CN102443135B - Single-component curing agent capable of being deblocked at low temperature - Google Patents
Single-component curing agent capable of being deblocked at low temperature Download PDFInfo
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- CN102443135B CN102443135B CN201110335756.8A CN201110335756A CN102443135B CN 102443135 B CN102443135 B CN 102443135B CN 201110335756 A CN201110335756 A CN 201110335756A CN 102443135 B CN102443135 B CN 102443135B
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- 239000003795 chemical substances by application Substances 0.000 claims abstract description 25
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 claims abstract description 12
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims abstract description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 7
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 4
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 3
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 3
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 abstract description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 3
- 229920005989 resin Polymers 0.000 abstract description 2
- 239000011347 resin Substances 0.000 abstract description 2
- 239000000565 sealant Substances 0.000 abstract 1
- 238000007789 sealing Methods 0.000 abstract 1
- 238000001723 curing Methods 0.000 description 18
- 238000000576 coating method Methods 0.000 description 11
- 239000011248 coating agent Substances 0.000 description 8
- 239000002981 blocking agent Substances 0.000 description 4
- 239000012948 isocyanate Substances 0.000 description 4
- 150000002513 isocyanates Chemical class 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 3
- 238000013035 low temperature curing Methods 0.000 description 3
- 238000002411 thermogravimetry Methods 0.000 description 3
- 239000003973 paint Substances 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000001962 electrophoresis Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
Images
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- Polyurethanes Or Polyureas (AREA)
- Sealing Material Composition (AREA)
Abstract
Description
技术领域 technical field
本发明涉及一种低温解封单组份固化剂，具体而言涉及单组分固化剂及其制备和应用。The invention relates to a low-temperature unblocking one-component curing agent, in particular to a one-component curing agent and its preparation and application.
背景技术 Background technique
与传统的溶剂型涂料和其它浸涂、喷涂水性烘烤漆相比，低温固化阴极电泳涂料具有无可比拟的优越性：①烘干温度低，节省燃料费用。采用低温固化型阴极电泳涂料后，可使涂料使用量降低约10％；低温固化烘烤，温度降低10％，可节能10％。；②烘干时不产生烟及烟油。减轻电泳烘干炉污染，减少废气排放量，有利于环保；③涂装汽车底盘等大型工件时不会产生应变，减少漆膜因烘烤的色变，从而提高涂膜质量；④可整件涂装塑料、橡胶与钢板组装工件；⑤可涂装铸件等壁厚的工件。涂层耐蚀性能优良，覆盖能力好，涂装设备自动化程度高，涂料利用率高。然而，要得到低温解封阴极电泳漆，首先要制备一种能在低温下解封的单组份固化剂.Compared with traditional solvent-based coatings and other dipping and spraying water-based baking varnishes, low-temperature curing cathodic electrophoretic coatings have incomparable advantages: ① Low drying temperature, saving fuel costs. After adopting low-temperature curing cathodic electrophoretic coating, the amount of coating can be reduced by about 10%; low-temperature curing and baking can reduce the temperature by 10% and save energy by 10%. ; ② No smoke and smoke oil will be produced during drying. Reduce the pollution of the electrophoresis drying furnace, reduce the emission of exhaust gas, and be beneficial to environmental protection; ③When coating large workpieces such as automobile chassis, there will be no strain, which will reduce the color change of the paint film due to baking, thereby improving the quality of the coating film; ④The whole piece can be used Coating plastic, rubber and steel plate assembly workpieces; ⑤ Coating workpieces with wall thickness such as castings. The coating has excellent corrosion resistance, good coverage, high degree of automation of coating equipment, and high utilization rate of coatings. However, in order to obtain low-temperature unblocking cathodic electrophoretic paint, a one-component curing agent that can be unblocked at low temperature must first be prepared.
本发明公开了一种己内酰胺作为封闭剂封闭TDI获得的低温解封单组份固化剂，具有快干、高硬度、强附着性等优点，而且能够提高其与羟基树脂的相容性，扩充其使用范围。The invention discloses a low-temperature unblocking single-component curing agent obtained by blocking TDI with caprolactam as a blocking agent. It has the advantages of fast drying, high hardness, strong adhesion, etc., and can improve its compatibility with hydroxyl resins, expand its scope of use.
发明内容 Contents of the invention
为了能够获得能够与羟基数值相容的低温解封单组份固化剂，本发明采用如下的技术方案：In order to obtain a low-temperature unblocking single-component curing agent compatible with the hydroxyl value, the present invention adopts the following technical scheme:
本发明一方面涉及一种低温解封单组份固化剂，其特征在于是以己内酰胺作为封闭剂封端的聚甲苯二异氰酸酯。One aspect of the present invention relates to a low-temperature unblocking one-component curing agent, which is characterized in that caprolactam is used as a blocking agent to block polytoluene diisocyanate.
在本发明的一个优选实施方式中，其特征在乙二醇单丁醚进行单组分固化剂的封端反应得到本发明的低温解封单组份固化剂。In a preferred embodiment of the present invention, it is characterized in that the one-component curing agent is subjected to a capping reaction in ethylene glycol monobutyl ether to obtain the low-temperature unblocking one-component curing agent of the present invention.
本发明还涉及上述低温解封单组份固化剂的制备方法，其特征在于包括如下步骤：(1)容器中加入甲苯二异氰酸酯和催化剂，加热容器并控制温度在50℃到55℃之间；(2)在容器中加入含有甲醇、乙二醇单丁醚和己内酰胺的混合溶液；(3)反应容器中加入一定量的三羟基丙烷。The present invention also relates to the preparation method of the above-mentioned low-temperature unblocking one-component curing agent, which is characterized in that it comprises the following steps: (1) adding toluene diisocyanate and a catalyst into the container, heating the container and controlling the temperature between 50°C and 55°C; (2) adding a mixed solution containing methanol, ethylene glycol monobutyl ether and caprolactam into the container; (3) adding a certain amount of trihydroxypropane into the reaction container.
在本发明的一个优选实施方式中，其特征在于步骤(1)中的催化剂是二月桂酸二丁基锡。In a preferred embodiment of the present invention, it is characterized in that the catalyst in step (1) is dibutyltin dilaurate.
在本发明的一个优选实施方式中，其特征在于步骤(2)中的混合溶液缓慢滴加到反应容器中，在步骤(3)中加入三羟甲基丙烷之后，将反应体系升温到75-95℃之间进行反应。In a preferred embodiment of the present invention, it is characterized in that the mixed solution in step (2) is slowly added dropwise in the reaction vessel, after adding trimethylolpropane in step (3), the reaction system is warmed up to 75- The reaction was carried out between 95°C.
在本发明的一个优选实施方式中，其特征在于还包括用二正丁胺法测定-NCO的含量来判断反应完成情况的步骤。In a preferred embodiment of the present invention, it is characterized in that it also includes the step of measuring the content of -NCO by di-n-butylamine method to judge the completion of the reaction.
本发明还涉及上述低温解封单组份固化剂作为固化剂的应用。The present invention also relates to the application of the above-mentioned low-temperature deblocking one-component curing agent as a curing agent.
附图说明： Description of drawings:
图1：低温解封单组份固化剂的红外光谱；Figure 1: Infrared spectrum of low-temperature deblocking one-component curing agent;
图2：低温解封单组份固化剂解封温度及其热重分析。Figure 2: Unblocking temperature and thermogravimetric analysis of low-temperature unblocking one-component curing agent.
具体实施方式 Detailed ways
实施例1：Example 1:
1.1 原料1.1 Raw materials
制备步骤preparation steps
(1)在装有温度计、搅拌器、冷凝管的250ml三口烧瓶中加入甲苯二异氰酸酯(TDI)及少量的催化剂二月桂酸二丁基锡，将三口烧瓶置于恒温水浴槽内，温度控制在50℃到55℃之间；(1) Add toluene diisocyanate (TDI) and a small amount of catalyst dibutyltin dilaurate into a 250ml three-necked flask equipped with a thermometer, agitator, and condenser, and place the three-necked flask in a constant temperature water bath with the temperature controlled at 50°C to 55°C;
(2)在50℃到55℃下向三口烧瓶中缓慢滴加无水甲醇、乙二醇单丁醚、己内酰胺的混合溶液，30分钟内滴加完.升温到60℃并保温3个小时.(2) Slowly add the mixed solution of anhydrous methanol, ethylene glycol monobutyl ether, and caprolactam dropwise to the three-necked flask at 50°C to 55°C, and finish adding dropwise within 30 minutes. Raise the temperature to 60°C and keep it warm for 3 hours.
(3)3小时后向三口烧瓶中加入定量的三羟甲基丙烷，升温至80℃并保温2个小时.用二正丁胺法测定-NCO的含量，达到要求降温出料.(3) After 3 hours, add a certain amount of trimethylolpropane to the three-necked flask, raise the temperature to 80°C and keep it warm for 2 hours. Use the di-n-butylamine method to measure the content of -NCO, and cool down and discharge the material when it meets the requirements.
2.结果讨论2. Discussion of results
2.1 二正丁胺法测-NCO含量随时间变化数据见下表2.1 The change of NCO content with time by di-n-butylamine method is shown in the table below
封闭型异氰酸酯固化剂升高到一定温度，封闭剂小分子从大分子上脱落下来，产生失重，释放出-NCO基团。将上述封闭剂封闭的异氰酸酯固化剂进行了热重分析，得出的解封温度与红外光谱分析相符。其中乙二醇单丁醚封闭异氰酸酯固化剂的热重分析见附图2，由附图2可知当温度达到130℃时，小分子断裂。故乙二醇单丁醚封闭异氰酸酯固化剂的解封温度为130℃When the blocked isocyanate curing agent rises to a certain temperature, the small molecules of the blocking agent fall off from the macromolecules, resulting in weightlessness and releasing -NCO groups. The isocyanate curing agent blocked by the above blocking agent was subjected to thermogravimetric analysis, and the unblocking temperature obtained was consistent with the infrared spectrum analysis. Wherein the thermogravimetric analysis of ethylene glycol monobutyl ether blocked isocyanate curing agent is shown in accompanying
通过附图1所示的红外光谱，其显示固化剂的初始解封温度为105℃，最佳解封温度为130℃时，解封时间为20min。According to the infrared spectrum shown in Figure 1, it shows that the initial unblocking temperature of the curing agent is 105°C, and when the optimum unblocking temperature is 130°C, the unblocking time is 20 minutes.
当理解的是，对本领域普通技术人员来说，可以根据上述说明加以改进或变换，而所有这些改进和变换都应属于本发明所附权利要求的保护范围。It should be understood that those skilled in the art can make improvements or changes based on the above description, and all these improvements and changes should fall within the protection scope of the appended claims of the present invention.
Claims (5)
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| CN102443135B true CN102443135B (en) | 2014-05-07 |
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| CN110437408B (en) * | 2019-07-19 | 2021-07-23 | 中国石油集团川庆钻探工程有限公司 | Curing agent for high-temperature excitation type oil-based drilling fluid and preparation method thereof |
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| CN1665793A (en) * | 2002-04-30 | 2005-09-07 | 拜尔材料科学股份公司 | ionic liquid |
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| CN1865328A (en) * | 2006-04-27 | 2006-11-22 | 中国科学院广州化学研究所 | Water dispersible end capping diisocyanate cross-linking agent and its preparation method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR20020077156A (en) * | 2001-03-28 | 2002-10-11 | 닛본 페인트 가부시끼가이샤 | Lead-free cataionic electrodeposition coating composition, electrodeposition coating process, and process for forming double layered coated film |
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|---|---|---|---|---|
| CN1665793A (en) * | 2002-04-30 | 2005-09-07 | 拜尔材料科学股份公司 | ionic liquid |
| CN1675004A (en) * | 2002-08-13 | 2005-09-28 | 阿克佐诺贝尔国际涂料股份有限公司 | Multilayer coating system comprising thiol-functional compounds |
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| CN1865328A (en) * | 2006-04-27 | 2006-11-22 | 中国科学院广州化学研究所 | Water dispersible end capping diisocyanate cross-linking agent and its preparation method |
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| Title |
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