CN113912839A - Water-based non-isocyanate polyurethane prepolymer, coating and preparation method thereof - Google Patents
Water-based non-isocyanate polyurethane prepolymer, coating and preparation method thereof Download PDFInfo
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08G71/00—Macromolecular compounds obtained by reactions forming a ureide or urethane link, otherwise, than from isocyanate radicals in the main chain of the macromolecule
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
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- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
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Abstract
The invention discloses a water-based non-isocyanate polyurethane prepolymer, a paint and preparation methods thereof. The water-based non-isocyanate polyurethane prepolymer is prepared by taking ethylene carbonate, diamine and itaconic acid as raw materials through multi-step reaction, the use of polyisocyanate in the production process of polyurethane is radically reduced and avoided, hydrophilic groups are introduced into the non-isocyanate polyurethane prepolymer to enable the non-isocyanate polyurethane prepolymer to be water-based, and CO is introduced2Better dispersibility in water can be obtained. The non-isocyanate polyurethane coating prepolymer is compatible with acrylate, a leveling agent, a defoaming agent and the like to obtain the non-isocyanate polyurethane coating, and the obtained coating has the characteristics of low cost, low VOC, water resistance, high hardness and high surface gloss. The invention solves the problems of toxic isocyanate, high price, high VOC, poor water resistance and the like in the existing polyurethane synthesis process.
Description
Technical Field
The invention belongs to the field of new chemical materials, and relates to a water-based non-isocyanate polyurethane coating and a preparation method thereof.
Background
Polyurethane is a urethane polymer, and because of its abundant raw material varieties, it can be made into products with various forms, and is known as a "tailorable" polymer by chemical engineers. In recent years, with the economic growth, the demand of people for polyurethane products is increasing and the polyurethane products are accepted and developed on a global scale, and industrial products of the polyurethane products form a market at an extremely high speed, and the polyurethane products are one of bright spot products which form a market scale in recent years and have great development potential.
The development of non-isocyanate Polyurethane (NIPU) is an important direction in Polyurethane research. Non-isocyanate polyurethane generally refers to a new environmentally friendly polyurethane formed by reacting a cyclic carbonate compound with a polyamine. The non-isocyanate polyurethane makes up a weak bond structure in the conventional polyurethane molecule from the aspect of molecular structure, has excellent chemical resistance, hydrolysis resistance and permeability resistance, omits toxic polyisocyanate in the preparation process, uses no moisture-sensitive raw materials, brings convenience to the storage and construction of the raw materials, and does not form a structural defect due to the generation of bubbles. As environmental awareness of various countries is gradually strengthened, the traditional polyurethane synthesized by taking isocyanate as a raw material is limited in application, and the free monomer content in the isocyanate polymer is required to be controlled within 0.5% by the world health organization. And related laws and regulations in some European and American countries prohibit the use of isocyanate in some fields, and the insulation and packaging industries in European markets are gradually forbidding the use of isocyanate and beginning to adopt NIPU. The Eurotech company in the United states is in the lead of the world in the development of the NIPU, develops a plurality of NIPU coatings for replacing the conventional polyurethane, and has already established an industrial production base in Israel in 2002. However, the prior preparation conditions of the NIPU are harsh and expensive, which seriously hinders the further development of the NIPU. In addition, with the continuous enhancement of the market on the discharge amount of Volatile Organic Compounds (VOC) and the use limit of organic metals, the development of environment-friendly polyurethane with wide universality, high performance, no organic solvent and low cost is an important development direction in the industry at present.
Disclosure of Invention
The invention aims to provide a water-based non-isocyanate polyurethane prepolymer, a water-based non-isocyanate polyurethane coating and a preparation method thereof aiming at the problems of high price, high VOC (volatile organic compound), poor water resistance and the like caused by using toxic isocyanate in the existing polyurethane synthesis process, so that a green environment-friendly polyurethane coating with low cost, low VOC, high water resistance, high hardness and high surface gloss is obtained.
The water-based non-isocyanate polyurethane coating prepolymer provided by the invention has the following structural formula:
wherein x is 2-30; r is-CnH2n-，n＝1～15。
The invention provides a preparation method of the water-based non-isocyanate polyurethane coating prepolymer, which comprises the following steps:
(1) carrying out reflux reaction on ethylene carbonate and diamine in a solvent A at the temperature of 10-30 ℃ for 1-24 h, then washing and drying to obtain an intermediate product I; wherein the molar ratio of the ethylene carbonate to the diamine is (2-3) to 1;
(2) reacting the intermediate product I, itaconic acid and a catalyst A at 90-160 ℃ for 3-5 h in an anhydrous and oxygen-free atmosphere, adding a catalyst B, reacting at 130-170 ℃ for 3-4 h, and finally placing in a low-temperature drying place to obtain an intermediate product II; wherein the molar ratio of the intermediate product I to the itaconic acid is 1 (1-2);
(3) carrying out initiation reaction on dimethylaminoethyl methacrylate and thioglycerol in methanol under the protection of nitrogen for 4-8 h by using a catalyst C, removing most of solvent after the reaction is finished, and then carrying out freeze drying to obtain an intermediate product III; wherein the molar ratio of dimethylamine ethyl methacrylate to thioglycerol to catalyst C is 1 (1-2) to 0.0002-0.001;
the reaction formula is as follows:
(4) adding the product II into a solvent B, heating to 80-100 ℃, adding the product III and dibutyltin dilaurate to react for 1-8 h, cooling to 20-35 ℃ after the reaction is finished to obtain a polymer, and removing the solvent B to obtain a product IV, namely a non-isocyanate polyurethane coating prepolymer; wherein the molar ratio of the product II to the product III to the dibutyltin dilaurate is 1 (1-2) to 0.01-0.08.
In the above method, the solvent a in step (1) is at least one of dichloromethane, acetone, ethanol, methanol, tetrahydrofuran and toluene. The amount of the solvent is 1 to the mass ratio of the solvent A to the diamine.
In the method, the diamine in the step (1) is at least one of ethylenediamine, butanediamine, hexanediamine, diethylenetriamine, triethylenetetramine, hydroxyethylenediamine, lysine, m-phenylenediamine and p-phenylenediamine.
The above process, further, wherein said washing in step (1) is washing with acetone.
The above method, further, the drying in step (1) is vacuum drying at 60 deg.C for 24 h.
In the method, the catalyst A in the step (2) is one or two of sulfuric acid, p-toluenesulfonic acid, thionyl chloride, hydroquinone, p-benzoquinone and p-hydroxyanisole.
In the method, the catalyst B in the step (2) is one of methyl hydroquinone, p-hydroxyanisole, 2-tert-butyl hydroquinone and dibutyl tin dilaurate.
In the method, the catalyst A and the catalyst B are used in the step (2) according to the mass ratio of the intermediate product I, the catalyst A and the catalyst B being 1, (0.001-0.01) to (0.005-0.08).
In the above method, further, in the step (3), the catalyst C is one of azobisisobutyronitrile, ethyl aluminoxane, manganese dioxide, and hydrogen peroxide.
In the above method, the amount of methanol used in the step (3) is 1 to 5 by mass of dimethylamine ethyl methacrylate.
In the above method, further, in the step (4), the solvent B is one of acetone, ethanol, methanol, tetrahydrofuran and toluene.
In the method, the amount of water used in the step (4) is (20-5): 1, based on the mass ratio of water to the product IV.
The invention provides a non-isocyanate emulsion which comprises the components of the non-isocyanate polyurethane coating prepolymer, water and CO2Adding the non-isocyanate polyurethane coating prepolymer into water and introducing CO2Thus obtaining the product.
The preparation process comprises the following steps:
the invention also provides a non-isocyanate polyurethane coating which comprises the following components in parts by weight:
the invention also provides a preparation method of the non-isocyanate polyurethane coating, which comprises the steps of uniformly mixing the non-isocyanate polyurethane coating prepolymer, acrylic ester, a flatting agent, a defoaming agent, a thickening agent and a photoinitiator, adding water, and introducing CO2And stirring uniformly to obtain the photocureable coating.
Compared with the prior art, the invention has the beneficial effects
1. The non-isocyanate polyurethane coating prepolymer used in the invention adopts a product prepared by opening the ring of the ethylene carbonate and the diamine, radically reduces and avoids the use of polyisocyanate in the production process of polyurethane, meets the requirement of green sustainable development of the current society, and has wide raw material source, easy operation and good application prospect.
2. The invention successfully introduces hydrophilic groups into the non-isocyanate polyurethane to realize water-based performance, so that the coating based on the hydrophilic groups realizes low VOC (volatile organic compounds) and is green and environment-friendly.
3. The addition of the itaconic acid can enable polyfunctional carbon-carbon double bonds to exist in the water-based non-isocyanate polyurethane coating, can be used as a hyperbranched active center, and provides sites for further modification.
4. The chain extender (product III) synthesized by the invention contains amino, and the non-isocyanate (product IV) after chain extension is introduced with CO2Better dispersibility in water can be obtained.
5. The chain-extended water-based non-isocyanate polyurethane coating prepared by the invention has better hardness, water resistance and surface gloss.
Drawings
FIG. 1 is a drawing of product I from example 11H-NMR spectrum.
Nuclear magnetic resonance hydrogen spectrum (1H-NMR) is measured by adopting a nuclear magnetic resonance spectrometer, namely, Bruker company, Switzerland, AV II-600MHz, a small amount of test samples are put into a nuclear magnetic tube, a solvent is added for dissolution, and tetramethylsilane is used as an internal standard agent. From the figure, it can be seen that δ 2.5ppm is the solvent DMSO-d6The characteristic peaks of (a) are 6.73ppm and 7.1ppm of carbamate bonds, the characteristic peaks of (a) are 3.52ppm and (a) are 3.93ppm of characteristic peaks of (a) are 1.22ppm of characteristic peaks of (a) methylene groups connected with carbamate in a molecular chain of ethylene carbonate, and the characteristic peaks of (a) are 1.33ppm and (a) are 2.94ppm of characteristic peaks of methylene groups in an aliphatic diamine molecule, which initially indicates that the ethylene carbonate and the hexamethylene diamine are successfully reacted.
FIG. 2 is an infrared spectrum of product I from example 1.
The infrared characterization adopts a Fourier infrared spectrometer (Thermo Scientific Nicolet model 6700), samples were pressed with KBr, and infrared spectra were scanned for the product. In the infrared spectrogram of FIG. 2, the carbonyl stretch peak of ethylene carbonate is 1800cm-1On the left and right, this stretch peak did not appear in FIG. 2, indicating the successful synthesis of product I.
FIG. 3 is a drawing of product II from example 11H-NMR spectrum.
In FIG. 31In the H-NMR spectrum, 2.10ppm of delta was the solvent peak, and 3.37ppm of delta was CH2Shift of-CO-O, δ -3.67 ppm being CO-O-CH2The characteristic peak of methylene group (delta-4.06-4.31 ppm) is NH-CO-O-CH2The characteristic peaks of methylene in the figure, wherein delta-5.82 ppm and delta-6.30 ppm are characteristic peaks of unsaturated double bonds of itaconic acid, preliminarily illustrate that the product I and the itaconic acid have esterification reaction, and the product II is obtained.
FIG. 4 is an infrared spectrum of product II from example 1.
As can be seen from the infrared spectrum of FIG. 4, 3365cm-1And 1705cm-1Respectively are the absorption peaks of the stretching vibration of the carbamate structure of the structure, namely amino (-NH) and carbonyl (C ═ O), 2850-2946cm-1The successful preparation of product II is further demonstrated by the stretching vibration peak of methylene.
FIG. 5 is a drawing of product III from example 11H-NMR spectrum.
In FIG. 51In the H-NMR spectrum, there was no characteristic peak for mercapto hydrogen at the δ -1.77 ppm position, a characteristic peak for amino hydrogen at the δ -2.15 ppm position, and characteristic peaks for hydroxy hydrogen at the δ -5.72 ppm and δ -6.10 ppm positions, indicating successful production of product iii.
FIG. 6 is a gel permeation chromatogram of product II with number average molecular weight MnIs 10240 and the dispersion coefficient PDI is 1.12.
Detailed Description
The present invention will be described in detail with reference to examples. It is to be understood, however, that the following examples are illustrative of embodiments of the present invention and are not to be construed as limiting the scope of the invention.
Example 1
The preparation method of the water-based non-isocyanate polyurethane coating prepolymer specifically comprises the following steps:
(1) a100 mL round-bottomed flask equipped with a stirrer was charged with 18.5g of ethylene carbonate, 11.6g of hexamethylenediamine and 30mL of acetone in this order, and reacted at 25 ℃ for 6 hours. And (3) removing the product out of the reaction flask, washing the product with acetone, and then placing the washed product in a vacuum drying oven at 60 ℃ for drying for 24 hours to obtain an intermediate product I.
(2) Reacting 0.10mol of intermediate product I, 0.12mol of itaconic acid and 0.63mmol of p-toluenesulfonic acid at 110 ℃ in an anhydrous and oxygen-free atmosphere for 4h, adding 1.93mmol of p-hydroxyanisole, reacting at 160 ℃ for 4h, and finally placing in a low-temperature drying place to obtain intermediate product II.
(3) Adding 0.60mmol of azobisisobutyronitrile into 0.10mol of dimethylamine ethyl methacrylate and 0.12mol of thioglycerol in 30mL of methanol under the protection of nitrogen atmosphere, initiating for 6h, removing most of methanol by a rotary evaporator after the reaction is finished, and then freeze-drying for 48h to obtain an intermediate product III.
(4) And adding 14.2mmol of the product II into tetrahydrofuran, heating to 90 ℃, adding 17.0mmol of the product III and 0.29mmol of dibutyltin dilaurate, reacting for 2 hours, cooling to 30 ℃ to obtain a polymer, and performing rotary evaporation to remove a solvent tetrahydrofuran to obtain a product IV, namely the non-isocyanate polyurethane coating prepolymer.
Uniformly mixing the non-isocyanate polyurethane coating prepolymer, acrylic ester, a flatting agent, a defoaming agent, a thickening agent, a photoinitiator and water, and then introducing CO2And stirring at 1500-2000 rpm for 1-3 h to obtain the photocureable coating.
Examples 2 to 6;
the preparation methods of examples 2 to 6 are different from those of example 1 in table 1:
TABLE 1
Note: the remaining processes and conditions not given in the table are the same as in example 1.
The conventional aqueous polyurethane coating was used as comparative examples 1 and 2.
The photocuring coatings prepared in the above examples 1-6 and comparative examples 1-2 were coated on the surface of a glass plate, irradiated for 1-10 min with a 4 KW ultraviolet lamp as a radiation source, and cured, and then various performance tests and evaluations were performed on the sample plate, and the experimental results are shown in the following table 2:
TABLE 2
Note: performance testing of the materials in Table 2 the following test standards were tested
Pencil hardness: refer to the national standard GB/T6739 Pencil determination method for hardness of paint film.
Water resistance: the test was performed according to HG/T3655-. Water resistance expression method: 5 is optimal (no anomaly) and 1 is worst.
Adhesion force: refer to the national standard GB/T9286 test for marking paint films of colored paint and varnish.
Wear resistance: after the sample is rubbed back and forth 20 times by using 0000# steel wool (loaded with 1 kg), the number of scratches of more than or equal to 1cm on the surface of the sample is observed to judge the wear resistance of the coating film.
Impact: the test was carried out according to the GB/T1732-93 standard.
Gloss: pencil hardness was measured according to GB/T9754-2007 standard.
As can be seen from Table 2, the waterborne non-isocyanate polyurethane coating of the present invention has better physical properties such as water resistance, gloss and impact compared with the conventional waterborne polyurethane coating.
In summary, the water-based non-isocyanate polyurethane coating disclosed by the invention not only solves the problems of poor water resistance and the like of toxic isocyanate or water-based polyurethane acrylate coatings used in the existing water-based polyurethane acrylate synthesis process, but also has better physical properties. It is expected that the material will meet wide market prospect, and is particularly suitable for the fields of furniture and wood paint, floor paint, internal and external wall paint and the like.
In light of the foregoing, it is to be understood that various changes and modifications can be made by the worker in light of the above description without departing from the spirit of the invention. The technical scope of the present invention is not limited to the content of the specification, and must be determined according to the scope of the claims.
Claims (10)
1. The water-based non-isocyanate polyurethane coating prepolymer is characterized by having a structural formula as follows:
wherein x is 2-30; r is-CnH2n-，n＝1～15。
2. The method of preparing the aqueous non-isocyanate polyurethane coating prepolymer of claim 1, comprising the steps of:
(1) carrying out reflux reaction on ethylene carbonate and diamine in a solvent A at the temperature of 10-30 ℃ for 1-24 h, then washing and drying to obtain an intermediate product I; wherein the molar ratio of the ethylene carbonate to the diamine is (2-3) to 1;
(2) reacting the intermediate product I, itaconic acid and a catalyst A at 90-160 ℃ for 3-5 h in an anhydrous and oxygen-free atmosphere, adding a catalyst B, reacting at 130-170 ℃ for 3-4 h, and finally placing in a low-temperature drying place to obtain an intermediate product II; wherein the molar ratio of the intermediate product I to the itaconic acid is 1 (1-2);
(3) carrying out initiation reaction on dimethylaminoethyl methacrylate and thioglycerol in methanol under the protection of nitrogen for 4-8 h by using a catalyst C, removing most of solvent after the reaction is finished, and then carrying out freeze drying to obtain an intermediate product III; wherein the molar ratio of dimethylamine ethyl methacrylate to thioglycerol to catalyst C is 1 (1-2) to 0.0002-0.001;
(4) adding the product II into a solvent B, heating to 80-100 ℃, adding the product III and dibutyltin dilaurate to react for 1-8 h, cooling to 20-35 ℃ after the reaction is finished to obtain a polymer, and removing the solvent B to obtain a product IV, namely a non-isocyanate polyurethane coating prepolymer; wherein the molar ratio of the product II to the product III to the dibutyltin dilaurate is 1 (1-2) to 0.01-0.08.
3. The method according to claim 2, wherein the solvent A in step (1) is at least one of dichloromethane, acetone, ethanol, methanol, tetrahydrofuran and toluene; the amount of the solvent is 1 to the mass ratio of the solvent A to the diamine.
4. The method according to claim 2, wherein the diamine in step (1) is at least one of ethylenediamine, butanediamine, hexanediamine, diethylenetriamine, triethylenetetramine, hydroxyethylenediamine, lysine, m-phenylenediamine, and p-phenylenediamine; the washing in the step (1) is washing with acetone; the drying in the step (1) is vacuum drying at 60 ℃ for 24 h.
5. The method according to claim 2, wherein the catalyst A in the step (2) is one or two of sulfuric acid, p-toluenesulfonic acid, thionyl chloride, hydroquinone, p-benzoquinone and p-hydroxyanisole; the catalyst B is one of methyl hydroquinone, p-hydroxyanisole, 2-tert-butyl hydroquinone and dibutyl tin dilaurate.
6. The method of claim 2, wherein the catalyst C in step (3) is one of azobisisobutyronitrile, ethyl aluminoxane, manganese dioxide, and hydrogen peroxide; the amount of the methanol in the step (3) is (5-10) 1 by mass of the methanol to the dimethylaminoethyl methacrylate.
7. The method according to claim 2, wherein the solvent B in step (4) is one of acetone, ethanol, methanol, tetrahydrofuran and toluene; and (4) the amount of water used in the step (4) is that the mass ratio of water to the product IV is (20-5): 1.
8. The non-isocyanate emulsion is characterized by comprising the non-isocyanate polyurethane coating prepolymer, water and CO2Adding the non-isocyanate polyurethane coating prepolymer into water and introducing CO2Thus obtaining the product.
9. A non-isocyanate polyurethane coating is characterized by comprising the following components in parts by weight:
10. the method of claim 9, wherein the non-isocyanate polyurethane coating prepolymer, the acrylate, the leveling agent, the defoamer, the thickener, and the photoinitiator are mixed uniformly, water is added, and CO is introduced2Stirring and mixing uniformly to obtain the photocureable coating.
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