CN108659191B - Solvent-free water-based polyisocyanate curing agent and preparation method and application thereof - Google Patents
Solvent-free water-based polyisocyanate curing agent and preparation method and application thereof Download PDFInfo
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- CN108659191B CN108659191B CN201810366557.5A CN201810366557A CN108659191B CN 108659191 B CN108659191 B CN 108659191B CN 201810366557 A CN201810366557 A CN 201810366557A CN 108659191 B CN108659191 B CN 108659191B
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- 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
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
- C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
- C08G18/0828—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing sulfonate groups or groups forming them
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- 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
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- 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
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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- 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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- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
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- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
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- C09J175/04—Polyurethanes
Abstract
The invention discloses a solvent-free water-based polyisocyanate curing agent, and a preparation method and application thereof. The solvent-free aqueous polyisocyanate curing agent is a polyisocyanate prepolymer containing sulfonic acid groups. The preparation method of the solvent-free water-based polyisocyanate curing agent comprises the steps of dissolving dicarboxyl sulfonate in an organic solvent, reacting with a polyisocyanate prepolymer, and distilling the organic solvent to obtain the solvent-free water-based polyisocyanate curing agent. The application of the solvent-free water-based polyisocyanate curing agent is also disclosed. The solvent-free water-based polyisocyanate curing agent is a real VOC zero-emission product, has excellent water dispersibility and storage stability, high NCO content and low viscosity, can be matched with various resins containing hydroxyl or carboxyl or amino to prepare a two-component polyurethane coating and a two-component polyurethane adhesive, and can endow the product with good water resistance and high strength.
Description
Technical Field
The invention relates to a solvent-free water-based polyisocyanate curing agent, a preparation method and application thereof.
Background
Along with the enhancement of the environmental awareness of people and the increase of the execution force of national environmental regulations, the research on the aquosity of two-component polyurethane coatings and polyurethane adhesives is actively developed, the research on the aquosity of hydroxyl-containing polyurethane resin is relatively deep at present, but most of hydroxyl-containing polyurethane resin contains a certain solvent, and the problem of toxicity of volatile organic solvents still exists.
CN105949436A discloses a water dispersible HDI-TDI mixed trimer curing agent, which is prepared into a trimer, after unreacted monomers are removed, dimethylol propionic acid (DMPA) in a solid state is directly added into the solvent-free HDI-TDI trimer to react to prepare the solvent-free curing agent, and the manufacturing process is difficult because the DMPA can not be dissolved in the trimer, and solid materials are adhered to the wall of a reactor after being added and stirred. CN105968304A discloses a high-performance water-based polyurethane curing agent, which is prepared by directly mixing solid hydroxycarboxylic acid, cyclohexane and hydrophilic polyether, dripping the mixture into solvent-free polyisocyanate, and reacting to obtain the curing agent with 100% solid content. In conclusion, the technical difficulties of the processes for preparing the solvent-free polyisocyanate curing agents disclosed in the prior documents are still large, the industrial production is still under intensive research, and the market demand of Japanese forces the technicians in the field to develop more technologies for the solvent-free aqueous polyisocyanate curing agents.
Disclosure of Invention
One of the purposes of the invention is to provide a solvent-free water-based polyisocyanate curing agent, which can realize the zero emission of VOC of a polyurethane curing agent; the second object of the present invention is to provide a process for producing such a solvent-free aqueous polyisocyanate curing agent; the third purpose of the invention is to provide the application of the solvent-free water-based polyisocyanate curing agent.
The technical scheme adopted by the invention is as follows:
a solvent-free water-based polyisocyanate curing agent is a polyisocyanate prepolymer containing sulfonic acid groups.
The preparation method of the solvent-free water-based polyisocyanate curing agent comprises the steps of dissolving dicarboxyl sulfonate in an organic solvent, reacting with a polyisocyanate prepolymer, and distilling the organic solvent to obtain the solvent-free water-based polyisocyanate curing agent.
In the preparation method, the molar ratio of the dicarboxyl sulfonate to the polyisocyanate prepolymer is (0.03-0.2): 1; the adding amount of the organic solvent is 3-10 times of the mass of the dicarboxyl sulfonate.
In the preparation method, the organic solvent is N-methyl pyrrolidone.
In the preparation method, the dicarboxyl sulfonate is dicarboxyl sulfonic acid alkali metal salt.
In the preparation method, the polyisocyanate prepolymer is at least one of HDI trimer, HDI biuret, HDI prepolymer, IPDI trimer and HMDI prepolymer.
In the preparation method, the distillation method is one of a vacuum distillation method, a thin film distillation method and a hot gas bubbling method.
The preparation method specifically comprises the following steps:
a) adding dicarboxyl sulfonate and N-methyl pyrrolidone into a reaction vessel, heating to 50-60 ℃, stirring and dissolving for 0.5-1 h, and adding polyisocyanate prepolymer accounting for 30-70% of the total amount of the polyisocyanate prepolymer for reaction;
b) adding an antioxidant, sealing the reactor, introducing protective gas, reacting for 5-10 h at 50-100 ℃, adding the remaining polyisocyanate prepolymer, and stirring and mixing uniformly;
c) distilling the organic solvent, cooling to 60 ℃, and discharging to obtain the solvent-free water-based polyisocyanate curing agent.
In the step b) of the preparation method, the addition amount of the antioxidant accounts for 0.01 to 0.5 percent of the total mass of the dicarboxyl sulfonate and the polyisocyanate prepolymer.
The solvent-free water-based polyisocyanate curing agent is applied to the preparation of water-based polyurethane paint or water-based polyurethane adhesive.
The invention has the beneficial effects that:
the solvent-free water-based polyisocyanate curing agent is a real VOC zero-emission product, has excellent water dispersibility and storage stability, high NCO content and low viscosity, can be matched with various resins containing hydroxyl or carboxyl or amino to prepare a two-component polyurethane coating and a two-component polyurethane adhesive, and can endow the product with good water resistance and high strength.
Compared with the prior art, the invention has the following advantages:
1. the invention adopts dicarboxyl sulfonate to directly carry out chain extension reaction on polyisocyanate to prepare the waterborne polyurethane curing agent, which is information not disclosed in other patent documents, the prior art discloses a method for preparing the waterborne polyurethane curing agent by directly reacting hydroxyl sulfonate or sulfamate with polyisocyanate, CN106366291A adopts hydroxyl type sulfonic acid derivatives to directly react with polyisocyanate to prepare the self-emulsifying anionic waterborne polyurethane curing agent, and CN1183791A adopts ammonium sulfonate and nonionic hydrophilic substances to directly react with polyisocyanate to prepare the waterborne polyurethane curing agent. The main reason why the prior patent documents do not disclose the direct reaction of the carboxyl sulfonate with the polyisocyanate is that the carboxyl sulfonate has stronger polarity and better hydrophilicity than the hydroxyl sulfonate and the amine sulfonate, is basically insoluble in organic solvents and is insoluble in isocyanate, and is difficult to find a medium for carrying out chemical reaction, while the hydroxyl sulfonate and the amino sulfonate can be dissolved in most solvents, and the chemical reaction is easy to carry out. The invention adopts a method of moving the dissolution balance to increase the solubility of NMP to carboxyl sulfonate at the reaction temperature, improves the solubility of the carboxyl sulfonate by a feeding mode of adding polyisocyanate prepolymer for the second time, and solves the problem that the carboxyl sulfonate which is almost insoluble in an organic solvent can react with the polyisocyanate prepolymer in the organic solvent.
2. The method adopts dicarboxyl sulfonate to directly carry out chain extension reaction with polyisocyanate, the molecular weight of a reactant (carboxyl sulfonate) is smaller, the molecular weight of a product is also small, namely the viscosity of the product is low, the subsequent procedure is facilitated to distill and remove an organic solvent, and meanwhile, a low-viscosity curing agent is easier to disperse in aqueous resin. CN107082860A is a polyurethane curing agent prepared by reacting a small-molecular diol containing a sulfonic acid group and diisocyanate, wherein the molecular weight of the reactant (the small-molecular diol containing the sulfonic acid group) is relatively large, and the viscosity of the product is relatively high. Therefore, the present invention is more advanced than the prior art.
3. The dicarboxyl sulfonate adopted by the invention has rich raw material sources and low price, and is only one fifth of the price of the corresponding dihydroxy sulfonate or diamino sulfonate, so the practicability of the technology of the invention is stronger.
4. The NMP adopted by the invention is not only a solvent of the dicarboxyl sulfonate, but also a catalyst for isocyanate reaction, and the double functions play a positive and beneficial role in hydrophilic reaction of the polyisocyanate, so that the reaction temperature is reduced, and the reaction time is shortened.
5. The invention prefers the hot gas bubbling method, and introduces low-temperature hot gas with the temperature of below 100 ℃ into the product to remove the solvent, thereby having no influence on the product quality.
6. The solvent-free water-based polyisocyanate curing agent prepared by the invention really achieves the environmental protection concept of VOC zero emission, has the advantages of light color, low viscosity, high effective functionality, difficult yellowing, good water dispersibility, good storage stability and the like, and is suitable for being matched with water-based polyurethane dispersoid, water-based acrylic emulsion, water-based alkyd resin and the like to prepare water-based double-component polyurethane coating and adhesive.
Detailed Description
A solvent-free water-based polyisocyanate curing agent is a polyisocyanate prepolymer containing sulfonic acid groups.
Further, the solid content of the solvent-free aqueous polyisocyanate curing agent is more than 99 wt%; still further, the solid content of the solvent-free water-based polyisocyanate curing agent can reach more than 99.5 weight percent.
The preparation method of the solvent-free water-based polyisocyanate curing agent comprises the steps of dissolving dicarboxyl sulfonate in an organic solvent, reacting with a polyisocyanate prepolymer to generate a polyisocyanate prepolymer containing sulfonic acid groups, and distilling the organic solvent to obtain the solvent-free water-based polyisocyanate curing agent.
Preferably, in the preparation method, the molar ratio of the dicarboxyl sulfonate to the polyisocyanate prepolymer is (0.03-0.2): 1; the adding amount of the organic solvent is 3-10 times of the mass of the dicarboxyl sulfonate.
Preferably, in the preparation method, the organic solvent is N-methylpyrrolidone (NMP).
Preferably, in the preparation method, the dicarboxyl sulfonate is dicarboxyl sulfonate alkali metal salt; further preferably, in the preparation method, the dicarboxyl sulfonate is dicarboxyl sodium sulfonate; still further preferably, in the preparation method, the dicarboxy sulfonate is sodium 5-benzenedicarboxylic acid sulfonate.
Preferably, in the preparation method, the polyisocyanate prepolymer is at least one of HDI trimer, HDI biuret, HDI prepolymer, IPDI trimer and HMDI prepolymer.
Preferably, in the preparation method, the distillation is performed by one of a vacuum distillation method, a thin film distillation method and a hot gas bubbling method; further preferably, in the preparation method, a specific method of distillation is a hot gas bubbling method.
The preparation method specifically comprises the following steps:
a) adding dicarboxyl sulfonate and N-methyl pyrrolidone into a reaction vessel, heating to 50-60 ℃, stirring and dissolving for 0.5-1 h, and adding polyisocyanate prepolymer accounting for 30-70% of the total amount of the polyisocyanate prepolymer for reaction;
b) adding an antioxidant, sealing the reactor, introducing protective gas, reacting for 5-10 h at 50-100 ℃, adding the remaining polyisocyanate prepolymer, and stirring and mixing uniformly;
c) distilling the organic solvent, cooling to 60 ℃, and discharging to obtain the solvent-free water-based polyisocyanate curing agent.
Preferably, in step b) of the preparation method, the addition amount of the antioxidant accounts for 0.01-0.5% of the total mass of the dicarboxyl sulfonate and the polyisocyanate prepolymer.
Preferably, in the step b) of the preparation method, the antioxidant is a hindered phenol antioxidant; more preferably, in step b) of the preparation method, the antioxidant is at least one of antioxidant 1010, antioxidant 1076 and antioxidant 3114.
Preferably, in step b) of the preparation method, the shielding gas is one of nitrogen, argon, helium and neon.
Further, in step b) of the preparation process, when the measured NCO mass content of the reactants drops close to the theoretical calculation value, the reaction is stopped and the remaining polyisocyanate prepolymer is added.
Further, NMP, which is an organic solvent separated by distillation, can be reused after being collected.
The isocyanate molecular structure of the solvent-free water-based polyisocyanate curing agent provided by the invention has anionic sulfonic acid groups with good hydrophilic property, so that the solvent-free water-based polyisocyanate curing agent can be stably dispersed in water-based resin, and the viscosity of the prepared water-based polyisocyanate prepolymer is low due to the small molecular weight of the modified dicarboxy sulfonate, so that the solvent adopted in the preparation process is easy to distill and remove, and the aim of zero emission of VOC (volatile organic compounds) of the polyurethane curing agent is fulfilled.
The solvent-free water-based polyisocyanate curing agent is applied to the preparation of water-based polyurethane paint or water-based polyurethane adhesive.
Furthermore, the solvent-free waterborne polyisocyanate curing agent can be dispersed in waterborne polyurethane resin, waterborne acrylic resin, waterborne alkyd resin and other resins to prepare a two-component waterborne polyurethane coating or adhesive, thereby really solving the zero emission problem of VOC.
The method for preparing the solvent-free water-based curing agent is different from the method disclosed by the prior art, and specifically comprises the following steps:
1. first, modified hydrophilic substances are used differently. The invention adopts dicarboxyl sulfonate as hydrophilic modifier, the carboxyl property of the dicarboxyl sulfonate is a monomer with higher polarity, the dicarboxyl sulfonate can endow resin with stronger water solubility, so the addition amount is smaller when the dicarboxyl sulfonate is used, and the aromatic ring structure of the dicarboxyl sulfonate endows products with excellent hardness and high glossiness. CN106366291A discloses a self-emulsifying anionic waterborne polyurethane curing agent which adopts hydroxysulfonic acid (salt) as a hydrophilic modifier; CN1183791A discloses a polyisocyanate composition with high emulsifiability and stability, which uses ammonium alkylbenzene sulfonate and polyethylene glycol monomethyl ether nonionic as hydrophilic modifier.
2. The solvents are different. The inventors of the present invention have tried that many hydrophilic, highly polar solvents suitable for isocyanates (e.g., diethylene glycol dimethyl ether, methyl ethyl ketone, N-dimethylformamide) are difficult to dissolve, and that even though dimethyl sulfoxide can dissolve the salts, thiol species are released at the reaction temperature with isocyanate, thereby changing the properties of the prepolymer. The present invention uses N-methylpyrrolidone as a solvent for the dicarboxy-late salt, which is also only slightly soluble, since the solid dicarboxy-late salt is substantially insoluble in organic solvents.
3. The catalysts are different. Because the reactivity of the carboxyl and-NCO is much weaker than that of hydroxyl and amino, a catalyst is generally added to ensure that the reaction speed is suitable for the requirement of industrial production. The invention uses N-methyl pyrrolidone (NMP) as a solvent of dicarboxyl sulfonate and a catalyst for the reaction of the dicarboxyl sulfonate and isocyanate, because a tertiary nitrogen atom on a five-membered ring of NMP has catalysis to the reaction of-NCO and-COOH.
4. After the reaction temperature and concentration are reached, the solubility equilibrium is broken, the granular dicarboxylates are continuously dissolved in NMP, and the granular dicarboxylates are dissolved while reacting until the reaction is completed, the reason why the sulfonates are dissolved is that the solid sulfonates are directly mixed with the isocyanate compound, the chemical reaction can only occur at the interface of solid-liquid contact, one solid powder contains tens of thousands of molecules, the products of the reaction of the molecules of the outer layer of the granules and the isocyanate may be attached to the surfaces of the granules, so that the molecules of the inner layer of the granules are in contact with the outer layer of the granules, the molecular viscosity of the prepolymers after the reaction of the granules and the isocyanate is very low, the molecular viscosity of the prepolymers after the reaction of the granules and the molecular viscosity of the isocyanate are very low, the molecular viscosity of the prepolymers after the reaction of the granules is increased, the molecular viscosity of the dicarboxylic sulfonates is increased, the molecular viscosity of the prepolymers after the reaction of the granules and the molecular viscosity of the molecular sulfonates are increased, and the molecular viscosity of the molecular sulfonates is increased.
The invention divides the polyisocyanate prepolymer with the formula amount into two parts and feeds the two parts, and because the product has hydrophilicity or dispersibility as long as part of the polyisocyanate is connected with hydrophilic groups, the whole polyisocyanate does not need to be added into the reaction system.
5. The process parameters are different. The technological parameters of the invention are that the reaction is carried out for 5-10 hours at 50-100 ℃, and the temperature of-NCO of aliphatic polyisocyanate prepolymer participating in the reaction is generally 90-120 ℃ and the time is more than 20 hours under the condition of no catalyst. Because of its lower activity, the NMP used in the present invention is both a solvent and a catalyst, which lowers the temperature and shortens the time of the chemical reaction.
The present invention will be described in further detail with reference to specific examples. The starting materials used in the examples are, unless otherwise specified, commercially available from conventional sources.
In the following examples, the detection method is illustrated as follows:
1. the viscosity was measured according to the national Standard GB/T2794-1995 determination of the viscosity of the adhesive.
2. The NCO content was measured according to the Standard of chemical industry "determination of isocyanate group content in HG/T2409-92 polyurethane prepolymer".
3. The detection of the solid content is carried out according to the national standard GB/T2793-1995 determination of the content of the adhesive non-volatile matter.
4. The VOC content is detected according to the determination of the content of volatile organic compounds (VOC in a tank) in GB/T23984-.
Example 1:
the solvent-free aqueous polyisocyanate curing agent of example 1 was prepared as follows:
a) 24g of isophthalic acid-5-sodium sulfonate and 230g of N-methylpyrrolidone are added into a reaction vessel, the temperature is increased to 60 ℃, stirring is carried out for dissolving for 1 hour, 200g of HDI trimer (no solvent, and NCO percent is 23 percent) is added, and the mixture is uniformly mixed and stirred.
b) Adding 0.8g of antioxidant 1010, sealing the reactor, introducing nitrogen, reacting for 8 hours at 50-80 ℃, stopping the reaction when the percentage content of NCO of the reactant is reduced to be close to 9%, adding 200g of HDI tripolymer, and stirring and mixing uniformly.
c) Filling nitrogen heated to 80 ℃ into the kettle from the bottom of the reactor to bubble liquid in the kettle, introducing the evaporated NMP and the filled nitrogen into a condenser under the action of vacuum, and introducing the distilled NMP into a storage tank for recycling for later use; after 3 hours, no liquid drop flows out from the outlet of the condenser, when the content of the residual NMP is detected to be lower than 1 percent, the nitrogen charging and the vacuum pumping are stopped to obtain the solvent-free aqueous HDI trimer curing agent, the temperature is reduced to 60 ℃, and the material is discharged.
The performance indexes of the solvent-free water-based polyisocyanate curing agent in the example 1, which are detected by the product, are as follows: the appearance was a pale yellow transparent liquid with a VOC content of 0.48%, a viscosity of 3600 mPas at 25 ℃ and an NCO% content of 19.8%.
Example 2:
the solvent-free aqueous polyisocyanate curing agent of example 2 was prepared as follows:
a) 32g of isophthalic acid-5-sodium sulfonate and 250g of N-methylpyrrolidone are added into a reaction vessel, the temperature is increased to 60 ℃, stirring is carried out for dissolving for 1 hour, 200g of HDI biuret (without solvent, NCO percent is 22 percent) is added, and the mixture is uniformly mixed and stirred.
b) Adding 0.8g of antioxidant 1010, sealing the reactor, introducing nitrogen, reacting for 9 hours at 50-80 ℃, stopping the reaction when the percentage content of NCO of the reactant is reduced to be close to 8%, adding 200g of HDI biuret, and stirring and mixing uniformly.
c) Filling nitrogen heated to 80 ℃ into the kettle from the bottom of the reactor to bubble liquid in the kettle, introducing the evaporated NMP and the filled nitrogen into a condenser under the action of vacuum, and introducing the distilled NMP into a storage tank for recycling for later use; after 3 hours, no liquid drop flows out from the outlet of the condenser, when the content of the residual NMP is detected to be lower than 1 percent, the nitrogen charging and the vacuum pumping are stopped to obtain the solvent-free water-based HDI biuret curing agent, the temperature is reduced to 60 ℃, and the material is discharged.
The performance indexes of the solvent-free water-based polyisocyanate curing agent in the example 2 after the detection of the product performance are as follows: the appearance was a pale yellow transparent liquid having a VOC content of 0.62%, a viscosity of 4800 mPas at 25 ℃ and an NCO% content of 18.5%.
Example 3:
the solvent-free aqueous polyisocyanate curing agent of example 3 was prepared as follows:
a) 20g of sodium isophthalate-5-sulfonate and 100g of NMP were added to a reaction vessel, heated to 50 ℃ and dissolved with stirring for 1 hour, and then 300g of HDI prepolymer solution (solid content: 75%, NCO%: 14.2%) was added thereto, and mixed and stirred uniformly.
b) Adding 0.8g of antioxidant 1010, sealing the reactor, introducing nitrogen, reacting for 8.5 hours at 50-80 ℃, stopping the reaction when the percentage content of NCO of the reactant is detected to be reduced to be close to 9%, adding 300g of HDI prepolymer solution, and stirring and mixing uniformly.
c) Filling nitrogen heated to 80 ℃ into the kettle from the bottom of the reactor to bubble liquid in the kettle, introducing the evaporated solvent and the filled nitrogen into a condenser under the vacuum action, and introducing the distilled solvent into a storage tank; after 3 hours, no liquid drop flows out from the outlet of the condenser, when the content of the solvent is detected to be lower than 1%, the nitrogen charging and the vacuum pumping are stopped to obtain the solvent-free water-based HDI prepolymer curing agent, the temperature is reduced to 60 ℃, and the material is discharged.
The performance indexes of the solvent-free water-based polyisocyanate curing agent in example 3 in the product detection are as follows: the appearance is light yellow transparent liquid, the VOC content is 1.84%, the viscosity at 25 ℃ is 9300 mPa.s, and the NCO% content is 16.1%.
Example 4:
the solvent-free aqueous polyisocyanate curing agent of example 4 was prepared as follows:
a) 28g of isophthalic acid-5-sodium sulfonate and 250g of N-methylpyrrolidone are added into a reaction vessel, heated to 60 ℃, stirred and dissolved for 1 hour, and then 300g of IPDI trimer solution (solid content is 70%, and NCO% ═ 12.3%) is added, mixed and stirred uniformly.
b) Adding 0.8g of antioxidant 1010, sealing the reactor, introducing nitrogen, reacting for 9 hours at 50-90 ℃, stopping the reaction when the percentage content of NCO of the reactant is reduced to 5%, adding 300g of IPDI tripolymer solution, and stirring and mixing uniformly.
c) Cooling to 60 ℃, discharging to obtain the aqueous IPDI trimer curing agent.
The performance index of the product of the solvent-free aqueous polyisocyanate curing agent of example 4 was measured: the appearance was a pale yellow transparent liquid with a solids content of 51%, a viscosity of 2500 mPas at 25 ℃ and an NCO% content of 7.2%.
Example 5:
the solvent-free aqueous polyisocyanate curing agent of example 5 was prepared as follows:
a) 26g of sodium 5-sulfoisophthalate and 200g of NMP were placed in a reaction vessel, heated to 55 ℃ and dissolved with stirring for 1 hour, and then 200g of HMDI prepolymer (solid content: 75%, NCO%: 10.8%) and 100g of HDI trimer were added thereto, and mixed and stirred uniformly.
b) Adding 0.8g of antioxidant 1010, sealing the reactor, introducing nitrogen, reacting for 9.5 hours at 50-90 ℃, stopping the reaction when the percentage content of NCO of the reactants is measured to be reduced to approach 6%, then adding 200g of HMDI prepolymer and 100g of HDI trimer, and stirring and mixing uniformly.
c) Cooling to 60 ℃, and discharging to obtain the water-based polyisocyanate curing agent.
The product performance index of the solvent-free aqueous polyisocyanate curing agent of example 5 was measured: the appearance was a pale yellow transparent liquid with a solids content of 63%, a viscosity of 4400 mPas at 25 ℃ and an NCO% content of 9.0%.
Application example 1:
the product of example 1 and the water-based alkyd resin with hydroxyl groups are stirred and mixed, and a proper amount of tap water is added if necessary and stirred uniformly to prepare the two-component water-based alkyd resin coating, wherein the pot life is as follows: 3h, the surface drying time of the test piece is 1 hour, the test piece is placed in a drying room at 50 ℃ for curing for 48 hours, and the properties of the prepared paint film are as follows: gloss (60 °): more than or equal to 88 percent; the hardness is more than or equal to Shore D70; impact strength: 58KJ/m2(ii) a Adhesion force: grade 1; flexibility: 1 mm; the water resistance (25 ℃/24h) is unchanged; storage stability (50 ℃/7 day): no obvious change.
The detection method comprises the following steps: the gloss is in accordance with GB9754-88, the hardness is in accordance with GB1730-79, the impact strength is in accordance with GB/T2571-1995, the adhesion is in accordance with GB1720-89, and the flexibility is in accordance with GB1731-79 standard.
Application example 2:
the product of example 2 is mixed with the waterborne polyurethane resin with hydroxyl to prepare a two-component waterborne polyurethane adhesive, wherein the pot life is as follows: 5h, the adhesive is used for bonding the PVC film and the tin plate, after the adhesive is cured for 48 hours at 50 ℃, the 180-degree peel strength test is carried out according to GB/T2790-1995 '180-degree peel strength test method of adhesive, flexible material to rigid material', and the PVC film is torn.
Application example 3:
the product of example 1 was mixed with a hydroxyl-containing aqueous acrylic emulsion under stirring to produce a two-component aqueous acrylic coating, which was cured at 50 ℃ for 48 hours to produce a coating film having the following properties: light (es)Ze (60 °): more than or equal to 90 percent; the hardness is more than or equal to Shore D68; impact strength: 64KJ/m2(ii) a Adhesion force: grade 1; flexibility: 1 mm.
Claims (8)
1. A solvent-free water-based polyisocyanate curing agent is characterized in that: is a polyisocyanate prepolymer containing sulfonic acid groups; the solvent-free water-based polyisocyanate curing agent is prepared by the following preparation method:
a) adding dicarboxyl sulfonate and N-methyl pyrrolidone into a reaction vessel, heating to 50-60 ℃, stirring and dissolving for 0.5-1 h, and adding polyisocyanate prepolymer accounting for 30-70% of the total amount of the polyisocyanate prepolymer for reaction;
b) adding an antioxidant, sealing the reactor, introducing protective gas, reacting for 5-10 h at 50-100 ℃, adding the remaining polyisocyanate prepolymer, and stirring and mixing uniformly;
c) distilling out the N-methyl pyrrolidone, cooling to 60 ℃, and discharging to obtain the solvent-free water-based polyisocyanate curing agent.
2. The process for preparing a solvent-free aqueous polyisocyanate curing agent according to claim 1, wherein: the method specifically comprises the following steps:
a) adding dicarboxyl sulfonate and N-methyl pyrrolidone into a reaction vessel, heating to 50-60 ℃, stirring and dissolving for 0.5-1 h, and adding polyisocyanate prepolymer accounting for 30-70% of the total amount of the polyisocyanate prepolymer for reaction;
b) adding an antioxidant, sealing the reactor, introducing protective gas, reacting for 5-10 h at 50-100 ℃, adding the remaining polyisocyanate prepolymer, and stirring and mixing uniformly;
c) distilling out the N-methyl pyrrolidone, cooling to 60 ℃, and discharging to obtain the solvent-free water-based polyisocyanate curing agent.
3. The method for preparing a solventless aqueous polyisocyanate curing agent according to claim 2, wherein: the molar ratio of the dicarboxyl sulfonate to the polyisocyanate prepolymer is (0.03-0.2): 1; the adding amount of the organic solvent is 3-10 times of the mass of the dicarboxyl sulfonate.
4. The method for preparing a solventless aqueous polyisocyanate curing agent according to claim 3, characterized in that: the dicarboxy sulfonate is an alkali metal salt of dicarboxy sulfonate.
5. The method for preparing a solventless aqueous polyisocyanate curing agent according to claim 3, characterized in that: the polyisocyanate prepolymer is at least one of HDI trimer, HDI biuret, HDI prepolymer, IPDI trimer and HMDI prepolymer.
6. The method for preparing a solventless aqueous polyisocyanate curing agent according to claim 2, wherein: the distillation method is one of vacuum distillation, thin film distillation and hot gas bubbling.
7. The method for preparing a solventless aqueous polyisocyanate curing agent according to claim 2, wherein: in the step b), the addition amount of the antioxidant accounts for 0.01-0.5 percent of the sum of the mass of the dicarboxyl sulfonate and the mass of the polyisocyanate prepolymer.
8. Use of a solvent-free aqueous polyisocyanate curing agent according to claim 1 for the preparation of an aqueous polyurethane coating or an aqueous polyurethane adhesive.
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| CN111423343B (en) * | 2020-03-20 | 2021-04-09 | 佛山市精信汇明科技有限公司 | Hydrophilic diisocyanate and preparation method and application thereof |
| CN115785881B (en) * | 2022-12-14 | 2024-03-12 | 佛山市精信汇明科技有限公司 | Water-based polyurethane adhesive for shoemaking and application thereof |
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