CN111848923A - Preparation method of water-based polyisocyanate curing agent - Google Patents
Preparation method of water-based polyisocyanate curing agent Download PDFInfo
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- CN111848923A CN111848923A CN202010734568.1A CN202010734568A CN111848923A CN 111848923 A CN111848923 A CN 111848923A CN 202010734568 A CN202010734568 A CN 202010734568A CN 111848923 A CN111848923 A CN 111848923A
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- 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
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- 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
- C08G18/16—Catalysts
- C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
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- 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
- C08G18/16—Catalysts
- C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
- C08G18/1816—Catalysts containing secondary or tertiary amines or salts thereof having carbocyclic groups
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- 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
- C08G18/2805—Compounds having only one group containing active hydrogen
- C08G18/2815—Monohydroxy compounds
- C08G18/283—Compounds containing ether groups, e.g. oxyalkylated monohydroxy compounds
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a preparation method of a water-based polyisocyanate curing agent, which is mainly prepared by the following components: polyisocyanate, hydrophilic modifier, phase transfer catalyst, organic solvent and acid neutralizer; the hydrophilic modifier comprises amino/hydroxyl functional sulfonic acid and polyoxyalkylene alkyl ether with the average molecular weight of 300-2000; the phase transfer catalyst is tertiary amine, the organic solvent is ester/ether solvent which does not contain isocyanate, and the pKa of the acid neutralizing agent11 to 4. The water-based polyisocyanate curing agent prepared by the method can be well dispersed in water without high-speed shearing, and has excellent storage stability and longer construction pot life.
Description
Technical Field
The invention belongs to the field of water-based paint, and particularly relates to a preparation method of a water-based polyisocyanate curing agent.
Background
The water paint is one of the development directions of the environmental protection transformation of the paint industry. The water is used as a dispersion medium, the VOC emission is small in the production and use processes, and the storage and transportation are safe. Traditional solvent-borne acrylic polyurethane coating systems also face waterborne transitions, which consist of two parts: a hydroxy acrylic resin component and a polyisocyanate curing agent component.
The non-hydrophilically modified polyisocyanate curing agent is difficult to mix with the waterborne hydroxyl resin component, so that the phase separation of the coating or paint film is easily caused, and the performance of the paint film is reduced, so that the polyisocyanate curing agent needs to be hydrophilically modified, and three methods, namely anionic modification, nonionic modification and mixing modification, are mainly adopted. Cationic modification methods are less preferred because the tertiary amine modifiers used tend to catalyze the reaction of isocyanate with water.
US5583176 modifies polyisocyanates using hydroxysulfonic acids as ionic hydrophilic modifiers to produce aqueous isocyanate curing agents which are excellent in water dispersibility. The triethylamine is also used as a neutralizing agent to neutralize sulfonic acid, so that the problem that the curing agent is incompatible with polyisocyanate due to the fact that the pH value of the curing agent is less than 5 is avoided, and the storage stability of the curing agent and the construction trial period after paint preparation are affected, so that the curing agent needs to be neutralized immediately before paint preparation, and further the construction complexity is increased.
EP0443138A discloses a process using carboxylic acid salts as hydrophilic modifiers which has the disadvantage that the carboxylic acid salts are not very water dispersible as the sulfonic acid salts, and that a large amount of modifier is required to achieve the same water dispersibility, with the consequent need for more tertiary amine neutralizing agent to neutralize the carboxylic acid, resulting in poor storage stability of the curing agent.
CN104448232A discloses a polyisocyanate of sulfamic acid modifier and a preparation method and application thereof, wherein, the polyisocyanate is successfully modified in a short time by adding isocyanate into a reaction system in two steps and increasing the reaction temperature, so that sulfonic acid type hydrophilic modifier such as cyclohexylaminoethanesulfonic acid and the like is disclosed. In the modification reaction, tertiary amine neutralizes sulfonate, and quaternary ammonium salt generated by neutralizing sulfonic acid is used as a solubilizing reaction component of a phase transfer catalyst (heterogeneous reaction which is more typical of the modification reaction) of the modification reaction to promote the generation of the modification reaction and accelerate the reaction rate; the tertiary amine is added in two steps, so that the concentration and the catalyst equivalent of the phase transfer catalyst (tertiary amine) in the first step are relatively increased, the modification reaction rate is further accelerated, and the problems of poor storage stability and short construction application period of the curing agent caused by excessive addition of the tertiary amine for improving the reaction rate are also avoided. Although the method reduces the content of the tertiary amine and the quaternary ammonium salt which are not salified in the final finished product as much as possible, the existence of the tertiary amine and the quaternary ammonium salt can catalyze the reaction of water and NCO in air, and the storage stability of the curing agent or the construction pot life can be influenced to a certain extent.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method of a water-based polyisocyanate curing agent, which can improve the storage stability of the curing agent and the construction pot life after paint preparation on the premise of keeping good water dispersibility of the curing agent.
The technical scheme adopted by the invention for solving the technical problems is as follows:
a preparation method of water-based polyisocyanate is characterized in that the water-based polyisocyanate curing agent is mainly prepared by the reaction of the following components: polyisocyanate, hydrophilic modifier, phase transfer catalyst, organic solvent and acid neutralizer; the hydrophilic modifier comprises amino/hydroxyl functional sulfonic acid and polyoxyalkylene alkyl ether with the average molecular weight of 300-2000; the phase transfer catalyst is tertiary amine, the organic solvent is ester/ether solvent which does not contain isocyanate, and the pKa of the acid neutralizing agent11 to 4;
the preparation method comprises the following steps:
(1) under inert atmosphere, uniformly mixing part of polyisocyanate with a hydrophilic modifier, a phase transfer catalyst and an organic solvent, heating to 80-120 ℃, and reacting for 0.5-5 h to obtain a modified system;
(2) and (2) cooling the modified system obtained in the step (1) to 50-80 ℃, adding the rest polyisocyanate (A), uniformly stirring, adding an acid neutralizer, reacting for 0.5-5 h, and cooling to room temperature to obtain the water-based polyisocyanate curing agent.
Preferably, the polyisocyanate is selected from one or more of hexamethylene diisocyanate, isophorone diisocyanate and derivatives of both, and the isocyanate has an NCO content of 15-24% and a solid content of 100%.
Preferably, the mass ratio of the polyisocyanate added twice to the polyisocyanate added twice is 10-0.1: 1, preferably 6-0.5: 1, most preferably 3 to 1: 1.
Preferably, the amino/hydroxy functional sulphonic acid is selected from one or more of isethionic acid, hydroxymethylsulphonic acid, 3- (cyclohexylamine) -propanesulphonic acid, 3-chloro-2-hydroxypropylsulphonic acid and 4-hydroxybutylsulphonic acid;
preferably, the polyoxyalkylene alkyl ether is selected from one of polyoxyethylene alkyl ether, polyoxyethylene/propylene oxide mixed alkyl ether or a mixture thereof; the average molecular weight of the polyoxyalkylene alkyl ether is 400 to 1000, preferably 500 to 800.
Preferably, the molar ratio of polyisocyanate to amino/hydroxy functional sulfonic acid is 1 to 50:1, preferably 1 to 40:1, most preferably 5 to 30: 1.
Preferably, the molar ratio of polyisocyanate to polyoxyalkylene alkyl ether is 1 to 600:1, preferably 10 to 300:1, most preferably 20 to 100: 1.
Preferably, the phase transfer catalyst is selected from one or more of trimethylamine, triethylamine, dimethylethylamine, tributylamine, N-dimethylcyclohexylamine, and N, N-diethylcyclohexylamine, preferably N, N-dimethylcyclohexylamine.
Preferably, the molar ratio of phase transfer catalyst to amino/hydroxy functional sulfonic acid is from 0.1 to 10:1, preferably from 0.3 to 6:1, most preferably from 0.5 to 3: 1.
Preferably, the organic solvent is selected from one or more of propylene glycol methyl ether acetate, propylene glycol diethyl ester, ethylene glycol butyl ether acetate, propylene glycol butyl ether acetate and butyl acetate, preferably propylene glycol methyl ether acetate and/or propylene glycol diethyl ester.
Preferably, the mass fraction of the organic solvent is 0 to 50%, preferably 0 to 40%, and more preferably 0 to 30%.
Preferably, the acid neutralizing agent is selected from the group consisting of pKa' s1Acids with a value of 1-4, such as one or more of phosphoric acid, pyruvic acid, alpha-chlorobutyric acid, malonic acid, p-nitrobenzoic acid, glyceric acid, formic acid, m-nitrobenzoic acid, tartaric acidPhosphoric acid and pyruvic acid are preferred.
Preferably, the molar ratio of the phase transfer catalyst to the acid neutralizing agent is 1-100: 1, preferably 5 to 50:1, most preferably 10 to 40: 1.
a water-based two-component polyurethane coating comprises the water-based polyisocyanate curing agent.
Preferably, the two-component polyurethane coating is used to coat metal, wood, concrete or other polymeric coating substrates.
Compared with the prior art, the invention has the beneficial effects that:
(1) according to the preparation method disclosed by the invention, after the modification reaction is finished, the acid neutralizer with a specific acidity coefficient is added into the reaction system, so that the storage stability of the obtained water-based polyisocyanate curing agent is more excellent.
(2) The construction pot life of the water-based polyisocyanate curing agent prepared by the method is obviously prolonged in a water-based two-component coating system.
Detailed Description
The present invention is further illustrated by the following examples, which should be noted that the range of the mixture ratio of each reaction component and the process flow in the examples should not be construed as limiting the technical scope of the present invention.
Raw materials and abbreviations:
TABLE 1 raw materials, abbreviations and suppliers to this patent
The test method comprises the following steps:
appearance: and (3) detecting the appearance of the finished product of the water-based isocyanate curing agent by adopting a visual method, and showing the result in a clear and turbid manner.
Isocyanate (NCO) value: the isocyanate content was determined using DIN EN ISO 11909 and the results are expressed in%.
Viscosity: the shear viscosity was characterized using an Anton Paar MC1 rheometer at 23 ℃ with a Z3 rotor, 1001/s shear velocity.
The Nano pendulum rod hardness of K: the coating is applied to glass panels with a wet film thickness of about 100 microns, and the hardness of the tins is tested in accordance with DIN EN ISO 1522 after the paint film has been dried for 4h at room temperature (23 ℃, 50% relative humidity) and for 12h in an oven at 50 ℃.
Gloss: the coatings were applied to Leneta 2A cardboard at a wet film thickness of 200 μm, likewise dried at room temperature for 4h, and after drying at 50 ℃ for 12h, measured for 20 ℃ and 60 ℃ gloss using a BYK-Gardener reflectometer in accordance with DIN EN ISO 2813.
Pencil hardness: the test panel preparation conditions were consistent with the tinig pendulum hardness, with the paint film pencil hardness being tested using DIN EN ISO 13523-4, with results expressed as a certain scale from 8B (softest) to 8H (hardest).
Adhesion (X cut and cross cut): the adhesion of the paint film on the substrate was tested using ASTM D3359-93.
Construction Pot life (Pot life): the prepared two-component water-based polyurethane paint is placed in a constant temperature and humidity room (23 ℃, 50 percent relative humidity), and samples are taken every 0.5 h to test the glossiness of the paint film. The time for the 60-degree gloss to be reduced to 90% of the initial value is taken as the construction working life of the two-component coating.
Storage stability: the prepared water-based isocyanate curing agent is sealed in a 500 ml plastic wide-mouth bottle, the wide-mouth bottle is placed in an oven at 50 ℃ for 14 days, the appearance of the curing agent after heat storage and the reduction degree of the NCO value are observed, and if the appearance of the curing agent is not changed after heat storage, the NCO value is reduced within 10 percent, the hot storage test is judged to pass.
Example 1:
the present embodiment includes the following steps
(1) A round-bottomed four-necked flask equipped with nitrogen inlet, mechanical stirrer, condenser, thermometer, heating mantle was charged with 10g of MPEG 600, 463.7g of HDI trimer, 34g of CAPS, 20.8g of DMCHA, and 170.5g of PMA, and the mixture was heated to 90 ℃ to react for 3.5 hours to obtain a clear and transparent liquid.
(2) The temperature is reduced to 80 ℃, 300g of HDI tripolymer and 1.0 g of 85% phosphoric acid aqueous solution are added, stirred for 15 min and filtered by a 50 mu m filter cloth to discharge. The obtained water-based isocyanate curing agent has the following characteristics: NCO value =15.61%, solids =83.0%, viscosity =644 mpa.s, clear and transparent in appearance.
The raw material ratios and the final product parameters of example 2 and comparative examples 1 to 4 are given in Table 2. The reaction temperature and time were the same as in example 1.
TABLE 2 raw material composition and finished product parameters for preparing the aqueous isocyanate curing agent of the present invention
The chemicals used for preparing the aqueous two-component polyurethane varnish are summarized as follows:
bayhydrol a 2470: acrylic secondary dispersion of kesichu (solids = 45%; solvent composition water: 100# mineral spirits: propylene glycol butyl ether =44.3:4: 4; neutralizer dimethylethanolamine; solids hydroxyl value = 4.0%)
BYK 028: silicone antifoam of Picker chemistry
BYK 346: polyether modified organosilicon base material wetting agent of Picker chemistry
BG: ethylene glycol butyl ether, Dow chemical
BDG: diethylene glycol monobutyl ether, Dow chemical
BGA: ethylene glycol monobutyl ether acetate, Dow chemical
Deionized water: self-made
The varnish is prepared by the following steps:
1. preparing a varnish of the resin component A: 90 g of Bayhydrol A2470 and 0.6 g of BYK 028, 2 g of BG, 1.5 g of BDG, 0.4 g of BYK 346 and 5.5 g of deionized water were dispersed on a high-speed disperser until the varnish was free of craters.
2. Preparation of curing agent component B: the curing agents in the examples and comparative examples were diluted to 70% solids with BGA.
3. Mixing the component A and the component B according to the ratio of isocyanate: hydroxyl molar ratio =1.5, and then adjusting the two-component varnish viscosity with deionized water to 4 cups 25s for use.
The prepared varnish is subjected to various paint film performance tests according to the method, and the performance indexes of the obtained paint film are shown in the table 3:
TABLE 3 basic Performance test results for aqueous two-component polyurethane varnishes
From the results in table 3, it can be seen that the incorporation of a certain amount of phosphoric acid into the curing agent formulation can significantly improve the pot life and storage stability of the construction, as compared with the results in example 1 and comparative example 1. Comparative example 2 shows that with increasing DMCHA content, the pot life and storage stability of the construction is further reduced due to the catalytic action of the tertiary amine on the isocyanate and water reaction in the storage and coating components. In example 2, the DMCHA dosage is less, the phosphoric acid dosage is more, and the longest construction pot life is obtained. Comparative examples 3, 4 and 5 show the introduction of other pKa' s1The Lewis acid in the range is difficult to achieve the effect of phosphoric acid on prolonging the construction pot life and the storage stability.
Claims (10)
1. The preparation method of the water-based polyisocyanate is characterized by mainly reacting the following components: polyisocyanate, hydrophilic modifier, phase transfer catalyst, organic solvent and acid neutralizer; the hydrophilic modifier comprises amino/hydroxyl functional sulfonic acid and polyoxyalkylene alkyl ether with the average molecular weight of 300-2000; the phase transfer catalyst is tertiary amine, the organic solvent is ester/ether solvent which does not contain isocyanate, and the pKa of the acid neutralizing agent11 to 4; the preparation method comprises the following steps:
(1) under inert atmosphere, uniformly mixing part of polyisocyanate with a hydrophilic modifier, a phase transfer catalyst and an organic solvent, heating to 80-120 ℃, and reacting for 0.5-5 h to obtain a modified system;
(2) and (2) cooling the modified system obtained in the step (1) to 50-80 ℃, adding the rest polyisocyanate, uniformly stirring, adding an acid neutralizer, reacting for 0.5-5 h, and cooling to room temperature to obtain the water-based polyisocyanate curing agent.
2. The method for preparing the aqueous polyisocyanate according to claim 1, wherein the polyisocyanate is one or more selected from the group consisting of hexamethylene diisocyanate, isophorone diisocyanate and derivatives thereof, and the isocyanate has an NCO content of 15% to 24% and a solid content of 100%.
3. The process for preparing the aqueous polyisocyanate according to claim 1 or 2, wherein the mass ratio of the polyisocyanate added in two times before and after addition is 10 to 0.1:1, preferably 6 to 0.5: 1, most preferably 3 to 1: 1.
4. The process for preparing the aqueous polyisocyanate according to any one of claims 1 to 3, wherein the amino/hydroxy functional sulfonic acid is one or more selected from the group consisting of isethionic acid, hydroxymethylsulfonic acid, 3- (cyclohexylamine) -propanesulfonic acid, 3-chloro-2-hydroxypropylsulfonic acid and 4-hydroxybutylsulfonic acid; the molar ratio of polyisocyanate to amino/hydroxy functional sulfonic acid is 1 to 50:1, preferably 1 to 40:1, most preferably 5 to 30: 1.
5. The method for preparing the water-based polyisocyanate according to any one of claims 1 to 4, wherein the polyoxyalkylene alkyl ether is selected from one or more of polyoxyethylene alkyl ether and polyoxyethylene/oxypropylene mixed alkyl ether; the average molecular weight of the polyoxyalkylene alkyl ether is 400-1000, preferably 500-800; the molar ratio of the polyisocyanate to the polyoxyalkylene alkyl ether is 1 to 600:1, preferably 10 to 300:1, and most preferably 20 to 100: 1.
6. The process for preparing an aqueous polyisocyanate according to any one of claims 1 to 5, wherein the phase transfer catalyst is selected from one or more of trimethylamine, triethylamine, dimethylethylamine, tributylamine, N-dimethylcyclohexylamine and N, N-diethylcyclohexylamine, preferably N, N-dimethylcyclohexylamine; preferably, the molar ratio of phase transfer catalyst to amino/hydroxy functional sulfonic acid is from 0.1 to 10:1, preferably from 0.3 to 6:1, most preferably from 0.5 to 3: 1.
7. The method for preparing the aqueous polyisocyanate according to any one of claims 1 to 6, wherein the organic solvent is one or more selected from propylene glycol methyl ether acetate, propylene glycol diethyl ester, ethylene glycol butyl ether acetate, propylene glycol butyl ether acetate and butyl acetate, preferably propylene glycol methyl ether acetate and/or propylene glycol diethyl ester; preferably, the mass fraction of the organic solvent is 0 to 50%, preferably 0 to 40%, and more preferably 0 to 30%.
8. The process for preparing the aqueous polyisocyanate according to any one of claims 1 to 7, wherein the acid neutralizing agent is one or more selected from phosphoric acid, pyruvic acid, α -chlorobutyric acid, malonic acid, p-nitrobenzoic acid, glyceric acid, formic acid, m-nitrobenzoic acid, tartaric acid, preferably phosphoric acid and pyruvic acid; preferably, the molar ratio of the phase transfer catalyst to the acid neutralizing agent is 1-100: 1, preferably 5 to 50:1, most preferably 10 to 40: 1.
9. a water-borne two-component polyurethane coating, characterized by comprising the water-borne polyisocyanate curing agent prepared by the method of any one of claims 1 to 9.
10. The aqueous two-component polyurethane coating of claim 9, wherein the two-component polyurethane coating is used to coat metal, wood, concrete or other polymer coated substrates.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112679687A (en) * | 2020-12-24 | 2021-04-20 | 华南理工大学 | Hydroxysulfonic acid hydrophilic monomer and preparation method and application thereof |
| CN114933845A (en) * | 2022-05-07 | 2022-08-23 | 浙江鑫柔科技有限公司 | Thermosetting weather-proof protective coating material and preparation method and application thereof |
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| CN114933845B (en) * | 2022-05-07 | 2023-05-26 | 浙江鑫柔科技有限公司 | Thermosetting weather-proof protective coating material and preparation method and application thereof |
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Denomination of invention: Preparation method of a water-based polyisocyanate curing agent Effective date of registration: 20230731 Granted publication date: 20220322 Pledgee: Agricultural Bank of China Limited Changsha Wangcheng District sub branch Pledgor: XIANGJIANG PAINT TECHNOLOGY CO.,LTD. Registration number: Y2023980050457 |