CN116102695A - Preparation method and application of modified polyurethane emulsion with high acrylic acid content - Google Patents
Preparation method and application of modified polyurethane emulsion with high acrylic acid content Download PDFInfo
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- CN116102695A CN116102695A CN202310012341.XA CN202310012341A CN116102695A CN 116102695 A CN116102695 A CN 116102695A CN 202310012341 A CN202310012341 A CN 202310012341A CN 116102695 A CN116102695 A CN 116102695A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
- C08F290/067—Polyurethanes; Polyureas
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
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- C08F2/30—Emulsion polymerisation with the aid of emulsifying agents non-ionic
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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Abstract
The invention discloses a preparation method and application of modified polyurethane emulsion with high acrylic acid content, wherein the method comprises the following steps: adding polymer polyol a, polyisocyanate b, a hydrophilic chain extender c, a non-hydrophilic alcohol chain extender d, a nonionic hydrophilic compound e containing NCO reactive groups and part of acrylic monomer f into a prepolymerization reactor, and reacting to obtain an NCO-terminated prepolymer; adding part of acrylic monomer f and a neutralizing agent, and mixing; dripping part of emulsifier solution, uniformly dispersing, and then adding polyamine to perform chain extension reaction to obtain coarse emulsion a; 4) Under the high-speed shearing condition, adding the rest acrylic ester monomer f and an emulsifier into the coarse emulsion a to obtain coarse emulsion b with high acrylic acid content; 5) Transferring the crude emulsion b into a polymerization kettle, initiating polymerization, cooling and filtering to obtain the modified polyurethane emulsion.
Description
Technical Field
The invention relates to a modified polyurethane emulsion, in particular to a preparation method and application of a modified polyurethane emulsion with high acrylic acid content.
Background
The clear primer for the outer coating of the solid wood furniture mainly comprises an oily UV clear primer and a water-based clear primer. The traditional oily UV coating can improve the performance of a coating film by adding a diluent to regulate the rheology and the viscosity due to higher viscosity of the oligomer. The added diluent comprises reactive diluent monomers or cross-linking agents, has strong irritation to eyes, and is easy to cause allergy when contacted with skin, thus affecting the health of operators. The water-based clear primer uses water as a dispersion medium, so that compared with the oily UV clear primer, the water-based clear primer has the advantages of no toxicity, difficult combustion, no environmental pollution, energy saving, safety, reliability and the like, and becomes a development trend in recent years.
In addition, in the application of the outer coating of the solid wood furniture, the acrylic emulsion is more prone to be formed in resin selection due to the limitation of finished products, but the pure acrylic emulsion is low in film forming fullness, and the polyurethane emulsion is good in adhesive force, good in fullness and poor in water resistance and weather resistance, so that the acrylic modified polyurethane has the low cost of the acrylic emulsion and the good toughness of the polyurethane emulsion, and the good coating fullness.
In order to obtain better coating effect, the solid wood furniture industry usually performs multiple lacquering and undergoes multiple manual polishing of lacquer surfaces during the period to enhance the luxurious log highlight effect, which requires that the acrylic acid content in the modified polyurethane emulsion is as high as possible, and simultaneously ensures that the appearance of the product is transparent and stable and does not slag, which has quite difficulty for those skilled in the art to prepare the aqueous modified polyurethane emulsion with high acrylic acid content.
The patent CN105315415A provides a high-carboxylic acid content water-based acrylic acid modified polyurethane emulsion, a polyurethane oligomer is prepared and then is blocked by a hydroxy acrylic acid monomer, the obtained macromer M is subjected to free radical copolymerization with an acrylic acid monomer, a hydroxy monomer containing functional groups or a carboxylic acid monomer in a solvent to obtain an acrylic acid modified polyurethane polymer with a grafted structure, and finally, alkali is added for neutralization and water is added dropwise for phase inversion to obtain an acrylic acid modified polyurethane water dispersion. However, the process still adopts acetone as a solvent, so that the environmental protection performance is poor; and the solid content of the emulsion can only be 30%, so that the economical efficiency is poor.
Disclosure of Invention
In order to solve the technical problems, the invention provides a preparation method and application of modified polyurethane emulsion with high acrylic acid content. The invention can stably prepare the modified polyurethane emulsion with high acrylic acid content on the premise of not adding solvent, and can obtain excellent manual polishing performance of a paint film.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
a preparation method of modified polyurethane emulsion with high acrylic acid content comprises the following steps:
1) Adding polymer polyol a, polyisocyanate b, a hydrophilic chain extender c, a non-hydrophilic alcohol chain extender d, a non-ionic hydrophilic compound e containing NCO reactive groups and part of acrylic monomer f into a prepolymerization reactor, and completing chain extension and end capping reaction at 60-100 ℃ to obtain an NCO-terminated prepolymer;
2) Adding part of acrylic monomer f and neutralizing agent into the NCO-terminated prepolymer, mixing and transferring to a dispersion chain extender;
3) Dropwise adding part of emulsifier solution into a dispersing chain extender, uniformly dispersing, and then adding polyamine for chain extension reaction to obtain coarse emulsion a;
4) Under the high-speed shearing condition, adding the rest acrylic ester monomer f and an emulsifier into the coarse emulsion a to obtain coarse emulsion b with high acrylic acid content;
5) Transferring the crude emulsion b into a polymerization kettle, dropwise adding part of the redox agent 1 at the temperature of 20-40 ℃ in the kettle, controlling the dropwise adding time to be 5-20min, and continuously dropwise adding the rest redox agent 2 after the dropwise adding is finished, wherein the dropwise adding time is 10-40min; cooling and filtering to obtain the modified polyurethane emulsion.
In the process, acrylate monomers are used for replacing solvents in the pre-polymerization stage to obtain narrower number average molecular weight, in addition, a part of acrylate monomers are added in the prior dispersing stage, the dispersing process is completed after an anionic and nonionic emulsifier is added, finally, the rest acrylate monomers are continuously added under the high shearing condition to quickly complete swelling, and then polymerization is initiated to prepare modified polyurethane emulsion, so that the modified polyurethane emulsion with high acrylic acid content is obtained on the premise of not using solvents.
In step 1), as a preferred embodiment of the present invention, the raw materials are used in the following amounts in parts by mass:
90 to 120 parts, preferably 100 to 110 parts,
60 to 80 parts, preferably 65 to 75 parts,
10 to 20 parts, preferably 11 to 15 parts,
0.1 to 3 parts, preferably 2 to 3 parts,
0.1 to 3 parts, preferably 1 to 2 parts,
10 to 45 parts, preferably 20 to 30 parts,
in the step 2), the dosage of the acrylic monomer f is 100-200 parts by mass, preferably 150-170 parts by mass; the dosage of the neutralizing agent is 5-15 parts by mass, preferably 8-10 parts by mass;
in step 3), the amount of the emulsifier is 5-15 parts by mass, preferably 8-10 parts by mass; the consumption of the polyamine is 2-5 parts by mass, preferably 2-4 parts by mass;
in the step 4), the dosage of the acrylic monomer f is 40-70 parts by mass, preferably 50-60 parts by mass; the dosage of the emulsifier is 3-10 parts by mass, preferably 3-5 parts by mass;
in step 5), the amount of the redox agent 1 used is 0.08 to 0.30 parts by mass, preferably 0.10 to 0.20 parts by mass; the amount of the redox agent 2 used is 0.65 to 0.85 parts by mass, preferably 0.65 to 0.75 parts by mass.
As a preferred embodiment of the present invention, the polymer polyol a is a polyester polyol and/or a polyether polyol having a functionality of 2 to 4 and a weight average molecular weight of 500 to 4000, preferably one or more of polyether polyol, polytetrahydrofuran diol, polycarbonate diol, polycaprolactone diol, polypropylene diol, poly (1, 4-butylene adipate) diol, poly (neopentyl glycol adipate) diol, poly (hexamethylene adipate) diol, polyglycerol, more preferably one or more of polyether polyol DL2000, polyether polyol DL3000, polyether polyol DL 4000;
preferably, the polyisocyanate b is one or more of an aliphatic diisocyanate and/or an aromatic diisocyanate, preferably toluene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, cyclohexanedimethylene diisocyanate, 4' -dicyclohexylmethane diisocyanate;
preferably, the hydrophilic chain extender c is one or more of a carboxyl diol, a sulfonate diamine and a polyoxyethylene glycol, preferably a carboxyl diol, more preferably dimethylolpropionic acid and/or dimethylolbutyric acid;
preferably, the non-hydrophilic alcohol chain extender d is one or more of aliphatic diols and/or aliphatic triols with molecular weight lower than 500, preferably 1, 2-propanediol, 1, 4-butanediol, 1, 5-pentanediol, neopentyl glycol, diethylene glycol, trimethylolpropane;
preferably, the nonionic hydrophilic compound e is a polyethoxy ether containing one hydroxyl group or amino group, preferably a monofunctional polyoxyethylene ether having a weight average molecular weight of 200-3000 and an ethylene oxide number of 4-200, more preferably a monomethyl polyoxyethylene ether having a weight average molecular weight of 500-3000 and an ethylene oxide number of 12-75, and still more preferably polyethylene glycol monomethyl ether.
As a preferred embodiment of the present invention, the acrylic monomer f is one or more of hydroxyethyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, butyl methacrylate, phenyl methacrylate, ethyl acrylate, butyl acrylate, and trimethacrylate; preferably, the acrylic monomer f in the step 1) at least comprises 30wt% of hydroxyethyl acrylate, hydroxyl groups contained in the hydroxyethyl acrylate can react with NCO groups at the end of polyurethane molecules to achieve a partial end-capping effect, so that the relative molecular mass of a pre-polymerized chain segment is smaller, the relative movement of the chain segment is easier in a subsequent shearing and emulsifying process, the chain segment is easier to wind into groups, and the shearing and emulsifying process is easier to realize, meanwhile, the hydroxyethyl acrylate is introduced into the polyurethane chain segment, and double bond groups contained in the hydroxyethyl acrylate can be subjected to free radical polymerization with other added acrylic monomers in a subsequent free radical polymerization process, so that the acrylic ester copolymerization modification is really completed from the molecular design, the polymerization process is more stable, and the application performance is more excellent.
Preferably, the neutralizing agent is one or more of triethylamine, triethanolamine, tripropylamine, ammonia water, sodium hydroxide, potassium hydroxide and dimethylethanolamine.
As a preferred embodiment of the present invention, the emulsifier is an anionic nonionic emulsifier having a molecular weight of less than 1 ten thousand, preferably one or more of sodium dodecyl sulfate SDS, sodium dodecyl benzene sulfonate SDBS, ethoxylated sodium alkyl sulfate salt CM30, isomeric tridecyl alcohol sodium sulfate salt 2030S, rhamnolipid, more preferably rhamnolipid;
preferably, one or more of the polyamines ethylenediamine, 1,6 hexamethylenediamine, 4-dicyclohexylmethane diamine, isophorone diamine, diethylenetriamine.
As a preferred embodiment of the present invention, the redox agent 1 and the redox agent 2 are each independently selected from at least one of t-butyl hydroperoxide, t-amyl hydroperoxide, sodium bisulphite, sodium dithionite and erythorbic acid, preferably t-butyl hydroperoxide and/or erythorbic acid.
As a preferred embodiment of the invention, the NCO prepolymer at the end in the step 2) is firstly cooled to 60-70 ℃ before the acrylic monomer f is added;
preferably, in the step 3), the dripping time of the emulsifier solution is controlled to be 10-30min; the reaction temperature after adding polyamine is 25-40 deg.c and the reaction time is 5-20min.
In step 4), as a preferred embodiment of the present invention, the high-speed shearing conditions are: stirring at 1500-3000rpm for 5-10min.
In addition, in the emulsion preparation process provided by the invention, a polymerization catalyst, a polymerization inhibitor and the like can be optionally added. Wherein the catalyst may be selected from the group consisting of bis-dimethylaminoethyl ether, pentamethyldiethylenetriamine, dimethylcyclohexylamine, dibutyltin dilaurate, organobismuth, triazine trimerization catalysts, preferably dibutyltin dilaurate and organobismuth, to promote the reaction of hydroxyl groups and isocyanate, or to ensure that the reaction reaches an end point; the polymerization inhibitor is selected from hydroquinone, hydroquinone methyl ether, dibutyl dithiocarbamic acid copper, phenothiazine, piperidinol, copper salt, manganese acetate, preferably piperidinol and hydroquinone methyl ether, so as to avoid self-polymerization of each monomer in the long-time reaction process and further reduce the reaction conversion rate.
Preferably, the catalyst is used in an amount of 300 to 800ppm based on the total mass of polymer polyol a, polyisocyanate b, non-hydrophilic alcohol chain extender d and non-ionic hydrophilic compound e in step 1;
preferably, the polymerization inhibitor is used in an amount of 300 to 500ppm based on the total mass of the acrylic monomer f in step 1;
as a preferred embodiment of the present invention, the modified polyurethane emulsion has a solid content of not less than 40%, preferably 40 to 42% by weight, a pH of 6 to 10 and a particle diameter of 50 to 150nm.
The application of the modified polyurethane emulsion with high acrylic acid content prepared by the method in the field of solid wood furniture coating.
The preparation method of the modified polyurethane emulsion provided by the invention has the following advantages:
1. the invention does not use solvent in the production process, saves the production cost, is green and environment-friendly in production, and eliminates the safety risk brought by the solvent in the production process.
2. According to the invention, the acrylic ester monomer is added for three times, so that the highest acrylic acid content allowed by the formula is achieved, and excellent manual polishing performance is ensured.
3. The anionic and nonionic emulsifier, especially the rhamnolipid, is used for carrying out phase transition dispersion, so that the problem of solvent-free dispersion is solved, meanwhile, the addition of the emulsifier is added after dispersion, so that the final emulsion has small particle size and transparent appearance, and the yellow color of the rhamnolipid appears in the emulsion, thereby bringing the orange-yellow appearance to the emulsion and being favored by customers in the field of solid wood processing.
4. The oxidation-reduction agent is dropwise added in sections, so that normal initiation of the early-stage explosion polymerization reaction is ensured, the problems of high slag tapping and fineness caused by the traditional explosion polymerization process are solved, and the filtering of the 1250-mesh filter bag of the emulsion is smooth, and the fineness is extremely low.
Detailed Description
The invention will now be further illustrated by means of specific examples which are given solely by way of illustration of the invention and do not limit the scope thereof.
The following examples of the present invention relate to the following main raw material information:
TABLE 1 Main raw Material information
Other materials and reagents, unless otherwise specified, can be purchased from commercial sources.
[ example 1 ]
(1) 100g of DL2000 (Mw=2000), 65.6g of IPDI, 13.5g of DMPA, 2.29g of BDO, 2g of polyethylene glycol monomethyl ether (Mw=1200), 30g of MMA, 10g of HEA, 0.08g of BI8108 and 0.02g of TEMPO are put into a prepolymerization reactor and reacted at 75 ℃ until NCO reaches the theoretical value of 2.88%, to obtain a terminal NCO prepolymer.
(2) The NCO-terminated prepolymer is cooled to 60 ℃, 161g of MMA and 9g of DMEA are added, and the mixture is transferred to a dispersing chain extender after being uniformly mixed.
(3) 344g of water and 10g of rhamnolipid are mixed to obtain an emulsifier solution, the emulsifier solution is dripped into a dispersing chain extender kettle within 10min, the temperature of the kettle is controlled to be 30 ℃ after uniform dispersion, 3g of ethylenediamine and 1.6g of diethylenetriamine are added for chain extension reaction, and crude emulsion a is obtained after the reaction for 10 min;
(4) Adding the rest 60g MMA, 30g water and 5g rhamnolipid into the crude emulsion a for 5min under the high-speed shearing condition with the stirring rotating speed of 1500rpm to prepare an emulsifier solution, so as to obtain a crude emulsion b with high acrylic acid content;
(5) Transferring the crude emulsion b into a polymerization kettle, controlling the temperature in the kettle to be 30 ℃, synchronously dripping 1.1g of 10% concentration TBHP solution and 7.83g of 1% concentration sodium metabisulfite solution into the polymerization kettle in 5min, gradually and obviously raising the temperature in the kettle, and synchronously dripping 4.4g of 10% concentration t-BHP aqueous solution and 31.32g of 1% concentration sodium metabisulfite aqueous solution into the polymerization kettle in 30min without performing temperature control treatment after the temperature reaches the highest temperature, so as to complete the residue elimination list. Cooling after the reaction is finished, and filtering the emulsion by using a 1250-mesh filter bag to obtain the modified polyurethane emulsion.
In the modified polyurethane emulsion prepared in the embodiment, the emulsion solid content is 40wt%, the particle size is 75nm, and the pH is 7.9; the slag filtered through a 100-mesh metal screen had a content of 13ppm and a fineness of 5. Mu.m.
[ examples 2 to 8 ]
Modified polyurethane emulsion having a solids content of 40wt% was prepared according to substantially the same process conditions as in example 1, except that the raw materials and amounts thereof, and process parameters were different in table 2:
TABLE 2 raw materials and amounts (g) thereof, process parameters in each example
Comparative example 1
A modified polyurethane emulsion was prepared in substantially the same manner as in example 1, except that the anionic non-ionic emulsifier rhamnolipid in step (3) was replaced with a non-ionic polyether emulsifier LCN407 of the same mass.
In the process of the comparative example, in the dispersing process of the step (3), the emulsion phase is difficult to change, and the material is obviously thickened, so that the dispersing failure is indicated.
Comparative example 2
A modified polyurethane emulsion was prepared in substantially the same manner as in example 1, except that the MMA content in step (2) was adjusted to 221g, and step (4) was removed, whereby the crude emulsion a obtained in step (3) was directly transferred to the polymerization vessel in step (5) to conduct the initiation polymerization.
In the process of the comparative example, in the dispersion process of the step (3), the phase transition viscosity of the emulsion is huge, and 150g of water is additionally added to obtain a coarse emulsion. The modified polyurethane emulsion prepared in this comparative example is extremely difficult in the filtration and deslagging process.
[ comparative example 3 ]
A modified polyurethane emulsion was prepared in substantially the same manner as in example 1 except that step (4) was omitted, and the crude emulsion a obtained in step (3) was directly transferred to the polymerization vessel in step (5) to carry out the initiation polymerization, to obtain a modified polyurethane emulsion having a relatively low acrylic acid content.
[ comparative example 4 ]
A modified polyurethane emulsion was prepared in substantially the same manner as in example 1, except that the modification of step (5) was: transferring the crude emulsion b into a polymerization kettle, controlling the temperature in the kettle to be 30 ℃, synchronously dripping 5.5g of 10% concentration TBHP water solution and 39.15g of 1% concentration sodium metabisulfite water solution into the polymerization kettle in 5min, cooling after the reaction is finished when the temperature in the kettle is not increased, and filtering the emulsion by using a 1250-mesh filter bag to obtain the modified polyurethane emulsion.
The modified polyurethane emulsions prepared in each example and comparative example were tested in Table 3 and the results were as follows:
TABLE 3 emulsion parameter test
[ application example ]
Using the modified polyurethane emulsions provided in each example, comparative example, different test varnishes were prepared according to the varnish formulations in Table 4.
Table 4, varnish formulation
| Polyurethane emulsion | 80g | |
| Organosilicon defoamer BYK-024 | 0.4g | Bi Ke |
| Wetting agent Tego-245 | 0.3g | Digao (Digao) |
| Wetting agent Tego-270 | 0.3g | Digao (Digao) |
| Propylene glycol methyl ether | 4g | Ceramic' s |
| Dipropylene glycol butyl ether | 4g | Ceramic' s |
| Polyurethane thickener U605 | 0.4g | Vanilla thickening agent |
| Water and its preparation method | 10.6g | / |
| Totalizing | 100g |
Spraying the prepared varnishes on oak boards with the spraying amount of 80g/m 2 Baking at 50deg.C for 30min, taking out, standing at room temperature, and polishing with 400 mesh sand paper for 50 times. And (3) grading the paint film state after polishing according to the difficulty degree of skin breaking, the powder discharge amount, the sand-sticking paper degree and the polishing, wherein each test is sequentially divided into 1-5 minutes from poor to excellent, and 3 minutes are qualified. The test results are shown in table 5:
TABLE 5 test results of the abrasion resistance of paint films
The foregoing is merely a preferred embodiment of the present invention, and it should be noted that modifications and additions may be made to those skilled in the art without departing from the method of the present invention, which modifications and additions are also to be considered as within the scope of the present invention.
Claims (10)
1. The preparation method of the modified polyurethane emulsion with high acrylic acid content is characterized by comprising the following steps:
1) Adding polymer polyol a, polyisocyanate b, a hydrophilic chain extender c, a non-hydrophilic alcohol chain extender d, a non-ionic hydrophilic compound e containing NCO reactive groups and part of acrylic monomer f into a prepolymerization reactor, and completing chain extension and end capping reaction at 60-100 ℃ to obtain an NCO-terminated prepolymer;
2) Adding part of acrylic monomer f and neutralizing agent into the NCO-terminated prepolymer, mixing and transferring to a dispersion chain extender;
3) Dropwise adding part of emulsifier solution into a dispersing chain extender, uniformly dispersing, and then adding polyamine for chain extension reaction to obtain coarse emulsion a;
4) Under the high-speed shearing condition, adding the rest acrylic ester monomer f and an emulsifier into the coarse emulsion a to obtain coarse emulsion b with high acrylic acid content;
5) Transferring the crude emulsion b into a polymerization kettle, dropwise adding part of the redox agent 1 at the temperature of 20-40 ℃ in the kettle, controlling the dropwise adding time to be 5-20min, and continuously dropwise adding the rest redox agent 2 after the dropwise adding is finished, wherein the dropwise adding time is 10-40min; cooling and filtering to obtain the modified polyurethane emulsion.
2. The method for preparing a modified polyurethane emulsion with high acrylic acid content according to claim 1, wherein in the step 1), the raw materials are respectively as follows in parts by mass:
90 to 120 parts, preferably 100 to 110 parts,
60 to 80 parts, preferably 65 to 75 parts,
10 to 20 parts, preferably 11 to 15 parts,
0.1 to 3 parts, preferably 2 to 3 parts,
0.1 to 3 parts, preferably 1 to 2 parts,
10 to 45 parts, preferably 20 to 30 parts,
in the step 2), the dosage of the acrylic monomer f is 100-200 parts by mass, preferably 150-170 parts by mass; the dosage of the neutralizing agent is 5-15 parts by mass, preferably 8-10 parts by mass;
in step 3), the amount of the emulsifier is 5-15 parts by mass, preferably 8-10 parts by mass; the consumption of the polyamine is 2-5 parts by mass, preferably 2-4 parts by mass;
in the step 4), the dosage of the acrylic monomer f is 40-70 parts by mass, preferably 50-60 parts by mass; the dosage of the emulsifier is 3-10 parts by mass, preferably 3-5 parts by mass;
in step 5), the amount of the redox agent 1 used is 0.08 to 0.30 parts by mass, preferably 0.10 to 0.20 parts by mass; the amount of the redox agent 2 used is 0.65 to 0.85 parts by mass, preferably 0.65 to 0.75 parts by mass.
3. The method for preparing the modified polyurethane emulsion with high acrylic content according to claim 2, wherein the polymer polyol a is one or more of polyester polyol and/or polyether polyol with functionality of 2-4 and weight average molecular weight of 500-4000, preferably polyether polyol, polytetrahydrofuran glycol, polycarbonate diol, polycaprolactone diol, polypropylene glycol, poly (1, 4-butylene glycol adipate) diol, poly (neopentyl glycol adipate) diol, poly (hexamethylene adipate) diol, polyglycerol, more preferably one or more of polyether polyol DL2000, polyether polyol DL3000, polyether polyol DL 4000;
preferably, the polyisocyanate b is one or more of an aliphatic diisocyanate and/or an aromatic diisocyanate, preferably toluene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, cyclohexanedimethylene diisocyanate, 4' -dicyclohexylmethane diisocyanate;
preferably, the hydrophilic chain extender c is one or more of a carboxyl diol, a sulfonate diamine and a polyoxyethylene glycol, preferably a carboxyl diol, more preferably dimethylolpropionic acid and/or dimethylolbutyric acid;
preferably, the non-hydrophilic alcohol chain extender d is one or more of aliphatic diols and/or aliphatic triols with molecular weight lower than 500, preferably 1, 2-propanediol, 1, 4-butanediol, 1, 5-pentanediol, neopentyl glycol, diethylene glycol, trimethylolpropane;
preferably, the nonionic hydrophilic compound e is a polyethoxy ether containing one hydroxyl group or amino group, preferably a monofunctional polyoxyethylene ether having a weight average molecular weight of 200-3000 and an ethylene oxide number of 4-200, more preferably a monomethyl polyoxyethylene ether having a weight average molecular weight of 500-3000 and an ethylene oxide number of 12-75, and still more preferably polyethylene glycol monomethyl ether.
4. The method for preparing the modified polyurethane emulsion with high acrylic acid content according to any one of claims 1 to 3, wherein the acrylic monomer f is one or more of hydroxyethyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, butyl methacrylate, phenyl methacrylate, ethyl acrylate, butyl acrylate and trimethyl acrylate; preferably, the acrylic monomer f in step 1) comprises at least 30% by weight of hydroxyethyl acrylate;
preferably, the neutralizing agent is one or more of triethylamine, triethanolamine, tripropylamine, ammonia water, sodium hydroxide, potassium hydroxide and dimethylethanolamine.
5. The method for preparing a modified polyurethane emulsion with high acrylic acid content according to claim 4, wherein the emulsifier is an anionic nonionic emulsifier with molecular weight lower than 1 ten thousand, preferably one or more of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, ethoxylated alkyl sodium sulfate, isomeric tridecyl alcohol sodium sulfate and rhamnolipid, more preferably rhamnolipid;
preferably, one or more of the polyamines ethylenediamine, 1,6 hexamethylenediamine, 4-dicyclohexylmethane diamine, isophorone diamine, diethylenetriamine.
6. The method for producing a modified polyurethane emulsion having a high acrylic acid content according to claim 4, wherein the redox agent 1 and the redox agent 2 are each independently at least one selected from the group consisting of t-butyl hydroperoxide, t-amyl hydroperoxide, sodium bisulphite, sodium dithionite and isoascorbic acid, preferably t-butyl hydroperoxide and/or isoascorbic acid.
7. The method for preparing a modified polyurethane emulsion with high acrylic acid content according to any one of claims 1 to 6, wherein the terminal NCO prepolymer in step 2) is cooled to 60 to 70 ℃ before adding the acrylic monomer f;
preferably, in the step 3), the dripping time of the emulsifier solution is controlled to be 10-30min; the reaction temperature after adding polyamine is 25-40 deg.c and the reaction time is 5-20min.
8. The process for preparing a modified polyurethane emulsion having a high acrylic content as claimed in claim 7, wherein in step 4), the high-speed shearing conditions are: stirring at 1500-3000rpm for 5-10min.
9. The method for producing a modified polyurethane emulsion having a high acrylic content according to any one of claims 1 to 8, wherein the modified polyurethane emulsion has a solid content of not less than 40%, preferably 40 to 42% by weight, a pH of 6 to 10 and a particle diameter of 50 to 150nm.
10. Use of the modified polyurethane emulsion with high acrylic acid content prepared by the method of any one of claims 1 to 9 in the field of solid wood furniture coating.
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