CN109912766B - Waterborne self-extinction acrylic ester modified polyurethane resin and preparation method thereof - Google Patents
Waterborne self-extinction acrylic ester modified polyurethane resin and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a waterborne self-extinction acrylic ester modified polyurethane resin and a preparation method thereof, and the resin aims to solve the technical problems that the storage stability of the coating is poor, the polishing resistance of the coating is poor, the transparency of the coating is reduced, the temperature resistance and the brittleness are poor and the like due to the performance reduction of the coating caused by the process of adding an extinction agent into the existing extinction coating; the resin comprises the following raw materials in parts by weight: 25-50 parts of functional monomer, 15-50 parts of monomer, 1-10 parts of emulsifier, 0.1-5 parts of initiator, 50-100 parts of deionized water, 15-65 parts of polyisocyanate, 8-30 parts of polyol, 0.015-0.2 part of catalyst, 10-50 parts of solvent and 1-10 parts of blocking agent. The resin prepared by the technical scheme of the invention has excellent solvent resistance, acid resistance, alkali resistance and wear resistance, and can ensure the soft and elastic touch of external water while having excellent temperature resistance.
Description
Technical Field
The invention relates to the field of waterborne polyurethane resin, in particular to waterborne self-extinction acrylate modified polyurethane resin and a preparation method thereof.
Background
Along with the improvement of living standard of people, people have higher and higher living requirements, and the external sense of things also needs to be more and more fashionable, and the sense of simplicity can not be limited to use, the change of the aesthetic perception takes the surface decoration with matte touch as an example, and the product of the emerging surface decoration is more and more popular with consumers nowadays. At present, the matte resin appearing on the market has the traditional resin added with matte auxiliary agents, such as matte powder, micro-powder wax and the like, and also has the resin simply prepared by polyurethane dispersion; the existing method for preparing the water-based matte paint adopts a physical addition of a flatting agent, so that the prepared matte coating is poor in brittleness, and the addition of the flatting agent can cause the performance reduction of the coating, such as poor storage stability of the precipitated coating, poor polishing resistance of the coating, reduced transparency of the coating and the like; meanwhile, matte polyurethane dispersion resin has a great problem in the aspect of temperature resistance, and due to the structural limitation of a polyurethane material, the matte polyurethane dispersion resin also has a great defect in the aspect of temperature resistance, so that a touch matte resin coating is easy to have a coating structure collapse after hot pressing or high-temperature drying after coating, and the whole matte coating is not delustered any more or the gloss of a coating surface is uneven because the original delustering structure is not resistant to temperature.
In order to solve the above technical problems, the practitioner may also make improvements in a way to the best, such as the chinese patent publication No. CN103865031B, which discloses an aqueous polyurethane matting resin, which does not need to add any matting material, has a uniform coating, a good matting effect, and a long service life; the technical scheme is that the composition comprises the following components in parts by weight: 10-18 parts of diisocyanate, 0.5-5 parts of dimethylolpropionic acid (DMPA), 35-60 parts of dihydric alcohol, 0.05-1 part of organic bismuth catalyst, 0.5-5 parts of dimethylethanolamine, 0.5-10 parts of 2- [ (2-aminoethyl) amino ] ethanesulfonic acid sodium salt, 0.5-5 parts of hydrazine hydrate, 1-10 parts of N-methylpyrrolidone solvent and 180 parts of deionized water 104-; the extinction resin of the technical scheme can achieve certain effect, but has the defects of wear resistance, high temperature resistance, weather resistance, water resistance and alkali resistance. Also, as the chinese patent with publication No. CN105694651B, this patent discloses a preparation method of an aqueous self-crosslinking acrylic acid modified polyurethane matte resin, which mainly comprises isocyanate trimer, polyether polyol or polyester polyol, dimethylol propionic acid, acrylic ester, alkali neutralizer and deionized water; the waterborne self-crosslinking acrylic modified polyurethane matte resin can achieve a certain effect, but the resin is wrapped by polyurethane elastic resin through acrylic resin, so that the soft elastic feeling of the polyurethane straight resin completely disappears, and the polyurethane extinction structure is filled from the inner part through the wrapping method, so that the original extinction performance is greatly reduced.
Disclosure of Invention
(1) Technical problem to be solved
Aiming at the defects of the prior art, the invention aims to provide a water-based self-extinction acrylic ester modified polyurethane resin and a preparation method thereof, and the resin aims to solve the technical problems that the storage stability of the coating is poor, the polishing resistance of the coating is poor, the transparency of the coating is reduced, the temperature resistance and the brittleness are poor and the like due to the performance reduction of the coating caused by the addition of a flatting agent in the existing flatting coating; the resin prepared by the technical scheme of the invention has excellent solvent resistance, acid resistance, alkali resistance and wear resistance, and can ensure the soft and elastic touch of external water while having excellent temperature resistance.
(2) Technical scheme
In order to solve the technical problems, the invention provides a waterborne self-extinction acrylate modified polyurethane resin which comprises the following raw materials in parts by weight: 25-50 parts of functional monomer, 15-50 parts of monomer, 1-10 parts of emulsifier, 0.1-5 parts of initiator, 50-100 parts of deionized water, 15-65 parts of polyisocyanate, 8-30 parts of polyol, 0.015-0.2 part of catalyst, 10-50 parts of solvent and 1-10 parts of blocking agent.
Preferably, the resin comprises the following raw materials in parts by weight: 35-50 parts of functional monomer, 15-40 parts of monomer, 1-5 parts of emulsifier, 0.1-2 parts of initiator, 60-100 parts of deionized water, 15-45 parts of polyisocyanate, 15-30 parts of polyol, 0.015-0.2 part of catalyst, 10-50 parts of solvent and 5-10 parts of blocking agent.
Preferably, the functional monomer is one or a mixture of more of dimethylaminopropyl methacrylamide, N-hydroxymethyl acrylamide, tert-butylaminoethyl methacrylate, dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate.
Preferably, the monomer is one or a mixture of acrylic acid monomer, methacrylic acid monomer, hydroxyethyl methacrylate, isobornyl methacrylate, hydroxypropyl methacrylate and styrene.
Further, the acrylic acid monomer is one or a mixture of two of acrylic acid and acrylate, and the methacrylic acid monomer is one or a mixture of two of methacrylic acid and methacrylate.
Further, the acrylic monomer has a structural formula of CH2＝CH-COO-(CH2)n1-H, wherein n1 is an integer from 0 to 6.
Still further, the structural formula of the methacrylate is H2C＝C(CH3)-COO-(CH2)n2-H, wherein n2 is a natural number from 0 to 10.
Preferably, the emulsifier is one or a mixture of more of tween series, span series, isomeric tridecanol polyoxyethylene ether 7, palmityl alcohol polyoxyethylene ether 10, lauryl alcohol polyoxyethylene ether 5 ammonium sulfate, sodium succinate, diisobutyl sodium cai sulfonate, sodium dodecyl benzene sulfonate and sodium dodecyl sulfate.
Further, the tween series is one or a mixture of more of tween-20, tween-21, tween-40, tween-60, tween-61, tween-80, tween-81 and tween-85.
Further, the span series is one or a mixture of more of span-20, span-40 and span-80.
Preferably, the initiator is one or a mixture of two of potassium persulfate and ammonium persulfate.
Preferably, the polyisocyanate is one or a mixture of HDI trimer, IPDI trimer, H12MDI trimer, HDI, IPDI and HMDI.
Preferably, the polyalcohol is one or a mixture of more of Mn600-1200 polyethylene glycol, Mn400-1000 polypropylene oxide diol, Mn500-1000 polytetrahydrofuran diol, Mn500-1500 polycarbonate diol, Mn500-1000 polycaprolactone diol, Mn500-1500 poly adipate diol, Mr1000-2000 phthalic anhydride polyester diol, butanediol, hexanediol, 1, 4 cyclohexanedimethanol and dimethylolpropionic acid.
Preferably, the catalyst is one or a mixture of two of DBTDL and organic bismuth.
Preferably, the end-capping agent is one or a mixture of two of dimethylethanolamine and ethanolamine.
Preferably, the solvent is one or a mixture of two of acetone and butanone.
The invention also provides a preparation method of the waterborne self-extinction acrylate modified polyurethane resin, which is used for preparing the resin and comprises the following specific steps:
step one, preparing a pre-emulsion; dissolving an emulsifier in deionized water, uniformly stirring at the rotation speed of 400-800RPM, adding a functional monomer and a monomer, and emulsifying for 10-60min to obtain a pre-emulsion, wherein the mass of the deionized water used in the step is 40-80% of the total mass of the deionized water in the raw material ratio;
step two, preparing an initiator solution; dissolving an initiator in deionized water to obtain an initiator solution, wherein the mass of the deionized water used in the step is 5-10% of the total mass of the deionized water in the raw material ratio;
step three, preparing acrylic emulsion; adding the rest deionized water into a reaction kettle, heating to 75-80 ℃ at the rotation speed of 400-80 ℃ at 800RPM, simultaneously dropwise adding the pre-emulsion and the initiator solution at a constant speed, completing dropwise adding the pre-emulsion at a constant speed within 1.5-4 hours, completing dropwise adding the initiator solution at a constant speed within 2-4.5 hours, keeping the rotation speed of 400-80 RPM in the dropwise adding process, controlling the temperature to be 75-80 ℃, keeping the temperature to be 75-85 ℃ for 0.5-2 hours after completing dropwise adding the pre-emulsion and the initiator solution, heating to 85-95 ℃ for 0.5-3 hours, and cooling to 40-50 ℃ to obtain the acrylic emulsion containing amino groups;
step four, adding the polyhydric alcohol into the reaction kettle, heating to 110-2Cooling to 80 ℃, adding polyisocyanate and a catalyst, reacting for 2-3h under heat preservation, then heating to 90-95 ℃ for 0.5-2h, adding a solvent in the reaction process in a batch manner (the solvent is added in the step to reduce the viscosity of the system and ensure the reaction to be carried out quickly), and obtaining a prepolymer with an isocyanate group as a tail end after the reaction is finished;
and step five, adding the acrylic emulsion obtained in the step three into a high-speed dispersion machine with the rotation speed of 1000-2000RPM, adding the prepolymer obtained in the step four into the dispersion machine for chain extension, adding an end-capping agent for reaction for 0.5h after the chain extension is finished, starting vacuumizing, removing the solvent under vacuum, and cooling to room temperature to obtain the waterborne self-extinction acrylic ester modified polyurethane resin.
(3) Advantageous effects
Compared with the prior art, the invention has the beneficial effects that: the waterborne self-extinction acrylate modified polyurethane resin prepared by the invention has the advantages that the plate surface gloss is dull, the waterborne self-extinction acrylate modified polyurethane resin has excellent solvent resistance, acid resistance, alkali resistance and wear resistance, the obtained polyurethane resin taking acrylic acid as a framework has excellent temperature resistance, the excellent waterborne soft elastic touch of polyurethane cannot be lost, and finally the shell layer with high-hardness high-TG core and soft skin feeling is obtained, so that the prepared coating has excellent skin feeling while the extinction performance is ensured; in addition, the excellent temperature resistance of the coating is utilized, so that the gloss uniformity can be ensured under the conditions of hot pressing or hot stamping and the like, the original soft touch feeling is kept, and the coating can be widely applied to water-based plastic coatings, water-based leather coatings, water-based soft-feeling paper coatings and the like; in addition, the preparation method disclosed by the invention is simple in process and suitable for large-scale production.
Detailed Description
In order to make the technical means, the original characteristics, the achieved purposes and the effects of the invention easily understood and obvious, the technical scheme in the embodiment of the invention is clearly and completely described below to further illustrate the invention, and obviously, the embodiment described is only a part of the embodiment of the invention, but not a whole pattern.
Example 1
The specific embodiment is a formula of waterborne self-extinction acrylate modified polyurethane resin, and the raw material of the resin comprises: 25kg of dimethylaminopropyl methacrylamide, 50kg of acrylic monomer, 1kg of tween-20, 5kg of potassium sulfate, 50kg of deionized water, 65kg of HDI tripolymer, 8kg of Mn600-1200 polyethylene glycol, 0.2kg of organic bismuth, 10kg of butanone and 10kg of ethanolamine.
The formula is processed, and the processing steps are as follows:
step one, preparing a pre-emulsion; dissolving an emulsifier in deionized water, uniformly stirring at the rotating speed of 400RPM, adding a functional monomer and a monomer, and emulsifying for 60min to obtain a pre-emulsion, wherein the mass of the deionized water used in the step is 40% of the total mass of the deionized water in the raw material ratio;
step two, preparing an initiator solution; dissolving an initiator in deionized water to obtain an initiator solution, wherein the mass of the deionized water used in the step is 5% of the total mass of the deionized water in the raw material ratio;
step three, preparing acrylic emulsion; adding the rest deionized water into a reaction kettle, heating to 80 ℃ at the rotation speed of 400RPM, simultaneously dropwise adding a pre-emulsion and an initiator solution at a constant speed, completing dropwise adding the pre-emulsion at a constant speed for 1.5-4 hours, completing dropwise adding the initiator solution at a constant speed for 2 hours, keeping the rotation speed of 800RPM in the dropwise adding process, controlling the temperature to be 75 ℃, keeping the temperature at 85 ℃ for 0.5 hour after completing dropwise adding the pre-emulsion and the initiator solution, heating to 95 ℃ for 0.5 hour, and cooling to 50 ℃ to obtain an acrylic emulsion containing amino groups;
step four, adding the polyhydric alcohol into the reaction kettle, heating to 110 ℃, starting to vacuumize, dehydrating for 4 hours in vacuum, and then filling N2Cooling to 80 ℃, adding polyisocyanate and a catalyst, reacting for 3 hours under heat preservation, then heating to 90 ℃ again, reacting for 2 hours, adding a solvent in the reaction process in a batch manner (the solvent is added in the step to reduce the viscosity of the system and ensure the reaction to be carried out quickly), and obtaining a prepolymer with an isocyanate group as a tail end after the reaction is finished;
and step five, adding the acrylic emulsion obtained in the step three into a high-speed dispersion machine with the rotating speed of 1000RPM, adding the prepolymer obtained in the step four into the dispersion machine for chain extension, adding an end-capping reagent for reaction for 0.5h after the chain extension is finished, starting vacuumizing, removing the solvent under vacuum, and then cooling to room temperature to obtain the waterborne self-extinction acrylic ester modified polyurethane resin sample 1.
Example 2
The specific embodiment is a formula of waterborne self-extinction acrylate modified polyurethane resin, and the raw material of the resin comprises: 40 kg of tert-butyl aminoethyl methacrylate, 30kg of methacrylic acid, 3kg of sodium dodecyl benzene sulfonate, 1kg of potassium sulfate, 80kg of deionized water, 30kg of H12MDI tripolymer, 23kg of Mn500-1000 polycaprolactone diol, 0.1kg of DBTDL, 30kg of acetone and 8kg of dimethylethanolamine.
The formula is processed, and the processing steps are as follows:
step one, preparing a pre-emulsion; dissolving an emulsifier in deionized water, uniformly stirring at the rotating speed of 800RPM, adding a functional monomer and a monomer, and emulsifying for 10min to obtain a pre-emulsion, wherein the mass of the deionized water used in the step is 80% of the total mass of the deionized water in the raw material ratio;
step two, preparing an initiator solution; dissolving an initiator in deionized water to obtain an initiator solution, wherein the mass of the deionized water used in the step is 10% of the total mass of the deionized water in the raw material ratio;
step three, preparing acrylic emulsion; adding the rest deionized water into a reaction kettle, heating to 75 ℃ at the rotating speed of 800RPM, simultaneously dropwise adding a pre-emulsion and an initiator solution at a constant speed, dropwise adding the pre-emulsion at a constant speed for 4 hours, dropwise adding the initiator solution at a constant speed for 2 hours, keeping the rotating speed of 800RPM in the dropwise adding process, controlling the temperature to be 75 ℃, keeping the temperature at 85 ℃ for 0.5 hour after dropwise adding the pre-emulsion and the initiator solution, heating to 95 ℃ for 0.5 hour, and cooling to 50 ℃ to obtain an acrylic emulsion containing amino groups;
step four, adding the polyhydric alcohol into the reaction kettle, heating to 130 ℃, starting to vacuumize, dehydrating for 4 hours in vacuum, and then filling N2Cooling to 80 ℃, adding polyisocyanate and a catalyst, reacting for 2 hours in a heat preservation way, then heating to 95 ℃ for 0.5 hour, adding a solvent in the reaction process in an intermittent way (the solvent is added in the step to reduce the viscosity of the system and ensure the reaction to be carried out quickly), and obtaining a prepolymer with an isocyanate group as a tail end after the reaction is finished;
and step five, adding the acrylic emulsion obtained in the step three into a high-speed dispersion machine with the rotating speed of 2000RPM, adding the prepolymer obtained in the step four into the dispersion machine for chain extension, adding an end-capping reagent for reaction for 0.5h after the chain extension is finished, starting vacuumizing, removing the solvent in vacuum, and cooling to room temperature to obtain the waterborne self-extinction acrylic ester modified polyurethane resin sample 2.
Example 3
The specific embodiment is a formula of waterborne self-extinction acrylate modified polyurethane resin, and the raw material of the resin comprises: 50kg of diethylaminoethyl methacrylate, 15kg of hydroxypropyl methacrylate, 10kg of tween-80, 0.1kg of ammonium persulfate, 100kg of deionized water, 15kg of HMDI15kg, 30kg of hexanediol, 0.015kg of DBTDL, 50kg of acetone and 1kg of dimethylethanolamine.
The formula is processed, and the processing steps are as follows:
step one, preparing a pre-emulsion; dissolving an emulsifier in deionized water, uniformly stirring at the rotating speed of 600RPM, adding a functional monomer and a monomer, and emulsifying for 40min to obtain a pre-emulsion, wherein the mass of the deionized water used in the step is 60% of the total mass of the deionized water in the raw material ratio;
step two, preparing an initiator solution; dissolving an initiator in deionized water to obtain an initiator solution, wherein the mass of the deionized water used in the step is 8% of the total mass of the deionized water in the raw material ratio;
step three, preparing acrylic emulsion; adding the rest deionized water into a reaction kettle, heating to 78 ℃ at the rotating speed of 600RPM, simultaneously dropwise adding a pre-emulsion and an initiator solution at a constant speed, finishing dropwise adding the pre-emulsion at a constant speed for 3 hours, finishing dropwise adding the initiator solution at a constant speed for 3 hours, keeping the rotating speed of 600RPM in the dropwise adding process, controlling the temperature to 78 ℃, keeping the temperature at 80 ℃ for 1 hour after finishing dropwise adding the pre-emulsion and the initiator solution, heating to 90 ℃ for 2 hours, and cooling to 45 ℃ to obtain an acrylic emulsion containing amino groups;
step four, adding the polyhydric alcohol into the reaction kettle, heating to 120 ℃, starting to vacuumize, dehydrating for 4 hours in vacuum, and then filling N2Cooling to 80 ℃, adding polyisocyanate and a catalyst, reacting for 2.5h under heat preservation, then heating to 92 ℃ for 1h, adding a solvent in the reaction process in an intermittent manner (the solvent is added in the step for reducing the viscosity of the system and ensuring the reaction to be carried out quickly), and obtaining a prepolymer with an isocyanate group as a tail end after the reaction is finished;
and step five, adding the acrylic emulsion obtained in the step three into a high-speed dispersion machine with the rotating speed of 1500RPM, adding the prepolymer obtained in the step four into the dispersion machine for chain extension, adding an end-capping reagent for reaction for 0.5h after the chain extension is finished, starting vacuumizing, removing the solvent under vacuum, and then cooling to room temperature to obtain the waterborne self-extinction acrylic ester modified polyurethane resin sample 3.
Experimental detection
The samples 1, 2 and 3 prepared in example 1, 2 and 3 were tested for their properties, as shown in table 1:
TABLE 1
Having thus described the principal technical features and basic principles of the invention, and the advantages associated therewith, it will be apparent to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, but is capable of other embodiments without departing from the spirit or essential characteristics thereof. The present embodiments are, therefore, to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment contains only a single technical solution, and such description of the embodiments is for clarity reasons only, and those skilled in the art should make the description as a whole, and the technical solutions in the embodiments can also be combined appropriately to form other embodiments understood by those skilled in the art.
Claims (7)
1. The waterborne self-extinction acrylic ester modified polyurethane resin is characterized by comprising the following raw materials in parts by mass: 35-50 parts of functional monomer, 15-40 parts of monomer, 1-5 parts of emulsifier, 0.1-2 parts of initiator, 60-100 parts of deionized water, 15-45 parts of polyisocyanate, 15-30 parts of polyol, 0.015-0.2 part of catalyst, 10-50 parts of solvent and 5-10 parts of end capping agent;
the functional monomer is one or a mixture of more of dimethylaminopropyl methacrylamide, tert-butylaminoethyl methacrylate and diethylaminoethyl methacrylate;
the monomer is one or a mixture of acrylic acid monomer, methacrylic acid and hydroxypropyl methacrylate;
when the functional monomer is dimethylaminopropyl methacrylamide or tert-butylaminoethyl methacrylate, the monomer is an acrylic acid monomer or a methacrylic acid monomer;
when the functional monomer is diethylaminoethyl methacrylate, the monomer is hydroxypropyl methacrylate.
2. The waterborne self-extinction acrylic ester modified polyurethane resin as claimed in claim 1, wherein the acrylic monomer is one or a mixture of two of acrylic acid and acrylic ester, and the methacrylic monomer is one or a mixture of two of methacrylic acid and methacrylic ester; the structural formula of the acrylic monomer is CH2=CH-COO-（CH2）n1-H, wherein n1 is an integer from 0 to 6.
3. The waterborne self-extinction acrylic ester modified polyurethane resin as claimed in claim 2, wherein the structural formula of the methacrylate monomer is H2C=C(CH3)-COO-（CH2）n2-H, wherein n2 is a natural number from 0 to 10.
4. The waterborne self-extinction acrylic ester modified polyurethane resin as claimed in claim 1, wherein the emulsifier is one or a mixture of more of tween series, span series, isomeric tridecanol polyoxyethylene ether 7, palmitol polyoxyethylene ether 10, lauryl alcohol polyoxyethylene ether 5 ammonium sulfate, sodium succinate, diisobutyl sodium cai sulfonate, sodium dodecyl benzene sulfonate and sodium dodecyl sulfate.
5. The aqueous self-extinction acrylate modified polyurethane resin according to claim 4, wherein the tween series is one or a mixture of more of tween-20, tween-21, tween-40, tween-60, tween-61, tween-80, tween-81 and tween-85; the span series is one or a mixture of more of span-20, span-40 and span-80.
6. The waterborne self-extinction acrylic ester modified polyurethane resin as claimed in claim 1, wherein the initiator is one or a mixture of two of potassium persulfate and ammonium persulfate; the polyisocyanate is HDI trimer, IPDI trimer, or H12One or a mixture of more of MDI trimer, HDI, IPDI and HMDI; the polyalcohol is one or a mixture of more of Mn600-1200 polyethylene glycol, Mn400-1000 polypropylene oxide diol, Mn500-1000 polytetrahydrofuran diol, Mn500-1500 polycarbonate diol, Mn500-1000 polycaprolactone diol, Mn500-1500 poly adipate diol, Mn1000-2000 phthalic anhydride polyester diol, butanediol, hexanediol, 1, 4-cyclohexanedimethanol and dimethylolpropionic acid; the catalyst is one or a mixture of DBTDL and organic bismuth; the end capping agent is one or a mixture of two of dimethylethanolamine and ethanolamine; the solvent is one or a mixture of two of acetone and butanone.
7. A preparation method of the waterborne self-extinction acrylic ester modified polyurethane resin is characterized in that the method is used for preparing the resin as claimed in any one of claims 1 to 6, and comprises the following specific steps:
step one, preparing a pre-emulsion; dissolving an emulsifier in deionized water, uniformly stirring at the rotation speed of 400-800RPM, adding a functional monomer and a monomer, and emulsifying for 10-60min to obtain a pre-emulsion, wherein the mass of the deionized water used in the step is 40-80% of the total mass of the deionized water in the raw material ratio;
step two, preparing an initiator solution; dissolving an initiator in deionized water to obtain an initiator solution, wherein the mass of the deionized water used in the step is 5-10% of the total mass of the deionized water in the raw material ratio;
step three, preparing acrylic emulsion; adding the rest deionized water into a reaction kettle, heating to 75-80 ℃ at the rotation speed of 400-80 plus 800RPM, simultaneously dropwise adding the pre-emulsion and the initiator solution at a constant speed, completing dropwise adding the pre-emulsion at a constant speed within 1.5-4 hours, completing dropwise adding the initiator solution at a constant speed within 2-4.5 hours, keeping the rotation speed of 400-80 plus 800RPM in the dropwise adding process, controlling the temperature to be 75-80 ℃, keeping the temperature to be 75-85 ℃ after completing dropwise adding the pre-emulsion and the initiator solution, keeping the temperature to be 75-85 ℃ for 0.5-2 hours, heating to 85-95 ℃ for 0.5-3 hours, and cooling to 40-50 ℃ to obtain the acrylic emulsion containing amino groups;
step four, adding the polyhydric alcohol into the reaction kettle, heating to 110-2Cooling to 80 ℃, adding polyisocyanate and a catalyst, reacting for 2-3h under heat preservation, then heating to 90-95 ℃ for 0.5-2h, adding a solvent intermittently during the reaction process, and obtaining a prepolymer with an isocyanate group as a tail end after the reaction is finished;
and step five, adding the acrylic emulsion obtained in the step three into a high-speed dispersion machine with the rotation speed of 1000-2000RPM, adding the prepolymer obtained in the step four into the dispersion machine for chain extension, adding an end-capping agent for reaction for 0.5h after the chain extension is finished, starting vacuumizing, removing the solvent under vacuum, and cooling to room temperature to obtain the waterborne self-extinction acrylic modified polyurethane resin.
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| CN111171272A (en) * | 2020-03-12 | 2020-05-19 | 山东天庆科技发展有限公司 | Novel composite ion solvent-free waterborne polyurethane and preparation method thereof |
| CN112625579A (en) * | 2020-11-27 | 2021-04-09 | 中昊北方涂料工业研究设计院有限公司 | Low-glossiness self-extinction aircraft skin enamel and preparation method thereof |
| CN114672237A (en) * | 2022-02-14 | 2022-06-28 | 广东银洋环保新材料有限公司 | Polyurethane modified acrylic resin, preparation method thereof and wood lacquer |
| CN115260484B (en) * | 2022-07-25 | 2023-05-30 | 万华化学集团股份有限公司 | Preparation method of modified Tween-20 and application of modified Tween-20 in preparation process of vitamin E emulsion |
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