh) | 2016-03-11 | 2016-03-11 | 一种聚氨酯合成革水性表处用交联剂的制备方法 |
Publications (1)
Publication Number | Publication Date |
---|---|
CN105601884A true CN105601884A (zh) | 2016-05-25 |
Family
ID=55982283
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201610141365.5A Pending CN105601884A (zh) | 2016-03-11 | 2016-03-11 | 一种聚氨酯合成革水性表处用交联剂的制备方法 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN105601884A (zh) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109843955A (zh) * | 2016-10-11 | 2019-06-04 | 旭化成株式会社 | 多异氰酸酯组合物 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101885829A (zh) * | 2010-07-12 | 2010-11-17 | 中科院广州化学有限公司 | 一种醇类封端非离子型聚氨酯交联剂及其制备方法和应用 |
CN102516187A (zh) * | 2011-12-06 | 2012-06-27 | 东华大学 | 一种氨基磺酸盐改性异氰酸酯三聚体及其制备方法 |
CN103554430A (zh) * | 2013-10-10 | 2014-02-05 | 陕西科技大学 | 一种封闭型多异氰酸酯交联剂水乳液的制备方法 |
CN103626956A (zh) * | 2013-11-22 | 2014-03-12 | 深圳市新纶科技股份有限公司 | 一种改性多异氰酸酯、水分散性交联剂及其制备方法 |
-
2016
- 2016-03-11 CN CN201610141365.5A patent/CN105601884A/zh active Pending
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101885829A (zh) * | 2010-07-12 | 2010-11-17 | 中科院广州化学有限公司 | 一种醇类封端非离子型聚氨酯交联剂及其制备方法和应用 |
CN102516187A (zh) * | 2011-12-06 | 2012-06-27 | 东华大学 | 一种氨基磺酸盐改性异氰酸酯三聚体及其制备方法 |
CN103554430A (zh) * | 2013-10-10 | 2014-02-05 | 陕西科技大学 | 一种封闭型多异氰酸酯交联剂水乳液的制备方法 |
CN103626956A (zh) * | 2013-11-22 | 2014-03-12 | 深圳市新纶科技股份有限公司 | 一种改性多异氰酸酯、水分散性交联剂及其制备方法 |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109843955A (zh) * | 2016-10-11 | 2019-06-04 | 旭化成株式会社 | 多异氰酸酯组合物 |
CN109843955B (zh) * | 2016-10-11 | 2021-08-06 | 旭化成株式会社 | 多异氰酸酯组合物 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5035792B2 (ja) | 有機溶剤がなく、架橋剤として使用できる、安定したポリカルボジイミド分散液を製造する方法 | |
CN101531861B (zh) | 一种双组份喷涂聚脲防水涂料,其制备方法及施工方法 | |
He et al. | Facile and cost-effective synthesis of isocyanate microcapsules via polyvinyl alcohol-mediated interfacial polymerization and their application in self-healing materials | |
CN107586510B (zh) | 一种耐腐蚀聚氨酯改性环氧树脂乳液的制备方法 | |
EP2087023B1 (de) | Lösungen blockerter polyimide bzw. polyamidimide | |
CN105461891B (zh) | 一种具有良好耐温性能的柔性聚氨酯树脂及其制备方法 | |
CN101302394A (zh) | 脂肪族喷涂聚脲弹性体及其制备方法和施工方法 | |
CN104292412A (zh) | 一种纤维素基聚氨酯预聚体及使用其的密封材料、制备方法和应用 | |
CN103833956A (zh) | 一种大分子量聚氨酯丙烯酸酯树脂及其制备方法 | |
CN108299613B (zh) | 一种抗菌型阴离子水性聚氨酯树脂及其制备方法 | |
CN108610621A (zh) | 一种高吸声性低密度聚氨酯半硬质泡沫及其制备方法 | |
CN101818018A (zh) | 刮涂型聚脲防水涂料 | |
CN107903372A (zh) | 一种uv光固化柔性超支化聚氨酯丙烯酸酯树脂及其制备方法与应用 | |
Shen et al. | Synthesis and characterization of reactive blocked‐isocyanate coupling agents from methyl ethyl ketoxime, ethyl cellosolve/ε‐caprolactam blocked aromatic and aliphatic diisocyanates | |
CN107141442A (zh) | 一种端羟基液体橡胶改性水性聚氨酯消光树脂的方法 | |
CN104448308A (zh) | 聚乙烯亚胺骨架的水性封闭型聚异氰酸酯交联剂及其制备方法 | |
CN105504212A (zh) | 一种耐湿热老化聚氨酯弹性体的制备方法 | |
CN105601884A (zh) | 一种聚氨酯合成革水性表处用交联剂的制备方法 | |
CN104327696A (zh) | 一种聚碳酸酯多元醇型喷涂聚脲弹性体涂料及制备方法 | |
CN106832195A (zh) | 改性阳离子水性聚氨酯树脂及其制备方法 | |
Li et al. | Hydroxyl‐terminated polybutadiene based waterborne polyurethane acrylate emulsions: synthesis, characterization, and damping property | |
CN106928427A (zh) | 二氧化碳基阳离子水性聚氨酯树脂及其制备方法和应用 | |
CN105153904A (zh) | 一种聚脲防护涂料及其制备方法 | |
Liu et al. | Preparation and characterization of castor oil-based cationic waterborne polyurethane | |
RU2007105542A (ru) | Функционализованные водные смолы |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
RJ01 | Rejection of invention patent application after publication |
Application publication date: 20160525 |
|
RJ01 | Rejection of invention patent application after publication |