CN114763395B - Water-based polyurethane-acrylic ester hybrid copolymer and preparation method thereof - Google Patents

Water-based polyurethane-acrylic ester hybrid copolymer and preparation method thereof Download PDF

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CN114763395B
CN114763395B CN202110046209.1A CN202110046209A CN114763395B CN 114763395 B CN114763395 B CN 114763395B CN 202110046209 A CN202110046209 A CN 202110046209A CN 114763395 B CN114763395 B CN 114763395B
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aqueous polyurethane
hybrid copolymer
acrylate
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CN114763395A (en
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张延成
孙永建
纪学顺
宋泽峰
王远勇
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Wanhua Chemical Group Co Ltd
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    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
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Abstract

The invention discloses a waterborne polyurethane-acrylic ester hybrid copolymer and a preparation method thereof, wherein the prepared emulsion has the advantages of simple residue, lower residue content and more excellent low-temperature stability of the finished emulsion; in the process of post chain extension, modified dopamine DMA is added for chain extension modification, bisphenol A glycerol dimethacrylate is used for acrylic acid polymerization modification of the emulsion, and the two are matched to ensure that the polymer shows excellent black heel resistance and adhesive force and improves the low-temperature storage stability of the emulsion.

Description

Water-based polyurethane-acrylic ester hybrid copolymer and preparation method thereof
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
The traditional solvent polyurethane coating has been abandoned by the market step due to the poor environment protection and the large harm to human health, and the development of low-pollution environment-friendly aqueous polyurethane materials has become a common knowledge. The aqueous polyurethane coating is a new environment-friendly coating taking water as a dispersion medium instead of an organic solvent, and gradually replaces the traditional solvent polyurethane coating in a plurality of fields.
Vegetable oil polyols are increasingly receiving attention as a renewable resource. Since the molecular segment of the vegetable oil polyol has good hydrophobicity, the aqueous emulsion prepared by using the vegetable oil polyol as a part of the polyol component has excellent performance, but the use of the raw materials has obvious disadvantages: the monomer is difficult to initiate polymerization, and a large amount of uninitiated monomer remains after initiation, so that the difficulty is eliminated; and emulsion stability is poor in the production process, demulsification slag discharge phenomenon is serious, filtering packaging efficiency is low, consumption of consumables and labor is high, and production cost is high and production efficiency is low.
In the concrete use of the existing floor paint, the bottoms of the table legs and the stool legs are wrapped with rubber pads, the surfaces of the floors are paved with rubber pads, under long-term treading or gravity pressing, fillers with various colors in the rubber are easy to diffuse into the floors, color spots and various marks are generated, the appearance is affected, the existing water-based emulsion in the market has unsatisfactory performance on the problem, and the requirements on black heel resistance are urgent.
Disclosure of Invention
The invention aims to provide a waterborne polyurethane-acrylate hybrid copolymer and a preparation method thereof, so that the prepared copolymer has excellent wear resistance and paint film hardness, excellent black heel resistance, good film forming property and good adhesive force, solves the problem of difficult monomer initiation in the emulsion preparation process, and reduces the content of residual monomers after initiation; the emulsion stability in the process is improved, the packaging and filtering are improved, and the production cost is reduced.
The aqueous polyurethane-acrylate hybrid copolymer is prepared by reacting the following components in parts by mass:
12 to 42 parts by mass of aliphatic diisocyanate, preferably 20 to 35 parts by mass;
6 to 26 parts by mass of a polyester polyol, preferably 8 to 25 parts by mass;
4-32 parts by mass of a bio-based polyol, preferably 5-16 parts by mass;
20 to 60 parts by mass of an acrylate monomer, preferably 20 to 50 parts by mass;
2-10 parts by mass of a hydrophilic chain extender, preferably 2-5 parts by mass;
the total mass of the components is 100. In the present invention, the components further include: based on 100 parts by mass of the total components,
0 to 6 parts by mass of a low molecular weight non-hydrophilic alcohol chain extender, preferably 0.5 to 4 parts by mass; the molecular weight of the polymer is 60-400;
0 to 5 parts by mass of a low molecular weight organic amine chain extender, preferably 0.1 to 2 parts by mass; the molecular weight is 50-500;
0-7 parts by mass of a neutralizing agent, preferably 1-4 parts by mass;
0.01 to 4 parts by mass of a radical initiator, preferably 0.02 to 1 part by mass;
0 to 6 parts by mass of a monohydroxy hydrophilic polyether capping agent, preferably 0.1 to 4 parts by mass; the molecular weight is 800-1500;
0 to 0.05 parts by mass of a polyurethane reaction catalyst, preferably 0.005 to 0.04 parts by mass.
Preferably, the bio-based polyol is hydrogenated castor oil, soybean oil, preferably hydrogenated castor oil, which is a commercially available mature industrial feedstock having a hydroxyl number of 100 to 260mgKOH/g, preferably 130 to 200mgKOH/g.
Preferably, the hydrogenated castor oil is a flaky or powdery material at normal temperature or is a solid raw material at normal temperature in a barrel, and the iodine value is less than 5.
The aliphatic diisocyanate is selected from dicyclohexylmethane diisocyanate and/or isophorone diisocyanate.
Preferably, the average hydroxyl value of the polyester polyol is from 25 to 150mgKOH/g, preferably from 45 to 80mgKOH/g.
Preferably, the polyester polyol is selected from one or more of polycaprolactone polyol, polyacrylate polyol, poly 1, 4-butanediol adipate diol, poly neopentyl glycol adipate diol and poly hexanediol adipate diol, polytetrahydrofuran diol.
Preferably, 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, diacetone acrylamide, adipic acid dihydrazide and trimethacrylate, bisphenol a glycerol dimethacrylate, preferably selected from one or more of butyl acrylate, bisphenol a glycerol dimethacrylate, 2-ethylhexyl acrylate, methyl methacrylate, diacetone acrylamide, adipic acid dihydrazide and butyl methacrylate.
Preferably, the acrylic ester monomer comprises bisphenol A glycerol dimethacrylate, and the mass content of the bisphenol A glycerol dimethacrylate in the acrylic ester monomer is 1-20wt%, preferably 5-10wt%;
preferably, the hydrophilic chain extender is selected from one or more of a carboxyl group-containing diol, a sulfonate-containing diamine and a polyoxyethylene-containing diol, preferably from a carboxyl group-containing diol; the carboxyl group-containing diols are preferably selected from dimethylolpropionic acid and/or dimethylolbutyric acid.
Preferably, the low molecular weight non-hydrophilic alcoholic chain extender is selected from the group consisting of C2-C10 aliphatic diols, 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 low molecular organic amine chain extender is selected from one or more of ethylenediamine, hydroxyethylethylenediamine, 1, 6-hexamethylenediamine, 4-dicyclohexylmethane diamine, isophoronediamine, diethylenetriamine and triethylenetetramine, modified dopamine, tris (Tris-hydroxymethyl-aminomethane), polyetheramine, preferably from one or more of modified dopamine, tris (Tris-hydroxymethyl-aminomethane), ethylenediamine, isophoronediamine and hydroxyethylethylenediamine, more preferably modified dopamine.
The modified dopamine is a product obtained by reacting dopamine hydrochloride with methacrylic anhydride in an inert gas atmosphere under an alkaline condition.
The specific synthesis method of the modified dopamine can be referred to a master paper of southwest traffic university Yang Tao: preparation of organic functional coating based on dopamine derivative and performance research thereof.
The modified dopamine DMA is adopted for post chain extension, and can be mutually coordinated with an acrylic ester component, so that an excellent stability improving effect is achieved, and better adhesive force and strength and excellent black heel resistance are provided in subsequent use.
Preferably, the neutralizing agent is selected from one or more of triethylamine, triethanolamine, tripropylamine, N-dimethylethanolamine, N-methylglycol amine, ammonia water, potassium hydroxide, sodium hydroxide and lithium hydroxide; preferably selected from one or more of triethylamine, triethanolamine, N-dimethylethanolamine and sodium hydroxide.
Preferably, the free radical initiator is an oxidation-reduction 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 oxidizing agent is selected from one or more of potassium persulfate, ammonium persulfate, hydrogen peroxide, and t-butyl hydroperoxide;
preferably, the reducing agent is selected from one or more of sodium bisulphite, ferrous sulphate, formaldehyde sodium bisulphite, sodium dithionite and isoascorbic acid.
Preferably, the monohydroxy hydrophilic polyether capping agent is selected from one or more of MPEG1200, MPEG520 and MPEG 800.
Preferably, the polyurethane reaction catalyst is selected from organotin-based compounds and/or organobismuth-based compounds;
preferably, the organotin compound is dibutyltin dilaurate;
preferably, the organobismuth compound is selected from one or more of bismuth isooctanoate, bismuth laurate, bismuth neodecanoate, bismuth naphthenate and bismuth nitrate.
The preparation method comprises the following steps:
(1) Preparation of polyurethane prepolymer: contacting the aliphatic diisocyanate, polyester polyol and hydrogenated castor oil for reaction; after the NCO value is constant, carrying out chain extension reaction to obtain the hydrogenated castor oil modified polyurethane prepolymer;
(2) Preparing mixed emulsion: reacting the polyurethane prepolymer prepared in the step (1) with an acrylic ester monomer, adding water to disperse, and then optionally adding a low-molecular-weight organic amine chain extender to perform post chain extension to prepare the hydrogenated castor oil modified aqueous polyurethane-acrylic ester monomer mixed emulsion;
(3) And under the protection of inert gas, the aqueous polyurethane-acrylic ester monomer mixed emulsion is contacted with a free radical initiator for reaction to obtain coarse 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 are reacted at 60-105 ℃, and a polyurethane reaction catalyst can be added in the reaction to be more beneficial to the catalytic reaction; when all hydroxyl groups in the reaction system are reacted, after the measured NCO value is constant, reducing the system temperature to below 60 ℃, and adding a hydrophilic chain extender, an optional low molecular weight non-hydrophilic alcohol chain extender, an optional monohydroxy hydrophilic polyether end-capping agent and a solvent for chain extension reaction;
preferably, in the step (2), the polyurethane prepolymer prepared in the step (1) is contacted with an acrylic ester monomer and an optional neutralizer, mixed for 5-10 minutes, added with water for dispersing for 5-30 minutes, and then added with a low-molecular organic amine chain extender for chain extension for 5-30 minutes;
in the step (3), after the exothermic reaction of the reaction system is finished, a free radical initiator is added into the reaction system again for post-treatment so as to reduce the content of residual acrylic acid monomers. The polymerization process adopts a detonation polymerization method, and after the crude emulsion reaches a certain temperature value, an initiator is directly added.
According to the preparation method provided by the invention, preferably, the preparation method further comprises the following steps:
and (3) carrying out reduced pressure distillation on the crude emulsion obtained in the step (3) to remove the solvent, thereby obtaining the 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 from methyl ethyl ketone and/or acetone. In a preferred embodiment of the present invention, the solvent is acetone.
The hydrogenated castor oil modified waterborne polyurethane-acrylate hybrid copolymer resin prepared by the preparation method provided by the invention has good hardness and particularly excellent wear resistance and black heel resistance when being applied to products such as wood decoration, floor home furnishing and the like.
The technical scheme of the invention has the beneficial effects that:
the hydrogenated castor oil is adopted in the polyurethane-acrylic ester copolymer system for modification, so that the polyurethane-acrylic ester hybrid copolymer has excellent properties in terms of paint film hardness and polishing resistance, and has good hardness and particularly excellent wear resistance when being applied to wood coating; the problem of difficult monomer initiation in the emulsion preparation process is solved, and the content of residual monomers after initiation is reduced; the emulsion stability in the process is improved, the packaging and filtering are improved, and the production cost is reduced.
Bisphenol A glycerol dimethacrylate is added into the acrylate monomer for monomer polymerization modification, the black heel resistance of the copolymer system has excellent improvement effect, and the special structure of the bisphenol A glycerol dimethacrylate is introduced, so that the film forming property of the polymer is better, and the adhesive force is better.
The polyurethane-acrylic ester copolymer fundamentally solves the problem of difficult polymerization of the subsequent monomer part of the copolymer, so that the monomer polymerization process is rapid and efficient, the content of residual acrylic acid monomer after polymerization is extremely low, the intermolecular acting force of emulsion per se tends to be dynamic stable in the processes of residual monomer elimination and subsequent solvent removal, the molecular chain segment emulsifying effect is better, the emulsion cannot be broken and separated out in the whole processes of stirring, shearing and solvent removal, the content of residual monomer of the finally obtained polyurethane-acrylic ester hybrid copolymer is low, the content of demulsified slag in the process is low, the high-number filtering consumable data used in the packaging process is rapidly reduced, the packaging efficiency is greatly improved, the production line after production can be continuously used for subsequent production without excessive cleaning, and the low-temperature storage performance of the finished product emulsion is remarkably improved.
In the existing polyurethane-acrylic acid copolymerization system, the adhesion of a finished paint film to a wood substrate is poor due to the branching effect of vegetable oil, and in the application, the modified dopamine DMA is added in a post-chain extension stage, so that an excellent stability improvement effect is achieved on an acrylic acid component, better film forming property and adhesive force are provided in the use of a polymer paint film, and the black heel resistance of a copolymer system is improved.
Detailed Description
So that the technical features and content 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 to the embodiments set forth herein.
1. Raw material source
1. Dicyclohexylmethane diisocyanate: wanhua chemical group Co., ltd., industrial grade WANNATE HMDI.
2. Polycaprolactone diol: japanese Kagaku Kogyo Co., ltd., trade name PCL220N, molecular weight 2000.
3. Hydrogenated castor oil
Hydrogenated castor oil: shandong Tianxing biological technology Co., ltd, industrial products, moisture and volatile matters are less than or equal to 0.2%, acid value is less than or equal to 2mg/g, hydroxyl value is more than or equal to 155mg/g, iodine value is less than or equal to 2.5g/100g, and saponification value is 176-187 mg/g;
4. sodium dithionite: analytically pure, tianjin chemical reagents, inc.;
5. organobismuth catalyst: brand BiCAT8106, analytically pure, american leading chemical company;
6. trimethylolpropane: analytically pure, carbofuran technologies, inc;
7. dimethylolpropionic acid: analytically pure, carbofuran technologies, inc;
8. 1, 4-butanediol: analytically pure, shanghai Aba Ding Shenghua technologies Co., ltd;
9. methyl methacrylate: industrial products of petrochemical company in China;
10. triethylamine: analytically pure, shanghai Aba Ding Shenghua technologies Co., ltd;
11. bisphenol A glycerol dimethacrylate, analytical pure Shanghai Kanglang Biotechnology Co., ltd
12. Modified dopamine DMA: laboratory synthesis, purity is more than or equal to 98%
The preparation method comprises the following steps: the synthesis of N-3, 4-Dihydroxyphenethyl Methacrylamide (DMA) comprises the following steps:
(1) 100mL of deionized water was added to a clean, dry three-necked flask, and 10g of sodium tetraborate and 4g of sodium bicarbonate, weighed in advance, were rapidly transferred to the flask, respectively.
(2) And placing the ventilation catheter at the bottom of the solution, bubbling high-purity argon for 30min to remove the solution and oxygen in the reaction device, and ensuring that the reaction system is in an inert protective gas environment.
(3) After the oxygen removal is finished, 5g of dopamine hydrochloride weighed in advance is rapidly transferred into the reaction solution under the atmosphere of argon.
(4) 4.7mL of methacrylic anhydride was removed, dissolved in 25mL of tetrahydrofuran, and the mixed solution of methacrylic anhydride and tetrahydrofuran was added dropwise to the reaction solution under argon protection. After the completion of the dropwise addition, the pH value of the reaction solution was adjusted to not lower than 8 with a 1M sodium hydroxide solution. The whole reaction was allowed to react at room temperature under argon atmosphere for 14 hours.
(5) The white slurry solution obtained after the reaction was washed with 50mL of ethyl acetate to remove unreacted substances, and the resulting mixture was suction-filtered under reduced pressure, the filtrate obtained by suction-filtration was adjusted to ph=2 using a hydrochloric acid solution having a concentration of 6M, extracted three times with 50mL of ethyl acetate, and finally, an appropriate amount of anhydrous magnesium sulfate was added to the organic liquid obtained by extraction to dry.
(6) Concentrating the dried solution under reduced pressure to 25mL, dropwise adding the solution into 250mL petroleum ether for sedimentation, repeating the sedimentation process for three times, then placing the solution into a refrigerator for recrystallization, and finally placing the solid product obtained by recrystallization into a vacuum drying oven for drying and preserving. The reaction process is shown below.
The modified dopamine is prepared by the method for multiple times.
13. T-butyl hydroperoxide: analytically pure, tianjin chemical reagents, inc.;
14. sodium dithionite: analytically pure, tianjin chemical reagents, inc.
2. Test method
The solid content testing method comprises the following steps: 1.1g of the copolymer emulsion was weighed in a container made of tinfoil, and its weight change at 150℃for 20 minutes was measured to calculate the solid content.
The particle size testing method comprises the following steps: a malvern particle size meter was used.
The pH test method comprises the following steps: a pH meter was used.
The monomer content testing method comprises the following steps: liquid phase testing
The testing method of the coarse emulsion slag comprises the following steps: cutting a 150-mesh metal filter screen and a 325-mesh metal filter screen with certain sizes respectively, putting the metal filter screens into a 150 ℃ oven for five minutes, cooling, weighing 1000 g of coarse emulsion by using a four-position balance, filtering by using the 150-mesh metal filter screen and the 325-mesh metal filter screen respectively, flushing the filtered metal filter screen by using process water, reserving residues on the filter screen, weighing the residues, and calculating the weight change of the residues before and after the residues are at 150 ℃ for 20 minutes
The testing method of the finished emulsion residue comprises the following steps: cutting a 150-mesh metal filter screen and a 325-mesh metal filter screen with certain sizes respectively, putting the metal filter screens into a 150 ℃ oven for five minutes, cooling, weighing 1000 g of finished emulsion by using a four-position balance, filtering by using the 150-mesh metal filter screen and the 325-mesh metal filter screen respectively, flushing the filtered metal filter screen by using process water, reserving residues on the filter screen, weighing the residues, and calculating the weight change of the residues before and after the residues are at 150 ℃ for 20 minutes
The viscosity test method comprises the following steps: the test was performed using a BROOKFIELD viscometer, rotor number 62/30 rpm.
The appearance testing method comprises the following steps: and judging the eye view.
Minimum Film Formation Temperature (MFFT) test method: the standard was performed using a Coesfeld tester, germany: GB/T20623-2006.
Film forming property testing method: adding 8% of film forming auxiliary agent, scraping a glass plate by using a 100um bar, putting into a low-temperature box at 5 ℃, curing for 1h, and observing the phenomena of cracking, blackening, low glossiness and the like of a paint film.
The black heel resistance testing method comprises the following steps: after a 150um copolymer paint film is scraped on an ABS plastic plate and dried for two days at 50 ℃, a black rubber sheet (styrene-butadiene rubber, 5cm x 5 cm) is placed on the paint film, 9Kg of the upper pressure is weighed, the change of the paint film is compared at 50 ℃, and whether the paint film has phenomena of yellowing, color change and the like is observed. 0 to 5 minutes, 0 minutes being worst and 5 minutes being optimal.
The pencil hardness test method of the paint film comprises the following steps: the execution standard: GB/T6739
The hardness test method of the paint film swing rod comprises the following steps: the execution standard: GB/T1730
The stability test method comprises the following steps: 1 kg of emulsion is taken in a 1 kg plastic bottle, sealed, kept stand in a 50 ℃ oven for 1 month, and whether the physical properties of the emulsion change and whether the performance is stable are observed.
The method comprises the following steps: preparation method of copolymer test formula
80 parts by mass of copolymer resin, 0.5 part by mass of BYK-348 (wetting agent), 8.8 parts by mass of film forming auxiliary (DPM: DPnB: water=3:5:3), 10.7 parts by mass of water.
The parts are mass parts in the examples below.
Example 1
Into a four-necked flask equipped with a thermometer, a reflux condenser and a stirrer, 80 parts of WANNATE HMDI,40 parts of hydrogenated castor oil, 40 parts of PCL220N and 0.05 part of an organobismuth catalyst were charged, the temperature was raised to 85 ℃ and the reaction was kept at a constant NCO value, after which the temperature was lowered to 50 ℃,2 parts of trimethylolpropane (non-hydrophilic alcohol chain extender), 9 parts of dimethylolpropionic acid, 1 part of monohydroxy hydrophilic polyether end-capping agent, 2 parts of 1, 4-butanediol and 32 parts of acetone were added, and the reaction was carried out at 80 ℃ for 4 hours until the residual NCO was constant.
After cooling to 50 ℃, 78 parts of acetone, 110 parts of a mixture of methyl methacrylate and bisphenol A glycerol dimethacrylate (wherein the content of bisphenol A glycerol dimethacrylate is 10 parts) and 6.8 parts of triethylamine are added and stirred for 10 minutes until uniform. After cooling to room temperature, 450 parts of water was added at a shear rate of 1300rpm, and the mixture was emulsified and dispersed for 10 minutes. Adding 5 parts of modified dopamine DMA acetone solution with the mass concentration of 25% into the dispersed emulsion, and stirring for 5min;
the emulsion prepared in the above manner was added to a four-necked flask, the temperature of the emulsion was controlled at 40℃and the mixture was purged with nitrogen for 5 minutes, 1.6 parts of t-butyl hydroperoxide solution (0.16 parts of t-butyl hydroperoxide was dissolved in 1.44 parts of water) was added under stirring, and after stirring for 2 minutes, 1.6 parts of sodium dithionite solution (0.16 parts of sodium dithionite was dissolved in 1.44 parts of water) was added. The heat release of the system is obvious, and the residual list and the slag content are sampled and tested after the temperature is raised;
adding 0.5 part of tert-butyl hydroperoxide solution (0.05 part of tert-butyl hydroperoxide is dissolved in 0.45 part of water), stirring for 2min, adding 0.5 part of sodium dithionite solution (0.05 part of sodium dithionite is dissolved in 0.45 part of water), performing aftertreatment, continuously preserving heat and reacting at 50 ℃ for 1h, and sampling and testing residual monomers and slag contents;
the emulsion is decompressed and vacuumized to remove acetone, and the hydrogenated castor oil modified waterborne polyurethane-acrylic ester hybrid copolymer emulsion with transparent yellowish color can be obtained. The residue and slag content were sampled and tested, and the results of each performance test are shown in Table 1.
Example 2
Into a four-necked flask equipped with a thermometer, a reflux condenser and a stirrer, 80 parts of WANNATE HMDI,40 parts of hydrogenated castor oil, 40 parts of PCL220N and 0.05 part of an organobismuth catalyst were charged, the temperature was raised to 85 ℃ and the reaction was kept at a constant NCO value, after which the temperature was lowered to 50 ℃,2 parts of trimethylolpropane (non-hydrophilic alcohol chain extender), 9 parts of dimethylolpropionic acid, 1 part of monohydroxy hydrophilic polyether end-capping agent, 2 parts of 1, 4-butanediol and 32 parts of acetone were added, and the reaction was carried out at 80 ℃ for 4 hours until the residual NCO was constant.
After cooling to 50 ℃, 78 parts of acetone, 110 parts of a mixture of methyl methacrylate and bisphenol A glycerol dimethacrylate (wherein the content of bisphenol A glycerol dimethacrylate is 2 parts) and 6.8 parts of triethylamine are added and stirred for 10 minutes until uniform. After cooling to room temperature, 450 parts of water was added at a shear rate of 1300rpm, and the mixture was emulsified and dispersed for 10 minutes. 5 parts of modified dopamine DMA acetone solution with the mass concentration of 25% is added into the dispersed emulsion, and the mixture is stirred for 5 minutes.
The emulsion prepared in the above manner was added to a four-necked flask, the temperature of the emulsion was controlled at 40℃and the mixture was purged with nitrogen for 5 minutes, 1.6 parts of t-butyl hydroperoxide solution (0.16 parts of t-butyl hydroperoxide was dissolved in 1.44 parts of water) was added under stirring, and after stirring for 2 minutes, 1.6 parts of sodium dithionite solution (0.16 parts of sodium dithionite was dissolved in 1.44 parts of water) was added. The heat release of the system is obvious, and the residual list and the slag content are sampled and tested after the temperature is raised;
adding 0.5 part of tert-butyl hydroperoxide solution (0.05 part of tert-butyl hydroperoxide is dissolved in 0.45 part of water), stirring for 2min, adding 0.5 part of sodium dithionite solution (0.05 part of sodium dithionite is dissolved in 0.45 part of water), performing aftertreatment, continuously preserving heat and reacting at 50 ℃ for 1h, and sampling and testing residual monomers and slag contents;
the emulsion is decompressed and vacuumized to remove acetone, and the hydrogenated castor oil modified waterborne polyurethane-acrylic ester hybrid copolymer emulsion with transparent yellowish color can be obtained. The residue and slag content were sampled and tested, and the results of each performance test are shown in Table 1.
Example 3
To a four-necked flask equipped with a thermometer, a reflux condenser and a stirrer were added 70 parts of WANNATE HMDI,30 parts of hydrogenated castor oil, 35 parts of PCL220N and 0.01 part of an organobismuth catalyst, the temperature was raised to 85℃and the reaction was kept at a constant NCO value, after which the temperature was lowered to 50℃and 2 parts of trimethylolpropane (non-hydrophilic alcohol chain extender), 5 parts of dimethylolpropionic acid, 1 part of monohydroxy hydrophilic polyether end-capping agent, 2 parts of 1, 4-butanediol and 32 parts of acetone were added, and the reaction was carried out at 80℃for 4 hours until the residual NCO was constant.
After cooling to 50 ℃, 68 parts of acetone, 60 parts of a mixture of methyl methacrylate and bisphenol A glycerol dimethacrylate (wherein the content of bisphenol A glycerol dimethacrylate is 6 parts) and 6.0 parts of triethylamine are added, and the mixture is stirred for 10 minutes until the mixture is uniform. After cooling to room temperature, 450 parts of water was added at a shear rate of 1300rpm, and the mixture was emulsified and dispersed for 10 minutes. 5 parts of an acetone solution of modified dopamine DMA with the mass concentration of 25% is added into the dispersed emulsion, and the mixture is stirred for 5 minutes.
The emulsion prepared in the above manner was added to a four-necked flask, the temperature of the emulsion was controlled at 40℃and the mixture was purged with nitrogen for 5 minutes, 1.6 parts of t-butyl hydroperoxide solution (0.16 parts of t-butyl hydroperoxide was dissolved in 1.44 parts of water) was added under stirring, and after stirring for 2 minutes, 1.6 parts of sodium dithionite solution (0.16 parts of sodium dithionite was dissolved in 1.44 parts of water) was added. The heat release of the system is obvious, and the residual list and the slag content are sampled and tested after the temperature is raised;
adding 0.5 part of tert-butyl hydroperoxide solution (0.05 part of tert-butyl hydroperoxide is dissolved in 0.45 part of water), stirring for 2min, adding 0.5 part of sodium dithionite solution (0.05 part of sodium dithionite is dissolved in 0.45 part of water), performing aftertreatment, continuously preserving heat and reacting at 50 ℃ for 1h, and sampling and testing residual monomers and slag contents;
the emulsion is decompressed and vacuumized to remove acetone, and the hydrogenated castor oil modified waterborne polyurethane-acrylic ester hybrid copolymer emulsion with transparent yellowish color can be obtained. The residue and slag content were sampled and tested, and the results of each performance test are shown in Table 1.
Example 4
Into a four-neck flask equipped with a thermometer, a reflux condenser and a stirrer, 80 parts of WANNATE HMDI,40 parts of soybean oil alcoholysis, 40 parts of PCL220N and 0.05 part of organic bismuth catalyst are added, the temperature is raised to 85 ℃ and the temperature is kept for reaction, after the NCO value is constant, the temperature is reduced to 50 ℃,2 parts of trimethylolpropane, 9 parts of dimethylolpropionic acid, 1 part of monohydroxy hydrophilic polyether end-capping agent, 2 parts of 1.4-butanediol and 32 parts of acetone are added, and the reaction is carried out at 80 ℃ for 4 hours until the residual NCO is constant.
After cooling to 50 ℃, 78 parts of acetone, 110 parts of a mixture of methyl methacrylate and bisphenol A glycerol dimethacrylate (wherein the content of bisphenol A glycerol dimethacrylate is 10 parts) and 6.8 parts of triethylamine are added and stirred for 10 minutes until uniform. After cooling to room temperature, 450 parts of water was added at a shear rate of 1300rpm, and the mixture was emulsified and dispersed for 10 minutes. Adding 5 parts of modified dopamine DMA acetone solution with the mass concentration of 25% into the dispersed emulsion, and stirring for 5min;
the emulsion prepared in the above manner was added to a four-necked flask, the temperature of the emulsion was controlled at 40℃and the mixture was purged with nitrogen for 5 minutes, 1.6 parts of t-butyl hydroperoxide solution (0.16 parts of t-butyl hydroperoxide was dissolved in 1.44 parts of water) was added under stirring, and after stirring for 2 minutes, 1.6 parts of sodium dithionite solution (0.16 parts of sodium dithionite was dissolved in 1.44 parts of water) was added. The heat release of the system is obvious, and the residual list and the slag content are sampled and tested after the temperature is raised;
adding 0.5 part of tert-butyl hydroperoxide solution (0.05 part of tert-butyl hydroperoxide is dissolved in 0.45 part of water), stirring for 2min, adding 0.5 part of sodium dithionite solution (0.05 part of sodium dithionite is dissolved in 0.45 part of water), performing aftertreatment, continuously preserving heat and reacting at 50 ℃ for 1h, and sampling and testing residual monomers and slag contents;
the emulsion is decompressed and vacuumized to remove acetone, and the transparent yellowish soybean oil alcoholysis modified aqueous polyurethane-acrylic ester hybrid copolymer emulsion can be obtained. The residue and slag content were sampled and tested, and the results of each performance test are shown in Table 1.
Comparative example 1
Into a four-necked flask equipped with a thermometer, a reflux condenser and a stirrer, 80 parts of WANNATE HMDI,40 parts of hydrogenated castor oil, 40 parts of PCL220N and 0.05 part of an organobismuth catalyst were charged, the temperature was raised to 85℃and the reaction was kept at a constant NCO value, after which the temperature was lowered to 50℃and 1 part of trimethylolpropane, 16 parts of dimethylolpropionic acid, 1 part of 1.4-butanediol and 32 parts of acetone were added, and the reaction was carried out at 80℃for 4 hours until the residual NCO was constant.
After cooling to 50 ℃, 78 parts of acetone, 110 parts of methyl methacrylate and 6.8 parts of triethylamine are added and stirred for 10 minutes until uniform. After cooling to room temperature, 450 parts of water was added at a shear rate of 1300rpm, and the mixture was emulsified and dispersed for 10 minutes. 5 parts of modified dopamine DMA acetone solution with the mass concentration of 25% is added into the dispersed emulsion, and the mixture is stirred for 5 minutes. The method comprises the steps of carrying out a first treatment on the surface of the
The emulsion prepared in the above manner was added to a four-necked flask, the temperature of the emulsion was controlled at 40℃and the mixture was purged with nitrogen for 5 minutes, 1.6 parts of t-butyl hydroperoxide solution (0.16 parts of t-butyl hydroperoxide was dissolved in 1.44 parts of water) was added under stirring, and after stirring for 2 minutes, 1.6 parts of sodium dithionite solution (0.16 parts of sodium dithionite was dissolved in 1.44 parts of water) was added. The heat release of the system is obvious, and the residual list and the slag content are sampled and tested after the temperature is raised;
adding 0.5 part of tert-butyl hydroperoxide solution (0.05 part of tert-butyl hydroperoxide is dissolved in 0.45 part of water), stirring for 2min, adding 0.5 part of sodium dithionite solution (0.05 part of sodium dithionite is dissolved in 0.45 part of water), performing aftertreatment, continuously preserving heat and reacting at 50 ℃ for 1h, and sampling and testing residual monomers and slag contents;
comparative example 2
Into a four-necked flask equipped with a thermometer, a reflux condenser and a stirrer, 80 parts of WANNATE HMDI,40 parts of hydrogenated castor oil, 40 parts of PCL220N and 0.05 part of an organobismuth catalyst were charged, the temperature was raised to 85 ℃ and the reaction was kept at a constant NCO value, after which the temperature was lowered to 50 ℃,2 parts of trimethylolpropane (non-hydrophilic alcohol chain extender), 9 parts of dimethylolpropionic acid, 1 part of monohydroxy hydrophilic polyether end-capping agent, 2 parts of 1, 4-butanediol and 32 parts of acetone were added, and the reaction was carried out at 80 ℃ for 4 hours until the residual NCO was constant.
After cooling to 50 ℃, 78 parts of acetone, 110 parts of a mixture of methyl methacrylate and bisphenol A glycerol dimethacrylate (wherein the content of bisphenol A glycerol dimethacrylate is 10 parts) and 6.8 parts of triethylamine are added and stirred for 10 minutes until uniform. After cooling to room temperature, 450 parts of water was added at a shear rate of 1300rpm, and the mixture was emulsified and dispersed for 10 minutes. To the dispersed emulsion was added 5 parts of an aqueous solution of EDA of 25% by mass concentration, and stirred for 5 minutes.
The emulsion prepared in the above manner was added to a four-necked flask, the temperature of the emulsion was controlled at 40℃and the mixture was purged with nitrogen for 5 minutes, 1.6 parts of t-butyl hydroperoxide solution (0.16 parts of t-butyl hydroperoxide was dissolved in 1.44 parts of water) was added under stirring, and after stirring for 2 minutes, 1.6 parts of sodium dithionite solution (0.16 parts of sodium dithionite was dissolved in 1.44 parts of water) was added. The heat release of the system is obvious, and the residual list and the slag content are sampled and tested after the temperature is raised;
adding 0.5 part of tert-butyl hydroperoxide solution (0.05 part of tert-butyl hydroperoxide is dissolved in 0.45 part of water), stirring for 2min, adding 0.5 part of sodium dithionite solution (0.05 part of sodium dithionite is dissolved in 0.45 part of water), performing aftertreatment, continuously preserving heat and reacting at 50 ℃ for 1h, and sampling and testing residual monomers and slag contents;
the emulsion is decompressed and vacuumized to remove acetone, and the hydrogenated castor oil modified waterborne polyurethane-acrylic ester hybrid copolymer emulsion with transparent yellowish color can be obtained. The residue and slag content were sampled and tested, and the results of each performance test are shown in Table 1.
Comparative example 3
Into a four-necked flask equipped with a thermometer, a reflux condenser and a stirrer, 80 parts of WANNATE HMDI,40 parts of hydrogenated castor oil, 40 parts of PCL220N and 0.05 part of an organobismuth catalyst were charged, the temperature was raised to 85 ℃ and the reaction was kept at a constant NCO value, after which the temperature was lowered to 50 ℃,2 parts of trimethylolpropane (non-hydrophilic alcohol chain extender), 9 parts of dimethylolpropionic acid, 1 part of monohydroxy hydrophilic polyether end-capping agent, 2 parts of 1, 4-butanediol and 32 parts of acetone were added, and the reaction was carried out at 80 ℃ for 4 hours until the residual NCO was constant.
After cooling to 50 ℃, 78 parts of acetone, 110 parts of methyl methacrylate and 6.8 parts of triethylamine are added and stirred for 10 minutes until uniform. After cooling to room temperature, 450 parts of water was added at a shear rate of 1300rpm, and the mixture was emulsified and dispersed for 10 minutes. To the dispersed emulsion was added 5 parts of an aqueous solution of EDA of 25% by mass concentration, and stirred for 5 minutes.
The emulsion prepared in the above manner was added to a four-necked flask, the temperature of the emulsion was controlled at 40℃and the mixture was purged with nitrogen for 5 minutes, 1.6 parts of t-butyl hydroperoxide solution (0.16 parts of t-butyl hydroperoxide was dissolved in 1.44 parts of water) was added under stirring, and after stirring for 2 minutes, 1.6 parts of sodium dithionite solution (0.16 parts of sodium dithionite was dissolved in 1.44 parts of water) was added. The heat release of the system is obvious, and the residual list and the slag content are sampled and tested after the temperature is raised;
adding 0.5 part of tert-butyl hydroperoxide solution (0.05 part of tert-butyl hydroperoxide is dissolved in 0.45 part of water), stirring for 2min, adding 0.5 part of sodium dithionite solution (0.05 part of sodium dithionite is dissolved in 0.45 part of water), performing aftertreatment, continuously preserving heat and reacting at 50 ℃ for 1h, and sampling and testing residual monomers and slag contents;
the emulsion is decompressed and vacuumized to remove acetone, and the hydrogenated castor oil modified waterborne polyurethane-acrylic ester hybrid copolymer emulsion with transparent yellowish color can be obtained. The residue and slag content were sampled and tested, and the results of each performance test are shown in Table 1.
Table 1 results of performance testing of examples and comparative examples
From the test results, the hydrogenated castor oil provided by the invention can replace soybean oil alcoholysis, can keep lower residual monomer level at each stage in the whole experimental process, has lower slag content level and has better emulsion heat storage stability.
Surprisingly, we found that by adding modified dopamine DMA in the post chain extension stage and adding bisphenol A glycerol dimethacrylate in methyl methacrylate for monomer polymerization modification, benzene ring hydroxyl is introduced onto a PA molecular chain, and the two compound results in that the film forming property, adhesive force and black heel resistance of the polymer are improved to a great extent.
From the comparative experiments, it was found that the bisphenol A component plays a decisive role in the "black heel resistant" properties of the copolymer, but that the synergistic effect of the addition of modified dopamine on the "black heel resistant" is also evident. The hydroxyl contained in the bisphenol A has a wetting effect in the system after copolymerization is completed, and the hardness of the bisphenol A is better improved in the association process with the base material.
The foregoing description of embodiments of the invention has been presented for purposes of illustration and description, and is not intended to be exhaustive or 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 various embodiments described.

Claims (31)

1. The waterborne polyurethane-acrylate hybrid copolymer is characterized by being prepared by reacting the following components in parts by mass:
12-42 parts by mass of aliphatic diisocyanate;
6-26 parts by mass of a polyester polyol;
4-32 parts by mass of a bio-based polyol;
20-60 parts by mass of an acrylic ester monomer;
2-10 parts by mass of a hydrophilic chain extender;
the total mass parts of the components are 100;
the components further include: 0.1-5 parts by mass of modified dopamine chain extender;
the acrylate monomer comprises bisphenol A glycerol dimethacrylate, and the mass content of the bisphenol A glycerol dimethacrylate in the acrylate monomer is 1-20wt%.
2. The aqueous polyurethane-acrylate hybrid copolymer according to claim 1, which is prepared by reacting the following components in parts by mass:
20-35 parts by mass of aliphatic diisocyanate;
8-25 parts by mass of polyester polyol;
5-16 parts by mass of a bio-based polyol;
20-50 parts by mass of acrylate monomer;
2-5 parts by mass of a hydrophilic chain extender;
the total mass of the components is 100.
3. The aqueous polyurethane-acrylate hybrid copolymer of claim 1, wherein the components further comprise:
0-6 parts by mass of a low molecular weight non-hydrophilic alcohol chain extender;
0-7 parts by mass of a neutralizing agent;
0.01-4 parts by mass of a radical initiator;
0-6 parts by mass of a monohydroxy hydrophilic polyether end-capping agent;
0-0.05 parts by mass of a polyurethane reaction catalyst;
based on 100 parts by mass of the total components as claimed in claim 1.
4. The aqueous polyurethane-acrylate hybrid copolymer of claim 3 wherein the components further comprise:
0.5-4 parts by mass of low molecular weight non-hydrophilic alcohol chain extender; the molecular weight of the polymer is 60-400;
0.1-2 parts by mass of modified dopamine chain extender; the molecular weight is 50-500;
1-4 parts of neutralizing agent;
0.02-1 parts by mass of a free radical initiator;
0.1-4 parts by mass of monohydroxy hydrophilic polyether end capping agent; the molecular weight is 800-1500;
0.005-0.04 parts by mass of a polyurethane reaction catalyst;
based on 100 parts by mass of the total components as claimed in claim 1.
5. The aqueous polyurethane-acrylate hybrid copolymer according to claim 1 wherein the bio-based polyol is hydrogenated castor oil, soybean oil, having a hydroxyl number of 100 to 260mgKOH/g.
6. The aqueous polyurethane-acrylate hybrid copolymer according to claim 5 wherein the bio-based polyol is hydrogenated castor oil and the bio-based polyol has a hydroxyl value of 130 to 200mgKOH/g.
7. The aqueous polyurethane-acrylate hybrid copolymer according to claim 5 wherein the hydrogenated castor oil has an iodine value of less than 5.
8. The aqueous polyurethane-acrylate hybrid copolymer according to claim 1, characterized in that the aliphatic diisocyanate is selected from dicyclohexylmethane diisocyanate and/or isophorone diisocyanate.
9. The aqueous polyurethane-acrylate hybrid copolymer according to claim 1 wherein the polyester polyol has an average hydroxyl value of 25 to 150mgKOH/g.
10. The aqueous polyurethane-acrylate hybrid copolymer according to claim 9 wherein the polyester polyol has an average hydroxyl value of 45 to 80mgKOH/g.
11. The aqueous polyurethane-acrylate hybrid copolymer according to claim 1 wherein the polyester polyol is selected from one or more of polycaprolactone polyol, polyacrylate polyol, poly 1, 4-butylene glycol adipate diol, poly neopentyl glycol adipate diol, and poly hexylene glycol adipate diol, polytetrahydrofuran diol.
12. The aqueous polyurethane-acrylate hybrid copolymer of claim 11, wherein the acrylate monomer further comprises one or more of ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, benzyl acrylate, methyl methacrylate, butyl methacrylate, phenyl methacrylate, diacetone acrylamide, adipic acid dihydrazide, and trimethacrylate.
13. The aqueous polyurethane-acrylate hybrid copolymer of claim 12, wherein the acrylate monomer further comprises one or more of butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, diacetone acrylamide, adipic acid dihydrazide, and butyl methacrylate.
14. The aqueous polyurethane-acrylate hybrid copolymer according to claim 1, wherein the mass content of bisphenol a glycerol dimethacrylate in the acrylate monomer is 5-10 wt%.
15. The aqueous polyurethane-acrylate hybrid copolymer according to claim 1 wherein the hydrophilic chain extender is selected from one or more of carboxyl-containing diols, sulfonate-containing diamines, and polyoxyethylene-containing diols.
16. The aqueous polyurethane-acrylate hybrid copolymer according to claim 15 wherein the hydrophilic chain extender is selected from carboxyl-containing diols.
17. The aqueous polyurethane-acrylate hybrid copolymer according to claim 16 wherein the carboxyl group containing diol is selected from dimethylolpropionic acid and/or dimethylolbutyric acid.
18. The aqueous polyurethane-acrylate hybrid copolymer according to claim 4 wherein the low molecular weight non-hydrophilic alcoholic chain extender is selected from the group consisting of C2-C10 aliphatic diols.
19. The aqueous polyurethane-acrylate hybrid copolymer according to claim 18 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, and trimethylolpropane.
20. The aqueous polyurethane-acrylate hybrid copolymer according to claim 4 wherein the neutralizing agent is selected from one or more of triethylamine, triethanolamine, tripropylamine, N-dimethylethanolamine, N-methylglycol amine, aqueous ammonia, potassium hydroxide, sodium hydroxide, and lithium hydroxide.
21. The aqueous polyurethane-acrylate hybrid copolymer of claim 20 wherein the neutralizing agent is selected from one or more of triethylamine, triethanolamine, N-dimethylethanolamine, and sodium hydroxide.
22. The aqueous polyurethane-acrylate hybrid copolymer according to claim 4, wherein the free radical initiator is a redox initiator system consisting of an oxidizing agent and a reducing agent, and the mass ratio of the oxidizing agent to the reducing agent is 1:2-2:1.
23. The aqueous polyurethane-acrylate hybrid copolymer of claim 22 wherein the oxidizing agent is selected from one or more of potassium persulfate, ammonium persulfate, hydrogen peroxide, and t-butyl hydroperoxide.
24. The aqueous polyurethane-acrylate hybrid copolymer according to claim 22 wherein the reducing agent is selected from one or more of sodium bisulfite, ferrous sulfate, sodium formaldehyde sulfoxylate, sodium dithionite, and isoascorbic acid.
25. The aqueous polyurethane-acrylate hybrid copolymer according to claim 4 wherein the monohydroxy hydrophilic polyether capping agent is selected from one or more of MPEG1200, MPEG520 and MPEG 800.
26. The aqueous polyurethane-acrylate hybrid copolymer according to claim 25 wherein the polyurethane reaction catalyst is selected from organotin-based compounds and/or organobismuth-based compounds.
27. The aqueous polyurethane-acrylate hybrid copolymer according to claim 1, wherein the modified dopamine is a product obtained by reacting dopamine hydrochloride with methacrylic anhydride in an inert gas atmosphere under alkaline conditions.
28. A method for preparing the aqueous polyurethane-acrylate hybrid copolymer according to any one of claims 1 to 27, comprising the steps of:
(1) Preparation of polyurethane prepolymer: contacting the aliphatic diisocyanate, polyester polyol and hydrogenated castor oil for reaction; after the NCO value is constant, carrying out chain extension reaction to obtain the hydrogenated castor oil modified polyurethane prepolymer;
(2) Preparing mixed emulsion: reacting the polyurethane prepolymer prepared in the step (1) with an acrylic ester monomer, adding water to disperse, and then optionally adding a low-molecular-weight organic amine chain extender to perform post chain extension to prepare the hydrogenated castor oil modified aqueous polyurethane-acrylic ester monomer mixed emulsion;
(3) And under the protection of inert gas, the aqueous polyurethane-acrylic ester monomer mixed emulsion is contacted with a free radical initiator for reaction to obtain coarse emulsion.
29. The process of claim 28, wherein in step (1), the aliphatic diisocyanate, the polyester polyol and the hydrogenated castor oil are reacted at 60 to 105 ℃, and a polyurethane reaction catalyst is added to the reaction to further facilitate the catalytic reaction; after all hydroxyl groups in the reaction system are reacted, the measured NCO value is constant, the temperature of the system is reduced to below 60 ℃, and a hydrophilic chain extender, an optional low molecular weight non-hydrophilic alcohol chain extender, an optional monohydroxy hydrophilic polyether end-capping agent and a solvent are added for chain extension reaction.
30. The process of claim 28, wherein in step (2), the polyurethane prepolymer obtained in step (1) is contacted with an acrylic monomer and optionally a neutralizing agent, mixed for 5 to 10 minutes, then added with water to disperse for 5 to 30 minutes, and then added with a low molecular weight organic amine chain extender to chain-extend for 5 to 30 minutes.
31. The method according to claim 28, wherein in the step (3), after the exothermic reaction system is completed, a radical initiator is added again to the reaction system for post-treatment to reduce the content of the residual acrylic acid monomer.
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