CN110845698A - Polyether amine modified waterborne polyurethane resin and preparation method thereof - Google Patents
Polyether amine modified waterborne polyurethane resin and preparation method thereof Download PDFInfo
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- CN110845698A CN110845698A CN201911135934.5A CN201911135934A CN110845698A CN 110845698 A CN110845698 A CN 110845698A CN 201911135934 A CN201911135934 A CN 201911135934A CN 110845698 A CN110845698 A CN 110845698A
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- 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
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Abstract
The invention relates to polyether amine modified waterborne polyurethane resin which comprises the following components in parts by weight: 25.0-55.0 parts of diisocyanate, 20.0-45.0 parts of oligomer polyol, 5.0-10.0 parts of polyether amine, 6.0-10.0 parts of chain extender, 2.0-4.5 parts of dimethylolpropionic acid, 0.03-0.08 part of dibutyltin dilaurate, 1.5-3.0 parts of ethanol, 0.5-2.0 parts of sodium bicarbonate, 2.5-10.0 parts of neutralizer and 100.0-200.0 parts of deionized water; the polyether amine modified waterborne polyurethane resin prepared by the invention has excellent adhesive force, water resistance, impact resistance, corrosion inhibition, oxidation resistance, acid and alkali resistance, aging resistance and other properties, can obviously improve the hardness of a paint film, and can balance the hardness and flexibility of the paint film.
Description
Technical Field
The invention relates to a modified waterborne polyurethane resin, in particular to a polyether amine modified waterborne polyurethane resin and a preparation method thereof, belonging to the technical field of waterborne resin synthesis.
Background
The waterborne polyurethane takes water as a dispersion medium, has the advantages of non-inflammability, small smell, no toxicity, no pollution, energy conservation, convenient operation and the like compared with solvent type polyurethane, has been widely used as a leather finishing agent, a textile auxiliary agent, a papermaking industrial auxiliary agent, a coating, an adhesive and the like, is successfully applied to the industries of light textile, leather, wood processing, building, papermaking and the like, and has continuously expanded application fields.
However, the waterborne polyurethane adopts water as a solvent, so that the stability in the storage or transportation process is poor, the layering phenomenon is easy to occur, and the caking property is poor. Moreover, after the waterborne polyurethane is combined with the base material, because the surface tension of the medium water is too large, the polyurethane has poor water resistance and is easy to absorb water after forming a film on the surface of the base material, the film forming fastness is low, the polyurethane is easy to separate from the base material, and the sprayed product has hard hand feeling and poor flexibility. Meanwhile, the polyurethane resin has poor impact resistance, corrosion inhibition and oxidation resistance, and therefore, research workers begin to modify the polyurethane resin.
Chinese patent CN110054756A discloses an organosilicon modified fluorocarbon branched-chain-containing polyurethane resin and a preparation method thereof, wherein the polyurethane resin contains organosilane and fluorocarbon branched-chain, and can be reacted with hydroxyl on glass or metal, so that the polyurethane resin has good adhesive force, and meanwhile, the fluorocarbon branched-chain can enable the polyurethane resin to have hydrophobic and oleophobic effects; colorless and transparent, low viscosity, excellent weather resistance and good compatibility with various solvents; the polyurethane resin can be coated on various glass, stone and metal, and has the effects of water and oil repellency and easy cleaning; however, the invention has unsatisfactory weather resistance and oxidation resistance, and it is difficult to adjust hardness and flexibility simultaneously.
In view of the above, the present invention provides an improvement to the aqueous polyurethane resin in the prior art to solve the above technical problems.
Disclosure of Invention
In order to solve the technical problem, the invention adds the polyether amine which can simultaneously adjust the hardness and the flexibility of the waterborne polyurethane resin and the outdoor weather resistance, and connects the polyether amine containing two functionalities with the waterborne polyurethane resin structure through a chemical bond, thereby having stable performance.
The polyether amine is a polymer with a main chain of a polyether structure and an active functional group at the tail end of the polymer as an amino group. The special molecular structure of the polyether amine endows the polyether amine with excellent comprehensive performance, and the polyether amine has a series of performances of good toughness, impact resistance, hardness, corrosion inhibition, oxidation resistance and the like.
In order to solve the problems that the stability of the adhesive is poor, the delamination phenomenon is easy to occur, the caking property is poor and the like in the storage or transportation process, the adhesive is added with the stabilizer ethanol.
The invention aims to provide a polyether amine modified waterborne polyurethane resin.
The invention also provides a preparation method of the polyether amine modified waterborne polyurethane resin.
The polyether amine modified waterborne polyurethane resin comprises the following components in parts by weight: 25.0-55.0 parts of diisocyanate, 20.0-45.0 parts of oligomer polyol, 5.0-10.0 parts of polyether amine, 6.0-10.0 parts of chain extender, 2.0-4.5 parts of dimethylolpropionic acid, 0.03-0.08 part of dibutyltin dilaurate, 1.5-3.0 parts of ethanol, 0.5-2.0 parts of sodium bicarbonate, 2.5-10.0 parts of neutralizer and 100.0-200.0 parts of deionized water.
The polyether amine is difunctional polyether amine, and the average molecular weight of the difunctional polyether amine is 800-1500.
The diisocyanate is one or a combination of toluene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate and xylylene diisocyanate.
The oligomer polyalcohol is one or a combination of more of polytetrahydrofuran dihydric alcohol, polycarbonate dihydric alcohol, polycaprolactone dihydric alcohol, polyether dihydric alcohol and polypropylene oxide polyalcohol; the molecular weight of the oligomer polyol is 600-3000.
The chain extender is one or a combination of more of propylene glycol, butanediol, hexanediol, 1, 4-cyclohexanedimethanol, neopentyl glycol, diethylene glycol, dipropylene glycol and trimethylolpropane.
The neutralizing agent is at least one of triethylamine, ammonia water and dimethylethanolamine.
The invention provides a preparation method of polyether amine modified waterborne polyurethane resin, which comprises the following steps:
a) sequentially adding oligomer polyol and a chain extender into a multifunctional reactor according to the weight part of the formula, heating to 105-110 ℃, and dehydrating for 1.5-2.0 h under vacuum;
b) cooling to 70 ℃, adding dimethylolpropionic acid and diisocyanate, and introducing N2Stirring and reacting for 0.5h, dropwise adding dibutyltin dilaurate in a formula amount, heating to 80-82 ℃ and reacting for 2.0-2.5 h to obtain a hydrophilic polyurethane prepolymer; adding a proper amount of solvent to adjust viscosity, heating to 84-85 ℃, carrying out heat preservation reaction for 1.5-2.0 h, then cooling to 70 ℃, adding polyetheramine and sodium bicarbonate, carrying out stirring reaction for 1.5-2.0 h, and detecting until the NCO value is consistent with the designed value;
c) and cooling to below 50 ℃, slowly dripping a neutralizing agent, continuously stirring for reaction, adding a calculated amount of deionized water, dispersing uniformly at a high speed, finally adding ethanol, removing a solvent, and filtering to obtain the polyether amine modified waterborne polyurethane resin.
The solvent is acetone, and the solvent added in the invention only plays a role in adjusting the viscosity of a reaction system and is added according to the change of the viscosity.
The polyether amine modified waterborne polyurethane resin prepared by the invention has excellent adhesive force, water resistance, impact resistance, corrosion inhibition, oxidation resistance, acid and alkali resistance, aging resistance and other properties, can obviously improve the hardness of a paint film, and can balance the hardness and flexibility of the paint film.
Detailed Description
The invention is further described with reference to the following examples for the preparation of polyetheramine-modified aqueous polyurethane resins.
Example 1
The polyether amine modified waterborne polyurethane resin comprises the following components in parts by weight: 46.0 parts of isophorone diisocyanate, 30.0 parts of polytetrahydrofuran diol, 8.0 parts of polyetheramine, 5.0 parts of butanediol, 2.0 parts of trimethylolpropane, 3.2 parts of dimethylolpropionic acid, 0.05 part of dibutyltin dilaurate, 2.2 parts of ethanol, 1.6 parts of sodium bicarbonate, 8.0 parts of triethylamine and 160.0 parts of deionized water.
The preparation method of the polyether amine modified waterborne polyurethane resin in the embodiment comprises the following steps:
a) sequentially adding polytetrahydrofuran dihydric alcohol, butanediol and trimethylolpropane in a multifunctional reactor according to the weight part of the formula, heating to 110 ℃, and dehydrating for 1.5h under vacuum;
b) cooling to 70 ℃, adding dimethylolpropionic acid and isophorone diisocyanate, and introducing N2Stirring and reacting for 0.5h, dropwise adding dibutyltin dilaurate in a formula amount, heating to 80-82 ℃ and reacting for 2.5h to obtain a hydrophilic polyurethane prepolymer; adding a proper amount of solvent to adjust viscosity, heating to 84-85 ℃, carrying out heat preservation reaction for 1.5h, then cooling to 70 ℃, adding polyetheramine and sodium bicarbonate, stirring to react for 2.0h, and detecting until the NCO value is consistent with the designed value;
c) and cooling to 45 ℃, slowly dripping triethylamine, continuously stirring for reaction, adding a calculated amount of deionized water, dispersing uniformly at a high speed, finally adding ethanol, removing a solvent, and filtering to obtain the polyether amine modified waterborne polyurethane resin.
Example 2
The polyether amine modified waterborne polyurethane resin comprises the following components in parts by weight: 36.0 parts of toluene diisocyanate, 28.0 parts of polycarbonate diol, 7.0 parts of polyether amine, 8.0 parts of 1, 4-cyclohexanedimethanol, 3.0 parts of dimethylolpropionic acid, 0.04 part of dibutyltin dilaurate, 2.0 parts of ethanol, 1.5 parts of sodium bicarbonate, 6.0 parts of ammonia water and 140.0 parts of deionized water.
The preparation method of the polyether amine modified waterborne polyurethane resin in the embodiment comprises the following steps:
a) sequentially adding polycarbonate dihydric alcohol and 1, 4-cyclohexanedimethanol in parts by weight of the formula into a multifunctional reactor, heating to 105 ℃, and dehydrating for 2.0h under vacuum;
b) cooling to 70 ℃, adding dimethylolpropionic acid and toluene diisocyanate, and introducing N2Stirring and reacting for 0.5h, dropwise adding dibutyltin dilaurate in a formula amount, heating to 80-82 ℃ and reacting for 2.5h to obtain a hydrophilic polyurethane prepolymer; adding a proper amount of solvent to adjust viscosity, heating to 84-85 ℃, carrying out heat preservation reaction for 1.5h, then cooling to 70 ℃, adding polyetheramine and sodium bicarbonate, stirring to react for 2.0h, and detecting until the NCO value is consistent with the designed value;
c) and cooling to 48 ℃, slowly dripping ammonia water, continuously stirring for reaction, adding a calculated amount of deionized water, dispersing uniformly at a high speed, finally adding ethanol, removing a solvent, and filtering to obtain the polyether amine modified waterborne polyurethane resin.
Example 3
The polyether amine modified waterborne polyurethane resin comprises the following components in parts by weight: 30.0 parts of hexamethylene diisocyanate, 26.0 parts of polycaprolactone diol, 6.0 parts of polyetheramine, 5.0 parts of dipropylene glycol, 1.8 parts of trimethylolpropane, 3.5 parts of dimethylolpropionic acid, 0.05 part of dibutyltin dilaurate, 2.0 parts of ethanol, 1.3 parts of sodium bicarbonate, 7.0 parts of triethylamine and 130.0 parts of deionized water.
The preparation method of the polyether amine modified waterborne polyurethane resin in the embodiment comprises the following steps:
a) sequentially adding polycaprolactone diol, dipropylene glycol and trimethylolpropane in the multifunctional reactor according to the weight part of the formula, heating to 110 ℃, and dehydrating for 2.0h under vacuum;
b) cooling to 70 ℃, adding dimethylolpropionic acid and hexamethylene diisocyanate, and introducingN2Stirring and reacting for 0.5h, dropwise adding dibutyltin dilaurate in a formula amount, heating to 80-82 ℃ and reacting for 2.5h to obtain a hydrophilic polyurethane prepolymer; adding a proper amount of solvent to adjust viscosity, heating to 84-85 ℃, carrying out heat preservation reaction for 2.0h, then cooling to 70 ℃, adding polyetheramine and sodium bicarbonate, carrying out stirring reaction for 2.0h, and detecting until the NCO value is consistent with the designed value;
c) and cooling to 46 ℃, slowly dripping triethylamine, continuously stirring for reaction, adding a calculated amount of deionized water, dispersing uniformly at a high speed, finally adding ethanol, removing a solvent, and filtering to obtain the polyether amine modified waterborne polyurethane resin.
The examples of the present invention were subjected to performance index tests in accordance with the relevant standards of water resistance (GB/T1733-1993), adhesion (GB/T9286-1998), salt spray resistance (GB/T1771-2007), pencil hardness (GB/T6739-1996), flexibility (GB/T1731-1993), acid resistance ((10% HCl) GB/T1763-1979), alkali resistance ((10% NaOH) GB/1763-1979), filiform corrosion (GB/T13452.4-92), artificial aging resistance (GB/T14522), sag resistance (GB/T9264-2012), and the like, with conventional aqueous polyurethane resins (comparative examples), and the test results are shown in Table 1.
Table 1: performance specification of coating
It can be seen from table 1 that the adhesion, sagging resistance, salt fog resistance, artificial aging resistance, filiform corrosion resistance, flexibility, water resistance and the like of the samples of examples 1, 2 and 3 of the present invention far exceed those of the conventional aqueous polyurethane resin.
Although the present invention has been described in detail and with reference to exemplary embodiments thereof, it will be apparent to one skilled in the art that various changes, modifications and variations can be made therein without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (8)
1. A polyether amine modified waterborne polyurethane resin is characterized in that: the polyether amine modified waterborne polyurethane resin comprises the following components in parts by weight: 25.0-55.0 parts of diisocyanate, 20.0-45.0 parts of oligomer polyol, 5.0-10.0 parts of polyether amine, 6.0-10.0 parts of chain extender, 2.0-4.5 parts of dimethylolpropionic acid, 0.03-0.08 part of dibutyltin dilaurate, 1.5-3.0 parts of ethanol, 0.5-2.0 parts of sodium bicarbonate, 2.5-10.0 parts of neutralizer and 100.0-200.0 parts of deionized water.
2. The polyetheramine-modified aqueous polyurethane resin according to claim 1, characterized in that: the polyether amine is difunctional polyether amine, and the average molecular weight of the difunctional polyether amine is 800-1500.
3. The polyetheramine-modified aqueous polyurethane resin according to claim 1, characterized in that: the diisocyanate is one or a combination of toluene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate and xylylene diisocyanate.
4. The polyetheramine-modified aqueous polyurethane resin according to claim 1, characterized in that: the oligomer polyalcohol is one or a combination of more of polytetrahydrofuran dihydric alcohol, polycarbonate dihydric alcohol, polycaprolactone dihydric alcohol, polyether dihydric alcohol and polypropylene oxide polyalcohol; the molecular weight of the oligomer polyol is 600-3000.
5. The polyetheramine-modified aqueous polyurethane resin according to claim 1, characterized in that: the chain extender is one or a combination of more of propylene glycol, butanediol, hexanediol, 1, 4-cyclohexanedimethanol, neopentyl glycol, diethylene glycol, dipropylene glycol and trimethylolpropane.
6. The polyetheramine-modified aqueous polyurethane resin according to claim 1, characterized in that: the neutralizing agent is at least one of triethylamine, ammonia water and dimethylethanolamine.
7. The polyetheramine-modified aqueous polyurethane resin according to claim 1, characterized in that: the preparation process of the polyether amine modified waterborne polyurethane resin comprises the following steps:
a) sequentially adding oligomer polyol and a chain extender into a multifunctional reactor according to the weight part of the formula, heating to 105-110 ℃, and dehydrating for 1.5-2.0 h under vacuum;
b) cooling to 70 ℃, adding dimethylolpropionic acid and diisocyanate, and introducing N2Stirring and reacting for 0.5h, dropwise adding dibutyltin dilaurate in a formula amount, heating to 80-82 ℃ and reacting for 2.0-2.5 h to obtain a hydrophilic polyurethane prepolymer; adding a proper amount of solvent to adjust viscosity, heating to 84-85 ℃, carrying out heat preservation reaction for 1.5-2.0 h, then cooling to 70 ℃, adding polyetheramine and sodium bicarbonate, carrying out stirring reaction for 1.5-2.0 h, and detecting until the NCO value is consistent with the designed value;
c) and cooling to below 50 ℃, slowly dripping a neutralizing agent, continuously stirring for reaction, adding a calculated amount of deionized water, dispersing uniformly at a high speed, finally adding ethanol, removing a solvent, and filtering to obtain the polyether amine modified waterborne polyurethane resin.
8. The polyetheramine-modified aqueous polyurethane resin according to claim 1 or 7, characterized in that: the solvent is acetone, and the solvent added in the invention only plays a role in adjusting the viscosity of the prepolymer and is added according to the change of the viscosity.
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