WO2023116204A1 - 一种水性封闭型的聚异氰酸酯固化剂及其制备方法和应用 - Google Patents

一种水性封闭型的聚异氰酸酯固化剂及其制备方法和应用 Download PDF

Info

Publication number
WO2023116204A1
WO2023116204A1 PCT/CN2022/128657 CN2022128657W WO2023116204A1 WO 2023116204 A1 WO2023116204 A1 WO 2023116204A1 CN 2022128657 W CN2022128657 W CN 2022128657W WO 2023116204 A1 WO2023116204 A1 WO 2023116204A1
Authority
WO
WIPO (PCT)
Prior art keywords
water
curing agent
polyisocyanate curing
preparation
reaction
Prior art date
Application number
PCT/CN2022/128657
Other languages
English (en)
French (fr)
Inventor
陈阳
Original Assignee
嘉宝莉化工集团股份有限公司
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 嘉宝莉化工集团股份有限公司 filed Critical 嘉宝莉化工集团股份有限公司
Publication of WO2023116204A1 publication Critical patent/WO2023116204A1/zh
Priority to ZA2023/08970A priority Critical patent/ZA202308970B/en

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
    • C08G18/80—Masked polyisocyanates
    • C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
    • C08G18/8083—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with compounds containing at least one heteroatom other than oxygen or nitrogen
    • 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
    • C08G18/80—Masked polyisocyanates
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes

Definitions

  • the invention belongs to the technical field of coating curing agents, and in particular relates to a water-based closed polyisocyanate curing agent and its preparation method and application.
  • water-based coatings have undoubtedly become one of the important development directions of today's coating technology.
  • the obtained films have excellent abrasion resistance, chemical resistance and stain resistance, and are widely used.
  • Water-based isocyanate curing agent has excellent performance. Due to the high reactivity of isocyanate groups, it can be cross-linked and cured with polymers with active hydrogen atoms such as alcohols and amines at room temperature, so it can basically only be used in double In component coatings, its application is limited. Moreover, the water-based isocyanate curing agent is extremely sensitive to water in the environment because of the introduction of a large number of hydrophilic groups, which greatly increases the storage difficulty of the water-based isocyanate curing agent. In order to solve this technical problem, a water-based blocked polyisocyanate curing agent emerged as the times require. The active isocyanate group is protected by a small molecule blocking agent, so that the crosslinking agent can coexist stably with other components in the coating at room temperature. It also greatly reduces the difficulty of storage.
  • blocked polyisocyanate is mostly prepared by reacting HDI trimer (hexamethylene diisocyanate trimer) or IPDI trimer with 3,5-dimethylpyrazole or methyl ethyl ketone oxime as blocking agent. Then mix it with acrylic resin or amino resin in a certain proportion to prepare automotive coatings.
  • the product has the advantages of good chemical resistance and yellowing resistance, but its unsealing temperature (baking temperature) is relatively high, generally 100°C-150°C °C; and most of them contain a large amount of low boiling point solvents.
  • the present invention aims to solve at least one of the technical problems in the above-mentioned prior art. Therefore, the present invention proposes a water-based blocked polyisocyanate curing agent and its preparation method and application.
  • the water-based blocked polyisocyanate curing agent provided by the invention can reduce the consumption of low-boiling solvents and lower the unblocking temperature, and the prepared polyurethane coating has good storage stability.
  • the first aspect of the present invention provides a method for preparing a water-based blocked polyisocyanate curing agent.
  • a kind of preparation method of water-based closed polyisocyanate curing agent comprises the following steps:
  • the sulfonate, diisocyanate trimer and catalyst are mixed for the first reaction, and after the reaction is completed, bisulfite is added for the second reaction to obtain the water-based blocked polyisocyanate curing agent.
  • the sulfonate is sulfamate; further preferably, the sulfamate is sodium 2-tert-butyl-4-(cyclohexylamino)-1-butanesulfonate, 2- At least one of sodium tert-butyl-3-(cyclohexylamino)-1-propanesulfonate or sodium 2-isoamyl-3-(cyclohexylamino)-1-propanesulfonate; by using amino Sulfonate and diisocyanate trimer synthesize polyisocyanate, which provides hydrophilic property for polyisocyanate, so as to ensure that water-based polyisocyanate curing agent has excellent dispersibility without diluting with solvent.
  • the diisocyanate trimer is selected from isophorone diisocyanate trimer, hexamethylene diisocyanate trimer, toluene diisocyanate trimer or diphenylmethane diisocyanate trimer At least one; further preferably, the diisocyanate trimer is selected from isophorone diisocyanate trimer and/or hexamethylene diisocyanate trimer.
  • the reaction of hexamethylene diisocyanate trimer and isophorone diisocyanate trimer is mild and easy to control during the hydrophilization process.
  • the -NCO content in the diisocyanate trimer is 18%wt-28%wt; further preferably, the -NCO content in the diisocyanate trimer is 21%wt-24%wt.
  • the temperature of the first reaction is 70-110°C, and the time of the first reaction is 1-15h; more preferably, the temperature of the first reaction is 80-100°C, and the time of the first reaction is 1-15h; The time for the first reaction is 3-10h.
  • the bisulfite is at least one selected from sodium bisulfite, potassium bisulfite, magnesium bisulfite and calcium bisulfite.
  • the sulfonate is 1-8 parts
  • the diisocyanate trimer is 80-120 parts
  • the bisulfite is 40-70 parts .
  • the sulfonate is 1.5-5 parts
  • the diisocyanate trimer is 95-100 parts
  • the bisulfite is 50-60 parts share.
  • the catalyst is nitrogen nitrogen dimethylbenzylamine. In parts by weight, the catalyst is 0.15-0.5 parts.
  • the temperature of the second reaction is 40-70°C; the time of the second reaction is 2-10h; more preferably, the temperature of the second reaction is 50-60°C; the The time for the second reaction is 3-8h.
  • the second reaction ends when the mass content of -NCO in the reaction system is less than 0.05%.
  • the end point of the second reaction is based on the mass content of isocyanate falling below 0.05%, and the content of isocyanate is measured by toluene-di-n-butylamine titration.
  • the first reaction and the second reaction are performed under a protective gas, such as nitrogen.
  • the preparation method of the water-based blocked polyisocyanate curing agent comprises the following steps:
  • the preparation method of the water-based blocked polyisocyanate curing agent comprises the following steps:
  • the second aspect of the present invention provides a water-based blocked polyisocyanate curing agent.
  • a water-based blocked polyisocyanate curing agent is prepared by the above preparation method, the solid content of the polyisocyanate curing agent is 99-100%, and the sealing rate is greater than 99.9%.
  • the third aspect of the present invention provides an application of a water-based blocked polyisocyanate curing agent.
  • the application of the water-based blocked polyisocyanate curing agent in polyurethane coatings is water-based polyurethane coating.
  • a kind of water-based polyurethane coating comprises A component and B component, and described A component comprises water-based polyurethane dispersion, and described B component comprises the polyisocyanate curing agent of above-mentioned water-based blocked type.
  • the A component also includes a wetting agent, a thickener, a leveling agent and a solvent.
  • the mass ratio of the A component to the B component is (3-8):1.
  • the preparation method of the water-based polyurethane coating includes the following steps: mixing the A component and the B component to prepare.
  • the A component and the B component in the waterborne polyurethane coating provided by the present invention can be mixed and stored, which has good storage stability; the A component and the B component can also be mixed Store separately and mix until ready to use.
  • the specific method can be selected according to different environments and needs.
  • the invention uses hydrogen sulfite to seal the water-based polyisocyanate obtained by reacting sulfonate and diisocyanate trimer to prepare the water-based blocked polyisocyanate curing agent.
  • the catalyst existing in the reaction system is used as a phase transfer catalyst of bisulfite (sealing agent) to block the isocyanate group of the water-based polyisocyanate.
  • reaction conditions are mild and no additional catalyst is needed, which makes the system more stable during later storage;
  • the prepared water-based blocked polyisocyanate curing agent has a low unblocking temperature (about 75°C), and can be applied to various baking coatings;
  • the waterborne polyurethane paint prepared by using it has strong stability, little change in viscosity when stored at high temperature, and the formed paint film has high gloss.
  • the water-based blocked polyisocyanate curing agent provided by the present invention uses bisulfite as a blocking agent, which has excellent water dispersibility and storage stability, and has a low unblocking temperature (not exceeding 80°C), and can be applied to Various baking coatings.
  • the water-based closed polyisocyanate curing agent of the present invention can reduce the consumption of low-boiling point solvents, and does not need to use any high-boiling point solvents or ketone solvents to reduce viscosity, and VOC is effectively controlled in curing agents and coatings; and its The preparation process is simple and environmentally friendly.
  • the waterborne polyurethane dispersion Bayhydrol@2470 was purchased from Covestro Polymers (China) Co., Ltd., wetting agent Twin 4100, Twin 810 was purchased from Evonik Tego, and the thickener COAPUR XS71 was purchased from Coatex, France.
  • the rest of the raw materials, reagents or devices can be obtained from conventional commercial channels, or can be obtained by existing known methods, unless otherwise specified.
  • a preparation method of a water-based closed polyisocyanate curing agent comprising the following steps:
  • a preparation method of a water-based closed polyisocyanate curing agent comprising the following steps:
  • a preparation method of a water-based closed polyisocyanate curing agent comprising the following steps:
  • a preparation method of a water-based closed polyisocyanate curing agent comprising the following steps:
  • Comparative Example 1 Comparative Example 1 and Example 3 is that an equal amount of methyl ethyl ketone oxime is used instead of sodium bisulfite as the blocking agent, and the rest of the raw materials and preparation methods are the same as in Example 3.
  • a kind of preparation method of water-based closed polyisocyanate curing agent comprises the following steps:
  • Comparative Example 2 The difference between Comparative Example 2 and Example 3 is that sodium 2-tert-butyl-4-(cyclohexylamino)-1-butanesulfonate is not added, and the remaining raw materials and preparation methods are the same as in Example 3.
  • a preparation method of a blocked polyisocyanate curing agent comprising the following steps:
  • Comparative Example 3 The difference between Comparative Example 3 and Example 3 is that no blocking agent sodium bisulfite is added, and the rest of the raw materials and preparation methods are the same as in Example 3.
  • a preparation method of water-based polyisocyanate curing agent comprising the following steps:
  • the water-based blocked polyisocyanate curing agents prepared in Examples 1-4 were used to prepare water-based polyurethane coatings respectively.
  • the preparation method of waterborne polyurethane coating comprises the following steps:
  • component B the water-based blocked polyisocyanate curing agent prepared in Example 1-4
  • the polyisocyanate curing agent prepared in Comparative Examples 1-3 was used to prepare waterborne polyurethane coatings.
  • the preparation method of waterborne polyurethane coating comprises the following steps:
  • component B the polyisocyanate curing agent prepared in Comparative Example 1-3
  • component A After mixing evenly, a water-based Polyurethane coating.
  • water-based polyurethane coatings prepared in Application Examples 1-4 and Comparative Application Examples 1-3 respectively to prepare paint films with a 150 ⁇ m wet film preparer, and bake them at the unsealing temperature to obtain the paint film after drying and crosslinking .
  • the test of water-based blocked polyisocyanate curing agent includes the test of water solubility and unblocking temperature
  • the test of water-based polyurethane coating includes the test of high temperature storage (50 °C for 6 months) stability test (viscosity, paint film gloss)
  • Tests on paint films include a paint film gloss test.
  • the basic test method is as follows:
  • Viscosity measurement standard GB/T 1723-1993.
  • the water-based blocked polyisocyanate curing agent provided by the examples of the present invention has excellent water solubility, and often forms very fine particles after being dispersed in water (90% of the particle size of the system is less than 0.9 ⁇ m), thereby improving the water-based
  • the transparency and gloss of polyurethane coatings the unblocking temperature of the water-based blocked polyisocyanate curing agent is as low as 70 ° C; the water-based polyurethane coatings prepared by it have strong stability, and the viscosity changes little after being stored at 50 ° C for 6 months;
  • the gloss of the paint film prepared by using it is high, reaching 90° and above, and the paint film prepared after the water-based polyurethane coating is stored at 50°C for 6 months is still high in gloss, basically unchanged, and the water-based polyurethane coating has good storage stability.
  • the unsealing temperature in comparative application example 1 is as high as 140 °C; Although the curing agent also has lower unsealing temperature in comparative application example 2, its water solubility is poor, and the glossiness of its paint film is obviously not as good as application example; comparative application example 3 Poor storage stability.
  • the haze of the paint film prepared by the application example of the present invention is lower than 20%, the light transmittance is higher than 85%, and has relatively high transparency.

Abstract

本发明属于涂料固化剂技术领域，公开了一种水性封闭型的聚异氰酸酯固化剂及其制备方法和应用。该制备方法包括：将磺酸盐、二异氰酸酯三聚体和催化剂混合，进行第一次反应，待反应结束后加入亚硫酸氢盐，进行第二次反应，制得所述水性封闭型的聚异氰酸酯固化剂。本发明提供的水性封闭型的聚异氰酸酯固化剂，以亚硫酸氢盐作为封闭剂，其解封温度低，具有优异水分散性和储存稳定性，可应用于各种烘烤涂料中。利用本发明提供的水性封闭型的聚异氰酸酯固化剂制备的水性聚氨酯涂料的稳定性强，在高温下储存粘度变化小，形成的漆膜的光泽度高，透明度高。

Description

一种水性封闭型的聚异氰酸酯固化剂及其制备方法和应用 技术领域
本发明属于涂料固化剂技术领域，具体涉及一种水性封闭型的聚异氰酸酯固化剂及其制备方法和应用。
背景技术
随着人们对环境保护的重视，对环保要求的不断提高，水性涂料毋庸置疑成为了当今涂料技术的重要发展方向之一。其中通过使用具有异氰酸酯类化合物交联作用的水性聚氨酯类涂料，所获得的膜具有非常优秀的耐磨性、耐药性和耐污性，其应用广泛。
水性异氰酸酯固化剂，其性能优异，由于异氰酸酯基团的高反应活性，其与醇类、胺类等具有活泼氢原子的聚合物在室温下即可交联固化，因而其基本只能用在双组分涂料中，限制了其应用。而且水性异氰酸酯固化剂因为引入了大量亲水基团，其对环境中的水极其敏感，大大增加了水性异氰酸酯固化剂的储存难度。为解决此技术难题，水性封闭型的聚异氰酸酯固化剂应运而生，利用小分子封闭剂将活泼的异氰酸酯基团保护起来，使得交联剂在室温下能与涂料中的其他组分稳定共存，亦大大降低了储存难度。
目前封闭型聚异氰酸酯多以3，5-二甲基吡唑或者甲乙酮肟作为封闭剂，与HDI三聚体(六亚甲基二异氰酸酯三聚体)或IPDI三聚体反应制得。再与丙烯酸树脂或氨基树脂按一定比例混合制得汽车涂料，其产品具有良好的耐化学性、耐黄变性等优点，但其解封温度(烘烤温度)较高，一般为100℃-150℃；且多数含有 大量低沸点溶剂。
因此，亟需提供一种水性封闭型的聚异氰酸酯固化剂，能够减少低沸点溶剂的用量，降低解封温度，且制备的聚氨酯涂料具有良好的储存稳定性。
发明内容
本发明旨在至少解决上述现有技术中存在的技术问题之一。为此，本发明提出一种水性封闭型的聚异氰酸酯固化剂及其制备方法和应用。本发明提供的水性封闭型的聚异氰酸酯固化剂，能够减少低沸点溶剂的用量，降低解封温度，且制备的聚氨酯涂料具有良好的储存稳定性。
本发明第一方面提供了一种水性封闭型的聚异氰酸酯固化剂的制备方法。
具体的，一种水性封闭型的聚异氰酸酯固化剂的制备方法，包括以下步骤：
将磺酸盐、二异氰酸酯三聚体和催化剂混合，进行第一次反应，待反应结束后加入亚硫酸氢盐，进行第二次反应，制得所述水性封闭型的聚异氰酸酯固化剂。
优选地，所述磺酸盐为氨基磺酸盐；进一步优选地，所述氨基磺酸盐为2-叔丁基-4-(环己胺基)-1-丁烷磺酸钠、2-叔丁基-3-(环己胺基)-1-丙烷磺酸钠或2-异戊基-3-(环己胺基)-1-丙烷磺酸钠中的至少一种；通过使用氨基磺酸盐与二异氰酸酯三聚体合成聚异氰酸酯，为聚异氰酸酯提供亲水性能，从而保证水性聚异氰酸酯固化剂不用溶剂开稀即有优异的分散性。
优选地，所述二异氰酸酯三聚体选自异佛尔酮二异氰酸酯三聚体、六亚甲基二异氰酸酯三聚体、甲苯二异氰酸酯三聚体或二苯基甲烷二异氰酸酯三聚体中的至少一种；进一步优选地，所述二异氰酸酯三聚体选自异佛尔酮二异氰酸酯三聚 体和/或六亚甲基二异氰酸酯三聚体。六亚甲基二异氰酸酯三聚体和异佛尔酮二异氰酸酯三聚体在亲水化过程中，反应温和，易控制。
优选地，所述二异氰酸酯三聚体中-NCO的含量为18％wt-28％wt；进一步优选地，所述二异氰酸酯三聚体中-NCO的含量为21％wt-24％wt。
优选地，所述第一次反应的温度为70-110℃，所述第一次反应的时间为1-15h；进一步优选地，所述第一次反应的温度为80-100℃，所述第一次反应的时间为3-10h。
优选地，所述亚硫酸氢盐选自亚硫酸氢钠、亚硫酸氢钾、亚硫酸氢镁和亚硫酸氢钙中的至少一种。
优选地，在所述制备方法中，按重量份计，所述磺酸盐为1-8份，所述二异氰酸酯三聚体为80-120份，所述亚硫酸氢盐为40-70份。
进一步优选地，在所述制备方法中，按重量份计，所述磺酸盐为1.5-5份，所述二异氰酸酯三聚体为95-100份，所述亚硫酸氢盐为50-60份。
优选地，所述催化剂为氮氮二甲基苄胺。按重量份计，所述催化剂为0.15-0.5份。
优选地，所述第二次反应的温度为40-70℃；所述第二次反应的时间为2-10h；进一步优选地，所述第二次反应的温度为50-60℃；所述第二次反应的时间为3-8h。
优选地，所述第二次反应在反应体系中-NCO的质量含量小于0.05％时，结束反应。所述第二次反应的终点以异氰酸根的质量含量降至0.05％以下为准，所 述异氰酸根含量采用甲苯-二正丁胺滴定法测量。通过控制反应体系中-NCO的含量，避免在后续制备涂料等工序中加水稀释时，过多残留的-NCO与水反应扩链，使体系粘度过高，不利于分散和使用。
优选地，所述第一次反应和所述第二次反应在保护气体下进行，如氮气。
优选地，所述水性封闭型的聚异氰酸酯固化剂的制备方法，包括以下步骤：
将磺酸盐、二异氰酸酯三聚体和催化剂混合，在70-110℃下反应1-15小时，待反应结束后加入亚硫酸氢盐，在40-70℃反应至-NCO的质量含量小于0.05％时结束反应，制得所述水性封闭型的聚异氰酸酯固化剂。
进一步优选地，所述水性封闭型的聚异氰酸酯固化剂的制备方法，包括以下步骤：
将磺酸盐、二异氰酸酯三聚体和催化剂混合，在80-100℃下反应3-10小时，待反应结束后加入亚硫酸氢盐，在50-60℃反应至-NCO的含量小于0.05％wt时结束反应，制得所述水性封闭型的聚异氰酸酯固化剂。
本发明第二方面提供了一种水性封闭型的聚异氰酸酯固化剂。
具体的，一种水性封闭型的聚异氰酸酯固化剂，由上述制备方法制得，所述聚异氰酸酯固化剂的固含量为99-100％，封闭率大于99.9％。
本发明第三方面提供了一种水性封闭型的聚异氰酸酯固化剂的应用。
具体的，所述水性封闭型聚的异氰酸酯固化剂在聚氨酯涂料中的应用。优选地，所述聚氨酯涂料为水性聚氨酯涂料。
一种水性聚氨酯涂料，包括A组分和B组分，所述A组分包括水性聚氨酯分 散体，所述B组分包括上述水性封闭型的聚异氰酸酯固化剂。
进一步优选地，所述A组分还包括润湿剂、增稠剂、流平剂和溶剂。
优选地，所述A组分与所述B组分的质量比为(3-8):1。
优选地，所述水性聚氨酯涂料的制备方法，包括以下步骤：将所述A组分和所述B组分混合，即制得。实际上，本发明提供的水性聚氨酯涂料中的所述A组分和所述B组分可以混合后储存，其具有良好的储存稳定性；也可以将所述A组分和所述B组分分开储存，待使用时进行混合。具体的方式可以根据不同环境和需求进行选择。
本发明利用亚硫酸氢盐对以磺酸盐与二异氰酸酯三聚体反应得到的水性聚异氰酸酯进行封闭，制得水性封闭型的聚异氰酸酯固化剂。具体地，在制备中利用反应体系中本存的催化剂作为亚硫酸氢盐(封闭剂)的相转移催化剂，对水性聚异氰酸酯的异氰酸酯基进行封闭。其反应条件温和，无需额外催化剂，使得体系在后期储存时更加稳定；制备的水性封闭型的聚异氰酸酯固化剂的解封温度低(约为75℃)，可应用于各种烘烤涂料中；利用其制备的水性聚氨酯涂料的稳定性强，在高温下储存粘度变化小，形成的漆膜的光泽度高。
相对于现有技术，本发明的有益效果如下：
(1)本发明提供的水性封闭型的聚异氰酸酯固化剂，以亚硫酸氢盐作为封闭剂，其具有优异水分散性和储存稳定性，解封温度低(不超过80℃)，可应用于各种烘烤涂料中。
(2)利用本发明提供的水性封闭型的聚异氰酸酯固化剂制备的水性聚氨酯涂 料，其稳定性强，在高温下储存粘度变化小，形成的漆膜的光泽度高，透明度高。
(3)本发明的水性封闭型的聚异氰酸酯固化剂，能够减少低沸点溶剂的用量，也不需要使用任何高沸点溶剂或酮类溶剂降粘，固化剂和涂料中VOC得到有效控制；且其制备工艺简单，对环境友好。
具体实施方式
为了让本领域技术人员更加清楚明白本发明所述技术方案，现列举以下实施例进行说明。需要指出的是，以下实施例对本发明要求的保护范围不构成限制作用。
在以下实施例、对比例、应用例或对比应用例中，水性聚氨酯分散体Bayhydrol@2470购买于科思创聚合物(中国)有限公司，润湿剂
Figure PCTCN2022128657-appb-000001
Twin 4100、
Figure PCTCN2022128657-appb-000002
Twin 810购买于赢创迪高公司，增稠剂COAPUR XS71购买于法国高泰公司。其余原料、试剂或装置如无特殊说明，均可从常规商业途径得到，或者可以通过现有已知方法得到。
实施例1
一种水性封闭型的聚异氰酸酯固化剂的制备方法，包括以下步骤：
按照表1所示的配方准备原料。将97.1质量份六亚甲基二异氰酸酯三聚体投入装有搅拌器、温度计和氮气入口的四口烧瓶中，升温至60℃，搅拌条件下加入2.8质量份2-叔丁基-4-(环己胺基)-1-丁烷磺酸钠、0.2质量份氮氮二甲基苄胺，于80℃条件下反应6小时后，取样检测异氰酸根含量(异氰酸根含量测定采用HGT 2409-1992中的甲苯-二正丁胺滴定法)，至接近理论值(与理论值质量含 量0.05％相差不超过0.5％)时加入亚硫酸氢钠，于55℃条件下反应5小时，再取样检测异氰酸根含量，待异氰酸根的质量含量＜0.05％时结束反应，得到水性封闭型的聚异氰酸酯固化剂。制得的水性封闭型的聚异氰酸酯固化剂的固含量为99.7％，封闭率为99.97％。(通过测定-NCO的质量含量，计算封闭率，封闭率＝(封闭前-NCO的质量含量-封闭后-NCO的质量含量)/封闭前-NCO的质量含量。)
表1
原料种类 质量份
六亚甲基二异氰酸酯三聚体 97.1
2-叔丁基-4-(环己胺基)-1-丁烷磺酸钠 2.8
氮氮二甲基苄胺 0.2
亚硫酸氢钠 60
实施例2
一种水性封闭型的聚异氰酸酯固化剂的制备方法，包括以下步骤：
按照表2所示的配方准备原料。将96.9质量份六亚甲基二异氰酸酯三聚体投入装有搅拌器、温度计和氮气入口的四口烧瓶中，升温至60℃，于搅拌条件下加入3.0质量份2-叔丁基-4-(环己胺基)-1-丁烷磺酸钠、0.35质量份氮氮二甲基苄胺，于90℃条件反应4.5小时后，取样检测异氰酸根含量(异氰酸根含量测定采用HGT 2409-1992中的甲苯-二正丁胺滴定法)，至接近理论值(与理论值质量含量0.05％相差不超过0.5％)时加入亚硫酸氢钠，然后于55℃条件反应5小时后，待异氰酸根的质量含量＜0.05％时结束反应，得到水性封闭型的聚异氰酸 酯固化剂。制得的水性封闭型的聚异氰酸酯固化剂的固含量为99.5％，封闭率为99.5％。
表2
原料种类 质量份
六亚甲基二异氰酸酯三聚体 96.9
2-叔丁基-4-(环己胺基)-1-丁烷磺酸钠 3.0
氮氮二甲基苄胺 0.35
亚硫酸氢钠 55
实施例3
一种水性封闭型的聚异氰酸酯固化剂的制备方法，包括以下步骤：
按照表3所示的配方准备原料。将97.1质量份六亚甲基二异氰酸酯三聚体投入装有搅拌器、温度计和氮气入口的四口烧瓶中，升温至60℃，于搅拌条件下加入2.8质量份2-叔丁基-4-(环己胺基)-1-丁烷磺酸钠、0.5质量份氮氮二甲基苄胺；于80℃条件反应5.5小时后，取样检测异氰酸根含量(异氰酸根含量测定采用HGT 2409-1992中的甲苯-二正丁胺滴定法)，至接近理论值(与理论值质量含量0.05％相差不超过0.5％)时加入亚硫酸氢钠；再于55℃条件下反应5小时，待异氰酸根的质量含量＜0.05％时结束反应，得到水性封闭型的聚异氰酸酯固化剂。制得的水性封闭型的聚异氰酸酯固化剂的固含量为99.5％，封闭率为99.96％。
表3
原料种类 质量份
六亚甲基二异氰酸酯三聚体 97.1
2-叔丁基-4-(环己胺基)-1-丁烷磺酸钠 2.8
氮氮二甲基苄胺 0.5
亚硫酸氢钠 58
实施例4
一种水性封闭型的聚异氰酸酯固化剂的制备方法，包括以下步骤：
按照表4所示的配方准备原料。将97.1质量份异佛尔酮二异氰酸酯三聚体投入装有搅拌器、温度计和氮气入口的四口烧瓶中，升温至60℃，搅拌条件下加入2.8质量份2-叔丁基-3-(环己胺基)-1-丙烷磺酸钠、0.2质量份氮氮二甲基苄胺，于80℃条件下反应6小时后，取样检测异氰酸根含量(异氰酸根含量测定采用HGT 2409-1992中的甲苯-二正丁胺滴定法)，至接近理论值(与理论值质量含量0.05％相差不超过0.5％)时加入亚硫酸氢钾，于55℃条件下反应5小时，再取样检测异氰酸根含量，待异氰酸根的质量含量＜0.05％时结束反应，得到水性封闭型的聚异氰酸酯固化剂。制得的水性封闭型的聚异氰酸酯固化剂的固含量为99.8％，封闭率为99.97％。
表4
原料种类 质量份
异佛尔酮二异氰酸酯三聚体 97.1
2-叔丁基-3-(环己胺基)-1-丙烷磺酸钠 2.8
氮氮二甲基苄胺 0.2
亚硫酸氢钾 60
对比例1
对比例1与实施例3的区别在于，采用等量的甲乙酮肟替换亚硫酸氢钠作为封闭剂，其余原料和制备方法同实施例3。
具体的，一种水性封闭型的聚异氰酸酯固化剂的制备方法，包括以下步骤：
将97.1质量份六亚甲基二异氰酸酯三聚体投入装有搅拌器、温度计和氮气入口的四口烧瓶中，升温至60℃，于搅拌条件下加入2.8质量份2-叔丁基-4-(环己胺基)-1-丁烷磺酸钠、0.5质量份氮氮二甲基苄胺；于80℃条件反应5.5小时后，取样检测异氰酸根含量(异氰酸根含量测定采用HGT 2409-1992中的甲苯-二正丁胺滴定法)，至接近理论值(与理论值质量含量0.05％相差不超过0.5％)时加入58份甲乙酮肟；再于55℃条件下反应5小时，待异氰酸根的质量含量＜0.05％时结束反应，得到水性封闭型的聚异氰酸酯固化剂。制得的水性封闭型的聚异氰酸酯固化剂的固含量为99.8％，封闭率为99.95％。
对比例2
对比例2与实施例3的区别在于，不加入2-叔丁基-4-(环己胺基)-1-丁烷磺酸钠，其余原料和制备方法同实施例3。
一种封闭型的聚异氰酸酯固化剂的制备方法，包括以下步骤：
按照表3所示的配方准备原料。将97.1质量份六亚甲基二异氰酸酯三聚体投入装有搅拌器、温度计和氮气入口的四口烧瓶中，升温至60℃，于搅拌条件下加入0.5质量份氮氮二甲基苄胺和58质量份亚硫酸氢钠；于55℃条件下反应5小时，待异氰酸根的质量含量＜0.05％时结束反应，得到封闭型聚异氰酸酯固化剂。制得的封闭型的聚异氰酸酯固化剂的固含量为99.9％，封闭率为99.96％。
对比例3
对比例3与实施例3的区别在于，不加入封闭剂亚硫酸氢钠，其余原料和制备方法同实施例3。
一种水性聚异氰酸酯固化剂的制备方法，包括以下步骤：
将97.1质量份六亚甲基二异氰酸酯三聚体投入装有搅拌器、温度计和氮气入口的四口烧瓶中，升温至60℃，于搅拌条件下加入2.8质量份2-叔丁基-4-(环己胺基)-1-丁烷磺酸钠、0.5质量份氮氮二甲基苄胺；于80℃条件反应5.5小时后，取样检测异氰酸根含量(异氰酸根含量测定采用HGT 2409-1992中的甲苯-二正丁胺滴定法)，待异氰酸根的质量含量＜0.05％时结束反应，得到水性聚异氰酸酯固化剂。制得的水性聚异氰酸酯固化剂的固含量为99.9％，未封闭，无封闭率数据。
应用例1-4
采用实施例1-4制备的水性封闭型的聚异氰酸酯固化剂分别制备水性聚氨酯涂料。
具体的，水性聚氨酯涂料的制备方法包括以下步骤：
(1)按质量百分数计，取80％水性聚氨酯分散体Bayhydrol@2470、0.25％润湿剂
Figure PCTCN2022128657-appb-000003
Twin 4100、0.15％润湿剂
Figure PCTCN2022128657-appb-000004
Twin 810、2.5％二丙二醇丁醚、2.5％二丙二醇单甲醚、0.25％增稠剂COAPUR XS71、0.35％水性流平剂BYK-333和14％水，混合，制A组分；
(2)按A、B组分的质量比为5：1，分别称取B组分(实施例1-4制备的水性封闭型的聚异氰酸酯固化剂)加入到A组分中，混合均匀后，制得水性聚氨酯涂料。
对比应用例1-3
采用对比例1-3制备的聚异氰酸酯固化剂制备水性聚氨酯涂料。
具体的，水性聚氨酯涂料的制备方法包括以下步骤：
(1)按质量百分数计，取80％水性聚氨酯分散体Bayhydrol@2470、0.25％润湿剂
Figure PCTCN2022128657-appb-000005
Twin 4100、0.15％润湿剂
Figure PCTCN2022128657-appb-000006
Twin 810、2.5％二丙二醇丁醚、2.5％二丙二醇单甲醚、0.25％增稠剂COAPUR XS71、0.35％水性流平剂BYK-333和14％水，混合，制A组分；
(2)按A、B组分的质量比为5：1，分别称取B组分(对比例1-3制备的聚异氰酸酯固化剂)加入到A组分中，混合均匀后，制得水性聚氨酯涂料。
产品效果测试
分别利用应用例1-4和对比应用例1-3制得的水性聚氨酯涂料，用150μm湿膜制备器制备漆膜，并按其解封温度进行烘烤，待干燥交联后即得漆膜。对水 性封闭型的聚异氰酸酯固化剂、水性聚氨酯涂料，以及所制备的漆膜进行性能测试。对水性封闭型的聚异氰酸酯固化剂的测试包括水溶性和解封温度的测试，对水性聚氨酯涂料的测试包括高温储存(50℃保存6个月)稳定性的测试(粘度、漆膜光泽度)，对漆膜的测试包括漆膜光泽度测试。基础题的测试方法如下：
(1)解封温度测量方法：将水性封闭型异氰酸酯固化剂用丙酮溶解后，加入数滴苯酚，升温加热。出现浑浊时的温度就是该样品的初始解封温度。
(2)粘度的测量标准：GB/T 1723-1993。
(3)漆膜光泽度的测量标准：GBT 9754-2007。
测试结果见表5。
表5 水性封闭型的聚异氰酸酯固化剂技术指标及制成水性聚氨酯涂料测试结果
Figure PCTCN2022128657-appb-000007
Figure PCTCN2022128657-appb-000008
由表5可知，本发明实施例提供的水性封闭型的聚异氰酸酯固化剂具有优异的水溶性，在水中分散后往往形成极细小颗粒(体系90％粒径低于0.9μm)，从而提升了水性聚氨酯涂料的透明度和光泽度；水性封闭型的聚异氰酸酯固化剂的解封温度低至70℃；由其制备的水性聚氨酯涂料的稳定性强，在50℃下保存6个月后粘度变化小；利用其制备的漆膜的光泽度高，达到90°及以上，且水性聚氨酯涂料在50℃下保存6个月后制备的漆膜仍然光泽度高，基本无变化，水性聚氨酯涂料具有良好的储存稳定性。而对比应用例1中解封温度高达140℃；对比应用例2中固化剂虽然也具有较低的解封温度，但是其水溶性差，其漆膜的光泽度明显不如应用实施例；对比应用例3储存稳定性差。同时，经测试，本发明应用实施例制备的漆膜的雾度低于20％，透光率高于85％，具有较高透明度。

Claims (10)

  1. 一种聚异氰酸酯固化剂的制备方法，其特征在于，包括以下步骤：将磺酸盐、二异氰酸酯三聚体和催化剂混合，进行第一次反应，待反应结束后，加入亚硫酸氢盐，进行第二次反应，制得水性封闭型的聚异氰酸酯固化剂。
  2. 根据权利要求1所述的制备方法，其特征在于，所述磺酸盐为氨基磺酸盐。
  3. 根据权利要求1所述的制备方法，其特征在于，所述二异氰酸酯三聚体选自异佛尔酮二异氰酸酯三聚体、六亚甲基二异氰酸酯三聚体、甲苯二异氰酸酯三聚体或二苯基甲烷二异氰酸酯三聚体中的至少一种。
  4. 根据权利要求1所述的制备方法，其特征在于，所述亚硫酸氢盐选自亚硫酸氢钠、亚硫酸氢钾、亚硫酸氢镁和亚硫酸氢钙中的至少一种。
  5. 根据权利要求1-4中任一项所述的制备方法，其特征在于，在所述制备方法中，按重量份计，所述磺酸盐为1-8份，所述二异氰酸酯三聚体为80-120份，所述亚硫酸氢盐为40-70份。
  6. 根据权利要求1所述的制备方法，其特征在于，所述第二次反应的温度为40-70℃。
  7. 根据权利要求6所述的制备方法，其特征在于，所述第二次反应在反应体系中-NCO的质量含量小于0.05％时，结束反应。
  8. 一种聚异氰酸酯固化剂，其特征在于，由权利要求1-7中任一项所述的制备方法制得，所述聚异氰酸酯固化剂的固含量为99-100％，封闭率大于99.9％。
  9. 权利要求8所述的聚异氰酸酯固化剂在聚氨酯涂料中的应用。
  10. 一种水性聚氨酯涂料，其特征在于，包括A组分和B组分，所述A组分 包括水性聚氨酯分散体，所述B组分包括权利要求8所述的聚异氰酸酯固化剂。
PCT/CN2022/128657 2021-12-20 2022-10-31 一种水性封闭型的聚异氰酸酯固化剂及其制备方法和应用 WO2023116204A1 (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
ZA2023/08970A ZA202308970B (en) 2021-12-20 2023-09-21 Water-based sealed polyisocyanate curing agent and preparation method and application thereof

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN202111576048.3 2021-12-20
CN202111576048.3A CN114230764B (zh) 2021-12-20 2021-12-20 一种水性封闭型的聚异氰酸酯固化剂及其制备方法和应用

Publications (1)

Publication Number Publication Date
WO2023116204A1 true WO2023116204A1 (zh) 2023-06-29

Family

ID=80760948

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2022/128657 WO2023116204A1 (zh) 2021-12-20 2022-10-31 一种水性封闭型的聚异氰酸酯固化剂及其制备方法和应用

Country Status (3)

Country Link
CN (1) CN114230764B (zh)
WO (1) WO2023116204A1 (zh)
ZA (1) ZA202308970B (zh)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114230764B (zh) * 2021-12-20 2023-06-13 嘉宝莉化工集团股份有限公司 一种水性封闭型的聚异氰酸酯固化剂及其制备方法和应用
CN115613369B (zh) * 2022-10-20 2024-04-16 莆田达凯新材料有限公司 耐热压聚氨酯鞋面涂料、耐热压聚氨酯涂层鞋面及其制备方法
CN117304429B (zh) * 2023-11-29 2024-02-02 大庆市唯品科技开发有限公司 一种复合型耐高温、抗盐性堵水剂及其制备方法

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63125515A (ja) * 1986-11-14 1988-05-28 Ohara Parajiumu Kagaku Kk 水溶性ウレタン樹脂の製造方法
CN1429240A (zh) * 2000-05-18 2003-07-09 拜尔公司 改性聚异氰酸酯
CN101675132A (zh) * 2007-05-04 2010-03-17 巴斯福涂料股份公司 基于氨基甲酸酯的水基双层涂料体系，其用途和用其涂覆的基材
CN102731749A (zh) * 2012-07-18 2012-10-17 上海材料研究所 一种亚硫酸氢钠封闭型水性聚氨酯的无溶剂制备方法
CN104448232A (zh) * 2013-09-13 2015-03-25 万华化学集团股份有限公司 一种氨基磺酸改性的多异氰酸酯及其制备方法和用途
CN108047645A (zh) * 2017-12-22 2018-05-18 合肥工业大学 一种以封端的异佛尔酮二异氰酸酯为固化剂制备的密胺泡沫
CN111154069A (zh) * 2020-01-15 2020-05-15 广州康狄夫环保科技有限公司 聚氨酯固化剂、水性聚氨酯、涂料及其制备方法和应用
CN114230764A (zh) * 2021-12-20 2022-03-25 嘉宝莉化工集团股份有限公司 一种水性封闭型的聚异氰酸酯固化剂及其制备方法和应用

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63125515A (ja) * 1986-11-14 1988-05-28 Ohara Parajiumu Kagaku Kk 水溶性ウレタン樹脂の製造方法
CN1429240A (zh) * 2000-05-18 2003-07-09 拜尔公司 改性聚异氰酸酯
CN101675132A (zh) * 2007-05-04 2010-03-17 巴斯福涂料股份公司 基于氨基甲酸酯的水基双层涂料体系，其用途和用其涂覆的基材
CN102731749A (zh) * 2012-07-18 2012-10-17 上海材料研究所 一种亚硫酸氢钠封闭型水性聚氨酯的无溶剂制备方法
CN104448232A (zh) * 2013-09-13 2015-03-25 万华化学集团股份有限公司 一种氨基磺酸改性的多异氰酸酯及其制备方法和用途
CN108047645A (zh) * 2017-12-22 2018-05-18 合肥工业大学 一种以封端的异佛尔酮二异氰酸酯为固化剂制备的密胺泡沫
CN111154069A (zh) * 2020-01-15 2020-05-15 广州康狄夫环保科技有限公司 聚氨酯固化剂、水性聚氨酯、涂料及其制备方法和应用
CN114230764A (zh) * 2021-12-20 2022-03-25 嘉宝莉化工集团股份有限公司 一种水性封闭型的聚异氰酸酯固化剂及其制备方法和应用

Also Published As

Publication number Publication date
CN114230764B (zh) 2023-06-13
ZA202308970B (en) 2023-10-25
CN114230764A (zh) 2022-03-25

Similar Documents

Publication Publication Date Title
WO2023116204A1 (zh) 一种水性封闭型的聚异氰酸酯固化剂及其制备方法和应用
CN107245293B (zh) 适合海洋环境的丙烯酸改性氯化橡胶水性涂料及其制备方法
CN109867743B (zh) 一种室温自交联水性丙烯酸树脂分散体及其制备方法
CN108976371B (zh) 一种高性能磺酸型水性聚氨酯固化剂及其制备方法与应用
CN104910344A (zh) 一种快速uv光固化的含氟疏水性聚氨酯弹性涂层的制备方法
WO2016086631A1 (zh) 一种水性脂环族异氰酸酯改性聚酯光固化树脂的制备方法
WO2014146522A1 (zh) 一种tdi异氰脲酸酯的制备方法
CN101096475B (zh) 一种聚氨酯增稠剂的制备方法
CN107814936A (zh) 一种poss改性的低游离单体聚氨酯固化剂
CN110818881B (zh) 一种聚氨酯油墨树脂的制备方法及其制备的聚氨酯油墨树脂与油墨
CN112194769A (zh) 一种水性聚氨酯/聚丙烯酸酯改性酮醛树脂复合乳液及其制备方法与应用
WO2012093871A1 (en) Mono-fluid type paint composition for coating glass with excellent anti-alkalinity
JP7077073B2 (ja) 光輝性塗料組成物
EP3783070A1 (en) A waterborne white-base coating
CN114316173A (zh) 一种有机硅改性羟基聚丙烯酸酯分散体及其制备方法与应用
CN103626956A (zh) 一种改性多异氰酸酯、水分散性交联剂及其制备方法
CN112194753A (zh) 一种丙烯酸树脂、低voc丙聚涂层材料及其制备方法
CN112063286A (zh) 一种用于汽车铝型材部件的表面涂料
CN112143280B (zh) 一种含具有反应活性的阴离子表面活性剂的组合物及其制备方法
CN114045094B (zh) 一种水性环氧树脂分散体及其制备方法
CN111363425B (zh) 防雾剂、制备方法及其应用
CN109836754B (zh) 一种耐溶剂耐水煮的pc镜面树脂及其制备方法
CN102010649A (zh) 单组份pu烤漆的加工方法及其单组份pu烤漆
KR100575684B1 (ko) 자동차용 도료 조성물
CN112500779A (zh) 一种抑菌抗氧化铝箔保护剂及其制备方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 22909521

Country of ref document: EP

Kind code of ref document: A1