CN110951041B - Waterborne polyurethane-acrylate hybrid copolymer and preparation method thereof - Google Patents
Waterborne polyurethane-acrylate hybrid copolymer and preparation method thereof Download PDFInfo
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- CN110951041B CN110951041B CN201911289854.5A CN201911289854A CN110951041B CN 110951041 B CN110951041 B CN 110951041B CN 201911289854 A CN201911289854 A CN 201911289854A CN 110951041 B CN110951041 B CN 110951041B
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- C08G18/72—Polyisocyanates or polyisothiocyanates
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- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
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- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
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- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
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- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
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- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
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- C08G18/6651—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
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- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
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- C08G18/72—Polyisocyanates or polyisothiocyanates
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- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
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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
- 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
Abstract
The invention provides a waterborne polyurethane-acrylate hybrid copolymer and a preparation method thereof. According to the invention, the copolymer prepared by the method is subjected to crosslinking modification by hydrogenated castor oil and amine containing a rigid structure, and low-molecular organic amine containing a cyclic structure is added, so that the initiation times in the polymerization process are few, the residual amount after polymerization is low, the production process is stable and has no abnormality, the emulsion stability is good, and finally the waterborne polyurethane-acrylate hybrid copolymer with excellent comprehensive performances such as hardness and wear resistance is obtained.
Description
Technical Field
The invention belongs to the technical field of waterborne polyurethane materials, and particularly relates to a waterborne polyurethane-acrylate hybrid copolymer and a preparation method thereof.
Background
With the improvement of environmental awareness of people and the national restriction on the emission of Volatile Organic Compounds (VOC), the traditional solvent type polyurethane coating is gradually abandoned by the market in the application process, and the development of low-pollution and environment-friendly waterborne polyurethane materials is well known by people. The waterborne polyurethane coating takes water as a dispersing medium instead of an organic solvent, and has good environmental protection value. There have been many areas in which conventional solvent-borne polyurethane coatings have been gradually replaced.
In order to obtain a low-cost and high-performance waterborne polyurethane product, various modifications are made to waterborne polyurethane. The acrylic resin has excellent resistance and is low in cost. The acrylic resin is used for modifying the waterborne polyurethane, so that the advantages of the acrylic resin and the waterborne polyurethane can be fully combined, and the performance of a paint film is improved. Meanwhile, vegetable oil polyalcohol is regarded as a renewable resource and is gradually valued by people at present when petroleum resources are in short supply and prices rise. Compared with the traditional waterborne polyurethane, the waterborne polyurethane modified by the vegetable oil polyalcohol has higher safety and economy. For example, patent document CN101481451B discloses a high solid content, latent curing urethane acrylate hybrid emulsion, which improves various resistances by post-crosslinking; when the post-crosslinking equivalent is too high, the emulsion is unstable, and when the post-crosslinking equivalent is insufficient, the resistance is not remarkably improved, and the crosslinking equivalent is not easily controlled. Patent document CN101157749A discloses a polyurethane modified acrylic emulsion, which is prepared by introducing carbonyl groups into a polyurethane part and an acrylate part respectively, and adding a self-made hydrazide into the emulsion for crosslinking, so that the problem that the polyurethane and polyacrylate parts in a polyurethane-acrylate hybrid emulsion are not chemically crosslinked is solved, and certain resistance is increased; however, the crosslinking mode has no obvious increase on the resistance, and the added homemade hydrazide has certain toxicity, so that the application of the product is limited. Patent document CN101544739A discloses a polyurethane-acrylate hybrid copolymer emulsion with a special structure, which is prepared by introducing a self-made monomer with a double bond on a side chain into a polyurethane chain segment, and then copolymerizing the monomer with an acrylate monomer, so that a polyurethane part and a polyacrylate part in the chain segment can be separated from each other, and respective performances are maximized; however, the self-made monomer contains 4 functional groups capable of reacting with the isoamino acid ester, the prepolymerization process cannot be controlled, the gel is very easy to generate, the production process is unsafe, the cost is high, and the popularization is very difficult. Patent document CN108219106A discloses a preparation method of a waterborne polyurethane-acrylate hybrid copolymer modified by a home-made soybean oil hydrolysate, which improves the performance by adding the home-made soybean oil hydrolysate, but because the fatty acid chain of the prepared soybean oil hydrolysate contains unsaturated double bonds, part of monomers can be wrapped by the long fatty chain and the acrylic ester monomers when being wound, the initiator can be consumed by the double bonds when the initiation polymerization of the acrylic ester monomers is carried out, the internal part of monomers can not be polymerized by winding and wrapping, the residual monomer content of the emulsion after multiple polymerization is high, in the process of removing acetone after the process, the residual acrylic ester monomers can be subjected to polymerization reaction to block an acetone removal device, and the storage stability of the emulsion becomes poor.
Therefore, a new preparation method of the aqueous polyurethane-acrylate hybrid copolymer is needed, and the polyurethane-acrylate hybrid copolymer with simple and easily controlled reaction process, low residual monomer content, stable and abnormal production and excellent performance can be obtained.
Disclosure of Invention
The invention aims to provide a water-based polyurethane-acrylate hybrid copolymer and a preparation method thereof, aiming at the problems in the prior art.
In order to achieve the purpose, the invention provides a water-based polyurethane-acrylate hybrid copolymer, which is prepared by reacting the following components in mass content, wherein the total mass of the components is 100%:
17-35% of aliphatic di-iso-amino acid ester, preferably 18-25%;
5-17% polyester polyol, preferably 6-15%;
5-18% hydrogenated castor oil, preferably 6-15%;
30-50% acrylate monomer, preferably 35-45%.
According to the polyurethane-acrylate hybrid copolymer provided by the invention, the components further comprise:
0.005-0.08% of a polyurethane reaction catalyst, preferably 0.01-0.07%;
1.5-3.5% of a neutralizing agent, preferably 2-3%;
0.01-2% of a radical initiator, preferably 0.02-1%;
2.0-4.5% of a hydrophilic chain extender, preferably 2.1-4.0%;
0.5-3.5% of a low molecular weight non-hydrophilic alcohol chain extender, preferably 0.6-3.0%, having a molecular weight of 60-400;
3-6% of polyfunctional organic amine chain extender containing rigid structure, preferably 3.5-5.5%;
0.5-3.0% of low molecular organic amine containing ring structure, preferably 0.6-2.8%, and its molecular weight is 60-500.
According to the waterborne polyurethane-acrylate hybrid copolymer provided by the invention, the hydroxyl value of the hydrogenated castor oil is 158-163 mgKOH/g, and the iodine value is 0-20, preferably 10-15.
According to the waterborne polyurethane-acrylate hybrid copolymer provided by the invention, diisocyanate with an alicyclic structure in aliphatic isocyanate can reduce the elasticity of copolymer resin to a certain extent, and the hardness and the resistance of the resin are increased. Preferably, the aliphatic diisocyanate is selected from dicyclohexylmethane diisocyanate and/or isophorone diisocyanate. For example, isophorone diisocyanate has a good symmetrical structure, and the prepared resin has good elasticity and toughness.
The polyol used for synthesizing the polyurethane prepolymer can be polyether polyol and polyester polyol. The polyurethane prepared by polyether polyol is easy to yellow and has poor weather resistance. Therefore, the polyester polyol is selected, and the average hydroxyl value of the polyester polyol is preferably 30-150mgKOH/g, and preferably 45-80 mgKOH/g.
Preferably, the polyester polyol is selected from one or more of polycaprolactone polyol, polyacrylate polyol, 1, 4-butanediol adipate diol, neopentyl glycol adipate diol, and hexanediol adipate diol.
According to the aqueous polyurethane-acrylate hybrid copolymer provided by the invention, the acrylate monomer is selected from one or more of ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, benzyl acrylate, methyl methacrylate, butyl methacrylate, phenyl methacrylate and trimethacrylate, and is preferably selected from one or more of butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate and butyl methacrylate.
According to the aqueous polyurethane-acrylate hybrid copolymer provided by the invention, the hydrophilic chain extender is selected from one or more of carboxyl-containing dihydric alcohol, sulfonate-containing diamine and polyoxyethylene glycol, preferably selected from carboxyl-containing dihydric alcohol; the carboxyl group-containing diol is preferably selected from dimethylolpropionic acid and/or dimethylolbutyric acid.
Preferably, the low molecular weight non-hydrophilic alcohol chain extender is selected from the group consisting of C2-C10 aliphatic diols, more preferably from one or more of 1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol, neopentyl glycol, diethylene glycol, 1, 6-hexanediol, and trimethylolpropane.
Preferably, the multifunctional low-molecular-weight organic amine chain extender containing a rigid structure is selected from tri (4-aminophenyl) amine.
Preferably, the low molecular organic amine containing a cyclic structure is selected from diamines having a molecular weight of 60 to 500, more preferably from 4, 4-diaminodicyclohexylmethane and/or 1, 4-cyclohexanedi (methylamine).
Preferably, the neutralizing agent is selected from one or more of triethylamine, triethanolamine, tripropylamine, N-dimethylethanolamine, N-methyldialanolamine, ammonia water, potassium hydroxide, sodium hydroxide and lithium hydroxide; preferably one or more selected from the group consisting of triethylamine, triethanolamine, N-dimethylethanolamine and sodium hydroxide.
In the polymerization process of the acrylate monomer, the initiator system can be a free radical initiator system, the free radical initiator is a redox initiator system consisting of an oxidant and a reducing agent, and the mass ratio of the oxidant to the reducing agent is 1: 2-2: 1.
Preferably, the oxidant is selected from one or more of potassium persulfate, ammonium persulfate, hydrogen peroxide and tert-butyl hydroperoxide:
preferably, the reducing agent is selected from one or more of sodium bisulfite, ferrous sulfate, sodium formaldehyde sulfoxylate, sodium dithionite and erythorbic acid.
Different types of oxidants and reductants are selected, so that the requirements of polymerization reaction of monomers under different temperature conditions can be met.
The polyurethane reaction catalyst in the present invention is preferably selected from organotin compounds and/or organobismuth compounds.
Preferably, the organotin-based compound is dibutyltin dilaurate. Preferably, the organic bismuth compound is selected from one or more of bismuth isooctanoate, bismuth laurate, bismuth neodecanoate, bismuth naphthenate and bismuth nitrate.
Another object of the present invention is to provide a method for preparing the aqueous polyurethane-acrylate hybrid copolymer, which comprises the following steps:
(1) preparing a hydrogenated castor oil modified polyurethane prepolymer, namely contacting the aliphatic diisocyanate, polyester polyol and hydrogenated castor oil for reaction, and carrying out chain extension reaction after the NCO value is constant to prepare the hydrogenated castor oil modified polyurethane prepolymer;
(2) preparing hydrogenated castor oil modified aqueous polyurethane-acrylate monomer mixed emulsion, namely contacting the polyurethane prepolymer prepared in the step (1) with an acrylate monomer for neutralization reaction, adding water for dispersion, then carrying out chain extension, adding small molecular amine containing a cyclic structure to prepare the hydrogenated castor oil modified aqueous polyurethane-acrylate monomer mixed emulsion:
(3) under the protection of inert gas, the hydrogenated castor oil modified aqueous polyurethane-acrylate monomer mixed emulsion is contacted with a free radical initiator to react to obtain a hydrogenated castor oil modified aqueous polyurethane-acrylate hybrid copolymer crude emulsion.
According to the preparation method provided by the invention, preferably, in the step (1), the aliphatic diisocyanate, the polyester polyol and the hydrogenated castor oil react at 70-100 ℃ in the presence of a polyurethane reaction catalyst, wherein after the NCO value is constant, the temperature is reduced to 55-40 ℃, and a hydrophilic chain extender, a low-molecular-weight non-hydrophilic alcohol chain extender and a solvent are added for chain extension reaction; until the NCO value reached the theoretical value.
Preferably, in the step (2), the polyurethane prepolymer prepared in the step (1) is contacted with an acrylate monomer and a neutralizing agent, the mixture is dispersed in water for 5-30 minutes after being mixed for 5-10 minutes, then tris (4-aminophenyl) amine is added for chain extension for 5-10 minutes, the residual NCO is completely reacted, and amine containing a cyclic structure is added for continuous stirring for 5-10 minutes to enable the mixture to be fully fused.
Preferably, in the step (3), after the heat release of the reaction system is finished, heat preservation is continued for 1-2 hours, and the polymerization process adopts an implosion method, so that the initiator is directly added after the crude emulsion reaches a certain temperature value. As the crude emulsion of the invention contains more acrylate monomers, the monomers have obvious heat release when the initiator initiates polymerization, and the temperature can be raised by about 7-20 ℃. The end of the exotherm in the reaction system means the stage at which the temperature of the crude emulsion does not rise any more and begins to fall slowly. And keeping the temperature at the highest heat release temperature for 1-2 h.
According to the preparation method provided by the invention, preferably, the preparation method further comprises the following steps:
carrying out reduced pressure distillation on the crude emulsion prepared in the step (3) to remove the solvent, so as to obtain an emulsion of the hydrogenated castor oil modified waterborne polyurethane-acrylate hybrid copolymer;
preferably, the solvent is selected from one or more of acetone, methyl ethyl ketone, tert-butyl methyl ether and tetrahydrofuran, preferably selected from methyl ethyl ketone and/or acetone, more preferably acetone.
The invention has the positive effects that:
according to the invention, hydrogenated castor oil is introduced, so that the added acrylic ester can not be polymerized due to the fact that an initiator is not consumed due to the existence of excessive unsaturated double bonds in the subsequent polymerization process, the initiation times are increased, and the hydrogenated castor oil has a cross-linking reaction in the prepolymerization process; adding tri (4-aminophenyl) amine into the post chain extension part for post chain extension, and performing post crosslinking because the post chain extension part contains a plurality of rigid structures and the functionality is more than 2, thereby further improving the physical and mechanical properties of the aqueous polyurethane-acrylate hybrid copolymer, and controlling the content of the isocyanate group of the chain segment after the reaction is finished, so that no isocyanate group is remained in the final molecular chain; the small molecular amine containing a ring structure is added, does not participate in chain extension reaction and can exist in molecules, tri (4-aminophenyl) amine is added for post chain extension, so that tertiary amine exists in chain segments, the temperature is kept after monomer polymerization and temperature rise are finished in the polymerization process, the acrylic ester monomer which cannot be polymerized due to winding and wrapping of a fatty chain and the small molecular amine can be catalyzed to perform Michael addition reaction, residual monomers are further eliminated, and finally the waterborne polyurethane-acrylic ester hybrid copolymer which is stable and controllable in prepolymerization reaction, less in polymerization times, low in residual monomer amount, stable and abnormal in production process, excellent in comprehensive performances such as hardness and wear resistance is obtained.
Detailed Description
In order that the technical features and contents of the present invention can be understood in detail, preferred embodiments of the present invention will be described in more detail below. While the preferred embodiments of the present invention have been described in the examples, it should be understood that the present invention may be embodied in various forms and should not be limited by the embodiments set forth herein.
Firstly, the source of raw materials
1. Dicyclohexylmethane diisocyanate, a product of Wanhua chemical group, Inc., under the trade name WANNATE-HMDI.
2. Isophorone diisocyanate: wanhua chemical group, Inc., Industrial, under the WANNATE-IPDI designation.
3. Polycaprolactone diol, manufactured by Nippon Daiiol chemical industries, Inc., trade name PCL220N, molecular weight 2000.
4. Poly (neopentyl glycol adipate) glycol: large chemical, industrial products of petasites, PNA2000, molecular weight 2000.
5. Hydrogenated castor oil: hydroxyl value of 158-163 mgKOH/g, iodine value of 10-15: shanghai Baili Biotech Co Ltd
6. Hydrogenated castor oil: hydroxyl value of 158-163 mgKOH/g, iodine value of less than or equal to 5: shanghai Baili Biotech Co Ltd
7. Sodium dithionite analytically pure, Tianjin Kemi Euro Chemicals Co., Ltd:
8. the organic bismuth catalyst is the mark BiCAT8106, analytically pure, leading chemical company in the United states:
9. analytically pure dimethylolpropionic acid, welenger technologies ltd:
1, 4-butanediol analytically pure, Shanghai Allantin Biotechnology Ltd:
11. methyl methacrylate, petrochemical company, Lanzhou petrochemical company, China, Industrial products
12. Analytically pure triethylamine, Shanghai Aladdin Biotechnology Ltd:
13. analytically pure ethylenediamine, Shanghai Aladdin Biotechnology Ltd:
14. tris (4-aminophenyl) amine: analytical pure, Shanghai Ji to Biochemical technology, Inc
15.4, 4-diaminodicyclohexylmethane: shanghai Aladdin Biotechnology Ltd:
1, 4-Cyclohexanedi (methylamine): shanghai Aladdin Biotechnology Ltd
17. Analytically pure, Tianjin Kemi Euro Chemicals Ltd:
18. sodium dithionite was analytically pure, Tianjin Kemi Euro Chemicals Ltd.
19. Soybean oil alcoholysis polyol is industrial product of Wanhua chemical group GmbH, hydroxyl value is 280mgKOH/g, and the sum of the mass fractions of monoglyceride and glycerol is 54.5 wt%
Second, testing method
The solid content test method comprises weighing 0.6g of copolymer emulsion in a container made of tinfoil, weighing the weight change at 150 deg.C for 20min, and calculating the solid content.
The particle size testing method adopts a Malvern particle size analyzer.
The pH test method adopts a pH meter.
Viscosity test method the viscosity test was carried out using a Brookfield viscometer, spindle 62/30 rpm.
The Minimum Film Forming Temperature (MFFT) test method adopts a German Coesfeld tester and executes the standard GB/T20623-.
The film forming property test method comprises the steps of adding 8% of film forming auxiliary agent, scraping a glass plate by a 100-micron wire rod, placing the glass plate into a 50 ℃ low-temperature box, maintaining for 1 hour, and observing whether a paint film has the phenomena of cracking, blacking, low glossiness and the like.
The rubber friction resistance test method comprises the steps of scraping a varnish paint film of 150 mu m on an ABS plastic plate, drying for two days at 50 ℃, placing a black rubber sheet (styrene butadiene rubber, 5cm x 5cm) on the paint film, weighing 9Kg above the black rubber sheet, comparing the change of the paint film at 50 ℃, and observing whether the paint film has the phenomena of yellowing, discoloration and the like. 0-5 points, 0 points worst, and 5 points best.
Method for testing pencil hardness of paint film, execution standard GB/T6739
The method for testing the hardness of the paint film swing rod adopts the execution standard of GB/T1730
The water resistance test method comprises the steps of sticking a wood board on maple trees, and spraying 80g/m2And tested after 3 days at room temperature. The standard GB/T4893.1 is implemented.
The alcohol resistance and acid resistance test method comprises the steps of sticking a wood board on maple, and spraying 80g/m2And tested after 3 days at room temperature. 50% ethanol, 30% acetic acid for 1 h. The surface of the paint film has no morbid phenomena of the paint film such as blistering, cracking, peeling and the like, and slight discoloration and slight gloss change are allowed to appear, so the paint film is judged to have no abnormality.
The stability test method comprises taking 1 kg of emulsion, sealing, placing in a 50 deg.C oven, standing for one month, and observing whether the physical property and performance of the emulsion are changed;
preparation method of varnish (by mass)
80 parts of the copolymer emulsion prepared in example or comparative example, 0.5 part of BYK-348 (wetting agent), 8.8 parts of a film-forming aid (dipropylene glycol methyl ether (DPM): dipropylene glycol butyl ether (DPnB): water: 3:5:3), and 10.7 parts of water were mixed uniformly and used.
Example 1
Adding 80g of WANNATEHMDI, 40g of hydrogenated castor oil (iodine value is 10-15), 40g of PCL220N, 0.05g of organic bismuth catalyst and 24g of acetone into a four-neck flask with a thermometer, a reflux condenser and a stirrer, heating to 85 ℃, carrying out heat preservation reaction, cooling to 55 ℃ after the NCO value is constant to 10.36%, adding 8g of dimethylolpropionic acid, 10g of 1, 4-butanediol and 23g of acetone, reacting for 3-4h at 75-80 ℃ until the NCO value is constant to 2.72 wt%, cooling to 50 ℃, adding 76g of acetone, 153.73g of methyl methacrylate and 6.04g of triethylamine, and stirring for 10min to be uniform. Cooling to room temperature, adding 450g of water at a shearing speed of 1300rpm, emulsifying and dispersing for 10min, adding 14.17g of tris (4-aminophenyl) amine into the dispersed emulsion, diluting with 4 times of water, adding, and stirring for 5 min. 4, 4-diaminodicyclohexylmethane (1.92 g) was added, and after diluting with 4 times of water, the mixture was stirred for 8 min.
The emulsion prepared in the above manner was charged into a four-necked flask, the temperature was controlled at 40 ℃ and nitrogen gas was introduced for 5min, 3g of t-butyl hydroperoxide solution (0.3g of t-butyl hydroperoxide dissolved in 2.7g of water) was added under stirring, and after stirring for 2min, 3g of sodium dithionite solution (0.3g of sodium dithionite dissolved in 2.7g of water) was added. The system has obvious heat release, and the reaction is continued for 1 hour after the temperature rise is finished. And decompressing and vacuumizing the emulsion to remove acetone to obtain the transparent and yellowing hydrogenated castor oil modified waterborne polyurethane-acrylate hybrid copolymer emulsion. The performance tests of the varnish prepared by the method are shown in the table 1.
Example 2
Adding 80g of WANNATEHMDI, 20g of hydrogenated castor oil (iodine value is 10-15), 60g of PCL220N, 0.18g of organic bismuth catalyst and 24g of acetone into a four-neck flask with a thermometer, a reflux condenser and a stirrer, heating to 85 ℃, carrying out heat preservation reaction until the NCO value is constant and 11.23 wt%, cooling to 55 ℃, adding 10g of dimethylolpropionic acid, 12g of 1, 4-butanediol and 20g of acetone, reacting for 3-4h at 75-80 ℃ until the NCO value is constant and 2.16 wt%, cooling to 40 ℃, adding 77g of acetone, 154.65g of methyl methacrylate and 7.55g of triethylamine, and stirring for 10min to be uniform. After cooling to room temperature, 451g of water was added at a shearing speed of 1300rpm, emulsified and dispersed for 10min, 11.31g of tris (4-aminophenyl) amine was added to the dispersed emulsion, diluted with 4 times of water and added, and stirred for 5 min. 3.87g of 4, 4-diaminodicyclohexylmethane was added, diluted with 4 times of water, and then added, followed by stirring for 8 min.
The emulsion prepared in the above manner was charged into a four-necked flask, the temperature was controlled at 40 ℃ and nitrogen gas was introduced for 5min, 3g of t-butyl hydroperoxide solution (0.3g of t-butyl hydroperoxide dissolved in 2.7g of water) was added under stirring, and after stirring for 2min, 3g of sodium dithionite solution (0.3g of sodium dithionite dissolved in 2.7g of water) was added. The system has obvious heat release, and the reaction is continued for 1 hour after the temperature rise is finished. And decompressing and vacuumizing the emulsion to remove acetone to obtain the transparent and yellowing hydrogenated castor oil modified waterborne polyurethane-acrylate hybrid copolymer emulsion. The performance tests of the varnish prepared by the method are shown in the table 1.
Example 3
Adding 80g of WANNATEHMDI, 60g of hydrogenated castor oil (with an iodine value of 10-15), 20g of PNA2000, 0.18g of organic bismuth catalyst and 24g of acetone into a four-neck flask with a thermometer, a reflux condenser and a stirrer, heating to 85 ℃, carrying out heat preservation reaction until the NCO value is constant to 9.49 wt%, cooling to 55 ℃, adding 8g of dimethylolpropionic acid, 7g of 1, 4-butanediol and 26.3g of acetone, reacting for 3-4 hours at the temperature of 75-80 ℃ until the NCO value is constant to 3.07 wt%, cooling to 50 ℃, adding 79g of acetone, 152.77g of methyl methacrylate and 6.04g of triethylamine, and stirring for 10 minutes until the mixture is uniform. After cooling to room temperature, 451g of water was added at a shearing speed of 1300rpm, emulsified and dispersed for 10min, 15.96g of tris (4-aminophenyl) amine was added to the dispersed emulsion, diluted with 4 times of water and added, and stirred for 5 min. 7.64g of 4, 4-diaminodicyclohexylmethane was added, diluted with 4 times of water, and then added, followed by stirring for 8 min.
The emulsion prepared in the above manner was charged into a four-necked flask, the temperature was controlled at 40 ℃ and nitrogen gas was introduced for 5min, 3g of t-butyl hydroperoxide solution (0.3g of t-butyl hydroperoxide dissolved in 2.7g of water) was added under stirring, and after stirring for 2min, 3g of sodium dithionite solution (0.3g of sodium dithionite dissolved in 2.7g of water) was added. The system has obvious heat release, and the reaction is continued for 1 hour after the temperature rise is finished. And decompressing and vacuumizing the emulsion to remove acetone to obtain the transparent and yellowing hydrogenated castor oil modified waterborne polyurethane-acrylate hybrid copolymer emulsion. The performance tests of the varnish prepared by the method are shown in the table 1.
Example 4
Adding 100g of WANNATEHMDI, 30g of hydrogenated castor oil (with an iodine value of 10-15), 50g of PCL220N, 0.09g of organic bismuth catalyst and 27g of acetone into a four-neck flask with a thermometer, a reflux condenser and a stirrer, heating to 85 ℃, carrying out heat preservation reaction until the NCO value is constant and 12.69 wt%, cooling to 55 ℃, adding 15g of dimethylolpropionic acid, 10g of 1, 4-butanediol and 26.10g of acetone, reacting for 3-4 hours at the temperature of 75-80 ℃ until the NCO value is constant and 3.47%, cooling to 50 ℃, adding 102g of acetone, 112.84g of methyl methacrylate and 11.33g of triethylamine, and stirring for 10 minutes until the mixture is uniform. After cooling to room temperature, 524g of water was added at a shear rate of 1300rpm, emulsified and dispersed for 10min, 20.68g of tris (4-aminophenyl) amine was added to the dispersed emulsion, diluted with 4 times of water and added, and stirred for 5 min. 1, 4-cyclohexanedi (methylamine), 6.77g, was added, diluted with 4 times the amount of water, and the mixture was stirred for 8 min.
The emulsion prepared in the above manner was charged into a four-necked flask, the temperature was controlled at 40 ℃ and nitrogen gas was introduced for 5min, 2.2g of t-butyl hydroperoxide solution (0.22g of t-butyl hydroperoxide dissolved in 1.98g of water) was added under stirring, and 2.2g of sodium dithionite solution (0.22g of sodium dithionite dissolved in 1.98g of water) was added after stirring for 2 min. The system has obvious heat release, and the reaction is continued for 1 hour after the temperature rise is finished. And decompressing and vacuumizing the emulsion to remove acetone to obtain the transparent and yellowing hydrogenated castor oil modified waterborne polyurethane-acrylate hybrid copolymer emulsion. The performance tests of the varnish prepared by the method are shown in the table 1.
Example 5
Adding 60g of WANNATEHMDI, 60g of hydrogenated castor oil (with an iodine value of 10-15), 20g of PCL220N, 0.18g of organic bismuth catalyst and 21g of acetone into a four-neck flask with a thermometer, a reflux condenser and a stirrer, heating to 85 ℃, carrying out heat preservation reaction until the NCO value is constant and 6.87 wt%, cooling to 55 ℃, adding 8g of dimethylolpropionic acid, 2g of 1, 4-butanediol and 22.1g of acetone, reacting for 3-4h at 75-80 ℃ until the NCO value is constant and 2.31%, cooling to 40 ℃, adding 51g of acetone, 160.31g of methyl methacrylate and 6.04g of triethylamine, and stirring for 10 minutes until the mixture is uniform. After cooling to room temperature, 374g of water is added at a shearing speed of 1300rpm, emulsification and dispersion are carried out for 10min, 10.31g of tri (4-aminophenyl) amine is added into the dispersed emulsion, the mixture is diluted by 4 times of water and then added, and stirring is carried out for 5 min. 6.41g of 4, 4-diaminodicyclohexylmethane was added, diluted with 4 times of water, and then added, followed by stirring for 8 min.
The emulsion prepared in the above manner was charged into a four-necked flask, the temperature was controlled at 40 ℃ and nitrogen gas was introduced thereinto to protect the mixture for 5 minutes, 3.2g of t-butyl hydroperoxide solution (0.32g of t-butyl hydroperoxide dissolved in 2.88g of water) was added thereto under stirring, and after stirring for 2 minutes, 3.2g of sodium dithionite solution (0.32g of sodium dithionite dissolved in 2.88g of water) was added thereto. The system has obvious heat release, and the reaction is continued for 1 hour after the temperature rise is finished. And decompressing and vacuumizing the emulsion to remove acetone to obtain the transparent and yellowing hydrogenated castor oil modified waterborne polyurethane-acrylate hybrid copolymer emulsion. The performance tests of the varnish prepared by the method are shown in the table 1.
Example 6
Adding 75g of WANNATE IPDI, 59g of hydrogenated castor oil (with an iodine value of 10-15), 32g of PCL220N, 0.18g of organic bismuth catalyst and 25g of acetone into a four-neck flask with a thermometer, a reflux condenser and a stirrer, heating to 85 ℃, carrying out heat preservation reaction, cooling to 55 ℃ after the NCO value is constant to 8.11%, adding 8g of dimethylolpropionic acid, 6g of 1, 4-butanediol and 25.16g of acetone, reacting for 3-4h at 75-80 ℃ until the NCO value is constant to 2.49 wt%, cooling to 50 ℃, adding 66g of acetone, 162g of methyl methacrylate and 6.04g of triethylamine, and stirring for 10 minutes to be uniform. After cooling to room temperature, 451g of water was added at a shearing speed of 1300rpm, emulsified and dispersed for 10min, 23.19g of tris (4-aminophenyl) amine was added to the dispersed emulsion, diluted with 4 times of water and added, and stirred for 5 min. 10.16g of 4, 4-diaminodicyclohexylmethane was added, diluted with 4 times of water, and then added, followed by stirring for 8 min.
The emulsion prepared in the above manner was charged into a four-necked flask, the temperature was controlled at 40 ℃ and nitrogen gas was introduced thereinto to protect the mixture for 5 minutes, 3.2g of t-butyl hydroperoxide solution (0.32g of t-butyl hydroperoxide dissolved in 2.88g of water) was added thereto under stirring, and after stirring for 2 minutes, 3.2g of sodium dithionite solution (0.32g of sodium dithionite dissolved in 2.88g of water) was added thereto. The system has obvious heat release, and the reaction is continued for 1 hour after the temperature rise is finished. And decompressing and vacuumizing the emulsion to remove acetone to obtain the transparent and yellowing hydrogenated castor oil modified waterborne polyurethane-acrylate hybrid copolymer emulsion. The performance tests of the varnish prepared by the method are shown in the table 1.
Comparative example 1
Adding 80g of WANNATEHMDI, 40g of castor oil, 40g of PCL220N, 24g of acetone and 0.18g of organic bismuth catalyst into a four-neck flask with a thermometer, a reflux condenser and a stirrer, heating to 85 ℃, carrying out heat preservation reaction, cooling to 40 ℃ after the NCO value is constant and 10.36 wt%, adding 8g of dimethylolpropionic acid, 10g of 1, 4-butanediol and 23g of acetone, reacting for 3-4h at 75-80 ℃ until the NCO value is constant and 2.72 wt%, cooling to 50 ℃, adding 78g of acetone, 153.73g of methyl methacrylate and 6.04g of triethylamine, and stirring for 10min to be uniform. Cooling to room temperature, adding 450 parts of water at a shearing speed of 1300rpm, emulsifying and dispersing for 10min, adding 4.39g of ethylenediamine into the dispersed emulsion, diluting with 4 times of water, adding, and stirring for 5 min.
The emulsion prepared in the above manner was charged into a four-necked flask, the temperature was controlled at 40 ℃ and nitrogen gas was introduced for 5min, 3g of t-butyl hydroperoxide solution (0.3g of t-butyl hydroperoxide dissolved in 2.7g of water) was added under stirring, and after stirring for 2min, 3g of sodium dithionite solution (0.3g of sodium dithionite dissolved in 2.7g of water) was added. The system has obvious heat release, and the reaction is continued for 1 hour after the temperature rise is finished. And decompressing and vacuumizing the emulsion to remove acetone to obtain the transparent and yellowing hydrogenated castor oil modified waterborne polyurethane-acrylate hybrid copolymer emulsion. The performance tests of the varnish prepared by the method are shown in the table 1.
Comparative example 2
Adding 80g of WANNATEHMDI, 40g of soybean oil alcohol hydrolysate, 40g of PCL220N, 24g of acetone and 0.18g of organic bismuth catalyst into a four-neck flask with a thermometer, a reflux condenser and a stirrer, heating to 85 ℃, carrying out heat preservation reaction, cooling to 55 ℃ after the NCO value is constant to 8.20%, adding 9g of dimethylolpropionic acid, 2g of 1, 4-butanediol and 23g of acetone, reacting for 3-4h at 75-80 ℃ until the NCO value is constant to 3.62%, cooling to 50 ℃, adding 78g of acetone, 141.3g of methyl methacrylate and 6.8g of triethylamine, and stirring for 10min to be uniform. Cooling to room temperature, adding 450 parts of water at a shearing speed of 1300rpm, emulsifying and dispersing for 10min, adding 5.63g of ethylenediamine into the dispersed emulsion, diluting with 4 times of water, adding, and stirring for 5 min.
The emulsion prepared in the above manner was charged into a four-necked flask, the temperature was controlled at 40 ℃ and nitrogen gas was introduced thereinto to protect the mixture for 5 minutes, 2.8g of t-butyl hydroperoxide solution (0.28g of t-butyl hydroperoxide dissolved in 2.52g of water) was added thereto under stirring, and 2.8g of sodium dithionite solution (0.28g of sodium dithionite dissolved in 2.52g of water) was added thereto after stirring for 2 minutes. The system has obvious heat release, 0.5g of tert-butyl hydroperoxide solution (0.05g of tert-butyl hydroperoxide solution in 0.45g of water) is added after the temperature rise is finished, 0.5g of sodium hydrosulfite solution (0.05g of sodium hydrosulfite in 0.45g of water) is added after stirring for 2min for post-treatment, and the reaction is continued for 1h under heat preservation. And decompressing and vacuumizing the emulsion to remove acetone to obtain the transparent and yellowing soybean oil alcoholysis modified waterborne polyurethane-acrylate hybrid copolymer emulsion. The performance tests of the varnish prepared by the method are shown in the table 1.
Example 7
Adding 80g of WANNATEHMDI, 40g of hydrogenated castor oil (iodine value is 10-15), 40g of PCL220N, 0.09g of organic bismuth catalyst and 24g of acetone into a four-neck flask with a thermometer, a reflux condenser and a stirrer, heating to 85 ℃, carrying out heat preservation reaction, cooling to 55-40 ℃ after the NCO value is constant to 10.36%, adding 8g of dimethylolpropionic acid, 10g of 1, 4-butanediol and 23g of acetone, reacting for 3-4h at 75-80 ℃ until the NCO value is constant to 2.72%, cooling to 50 ℃, adding 76g of acetone, 153.73g of methyl methacrylate and 6.04g of triethylamine, and stirring for 10min to be uniform. Cooling to room temperature, adding 450g of water at a shearing speed of 1300rpm, emulsifying and dispersing for 10min, adding 4.39g of ethylenediamine into the dispersed emulsion, diluting with 4 times of water, adding, and stirring for 5 min.
The emulsion prepared in the above manner was charged into a four-necked flask, the temperature was controlled at 40 ℃ and nitrogen gas was introduced for 5min, 3g of t-butyl hydroperoxide solution (0.3g of t-butyl hydroperoxide dissolved in 2.7g of water) was added under stirring, and after stirring for 2min, 3g of sodium dithionite solution (0.3g of sodium dithionite dissolved in 2.7g of water) was added. The system has obvious heat release, and the reaction is continued for 1 hour after the temperature rise is finished. And decompressing and vacuumizing the emulsion to remove acetone to obtain the transparent and yellowing hydrogenated castor oil modified waterborne polyurethane-acrylate hybrid copolymer emulsion. The performance tests of the varnish prepared by the method are shown in the table 1.
Example 8
Adding 80g of WANNATEHMDI, 40g of hydrogenated castor oil (the iodine value is less than or equal to 5), 40g of PCL220N, 0.09g of organic bismuth catalyst and 24g of acetone into a four-neck flask with a thermometer, a reflux condenser and a stirrer, heating to 85 ℃, carrying out heat preservation reaction, cooling to 55-40 ℃ after the NCO value is constant to 10.36%, adding 8g of dimethylolpropionic acid, 10g of 1, 4-butanediol and 23g of acetone, reacting for 3-4h at 75-80 ℃ until the NCO value is constant to 2.72%, cooling to 50 ℃, adding 76g of acetone, 153.73g of methyl methacrylate and 6.04g of triethylamine, and stirring for 10min to be uniform. Cooling to room temperature, adding 450g of water at a shearing speed of 1300rpm, emulsifying and dispersing for 10min, adding 14.17g of tris (4-aminophenyl) amine into the dispersed emulsion, diluting with 4 times of water, adding, and stirring for 5 min. 4, 4-diaminodicyclohexylmethane (1.92 g) was added, and after diluting with 4 times of water, the mixture was stirred for 8 min.
The emulsion prepared in the above manner was charged into a four-necked flask, the temperature was controlled at 40 ℃ and nitrogen gas was introduced for 5min, 3g of t-butyl hydroperoxide solution (0.3g of t-butyl hydroperoxide dissolved in 2.7g of water) was added under stirring, and after stirring for 2min, 3g of sodium dithionite solution (0.3g of sodium dithionite dissolved in 2.7g of water) was added. The system has obvious heat release, and the reaction is continued for 1 hour after the temperature rise is finished. And decompressing and vacuumizing the emulsion to remove acetone to obtain the transparent and yellowing hydrogenated castor oil modified waterborne polyurethane-acrylate hybrid copolymer emulsion. The performance tests of the varnish prepared by the method are shown in the table 1.
Example 9 (without post-addition small molecule amine)
Adding 80g of WANNATEHMDI, 40g of hydrogenated castor oil (iodine value is 10-15), 40g of PCL220N, 0.09 part of organic bismuth catalyst and 24g of acetone into a four-neck flask with a thermometer, a reflux condenser and a stirrer, heating to 85 ℃, carrying out heat preservation reaction, cooling to 55-40 ℃ after the NCO value is constant to 10.36%, adding 8g of dimethylolpropionic acid, 10g of 1, 4-butanediol and 23g of acetone, reacting for 3-4h at 75-80 ℃ until the NCO value is constant to 2.72%, cooling to 50 ℃, adding 76g of acetone, 153.73g of methyl methacrylate and 6.04g of triethylamine, and stirring for 10min to be uniform. Cooling to room temperature, adding 450g of water at a shearing speed of 1300rpm, emulsifying and dispersing for 10min, adding 14.17g of tri (4-aminophenyl) amine into the dispersed emulsion, diluting with 4 times of water, adding, and stirring for 5 min.
The emulsion prepared in the above manner was charged into a four-necked flask, the temperature was controlled at 40 ℃ and nitrogen gas was introduced for 5min, 3g of t-butyl hydroperoxide solution (0.3g of t-butyl hydroperoxide dissolved in 2.7g of water) was added under stirring, and after stirring for 2min, 3g of sodium dithionite solution (0.3g of sodium dithionite dissolved in 2.7g of water) was added. The system has obvious heat release, and the reaction is continued for 1 hour after the temperature rise is finished. And decompressing and vacuumizing the emulsion to remove acetone to obtain the transparent and yellowing hydrogenated castor oil modified waterborne polyurethane-acrylate hybrid copolymer emulsion. The performance tests of the varnish prepared by the method are shown in the table 1.
Example 10 (post-addition of Cyclic organic amine in excess)
Adding 80g of WANNATEHMDI, 40g of hydrogenated castor oil (iodine value is 10-15), 40g of PCL220N, 0.09 part of organic bismuth catalyst and 24g of acetone into a four-neck flask with a thermometer, a reflux condenser and a stirrer, heating to 85 ℃, carrying out heat preservation reaction, cooling to 55-40 ℃ after the NCO value is constant to 10.36%, adding 8g of dimethylolpropionic acid, 10g of 1, 4-butanediol and 23g of acetone, reacting for 3-4h at 75-80 ℃ until the NCO value is constant to 2.72%, cooling to 50 ℃, adding 76g of acetone, 153.73g of methyl methacrylate and 6.04g of triethylamine, and stirring for 10min to be uniform. Cooling to room temperature, adding 450g of water at a shearing speed of 1300rpm, emulsifying and dispersing for 10min, adding 14.17 tri (4-aminophenyl) amine into the dispersed emulsion, diluting with 4 times of water, adding, and stirring for 5 min. 15.37g of 4, 4-diaminodicyclohexylmethane was added, diluted with 4 times of water, and then added, followed by stirring for 8 min.
The emulsion prepared in the above manner was charged into a four-necked flask, the temperature was controlled at 40 ℃ and nitrogen gas was introduced for 5min, 3g of t-butyl hydroperoxide solution (0.3g of t-butyl hydroperoxide dissolved in 2.7g of water) was added under stirring, and after stirring for 2min, 3g of sodium dithionite solution (0.3g of sodium dithionite dissolved in 2.7g of water) was added. The system has obvious heat release, and the reaction is continued for 1 hour after the temperature rise is finished. And decompressing and vacuumizing the emulsion to remove acetone to obtain the transparent and yellowing hydrogenated castor oil modified waterborne polyurethane-acrylate hybrid copolymer emulsion. The performance tests of the varnish prepared by the method are shown in the table 1.
TABLE 1 test results of examples and comparative examples
The test results show that the polyurethane-acrylate emulsion modified by the hydrogenated castor oil can obtain better water resistance, alcohol resistance, acid resistance and other resistances, and has excellent rubber friction resistance and pencil hardness. Meanwhile, the polymerization frequency is low, the residual monomer amount is low, and the stability is good.
Having described embodiments of the present invention, the foregoing description is intended to be exemplary, not exhaustive, and not limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments.
Claims (29)
1. The waterborne polyurethane-acrylate hybrid copolymer is characterized by being prepared by reacting the following components in mass content, wherein the total mass of the components is 100%:
17-35% aliphatic diisocyanate;
5-17% polyester polyol;
5-18% hydrogenated castor oil;
30-50% of an acrylate monomer;
0.5-3.0% of low-molecular organic amine containing a cyclic structure, wherein the low-molecular organic amine containing a cyclic structure is selected from 4, 4-diaminodicyclohexyl methane and/or 1, 4-cyclohexane bis (methylamine);
3-6% tris (4-aminophenyl) amine;
the preparation method of the waterborne polyurethane-acrylate hybrid copolymer comprises the following steps:
(1) preparing a hydrogenated castor oil modified polyurethane prepolymer: contacting the aliphatic diisocyanate, the polyester polyol and the hydrogenated castor oil for reaction; after the NCO value is constant, carrying out chain extension reaction to prepare the hydrogenated castor oil modified polyurethane prepolymer;
(2) preparing a hydrogenated castor oil modified waterborne polyurethane-acrylate monomer mixed emulsion: contacting the polyurethane prepolymer prepared in the step (1) with an acrylate monomer, carrying out neutralization reaction, adding water for dispersion, carrying out chain extension, wherein a chain extender is tri (4-aminophenyl) amine, completely reacting residual NCO, adding low-molecular organic amine containing a cyclic structure, continuously stirring to fully fuse the residual NCO and the low-molecular organic amine, and preparing the hydrogenated castor oil modified aqueous polyurethane-acrylate monomer mixed emulsion;
(3) and under the protection of inert gas, carrying out initiation reaction on the hydrogenated castor oil modified aqueous polyurethane-acrylate monomer mixed emulsion, and carrying out heat preservation for 1-2 h after the temperature is raised to obtain the hydrogenated castor oil modified aqueous polyurethane-acrylate hybrid copolymer crude emulsion.
2. The aqueous polyurethane-acrylate hybrid copolymer according to claim 1, wherein the aqueous polyurethane-acrylate hybrid copolymer is prepared by reacting the following components in mass percentage, based on 100% of the total mass of the components:
18-25% of an aliphatic diisocyanate;
6-15% of polyester polyol;
6-15% hydrogenated castor oil;
35-45% of acrylate monomer;
0.5-3.0% of 4, 4-diaminodicyclohexylmethane and/or 1, 4-cyclohexanedi (methylamine);
3.5-5.5% tris (4-aminophenyl) amine.
3. The aqueous polyurethane-acrylate hybrid copolymer according to claim 1, wherein the components further comprise:
0.005-0.08% of a polyurethane reaction catalyst;
1.5-3.5% of a neutralizing agent;
0.01-2% of a free radical initiator;
2.0-4.5% of hydrophilic chain extender;
0.5-3.5% of low molecular weight non-hydrophilic alcohol chain extender, and the molecular weight of the chain extender is 60-400.
4. The aqueous polyurethane-acrylate hybrid copolymer according to claim 2, characterized by comprising 0.6-2.8% of 4, 4-diaminodicyclohexylmethane and/or 1, 4-cyclohexanedi (methylamine).
5. The aqueous polyurethane-acrylate hybrid copolymer according to claim 1, wherein the components further comprise:
0.01-0.07% of polyurethane reaction catalyst;
2-3% of a neutralizing agent;
0.02-1% of a free radical initiator;
2.1-4.0% of hydrophilic chain extender;
0.6-3.0% of low molecular weight non-hydrophilic alcohol chain extender, and the molecular weight of the chain extender is 60-400.
6. The aqueous polyurethane-acrylate hybrid copolymer according to any one of claims 1 to 5, wherein the hydrogenated castor oil has a hydroxyl value of 158 to 163mgKOH/g and an iodine value of 0 to 20.
7. The aqueous polyurethane-acrylate hybrid copolymer according to claim 6, wherein the iodine value of the hydrogenated castor oil is 10-15.
8. The aqueous polyurethane-acrylate hybrid copolymer according to any one of claims 1-5, wherein the aliphatic diisocyanate is selected from dicyclohexylmethane diisocyanate and/or isophorone diisocyanate.
9. The aqueous polyurethane-acrylate hybrid copolymer according to any one of claims 1 to 5, wherein the polyester polyol has an average hydroxyl value of 30 to 150 mgKOH/g.
10. The aqueous polyurethane-acrylate hybrid copolymer according to claim 9, wherein the average hydroxyl value of the polyester polyol is 45-80 mgKOH/g.
11. The aqueous polyurethane-acrylate hybrid copolymer according to claim 10, wherein the polyester polyol is selected from one or more of polycaprolactone polyol, poly-1, 4-butanediol adipate diol, poly-neopentyl glycol adipate diol, and poly-hexanediol adipate diol.
12. The aqueous polyurethane-acrylate hybrid copolymer according to any one of claims 1-5, wherein the acrylate monomer is selected from one or more of ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, benzyl acrylate, methyl methacrylate, butyl methacrylate, and phenyl methacrylate.
13. The aqueous polyurethane-acrylate hybrid copolymer according to claim 12 wherein the acrylate monomer is selected from one or more of butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate and butyl methacrylate.
14. The aqueous polyurethane-acrylate hybrid copolymer according to claim 3 or 5, wherein the hydrophilic chain extender is selected from one or more of carboxyl group-containing diols, sulfonate group-containing diamines and polyoxyethylene glycol-containing diols.
15. The aqueous polyurethane-acrylate hybrid copolymer according to claim 14, wherein the hydrophilic chain extender is a carboxyl group-containing diol.
16. The aqueous polyurethane-acrylate hybrid copolymer according to claim 15 wherein the carboxyl group-containing diol is selected from dimethylol propionic acid and/or dimethylol butyric acid.
17. The aqueous polyurethane-acrylate hybrid copolymer according to claim 3 or 5 wherein the low molecular weight non-hydrophilic alcohol chain extender is selected from the group consisting of C2-C10 aliphatic diols.
18. The aqueous polyurethane-acrylate hybrid copolymer according to claim 17 wherein the low molecular weight non-hydrophilic alcohol chain extender is selected from one or more of 1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol, neopentyl glycol, diethylene glycol, 1, 6-hexanediol.
19. The aqueous polyurethane-acrylate hybrid copolymer according to claim 3 or 5, wherein the neutralizing agent is selected from one or more of triethylamine, triethanolamine, tripropylamine, N-dimethylethanolamine, N-methyldialanolamine, ammonia water, potassium hydroxide, sodium hydroxide and lithium hydroxide;
and/or;
the free radical initiator is a redox initiator system consisting of an oxidant and a reducing agent, and the mass ratio of the oxidant to the reducing agent is 1: 2-2: 1;
and/or;
the polyurethane reaction catalyst is selected from organic tin compounds and/or organic bismuth compounds.
20. The aqueous polyurethane-acrylate hybrid copolymer according to claim 19, wherein the neutralizing agent is selected from one or more of triethylamine, triethanolamine, N dimethylethanolamine and sodium hydroxide.
21. The aqueous polyurethane-acrylate hybrid copolymer according to claim 19 wherein the oxidant is selected from one or more of potassium persulfate, ammonium persulfate, hydrogen peroxide and t-butyl hydroperoxide.
22. The aqueous polyurethane-acrylate hybrid copolymer according to claim 19 wherein the reducing agent is selected from one or more of sodium bisulfite, ferrous sulfate, sodium formaldehyde sulfoxylate, sodium hydrosulfite, and erythorbic acid.
23. The aqueous polyurethane-acrylate hybrid copolymer according to claim 19, wherein the organotin compound is dibutyltin dilaurate and the organobismuth compound is one or more selected from the group consisting of bismuth isooctanoate, bismuth laurate, bismuth neodecanoate, bismuth naphthenate and bismuth nitrate.
24. The waterborne polyurethane-acrylate hybrid copolymer according to claim 3, wherein in the step (1), the aliphatic diisocyanate, the polyester polyol and the hydrogenated castor oil are reacted at 70-100 ℃ in the presence of a polyurethane reaction catalyst, after the NCO value is constant, the temperature is reduced to 55-40 ℃, and a hydrophilic chain extender, a low molecular weight non-hydrophilic alcohol chain extender and a solvent are added for chain extension reaction.
25. The waterborne polyurethane-acrylate hybrid copolymer as claimed in claim 24, wherein in the step (2), the polyurethane prepolymer prepared in the step (1) is contacted with an acrylate monomer and a neutralizer, the mixture is dispersed in water for 5-30 minutes after being mixed for 5-10 minutes, tris (4-aminophenyl) amine is added for chain extension for 5-10 minutes, the residual NCO is completely reacted, 4-diaminodicyclohexylmethane and/or 1, 4-cyclohexanedi (methylamine) are added, and the mixture is continuously stirred for 5-10 minutes to be fully fused.
26. The aqueous polyurethane-acrylate hybrid copolymer according to claim 1, 24 or 25, wherein the preparation method further comprises the step of distilling the crude emulsion obtained in step (3) under reduced pressure to remove the solvent, thereby obtaining an emulsion of the hydrogenated castor oil-modified aqueous polyurethane-acrylate hybrid copolymer.
27. The aqueous polyurethane-acrylate hybrid copolymer according to claim 26 wherein the solvent is selected from one or more of acetone, methyl ethyl ketone, t-butyl methyl ether and tetrahydrofuran.
28. The aqueous polyurethane-acrylate hybrid copolymer according to claim 27 wherein the solvent is selected from methyl ethyl ketone and/or acetone.
29. The aqueous polyurethane-acrylate hybrid copolymer according to claim 28 wherein the solvent is selected from acetone.
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| CN114409852A (en) * | 2021-11-30 | 2022-04-29 | 顺德职业技术学院 | Acrylic acid modified aqueous polyurethane dispersion and preparation method thereof |
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