CN114316173B - Organosilicon modified hydroxyl polyacrylate dispersion and preparation method and application thereof - Google Patents
Organosilicon modified hydroxyl polyacrylate dispersion and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of polyurethane coating, and discloses an organosilicon modified hydroxyl polyacrylate dispersion, a preparation method and application thereof. The preparation method comprises the following steps: s1, mixing an acrylic acid monomer, an acrylic ester monomer, a vinyl monomer, an acrylic ester derivative monomer, an organosilicon monomer and an initiator to form a mixed solution A; s2, taking an active diluent, heating, then dropwise adding the mixed solution A, and preserving heat; then cooling, adding an isocyanate bridging agent, controlling the mass content of-NCO, and reacting to obtain a prepolymer; s3, adding a neutralizing agent into the prepolymer, adding water for dispersion, and filtering to obtain the polyurethane foam; the organic silicon monomer is organic silicon monomer containing double bond and no epoxy group. The organosilicon modified hydroxyl polyacrylate dispersoid prepared by the invention has low content of small molecular alcohol, strong storage stability and excellent high-temperature storage resistance; the paint film prepared by the method has quick drying and high hardness.
Description
Technical Field
The invention belongs to the technical field of polyurethane coating, and particularly relates to an organosilicon modified hydroxyl polyacrylate dispersion, a preparation method and application thereof.
Background
The surface of many objects now requires the use of paint for protection, decoration and special functions. Most of the existing wood coatings are solvent-based coatings, and contain more than 50% of organic solvents, the solvents volatilize into the atmosphere to pollute the environment in the construction process, the human health is damaged, and the organic solvents bring potential safety hazards. Therefore, the water-based wood coating is a trend of international coating development. The aqueous wood coating comprises a single-component aqueous wood coating and a double-component aqueous wood coating. The single-component water-based wood coating has larger differences between the water resistance, chemical resistance, hardness and other paint film performances and the oily coating, and severely limits the popularization and application of the water-based wood coating. The mechanical property, water resistance and chemical resistance of the two-component water-based wood coating are equivalent to those of the solvent-based wood coating, and the defect of the single-component water-based wood coating is overcome. Therefore, the two-component water-based wood coating is the first choice of the high-grade water-based wood coating.
The two-component aqueous polyurethane coating has been widely studied and applied because of its excellent coating properties. The two-component water-based polyurethane coating consists of water-based polymer polyol and water-based polyisocyanate curing agent, and is packaged separately and mixed in proportion when in use. The aqueous polymer polyol includes aqueous polyacrylate polyol (also called hydroxyl polyacrylate resin), aqueous polyurethane polyol, aqueous polyester polyol, polyether polyol, mixed polyol, and the like. The aqueous polyacrylate polyol has the advantages of low price, excellent color retention, gloss retention, weather resistance, easy adjustment of molecular weight, glass transition temperature and hydroxyl content and the like, and is an important choice of the aqueous polymer polyol in the existing two-component aqueous polyurethane coating. Both emulsion and dispersion types of polyacrylate polyols can be prepared using different polymerization processes. The emulsion type polyacrylate polyol (hydroxy polyacrylate emulsion) has simple production process and low cost, but has the problems of low hydroxy content, poor transparency, poor leveling property, poor chemical resistance, low hardness and the like of a paint film prepared by mixing the emulsion type polyacrylate polyol with the aqueous polyisocyanate curing agent. In contrast, the dispersion type polyacrylate polyol (hydroxyl polyacrylate dispersion) has higher hydroxyl content, and a paint film prepared by mixing the dispersion type polyacrylate polyol with the aqueous polyisocyanate curing agent has high transparency, good leveling property and excellent water resistance and chemical resistance (but the curing speed is lower than that of the emulsion type polyacrylate polyol). Therefore, there is more room for development of dispersion type polyacrylate polyols in the future.
The dispersion type polyacrylate polyol is also called hydroxyl polyacrylate dispersion, and is called hydroxypropyl dispersion for short. The existing hydroxyl polyacrylate dispersoid still has the problems of low solid content, poor high-temperature storage stability, poor milky appearance and the like, and a paint film prepared by mixing the existing hydroxyl polyacrylate dispersoid with the aqueous polyisocyanate curing agent has the problems of low drying speed, low hardness and the like. The main reason for the above problems is that the polymer macromolecules of the hydroxy polyacrylate dispersion are linear structures and have small molecular weights.
When the molecular weight of the polymer is increased by adopting a conventional synthesis process and adjusting the addition amount of an initiator or a chain transfer agent, the viscosity of the prepolymer of the hydroxy polyacrylate dispersion can be obviously increased, so that the prepolymer cannot be dispersed below the boiling point (100 ℃) of water, and gel can be formed in severe cases. In order to realize the dispersion of the high-viscosity prepolymer, it is reported that the water is added and dispersed at the temperature of more than 100 ℃ by adopting high-pressure equipment abroad, but the method has complex process and higher cost. Therefore, the conventional method cannot well improve the paint film prepared by mixing the hydroxyl polyacrylate dispersion and the aqueous polyisocyanate curing agent, and has the problems of low dry speed, low hardness and the like. There are also methods to increase the dry rate slightly by coating the aqueous dispersion with a metal ion catalyst to promote the reaction of the dispersion polymer with the aqueous polyisocyanate curing agent. However, the method cannot essentially solve the problems of low solid content, poor storage stability, poor milky appearance and the like caused by the small molecular weight of the prepolymer of the hydroxyl polyacrylate dispersion (especially the organosilicon modified hydroxyl polyacrylate dispersion) and the linear structure, and cannot solve the problems of low hardness and the like of a paint film prepared by mixing the hydroxyl polyacrylate dispersion with the aqueous polyisocyanate curing agent. In addition, the metal catalyst also brings problems such as heavy metal pollution and the like.
The method for modifying the hydroxyl polyacrylate dispersoid comprises polyester modification, organosilicon modification, epoxy modification, alkyd modification and the like. When the organic silicon is adopted for modification, the bond energy of Si-O in organic silicon monomer or resin is high, the bond angle is large, the Si-O-Si main chain is soft, the siloxane molecule is in a spiral structure, the methyl group is arranged outwards and rotates around the Si-O chain, the molecular volume is large, and the cohesive energy density is low. Because the organosilicon monomer containing double bond (vinyl) is cheap, the application range is wide, and the organosilicon monomer is one of the most commonly used modified organosilicon. However, the organosilicon modification is adopted to easily release the small molecular alcohol, which belongs to VOC, and the hydroxyl of the small molecular alcohol is monofunctional, and the hydroxyl of the small molecular alcohol, which is used as a blocking agent to react with a curing agent, can reduce the crosslinking density of the two-component aqueous polyurethane coating film, so that various performances of the coating film are deteriorated.
Therefore, there is a need to provide a method for preparing an organosilicon modified hydroxy polyacrylate dispersion, wherein the prepared organosilicon modified hydroxy polyacrylate dispersion has low content of small molecular alcohol, strong storage stability, and particularly excellent high-temperature storage resistance; the paint film prepared by the method has quick drying speed and high hardness.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems in the prior art described above. Therefore, the invention provides a preparation method of the organosilicon modified hydroxyl polyacrylate dispersion, and the prepared organosilicon modified hydroxyl polyacrylate dispersion has high solid content, low content of small molecular alcohol and strong storage stability, and particularly has excellent high-temperature-resistant storage performance; the paint film prepared by the method has quick drying speed and high hardness.
In a first aspect, the invention provides a method of preparing a silicone modified hydroxy polyacrylate dispersion.
A method for preparing an organosilicon modified hydroxy polyacrylate dispersion, comprising the steps of:
s1, mixing an acrylic acid monomer, an acrylic ester monomer, a vinyl monomer, an acrylic ester derivative monomer, an organosilicon monomer and an initiator to form a mixed solution A;
s2, taking an active diluent, heating, then dropwise adding the mixed solution A prepared in the step S1, and preserving heat; then cooling, adding isocyanate bridging agent, reacting, and controlling the mass content of-NCO to obtain prepolymer;
s3, adding a neutralizing agent into the prepolymer prepared in the step S2, adding water to disperse, and filtering to obtain filtrate, thus obtaining the organosilicon modified hydroxyl polyacrylate dispersion;
the acrylate derivative monomer is a hydroxy acrylate monomer;
the organic silicon monomer is an organic silicon monomer containing double bonds and no epoxy groups.
Preferably, in step S1, the acrylic monomer is Acrylic Acid (AA) and/or methacrylic acid (MAA).
Preferably, in step S1, the acrylate monomer is selected from at least one of Methyl Methacrylate (MMA), ethyl methacrylate, propyl methacrylate, or Butyl Acrylate (BA).
Preferably, in step S1, the vinyl monomer is styrene (St).
Preferably, in step S1, the hydroxy acrylate monomer is selected from at least one of hydroxyethyl acrylate (HEA), hydroxypropyl acrylate (HPA), hydroxyethyl methacrylate (HEMA) or hydroxypropyl methacrylate (HPMA).
Preferably, in step S1, the organosilicon monomer is selected from at least one of vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris (2-methoxyethoxy) silane, vinylmethyldimethoxysilane, or γ -methacryloxypropyl trimethoxysilane.
Preferably, in step S1, the initiator is di-tert-amyl hydroperoxide (DTAP) and/or di-tert-butyl hydroperoxide (DTBP).
Preferably, in step S2, the reactive diluent is a monomer containing one epoxy group and no double bond. The adoption of the reactive diluent without double bonds ensures that the reactive diluent does not react at 140-150 ℃; reactive diluents containing an epoxy group can gradually react with carboxyl groups on the backbone of the hydroxy polyacrylate polymer, eventually achieving solvent-free polymerization. The monomer containing one epoxy group and no double bond is used as a reactive diluent, so that the normal operation of the polymerization reaction can be ensured under the condition of no solvent, and the introduction of the polymer as a side chain is beneficial to the improvement of the molecular weight of the polymer without obvious increase of the viscosity.
Further preferably, the reactive diluent is selected from at least one of glycidyl versatate (E10P), glycidyl 4-tert-butylbenzoate or glycidyl P-toluenesulfonate.
Preferably, in step S2, the isocyanate bridging agent is an isocyanate containing two or more NCO groups; further preferably, the isocyanate bridging agent is selected from at least one of isophorone diisocyanate (IPDI), hexamethylene Diisocyanate (HDI), toluene Diisocyanate (TDI), diphenylmethane diisocyanate (MDI) or HDI trimer.
Preferably, in step S2, an isocyanate bridging agent is added according to the NCO/OH value of 0.12-0.4 in the system; further preferably, the NCO/OH number is from 0.20 to 0.33. The formula is characterized in that the addition amount of the organic silicon monomer is firstly set, the amount of the small molecular alcohol released by hydrolysis of the organic silicon monomer can be determined after the addition amount of the organic silicon monomer is determined, the amount of the isocyanato substance of the diisocyanate is set to be about 2 times of that of the small molecular alcohol, and then the addition amount of the diisocyanate can be calculated.
Preferably, in step S2, the mass content of-NCO in the prepolymer is 1.3% -2.2%, and the viscosity of the prepolymer is 4150-5500 mPa.s at 75-85 ℃. At the moment, the prepolymer in the reaction system plays a role of fixing isocyanate, so that free isocyanate is prevented from remaining in a water phase when the prepolymer is dispersed, and finally paint film defects such as oil pits and the like are caused. Because the isocyanate only participates in the reaction in this stage, chain extension is not caused, the molecular weight of the polymer is not obviously increased, the viscosity of the prepolymer is not obviously increased, and the subsequent water adding and dispersing can be easily realized.
Preferably, in step S3, the neutralizing agent is Triethylamine (TEA) and/or N, N-Dimethylcyclohexylamine (DMCHA).
Preferably, in step S3, the step of adding water is performed in two steps. Further preferably, the step of adding water is to add 5-30 parts of water firstly, react for 5-30 minutes, and then add 120-150 parts of water; more preferably, the step of adding water is to add 8-20 parts of water first, react for 8-20 minutes, and then add 127.3-148.3 parts of water.
The water required for complete hydrolysis of the silicone monomer is calculated to be 0.48-1.07 parts according to theory, but 0.48-1.07 parts of water does not allow complete hydrolysis of the silicone monomer due to steric hindrance of the polymer. Since isocyanate groups can react with both small molecule alcohols and water, the reaction rate of isocyanate groups with small molecule alcohols of primary hydroxyl groups is much greater than that with water. Thus, when a significant amount of water is present, the water consumes a portion of the isocyanate groups, making the isocyanate groups insufficient to fix the small alcohols produced by the hydrolysis of the silicone monomers. In the preparation of the organosilicon modified hydroxy polyacrylate dispersoid, water is added for dispersion in two steps. In the first step, a small amount of water is added to hydrolyze siloxane and release small molecule alcohol, and NCO groups on polymer macromolecules are fixed and released. And secondly, adding a large amount of water to realize phase inversion dispersion, and condensing silanol groups (-SiOH) generated by hydrolysis after phase inversion to realize chain extension of the prepolymer. Because the content of silanol (-SiOH) in most organosilicon modified hydroxyl polyacrylate prepolymer is more than 3, organosilicon modified hydroxyl polyacrylate dispersoids with large molecular weight and network structure can be prepared by condensation of silanol (-SiOH), so that the storage stability, especially the high-temperature storage resistance of the dispersoids are improved, and the comprehensive performance of the final two-component aqueous polyurethane coating film is improved.
Preferably, the water is deionized water.
Specifically, the preparation method of the organosilicon modified hydroxyl polyacrylate dispersion comprises the following steps:
s1, mixing 8-20 parts of acrylic acid monomer, 12-28 parts of acrylic ester monomer, 8-25 parts of vinyl monomer, 15-28 parts of acrylic ester derivative monomer, 1-8 parts of organosilicon monomer and 0.5-3 parts of initiator in parts by mass to form a mixed solution A;
s2, taking 25-30 parts of reactive diluent, heating to 140-150 ℃, dropwise adding the mixed solution A prepared in the step S1, stirring and preserving heat after the dripping, cooling, adding 3-18 parts of isocyanate bridging agent, reacting, and controlling the mass content of-NCO to be 1.3% -2.2%, thus obtaining prepolymer;
s3, adding 1-8 parts of neutralizing agent into the prepolymer prepared in the step S2, then adding 5-30 parts of water, reacting for 5-30 minutes, then adding 120-150 parts of water for dispersion, and finally filtering to obtain filtrate, thus obtaining the organosilicon modified hydroxyl polyacrylate dispersoid.
More specifically, the preparation method of the organosilicon modified hydroxyl polyacrylate dispersoid comprises the following steps:
s1, uniformly mixing 10.7-15 parts of acrylic acid monomer, 14-24.1 parts of acrylic ester monomer, 9.5-19.2 parts of vinyl monomer, 19.5-22.5 parts of acrylic ester derivative monomer (hydroxy acrylic ester monomer), 1.7-4.9 parts of organic silicon monomer and 1.6-2.5 parts of initiator in parts by mass to form a mixed solution A;
S2, stirring and heating 25-30 parts of reactive diluent, beginning to dropwise add the mixed solution A after the temperature reaches 140-150 ℃, finishing dripping 3.5-5 hours, stirring and preserving heat for 20-30 minutes after finishing dripping, then cooling to 75-85 ℃, adding 5.5-18 parts of isocyanate bridging agent, reacting for 15-25 minutes to obtain a prepolymer, controlling the mass content of-NCO of the prepolymer to be 1.3-2.2%, and controlling the viscosity of the prepolymer at 75-85 ℃ to be 4150-5500 mPa.s;
s3, adding 1.7-5.6 parts of neutralizer into the prepolymer prepared in the step S2, stirring for 1-10 minutes, adding 8-20 parts of deionized water, reacting for 8-20 minutes, adding 127.3-148.3 parts of deionized water, dispersing at a high speed for 1-10 minutes, heating to 55-75 ℃ for continuous reaction for 20-40 minutes, cooling to 30-50 ℃ and filtering to obtain filtrate, thus obtaining the organosilicon modified hydroxyl polyacrylate dispersion.
In a second aspect, the invention provides a silicone modified hydroxy polyacrylate dispersion.
Specifically, the organosilicon modified hydroxyl polyacrylate dispersoid is prepared by the preparation method. The pH of the organosilicon modified hydroxy polyacrylate dispersoid is 7.5-8.5, the particle size is smaller than 120nm, the solid content is 42% -50%, the content of hydroxy is 3.7% -4.5%, and the content of small molecular alcohol is smaller than 0.15%.
Preferably, the pH of the organosilicon modified hydroxy polyacrylate dispersion is 8.0-8.5, the particle size is less than 115nm, the solid content is 42-46%, the hydroxy content is 3.7% -4.4%, and the content of small molecular alcohol is less than 0.1%.
The organosilicon modified hydroxy polyacrylate dispersoid (dispersoid for short) provided by the invention is slightly alkaline, and the slightly alkaline is beneficial to improving the storage stability of the dispersoid; the particle size of the dispersion is small, so that the appearance of the dispersion can achieve a semi-permeable effect; the solid content of the dispersion is more than or equal to 42 percent (the solid content of the main stream product in the market is 40 percent); the hydroxyl content of the dispersion is 3.7-4.5%, which belongs to a high hydroxyl content product and is beneficial to improving the water resistance, medium resistance and the like of the double-component aqueous polyurethane coating; the content of the micromolecular alcohol is less than 0.1 percent, the VOC content is low, and the hardness, the water resistance and the medium resistance of the double-component aqueous polyurethane coating are improved.
In a third aspect the invention provides the use of a silicone modified hydroxy polyacrylate dispersion.
In particular to application of the organosilicon modified hydroxyl polyacrylate dispersion in polyurethane paint.
In a fourth aspect, the present invention provides an aqueous two-component polyurethane coating.
Specifically, the aqueous two-component polyurethane coating comprises an A component and a B component, wherein the A component comprises the organosilicon modified hydroxyl polyacrylate dispersion, and the B component comprises a curing agent.
Preferably, the A component further comprises a film forming aid, an antifoaming agent, a thickener, a wetting agent, a neutralizing agent and water.
Preferably, the B component is an aqueous polyisocyanate curing agent.
Preferably, the film forming aid is selected from at least one of propylene glycol methyl ether (PM), propylene glycol butyl ether (PNB), dipropylene glycol methyl ether (DPM) or dipropylene glycol butyl ether (DPNB).
Preferably, the defoamer is a polyether siloxane copolymer defoamer and/or a modified polysiloxane interpolymer solution. Further preferably, the defoamer is selected from at least one of defoamers TEGO-800, TEGO-805, TEGO-815, TEGO-825, BYK-019, or BYK-020.
Preferably, the thickener is at least one of a nonionic polyurethane associative thickener, a hydrophobically modified alkali-swellable associative thickener, or an alkali-swellable non-associative thickener. Further preferably, the thickener is selected from at least one of thickeners RM-8W, TT-935, ASE-60, TEGO viscoPlus 3000, TEGO viscoPlus 3030 or TEGO viscoPlus 3060.
Preferably, the wetting agent is one or more of TEGO corporation's polyether siloxane copolymer TEGO-245, nonionic organic surfactant TEGO-500, or BYK corporation's polyether modified polysiloxane solution BYK-346.
Preferably, the neutralizing agent is Triethylamine (TEA) and/or Dimethylethanolamine (DMEA).
Preferably, the polyisocyanate curing agent is Bayhydur XP 2487/1 and/or Bayhydur XP 2655.
The fifth aspect of the invention provides a method for preparing an aqueous two-component polyurethane coating.
Specifically, the preparation method of the aqueous two-component polyurethane coating comprises the following steps:
(1) Adding a film forming additive, a defoaming agent, a thickening agent, a wetting agent and a neutralizing agent into the organosilicon modified hydroxyl polyacrylate dispersion, dispersing, and filtering to obtain a filtrate to obtain the component A;
(2) And (3) mixing the component A prepared in the step (1) with the component B according to the molar ratio of NCO/OH of 1.0-3 to obtain the aqueous two-component polyurethane coating.
The aqueous two-component polyurethane coating can be applied to high-grade wood coatings, automobile coatings, metal anti-corrosion coatings and other industrial protective coatings. A paint film formed by the aqueous two-component polyurethane paint has high gloss, high transparency, high crosslinking density and high hardness, and is excellent in water resistance, chemical resistance, wear resistance and scratch resistance.
Preferably, in step (2), the NCO/OH molar ratio is from 1.0 to 1.8.
Compared with the prior art, the invention has the following beneficial effects:
(1) When the organosilicon modified hydroxyl polyacrylate dispersoid is prepared, the isocyanate is used as the bridging agent to fix the micromolecular alcohol released by the hydrolysis of the siloxane in the organosilicon monomer, so that the prepared organosilicon modified hydroxyl polyacrylate dispersoid has high solid content, low micromolecular alcohol content and strong storage stability, and the influence of the reaction of the micromolecular alcohol and the curing agent on the performance of the bi-component aqueous polyurethane coating is avoided.
(2) When the organosilicon modified hydroxyl polyacrylate dispersoid is prepared, the prepolymer is dispersed under low viscosity, so that the problem that the prepolymer is difficult to disperse due to high viscosity when the molecular weight of the polymer is too large is avoided; and each dispersed latex particle becomes a micro-reactor, and the condensation reaction of silanol groups (-SiOH, generated by the hydrolysis of siloxane) is carried out in the latex particle, so that the stability of the dispersion process is ensured, and the storage stability of the dispersion is ensured. The organic silicon modified hydroxyl polyacrylate dispersoid has high solid content and semi-transparent appearance, and a paint film prepared by mixing the organic silicon modified hydroxyl polyacrylate dispersoid with the aqueous polyisocyanate curing agent has high drying speed, high hardness and excellent wear resistance, water resistance, dry heat resistance and ethanol resistance.
(3) The prepared organosilicon modified hydroxyl polyacrylate dispersion has strong storage stability, particularly excellent high-temperature storage resistance, can be stored for 180 days at 50 ℃, has stable particle size, slightly increases viscosity and solid content only due to small volatilization of moisture and a neutralizing agent, and slightly decreases pH value.
Detailed Description
In order to make the technical solutions of the present invention more apparent to those skilled in the art, the following examples will be presented. It should be noted that the following examples do not limit the scope of the invention.
In the following examples, the reactive diluent, glycidyl versatate (E10P), was purchased from Maifanitum advanced materials (China) Inc., glycidyl 4-t-butylbenzoate was purchased from Shanghai Ala Biotechnology Co., ltd, and glycidyl P-toluenesulfonate was purchased from Barling technology Co., ltd; the neutralizing agents Triethylamine (TEA), N-Dimethylcyclohexylamine (DMCHA) were purchased from Dow chemical company. Isocyanate bridging agents isophorone diisocyanate (IPDI), hexamethylene Diisocyanate (HDI), toluene Diisocyanate (TDI), diphenylmethane diisocyanate (MDI), HDI trimer were purchased from Yu Mohua chemical groups inc. Acrylic Acid (AA), methacrylic acid (MAA), methyl Methacrylate (MMA), butyl Acrylate (BA), styrene (St) were purchased from Jiangsu Sanmu group limited; hydroxyethyl acrylate (HEA), hydroxypropyl acrylate (HPA), hydroxyethyl methacrylate (HEMA) and hydroxypropyl methacrylate (HPMA) are commercially available from Changxing materials industries, inc.; vinyl triethoxysilane, vinyl trimethoxysilane, vinyl tris (2-methoxyethoxy) silane, vinyl methyl dimethoxy silane and gamma-methacryloxypropyl trimethoxysilane are purchased from maitui materials (china) limited; di-t-amyl hydroperoxide (DTAP), di-t-butyl hydroperoxide (DTBP) were purchased from Jin Jinle chemical company, inc; film forming aids propylene glycol methyl ether (PM), propylene glycol butyl ether (PNB), dipropylene glycol methyl ether (DPM), dipropylene glycol butyl ether (DPNB) were purchased from dow chemical company; defoamers polyether siloxane copolymer defoamers TEGO-800, TEGO-805, TEGO-815, TEGO-825 were purchased from Shanghai corporation; the modified polysiloxane copolymer solution BYK-019, BYK-020 was purchased from Pick chemical company, germany; nonionic polyurethane associative thickener RM-8W, hydrophobically modified alkali-swellable associative thickener TT-935, alkali-swellable non-associative thickener ASE-60 purchased from Dow chemical company; nonionic associative thickeners TEGO Viscoplus 3000, TEGO Viscoplus 3030, TEGO Viscoplus 3060 are purchased from TEGO corporation; wetting agent polyether siloxane copolymer TEGO-245, nonionic organic surfactant TEGO-500 is purchased from TEGO corporation; polyether modified polysiloxane solution BYK-346 was purchased from Pick chemical company, germany; the polyisocyanate curing agents Bayhydur XP 2487/1 and Bayhydur XP 2655 are purchased from Kogyo Polymer (China Co.). Other materials, reagents, or apparatus are available from conventional commercial sources, or may be obtained by existing methods, unless otherwise specified.
Example 1
An organosilicon modified hydroxy polyacrylate dispersion 1, prepared by the steps of:
s1, uniformly mixing 11.7 parts of acrylic acid, 8 parts of methyl methacrylate, 18 parts of styrene, 11.1 parts of butyl acrylate, 19.5 parts of hydroxyethyl methacrylate, 2.7 parts of vinyl triethoxysilane and 1.6 parts of di-tert-amyl peroxide to form a mixed solution A for later use;
s2, adding 30 parts of tertiary glycidyl ester monomer into a four-neck flask provided with a thermometer, a condenser tube, a stirring paddle and a constant pressure dropping funnel, mixing, stirring and heating, starting to drop a mixed solution A after the temperature reaches 145 ℃, stirring and preserving heat for 30 minutes after the completion of the dropping, cooling to 80 ℃, adding 10.3 parts of isophorone diisocyanate, wherein NCO/OH is 0.33, reacting for 20 minutes, and testing the mass content of-NCO to be 1.9% by using a di-n-butylamine method, and then testing the viscosity to be 4750 mPa.s 80 ℃ to obtain a prepolymer;
s3, adding 3.4 parts of triethylamine into the prepolymer, stirring for 5 minutes, adding 10 parts of deionized water, reacting for 10 minutes, adding 127.3 parts of deionized water, dispersing at a high speed for 3 minutes, and heating to 60 ℃ for continuous reaction for 25 minutes; cooling to 40 ℃, filtering and discharging, and obtaining filtrate, namely the organosilicon modified hydroxy polyacrylate dispersoid. The dispersion was semi-transparent in appearance, pH 8.5, hydroxyl content 3.7%, solids content 45.7%, viscosity 1450 mPas, particle size 95nm and ethanol content <0.1% as determined by gas chromatography. The appearance, pH, solid content, viscosity of the silicone-modified hydroxyl polyacrylate dispersion were measured with reference to GB/T11175-2002 synthetic resin emulsion test method, and the average particle size of the dispersion was measured using a nanoparticle size analyzer (ZS Nano S) (the measurement methods of other examples and comparative examples in the present invention are the same as those of the present example). The silicone modified hydroxy polyacrylate dispersion was also tested for thermal storage stability at 50 ℃. The test results are shown in Table 1.
TABLE 1
| Time | Appearance of | Solid content, percent | pH | Viscosity, mPas | Particle size, nm | Ethanol content |
| For 7 days | Semipermeable membrane | 45.7 | 8.5 | 1450 | 95 | ＜0.1％ |
| 14 days | Semipermeable membrane | 45.7 | 8.5 | 1450 | 96 | ＜0.1％ |
| For 30 days | Semipermeable membrane | 46.0 | 8.5 | 1500 | 98 | ＜0.1％ |
| 90 days | Semipermeable membrane | 46.2 | 8 | 1600 | 98 | ＜0.1％ |
| 180 days | Semipermeable membrane | 47.0 | 8 | 1750 | 98 | ＜0.1％ |
From the above table, it can be seen that the silicone modified hydroxy polyacrylic acid dispersion only slightly increases in viscosity and solid content due to a small amount of volatilization of water within 180 days of heat storage time, and slightly decreases in pH due to a small amount of volatilization of the neutralizing agent, and the particle size remains stable, indicating that the dispersion has better high-temperature storage stability.
The high-performance water-based double-component polyurethane coating 1 is prepared from the following raw materials in parts by weight:
and (3) a component A:
and the component B comprises the following components: 23.3 parts of an aqueous polyisocyanate curing agent (Bayhydur XP 2487/1);
when in use, the molar ratio of NCO groups in the component B to OH groups in the component A is controlled to be 1.8:1.
The preparation method of the high-performance water-based two-component polyurethane coating 1 comprises the following steps: adding the dispersion into a stirring kettle at the rotating speed of 700 revolutions per minute, premixing 10 parts of water and a film-forming auxiliary agent, adding the mixture into the dispersion, sequentially adding a defoaming agent, a thickening agent, a wetting agent and a neutralizing agent, dispersing for 10-30 minutes, and filtering and discharging to obtain the component A of the high-performance water-based double-component polyurethane coating. During construction, the aqueous polyisocyanate curing agent is added into the component A of the high-performance aqueous two-component polyurethane coating, and the mixture is stirred for 5 to 8 minutes to obtain the high-performance aqueous two-component polyurethane coating 1.
The high-performance water-based two-component polyurethane coating 1 is prepared into a paint film, and the paint film is cured and dried for 7 days at normal temperature, and the performance of the paint film is shown in a table 2:
table 2 comprehensive Properties of high Performance waterborne two-component polyurethane coating 1
| Detecting items | Performance of | Detection method |
| Surface drying time/min | 40 | GB/T1728-2020 |
| Time to dry/d | 3 | GB/T1728-2020 |
| Hardness of pencil | H | GB/T6739-2006 |
| Abrasion resistance (750 g/500 r)/g | 0.01 | GB/T1768-2006 |
| Coating gloss/(60 degree,%) | 95 | GB/T9754-2007 |
| Water resistance (25 ℃,24 h) | Grade 1, no visual change | GB/T4893.1-2005 |
| Dry heat resistant (70+ -2deg.C, 15 h) | Grade 1, no visual change | GB/T4893.3-2005 |
| Ethanol tolerance (50%, 1 h) | Grade 1, no visual change | GB/T4893.1-2005 |
In the embodiment, a bridging agent isophorone diisocyanate is added before the organosilicon modified hydroxyl polyacrylate prepolymer is dispersed, NCO/OH is controlled to be 0.33, 1 NCO group of isophorone diisocyanate reacts with OH of the organosilicon modified hydroxyl polyacrylate prepolymer, and 1 NCO group is reserved. At the moment, the prepolymer plays a role of fixing isocyanate, so that the free isocyanate is prevented from remaining in a water phase when the prepolymer is dispersed, and finally the paint film defects such as oil pits and the like are caused. Since the isocyanate only participates in the reaction in this stage, chain extension is not caused, the molecular weight of the polymer is not obviously increased, the viscosity of the prepolymer is not obviously increased, and water adding and dispersing are easily realized.
The silicone modified hydroxyl polyacrylate dispersion in this example can be dispersed in water in two steps. In the first step, a small amount of water is added to hydrolyze siloxane and release small molecule alcohol, and NCO groups on polymer macromolecules are fixed and released. And in the second step, a large amount of deionized water is added to realize phase inversion dispersion, silanol groups (-SiOH) generated by hydrolysis after phase inversion are condensed, and prepolymer chain extension is realized. Because of the large content of silanol groups (-SiOH) in the vinyl triethoxysilane modified hydroxyl polyacrylate prepolymer, organosilicon modified hydroxyl polyacrylate dispersoids with large molecular weight and network structure are prepared by condensation of silanol groups (-SiOH).
Example 2
An organosilicon modified hydroxy polyacrylate dispersion 2 prepared by the steps of:
s1, uniformly mixing 14 parts of methacrylic acid, 18.1 parts of methyl methacrylate, 9.5 parts of styrene, 8 parts of butyl acrylate, 20 parts of hydroxyethyl acrylate, 1.7 parts of vinyl trimethoxy silane and 2 parts of di-tert-amyl peroxide in parts by mass to form a mixed solution A for standby;
s2, adding 30 parts of 4-tert-butyl glycidyl benzoate monomer into a four-neck flask provided with a thermometer, a condenser tube, a stirring paddle and a constant pressure dropping funnel, mixing, stirring and heating, starting to drop a mixed solution A after the temperature reaches 140 ℃, keeping the temperature for 30 minutes after the dropping is finished, cooling to 80 ℃, adding 6.5 parts of hexamethylene diisocyanate, wherein NCO/OH is 0.26, reacting for 20 minutes, and measuring 4760 mPa.s (80 ℃) of viscosity after the mass content of-NCO is 1.6% by a di-n-butylamine titration method to obtain a prepolymer;
S3, adding 3.2 parts of triethylamine into the prepolymer, stirring for 3 minutes, adding 15 parts of deionized water, reacting for 15 minutes, adding 138.3 parts of deionized water, dispersing at a high speed for 5 minutes, and heating to 65 ℃ for continuous reaction for 30 minutes; cooling to 40 ℃, filtering and discharging, and obtaining filtrate, namely the organosilicon modified hydroxy polyacrylate dispersoid. The dispersion is semi-transparent in appearance, pH is 8.0, hydroxyl content is 4.2%, solid content is 42.4%, viscosity is 1500 mPa.s, particle size is 100nm, and methanol content is less than 0.1% as measured by gas chromatography. The silicone modified hydroxy polyacrylate dispersion was also tested for thermal storage stability at 50 ℃. The test results are shown in Table 3.
TABLE 3 Table 3
From the above table, it can be seen that the silicone modified hydroxy polyacrylic acid dispersion only slightly increases in viscosity and solid content due to a small amount of volatilization of water within 180 days of heat storage time, and slightly decreases in pH due to a small amount of volatilization of the neutralizing agent, and the particle size remains substantially stable, indicating that the dispersion has better high temperature storage stability.
The high-performance water-based double-component polyurethane coating 2 is prepared from the following raw materials in parts by weight:
and (3) a component A:
and the component B comprises the following components: 24.5 parts of an aqueous polyisocyanate curing agent (Bayhydur XP 2655);
when in use, the molar ratio of NCO groups in the component B to OH groups in the component A is controlled to be 1.8:1.
The preparation method of the high-performance water-based two-component polyurethane coating 2 comprises the following steps: adding the dispersion into a stirring kettle at the rotating speed of 700 revolutions per minute, premixing 10 parts of water and a film-forming auxiliary agent, adding the mixture into the dispersion, sequentially adding a defoaming agent, a thickening agent, a wetting agent and a neutralizing agent, dispersing for 10-30 minutes, and filtering and discharging to obtain the component A of the high-performance water-based double-component polyurethane coating. During construction, the aqueous polyisocyanate curing agent is added into the component A of the high-performance aqueous two-component polyurethane coating, and stirred for 5-8 minutes to obtain the high-performance aqueous two-component polyurethane coating 2.
The high-performance water-based two-component polyurethane coating 2 is prepared into a paint film, and the paint film is cured and dried for 7 days at normal temperature, and the performance of the paint film is shown in a table 4:
table 4 overall properties of high performance waterborne two-component polyurethane coating 2
Example 3
A silicone modified hydroxyl polyacrylate dispersion 3 prepared by the steps of:
s1, uniformly mixing 12 parts of acrylic acid, 16 parts of methyl methacrylate, 13.2 parts of styrene, 7 parts of butyl acrylate, 21.5 parts of hydroxypropyl methacrylate, 2.6 parts of vinyl tri (2-methoxyethoxy) silane and 2.3 parts of di-tert-amyl peroxide to form a mixed solution A for standby;
S2, adding 29 parts of tertiary glycidyl ester monomer into a four-neck flask provided with a thermometer, a condenser tube, a stirring paddle and a constant pressure dropping funnel, mixing, stirring and heating, starting to drop a mixed solution A after the temperature reaches 150 ℃, stirring and preserving heat for 20 minutes after the completion of dropping, cooling to 75 ℃, adding 5.5 parts of toluene diisocyanate, wherein NCO/OH is 0.21, reacting for 15 minutes, and testing the viscosity to 5000 mPa.s (75 ℃) after titration test of-NCO content to 1.3% by a di-n-butylamine method to obtain a prepolymer;
s3, adding 5.6 parts of N, N-dimethylcyclohexylamine into the prepolymer, stirring for 5 minutes, adding 8 parts of deionized water, reacting for 10 minutes, adding 129.4 parts of deionized water, dispersing at a high speed for 5 minutes, and heating to 55 ℃ for continuous reaction for 20 minutes; cooling to 40 ℃, filtering and discharging, and obtaining filtrate, namely the organosilicon modified hydroxy polyacrylate dispersoid. The dispersion is semi-transparent in appearance, pH is 8.5, hydroxyl content is 3.7%, solid content is 45.3%, viscosity is 1400 mPa.s, particle size is 93nm, and ethylene glycol monomethyl ether content is less than 0.1% as measured by gas chromatography. The silicone modified hydroxy polyacrylate dispersion was also tested for thermal storage stability at 50 ℃. The test results are shown in Table 5.
TABLE 5
From the above table, it can be seen that the silicone modified hydroxy polyacrylic acid dispersion only slightly increases in viscosity and solid content due to a small amount of water volatilization in 180 days of heat storage time, and the particle size remains stable, indicating that the dispersion has better high-temperature storage stability.
The high-performance water-based double-component polyurethane coating 3 is prepared from the following raw materials in parts by weight:
and (3) a component A:
and the component B comprises the following components: 23.1 parts of an aqueous polyisocyanate curing agent (Bayhydur XP 2487/1);
when in use, the molar ratio of NCO groups in the component B to OH groups in the component A is controlled to be 1.8:1.
The preparation method of the high-performance water-based two-component polyurethane coating 3 comprises the following steps: adding the dispersion into a stirring kettle at the rotating speed of 700 revolutions per minute, premixing 10 parts of water and a film-forming auxiliary agent, adding the mixture into the dispersion, sequentially adding a defoaming agent, a thickening agent, a wetting agent and a neutralizing agent, dispersing for 10-30 minutes, and filtering and discharging to obtain the component A of the high-performance water-based double-component polyurethane coating. During construction, the aqueous polyisocyanate curing agent is added into the component A of the high-performance aqueous double-component polyurethane coating, and the mixture is stirred for 5 to 8 minutes to obtain the high-performance aqueous double-component polyurethane coating 3.
The high-performance water-based two-component polyurethane coating 3 is prepared into a paint film, and the paint film is cured and dried for 7 days at normal temperature, and the performance of the paint film is shown in a table 6:
table 6 comprehensive Properties of high Performance waterborne two-component polyurethane coating 3
Example 4
A silicone modified hydroxyl polyacrylate dispersion 4 prepared by the steps of:
S1, uniformly mixing 13 parts of methacrylic acid, 13 parts of methyl methacrylate, 14.4 parts of styrene, 7 parts of butyl acrylate, 20.3 parts of hydroxypropyl acrylate, 1.8 parts of vinyl methyl dimethoxy silane and 2.5 parts of di-tert-butyl peroxide according to parts by weight to form a mixed solution A for standby;
s2, adding 25 parts of tertiary glycidyl ester monomer into a four-neck flask provided with a thermometer, a condenser tube, a stirring paddle and a constant pressure dropping funnel, mixing, stirring and heating, starting to drop a mixed solution A after the temperature reaches 145 ℃, stirring and preserving heat for 20 minutes after the completion of dropping, cooling to 75 ℃, adding 7.3 parts of diphenylmethane diisocyanate, wherein NCO/OH is 0.22, reacting for 15 minutes, and testing the viscosity of 4150 mPa.s (75 ℃) after titration test-NCO content of 1.3% by a di-n-butylamine method to obtain a prepolymer;
s3, adding 5.3 parts of N, N-dimethylcyclohexylamine into the prepolymer, stirring for 3 minutes, adding 10 parts of deionized water, reacting for 20 minutes, adding 138.2 parts of deionized water, dispersing at a high speed for 3 minutes, and heating to 55 ℃ for continuous reaction for 20 minutes; cooling to 40 ℃, filtering and discharging, and obtaining filtrate, namely the organosilicon modified hydroxy polyacrylate dispersoid. The dispersion is semi-transparent in appearance, pH is 8, hydroxyl content is 3.9%, solid content is 42.5%, viscosity is 1420 mPa.s, particle size is 110nm, and methanol content is less than 0.1% as measured by gas chromatography. The silicone modified hydroxy polyacrylate dispersion was also tested for thermal storage stability at 50 ℃. The test results are shown in Table 7.
TABLE 7
From the above table, it can be seen that the silicone modified hydroxy polyacrylic acid dispersion only slightly increases in viscosity and solid content due to a small amount of water volatilization in 180 days of heat storage time, and the particle size remains stable, indicating that the dispersion has better high-temperature storage stability.
The high-performance water-based double-component polyurethane coating 4 is prepared from the following raw materials in parts by weight:
and (3) a component A:
and the component B comprises the following components: 23.2 parts of an aqueous polyisocyanate curing agent (Bayhydur XP 2655);
when in use, the molar ratio of NCO groups in the component B to OH groups in the component A is controlled to be 1.8:1.
The preparation method of the high-performance water-based two-component polyurethane coating 4 comprises the following steps: adding the dispersion into a stirring kettle at the rotating speed of 700 revolutions per minute, premixing 10 parts of water and a film-forming auxiliary agent, adding the mixture into the dispersion, sequentially adding a defoaming agent, a thickening agent, a wetting agent and a neutralizing agent, dispersing for 10-30 minutes, and filtering and discharging to obtain the component A of the high-performance water-based double-component polyurethane coating. During construction, the aqueous polyisocyanate curing agent is added into the component A of the high-performance aqueous two-component polyurethane coating, and the mixture is stirred for 5 to 8 minutes to obtain the high-performance aqueous two-component polyurethane coating 4.
The high-performance water-based two-component polyurethane coating 4 is prepared into a paint film, and the paint film is cured and dried for 7 days at normal temperature, and the performance of the paint film is shown in table 8:
Table 8 comprehensive Properties of high Performance waterborne two-component polyurethane coating 4
Example 5
A silicone modified hydroxyl polyacrylate dispersion 5 prepared by the steps of:
s1, uniformly mixing 15 parts of methacrylic acid, 10 parts of methyl methacrylate, 16 parts of styrene, 6.7 parts of butyl acrylate, 22.5 parts of hydroxyethyl methacrylate, 4.9 parts of gamma-methacryloxypropyl trimethoxysilane and 2 parts of di-tert-butyl peroxide according to parts by mass to form a mixed solution A for standby;
s2, adding 28 parts of tertiary glycidyl ester monomer into a four-neck flask provided with a thermometer, a condenser tube, a stirring paddle and a constant pressure dropping funnel, mixing, stirring and heating, starting to drop a mixed solution A after the temperature reaches 140 ℃, stirring and preserving heat for 25 minutes after the completion of the dropping, cooling to 85 ℃, adding 18 parts of HT-100, wherein NCO/OH is 0.31, reacting for 25 minutes, and measuring the viscosity of 5500 mPa.s (85 ℃) after the titration test of-NCO content of 2.2% by a di-n-butylamine method to obtain a prepolymer;
s3, adding 5.1 parts of N, N-dimethylcyclohexylamine into the prepolymer, stirring for 5 minutes, adding 20 parts of deionized water, reacting for 8 minutes, adding 146.5 parts of deionized water, dispersing at a high speed for 5 minutes, and heating to 75 ℃ for continuous reaction for 40 minutes; cooling to 40 ℃, filtering and discharging, and obtaining filtrate, namely the organosilicon modified hydroxy polyacrylate dispersoid. The dispersion is semi-transparent in appearance, pH is 8.5, hydroxyl content is 3.8%, solid content is 43.1%, viscosity is 1600 mPa.s, particle size is 113nm, and methanol content is less than 0.1% as measured by gas chromatography. The silicone modified hydroxy polyacrylate dispersion was also tested for thermal storage stability at 50 ℃. The test results are shown in Table 9.
TABLE 9
From the above table, it can be seen that the silicone modified hydroxy polyacrylic acid dispersion only slightly increases in viscosity and solid content due to a small amount of water volatilization in 180 days of heat storage time, and the particle size remains stable, indicating that the dispersion has better high-temperature storage stability.
The high-performance water-based double-component polyurethane coating 5 is prepared from the following raw materials in parts by weight:
and (3) a component A:
and the component B comprises the following components: 22.6 parts of an aqueous polyisocyanate curing agent (Bayhydur XP 2487/1);
when in use, the molar ratio of NCO groups in the component B to OH groups in the component A is controlled to be 1.8:1.
The preparation method of the high-performance water-based two-component polyurethane coating 5 comprises the following steps: adding the dispersion into a stirring kettle at the rotating speed of 700 revolutions per minute, premixing 10 parts of water and a film-forming auxiliary agent, adding the mixture into the dispersion, sequentially adding a defoaming agent, a thickening agent, a wetting agent and a neutralizing agent, dispersing for 10-30 minutes, and filtering and discharging to obtain the component A of the high-performance water-based double-component polyurethane coating. During construction, the aqueous polyisocyanate curing agent is added into the component A of the high-performance aqueous two-component polyurethane coating, and the mixture is stirred for 5 to 8 minutes to obtain the high-performance aqueous two-component polyurethane coating 5.
The high-performance water-based two-component polyurethane coating 5 is prepared into a paint film, and the paint film is cured and dried for 7 days at normal temperature, and the performance of the paint film is shown in a table 10:
Table 10 comprehensive Properties of high Performance waterborne two-component polyurethane 5
Example 6
A silicone modified hydroxyl polyacrylate dispersion 6 prepared by the steps of:
s1, uniformly mixing 10.7 parts of acrylic acid, 10 parts of methyl methacrylate, 19.2 parts of styrene, 4 parts of butyl acrylate, 19.5 parts of hydroxyethyl acrylate, 2.5 parts of vinyl tri (2-methoxyethoxy) silane and 1.7 parts of di-tert-butyl peroxide to form a mixed solution A for later use;
s2, adding 30 parts of p-toluenesulfonic acid glycidyl ester monomer into a four-neck flask provided with a thermometer, a condenser tube, a stirring paddle and a constant pressure dropping funnel, mixing, stirring and heating, starting to drop a mixed solution A after the temperature reaches 145 ℃, keeping the temperature for 20 minutes after the completion of the dropping, cooling to 80 ℃, adding 6.6 parts of isophorone diisocyanate, wherein NCO/OH is 0.20, reacting for 20 minutes, and testing the viscosity to 5000 mPa.s (80 ℃) after the titration test of-NCO content is 1.3% by a di-n-butylamine method to obtain a prepolymer;
s3, adding 1.7 parts of triethylamine into the prepolymer, stirring for 3 minutes, adding 10 parts of deionized water, reacting for 15 minutes, adding 130.5 parts of deionized water, dispersing at a high speed for 3 minutes, and heating to 60 ℃ for continuous reaction for 25 minutes; cooling to 40 ℃, filtering and discharging, and obtaining filtrate, namely the organosilicon modified hydroxy polyacrylate dispersoid. The dispersion is semi-transparent in appearance, pH is 8.5, hydroxyl content is 4.4%, solid content is 43.1%, viscosity is 1650 mPa.s, particle size is 95nm, and content of ethylene glycol monomethyl ether is less than 0.1% as measured by gas chromatography. The silicone modified hydroxy polyacrylate dispersion was also tested for thermal storage stability at 50 ℃. The test results are shown in Table 11.
TABLE 11
From the above table, it can be seen that the silicone modified hydroxy polyacrylic acid dispersion only slightly increases in viscosity and solid content due to a small amount of volatilization of water within 180 days of heat storage time, and slightly decreases in pH due to a small amount of volatilization of the neutralizing agent, and the particle size remains stable, indicating that the dispersion has better high-temperature storage stability.
The high-performance water-based double-component polyurethane coating 6 is prepared from the following raw materials in parts by weight:
and (3) a component A:
and the component B comprises the following components: 26.6 parts of an aqueous polyisocyanate curing agent (Bayhydur XP 2655);
when in use, the molar ratio of NCO groups in the component B to OH groups in the component A is controlled to be 1.8:1.
The preparation method of the high-performance water-based two-component polyurethane coating 6 comprises the following steps: adding the dispersion into a stirring kettle at the rotating speed of 700 revolutions per minute, premixing 10 parts of water and a film-forming auxiliary agent, adding the mixture into the dispersion, sequentially adding a defoaming agent, a thickening agent, a wetting agent and a neutralizing agent, dispersing for 10-30 minutes, and filtering and discharging to obtain the component A of the high-performance water-based double-component polyurethane coating. During construction, the aqueous polyisocyanate curing agent is added into the component A of the high-performance aqueous two-component polyurethane coating, and the mixture is stirred for 5 to 8 minutes to obtain the high-performance aqueous two-component polyurethane coating 6.
The high-performance water-based two-component polyurethane coating 6 is prepared into a paint film, and the paint film is cured and dried for 7 days at normal temperature, and the performance of the paint film is shown in table 12:
table 12 comprehensive Properties of high Performance waterborne two-component polyurethane coating 6
Comparative example 1
A hydroxyl polyacrylate dispersion 7 prepared by the steps of:
s1, uniformly mixing 11.7 parts of acrylic acid, 13.45 parts of methyl methacrylate, 20 parts of styrene, 12.15 parts of butyl acrylate, 15.3 parts of hydroxyethyl methacrylate and 0.75 part of di-tert-amyl peroxide in parts by mass to form a mixed solution A for standby;
s2, adding 30 parts of tertiary glycidyl ester monomer and stirring and heating in a four-neck flask with a thermometer, a condenser, a stirring paddle and a constant pressure dropping funnel, starting to drop the mixed solution A after the temperature reaches 145 ℃, stirring and preserving heat for 30 minutes after the completion of the dropping, cooling to 80 ℃ and testing the viscosity to 45000 mPa.s (80 ℃), thus obtaining a prepolymer;
s3, adding 3.4 parts of triethylamine into the prepolymer, stirring for 5 minutes, adding 159.3 parts of deionized water, dispersing at a high speed for 5 minutes, and cooling to a medium speed for continuing dispersing for 25 minutes; cooling to 40 ℃, filtering and discharging, and obtaining filtrate, namely the hydroxyl polyacrylate dispersoid. The dispersion had a milky appearance, a pH of 8, a hydroxyl content of 4.0%, a solids content of 40.0%, a viscosity of 1550 mPa.s and a particle size of 150nm. The silicone modified hydroxy polyacrylate dispersion was also tested for thermal storage stability at 50 ℃. The test results are shown in Table 13.
TABLE 13
As can be seen from the table, the hydroxy polyacrylic acid dispersion prepared by the conventional process has the phenomena of layering and particle size increase after heat storage for 7 days, and has the problem of bottom gelation after heat storage for 30 days, which indicates that the hydroxy polyacrylic acid dispersion prepared by the conventional process has poor heat storage stability.
The high-performance water-based two-component polyurethane coating 7 is prepared from the following raw materials in parts by weight:
and (3) a component A:
and the component B comprises the following components: 22.1 parts of aqueous polyisocyanate curing agent (Bayhydur XP 2487/1)
When in use, the molar ratio of NCO groups in the component B to OH groups in the component A is controlled to be 1.8:1.
The preparation method of the high-performance water-based two-component polyurethane coating 7 comprises the following steps: adding the dispersion into a stirring kettle at the rotating speed of 700 revolutions per minute, premixing 10 parts of water and a film-forming auxiliary agent, adding the mixture into the dispersion, sequentially adding a defoaming agent, a thickening agent, a wetting agent and a neutralizing agent, dispersing for 10-30 minutes, and filtering and discharging to obtain the component A of the high-performance water-based double-component polyurethane coating. During construction, the aqueous polyisocyanate curing agent is added into the component A of the high-performance aqueous two-component polyurethane coating, and stirred for 5-8 minutes to obtain the high-performance aqueous two-component polyurethane coating 7.
The high-performance water-based two-component polyurethane coating 7 is prepared into a paint film, and the paint film is cured and dried for 7 days at normal temperature, and the performance of the paint film is shown in table 14:
table 14 comprehensive Properties of high Performance waterborne two-component polyurethane coating 7
The comparative example is a hydroxy polyacrylate dispersion synthesized by conventional process and having a solids content and a hydroxyl content consistent with those of the mainstream products of the market. Through comparative analysis, the solid content of the organic silicon modified hydroxy polyacrylic acid dispersion provided by the invention in example 1 is still low, and the particle size is large, the appearance is poor, and the storage stability is poor. The main reason for the problems is that the conventional process needs less initiator addition amount to improve the performances such as paint film hardness as much as possible so as to improve the molecular weight of the prepolymer, but when the molecular weight of the prepolymer is too large, the viscosity of the prepolymer is too high, and water-adding dispersion is not easy to realize.
After the hydroxyl polyacrylate dispersion synthesized in comparative example 1 was formulated into a high-performance aqueous two-component polyurethane coating, as can be seen from comparison with example 1, comparative example 1 was equivalent to inventive example 1 only in terms of dry time and gloss; the surface drying time is longer than that of the embodiment 1 of the invention, which is not beneficial to improving the construction efficiency; the pencil hardness, wear resistance, water resistance, dry heat resistance and ethanol resistance of the paint film performance are far lower than those of the high-performance water-based two-component polyurethane paint provided in the embodiment 1 of the invention.
Comparative example 2
Comparative example 2 differs from example 1 in that isophorone diisocyanate is not added.
A silicone modified hydroxyl polyacrylate dispersion 8 prepared by the steps of:
s1, uniformly mixing 11.7 parts of acrylic acid, 8 parts of methyl methacrylate, 18 parts of styrene, 11.1 parts of butyl acrylate, 19.5 parts of hydroxyethyl methacrylate, 2.7 parts of vinyl triethoxysilane and 1.6 parts of di-tert-amyl peroxide to form a mixed solution A for standby;
s2, adding 30 parts of tertiary glycidyl ester monomer into a four-neck flask provided with a thermometer, a condenser, a stirring paddle and a constant pressure dropping funnel, mixing, stirring and heating, starting to drop a mixed solution A after the temperature reaches 145 ℃, keeping the temperature for 30 minutes after the completion of the dropping, cooling to 80 ℃, measuring the viscosity to 4500 mPa.s (80 ℃), adding 3.4 parts of triethylamine, stirring for 5 minutes, adding 10 parts of deionized water, reacting for 10 minutes, adding 127.3 parts of deionized water, dispersing for 3 minutes at a high speed, and heating to 60 ℃ for continuous reaction for 25 minutes;
s3, cooling to 40 ℃, filtering and discharging to obtain the organosilicon modified hydroxy polyacrylate dispersoid, wherein the dispersoid is semi-transparent in appearance, pH is 8.5, hydroxy content is 4.4%, solid content is 43.6%, viscosity is 1500 mPa.s, particle size is 100nm, and ethanol content is 0.8% as measured by gas chromatography. The silicone modified hydroxy polyacrylate dispersion was also tested for thermal storage stability at 50 ℃. The test results are shown in Table 15.
TABLE 15
| Time | Appearance of | Solid content, percent | pH | Viscosity, mPas | Particle size, nm | Ethanol content |
| For 7 days | Semipermeable membrane | 43.6 | 8.5 | 1500 | 95 | 0.8％ |
| 14 days | Semipermeable membrane | 43.5 | 8.5 | 1550 | 96 | 0.8％ |
| For 30 days | Semipermeable membrane | 44.5 | 8.5 | 1500 | 98 | 0.8％ |
| 90 days | Semipermeable membrane | 45.0 | 8 | 1600 | 98 | 0.8％ |
| 180 days | Semipermeable membrane | 46.0 | 8 | 1750 | 98 | 0.7％ |
As can be seen from the above table, the silicone modified hydroxy polyacrylic acid dispersion prepared in comparative example 2 also has better high temperature storage stability. However, this comparative example does not add diisocyanate (i.e., NCO/OH of 0) to treat ethanol generated upon hydrolysis of vinyltriethoxysilane, and thus the synthesized silicone modified hydroxy polyacrylate dispersion contains 0.8% ethanol, which is an environmentally polluting VOC. In addition, since ethanol has a small molecular weight and reacts with the aqueous polyisocyanate curing agent in the two-component aqueous polyurethane coating material, 0.8% methanol in 62 parts of the dispersion consumes 2.2 parts of the aqueous polyisocyanate curing agent, and thus the final paint film properties are remarkably deteriorated.
The high-performance water-based double-component polyurethane coating 8 is prepared from the following raw materials in parts by weight:
and (3) a component A:
and the component B comprises the following components: 26.4 parts of an aqueous polyisocyanate curing agent (Bayhydur XP 2487/1);
when in use, the molar ratio of NCO groups in the component B to OH groups in the component A is controlled to be 1.8:1.
The preparation method of the high-performance water-based two-component polyurethane coating 8 comprises the following steps: adding the dispersion into a stirring kettle at the rotating speed of 700 revolutions per minute, premixing 10 parts of water and a film-forming auxiliary agent, adding the mixture into the dispersion, sequentially adding a defoaming agent, a thickening agent, a wetting agent and a neutralizing agent, dispersing for 10-30 minutes, and filtering and discharging to obtain the component A of the high-performance water-based double-component polyurethane coating. During construction, the aqueous polyisocyanate curing agent is added into the component A of the high-performance aqueous two-component polyurethane coating, and the mixture is stirred for 5 to 8 minutes to obtain the high-performance aqueous two-component polyurethane coating 8.
The high-performance water-based two-component polyurethane coating 8 is prepared into a paint film, and the paint film is cured and dried for 7 days at normal temperature, and the performance of the paint film is shown in table 16:
table 16 comprehensive Properties of high Performance waterborne two-component polyurethane coating 8
| Detecting items | Performance of | Detection method |
| Surface drying time/min | 75 | GB/T1728-2020 |
| Time to dry/d | 3 | GB/T1728-2020 |
| Hardness of pencil | B | GB/T6739-2006 |
| Abrasion resistance (750 g/500 r)/g | 0.02 | GB/T1768-2006 |
| Coating gloss/(60 degree,%) | 98 | GB/T9754-2007 |
| Water resistance (25 ℃,24 h) | Grade 4, severe impression | GB/T4893.1-2005 |
| Dry heat resistant (70+ -2deg.C, 15 h) | Grade 4, severe impression | GB/T4893.3-2005 |
| Ethanol tolerance (50%, 1 h) | Grade 4, severe impression | GB/T4893.1-2005 |
The high-performance aqueous two-component polyurethane coating prepared by using the organosilicon modified hydroxyl polyacrylate dispersion synthesized by not adding isophorone diisocyanate in the comparative example 2 is compared with the comparative example 1, and the comparative example 1 is only equivalent to the invention in terms of the real drying time and the coating film gloss; the surface drying time is longer than that of the invention, which is not beneficial to improving the construction efficiency; the pencil hardness, abrasion resistance, water resistance, dry heat resistance and ethanol resistance of the paint film performance are far inferior to those of the embodiment 1.
Comparative example 3
Comparative example 3 differs from example 1 mainly in that an excess of isophorone diisocyanate is added.
Specifically, the organosilicon modified hydroxyl polyacrylate dispersion 9 is prepared by the following steps:
S1, uniformly mixing 11.7 parts of acrylic acid, 8 parts of methyl methacrylate, 18 parts of styrene, 11.1 parts of butyl acrylate, 19.5 parts of hydroxyethyl methacrylate, 2.7 parts of vinyl triethoxysilane and 1.6 parts of di-tert-amyl peroxide to form a mixed solution A for standby;
s2, adding 30 parts of tertiary glycidyl ester monomer into a four-neck flask provided with a thermometer, a condenser tube, a stirring paddle and a constant pressure dropping funnel, stirring and heating, starting to drop a mixed solution A after the temperature reaches 145 ℃, keeping the temperature for 30 minutes after the completion of the dropping, stirring and keeping the temperature for 30 minutes, cooling to 80 ℃, adding 18.8 parts of isophorone diisocyanate, enabling NCO/OH to be 0.66, reacting for 20 minutes, titrating the mass content of-NCO to be 5.7% by using a di-n-butylamine method, testing the viscosity to be 15500 mPa.s (80 ℃), adding 3.4 parts of triethylamine, stirring for 5 minutes, adding 10 parts of deionized water, adding 127.3 parts of deionized water after the reaction for 10 minutes, dispersing at a high speed for 3 minutes, and heating to 60 ℃ for continuing the reaction for 25 minutes;
s3, cooling to 40 ℃, filtering and discharging to obtain the organosilicon modified hydroxy polyacrylate dispersoid, wherein the dispersoid is milky in appearance, the pH value is 8.5, the hydroxy content is 2.1%, the solid content is 47.6%, the viscosity is 1550 mPa.s, the particle size is 130nm, and the methanol content is less than 0.1% as measured by a gas chromatography method. The silicone modified hydroxy polyacrylate dispersion was also tested for thermal storage stability at 50 ℃. The test results are shown in Table 17.
TABLE 17
| Time | Appearance of | Solid content, percent | pH | Viscosity, mPas | Particle size, nm | Ethanol content |
| For 7 days | Milk white | 47.6 | 8.5 | 1550 | 130 | ＜0.1％ |
| 14 days | Milk white | 47.6 | 8.5 | 1500 | 135 | ＜0.1％ |
| For 30 days | Milky white, layered | 48.0 | 8.5 | 1600 | 135 | ＜0.1％ |
| 90 days | Milky white, layered | 47.8 | 8 | 1600 | 140 | ＜0.1％ |
| 180 days | Milky white, layered | 48.5 | 8 | 1750 | 150 | ＜0.1％ |
As can be seen from the above table, the silicone-modified hydroxypolyacrylic dispersion prepared in comparative example 3 was far less stable at high temperature than in example 1, and had a delamination phenomenon at 30 days of storage, and the particle size was also significantly increased during storage.
In the comparative example, too much isophorone diisocyanate is added, and two isocyanate groups of too much isophorone diisocyanate react with the hydroxyl groups of the prepolymer, so that the chain extension effect is achieved, the viscosity of the prepolymer is too high, the water dispersion is not facilitated, and finally the particle size of the organosilicon modified hydroxyl polyacrylate dispersion is larger and the storage stability is poor. In addition, the urea groups produced by the reaction of excess isocyanate groups with water affect the gloss and transparency of the paint film.
The high-performance water-based double-component polyurethane coating 9 is prepared from the following raw materials in parts by weight:
and (3) a component A:
and the component B comprises the following components: 13.8 parts of an aqueous polyisocyanate curing agent (Bayhydur XP 2487/1);
when in use, the molar ratio of NCO groups in the component B to OH groups in the component A is controlled to be 1.8:1.
The preparation method of the high-performance water-based two-component polyurethane coating 9 comprises the following steps: adding the dispersion into a stirring kettle at the rotating speed of 700 revolutions per minute, premixing 10 parts of water and a film-forming auxiliary agent, adding the mixture into the dispersion, sequentially adding a defoaming agent, a thickening agent, a wetting agent and a neutralizing agent, dispersing for 10-30 minutes, and filtering and discharging to obtain the component A of the high-performance water-based double-component polyurethane coating. During construction, the aqueous polyisocyanate curing agent is added into the component A of the high-performance aqueous two-component polyurethane coating, and stirred for 5-8 minutes to obtain the high-performance aqueous two-component polyurethane coating 9.
The paint film prepared from the high-performance water-based two-component polyurethane paint 9 is cured and dried for 7 days at normal temperature, and the performance of the paint film is shown in table 18:
table 18 comprehensive properties of high performance waterborne two-component polyurethane coating 9
The comparative example was compared with example 1 to prepare a high performance aqueous two-component polyurethane coating from an organosilicon modified hydroxy polyacrylate dispersion synthesized by adding excess isocyanate, and the comparative example was comparable to inventive example 1 in terms of open time, dry time, pencil hardness and abrasion resistance; the gloss, water resistance, dry heat resistance, ethanol resistance, and the like are inferior to those of example 1 of the present invention.
Comparative example 4
Comparative example 4 is different from example 1 in that a single water addition operation was employed.
A silicone modified hydroxyl polyacrylate dispersion 10 prepared by the steps of:
s1, uniformly mixing 11.7 parts of acrylic acid, 8 parts of methyl methacrylate, 18 parts of styrene, 11.1 parts of butyl acrylate, 19.5 parts of hydroxyethyl methacrylate, 2.7 parts of vinyl triethoxysilane and 1.6 parts of di-tert-amyl peroxide to form a mixed solution A for later use;
s2, adding 30 parts of tertiary glycidyl ester monomer into a four-neck flask provided with a thermometer, a condenser tube, a stirring paddle and a constant pressure dropping funnel, stirring and heating, starting to drop a mixed solution A after the temperature reaches 145 ℃, stirring and preserving heat for 30 minutes after the completion of the dropping, cooling to 80 ℃, adding 10.3 parts of isophorone diisocyanate, wherein NCO/OH is 0.33, reacting for 20 minutes, and testing the prepolymer with the mass content of-NCO of 1.8% by a di-n-butylamine method and the test viscosity of 5550 mPa.s (80 ℃);
s3, adding 3.4 parts of triethylamine into the prepolymer, stirring for 5 minutes, adding 137.3 parts of deionized water, dispersing at a high speed for 3 minutes, and heating to 60 ℃ for continuous reaction for 25 minutes; cooling to 40 ℃, filtering and discharging, and obtaining filtrate, namely the organosilicon modified hydroxy polyacrylate dispersoid. The dispersion was semi-permeable in appearance, pH 8.5, hydroxyl content 3.7%, solids content 45.7%, viscosity 1400 mPa.s, particle size 100nm, and methanol content 0.5% as determined by gas chromatography. The silicone modified hydroxy polyacrylate dispersion was also tested for thermal storage stability at 50 ℃. The test results are shown in Table 19.
TABLE 19
As can be seen from the above table, the silicone modified hydroxy polyacrylic acid dispersion prepared in comparative example 4 has better high temperature storage stability.
Example 1 the final water dispersion was accomplished in two steps, the first step being the addition of a small amount of water to hydrolyze the vinyltriethoxysilane to release ethanol, and the NCO groups on the polymer macromolecules to fix the released ethanol. And in the second step, a large amount of deionized water is added to realize phase inversion dispersion, silanol groups (-SiOH) generated by hydrolysis after phase inversion are condensed, and prepolymer chain extension is realized. In the comparative example, the final water adding and dispersing process is a one-time water adding process, when vinyltriethoxysilane is hydrolyzed, isocyanate groups are not reacted with ethanol generated by hydrolysis, and are firstly exposed to excessive water, the isocyanate groups react with water, the purpose of fixing the ethanol generated by the hydrolysis of vinyltriethoxysilane is not achieved, more ethanol residues are caused, and the ethanol belongs to VOC (volatile organic compounds) which pollute the environment. In addition, the ethanol has a small molecular weight and reacts with the aqueous polyisocyanate curing agent in the two-component aqueous polyurethane coating, so that the final paint film performance is obviously deteriorated.
The high-performance water-based two-component polyurethane coating 10 is prepared from the following raw materials in parts by weight:
And (3) a component A:
and the component B comprises the following components: 23.3 parts of an aqueous polyisocyanate curing agent (Bayhydur XP 2487/1);
when in use, the molar ratio of NCO groups in the component B to OH groups in the component A is controlled to be 1.8:1.
The preparation method of the high-performance water-based two-component polyurethane coating 10 comprises the following steps: adding the dispersion into a stirring kettle at the rotating speed of 700 revolutions per minute, premixing 10 parts of water and a film-forming auxiliary agent, adding the mixture into the dispersion, sequentially adding a defoaming agent, a thickening agent, a wetting agent and a neutralizing agent, dispersing for 10-30 minutes, and filtering and discharging to obtain the component A of the high-performance water-based double-component polyurethane coating. During construction, the aqueous polyisocyanate curing agent is added into the component A of the high-performance aqueous two-component polyurethane coating, and stirred for 5-8 minutes to obtain the high-performance aqueous two-component polyurethane coating 10.
The paint film prepared by the high-performance water-based two-component polyurethane paint 10 is cured and dried for 7 days at normal temperature, and the performance is shown in a table 20:
table 20 overall properties of high performance waterborne two-component polyurethane coating 10
| Detecting items | Performance of | Detection method |
| Surface drying time/min | 60 | GB/T1728-2020 |
| Time to dry/d | 3 | GB/T1728-2020 |
| Hardness of pencil | B | GB/T6739-2006 |
| Abrasion resistance (750 g/500 r)/g | 0.02 | GB/T1768-2006 |
| Coating gloss/(60 degree,%) | 97 | GB/T9754-2007 |
| Water resistance (25 ℃,24 h) | Grade 4, severe impression | GB/T4893.1-2005 |
| Dry heat resistant (70+ -2deg.C, 15 h) | Grade 4, severe impression | GB/T4893.3-2005 |
| Ethanol tolerance (50%, 1 h) | Grade 4, severe impression | GB/T4893.1-2005 |
The silicone modified hydroxyl polyacrylate dispersion provided in this comparative example was formulated into a high performance aqueous two-component polyurethane coating, as compared to example 1, which was comparable to inventive example 1 only in terms of dry time and paint film gloss; the surface drying time is longer than that of the embodiment 1 of the invention, which is not beneficial to improving the construction efficiency; the pencil hardness, abrasion resistance, water resistance, dry heat resistance, ethanol resistance and the like of the paint film performance are far inferior to those of the embodiment 1.
Claims (8)
1. A method for preparing an organosilicon modified hydroxy polyacrylate dispersion, comprising the steps of:
s1, mixing an acrylic acid monomer, an acrylic ester monomer, a vinyl monomer, an acrylic ester derivative monomer, an organosilicon monomer and an initiator to form a mixed solution A;
s2, taking an active diluent, heating, then dropwise adding the mixed solution A prepared in the step S1, and preserving heat; then cooling, adding isocyanate bridging agent, controlling the mass content of-NCO, and reacting to obtain prepolymer;
s3, adding a neutralizing agent into the prepolymer prepared in the step S2, adding water to disperse, and filtering to obtain filtrate, thus obtaining the organosilicon modified hydroxyl polyacrylate dispersion;
The acrylate derivative monomer is a hydroxy acrylate monomer;
the organic silicon monomer is an organic silicon monomer containing double bonds and not containing epoxy groups;
in step S2, the reactive diluent is a monomer containing one epoxy group and no double bond;
in step S2, the isocyanate bridging agent is isocyanate containing more than two-NCO groups;
in the step S2, adding an isocyanate bridging agent according to the NCO/OH value of 0.12-0.4 in the system;
in step S3, the water is added in two steps.
2. The method according to claim 1, wherein in step S1, the silicone monomer is at least one selected from vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris (2-methoxyethoxy) silane, vinylmethyldimethoxysilane, and γ -methacryloxypropyl trimethoxysilane.
3. The preparation method according to claim 1 or 2, wherein the reactive diluent is at least one selected from the group consisting of glycidyl versatate, glycidyl 4-t-butylbenzoate and glycidyl p-toluenesulfonate.
4. The process according to claim 1 or 2, wherein in step S2 the prepolymer has an NCO content of 1.3% to 2.2% and a viscosity of 4000 to 5500 mPa-S at 75 to 85 ℃.
5. The preparation method according to claim 1 or 2, characterized by comprising the steps of:
s1, mixing 8-20 parts of acrylic acid monomer, 12-28 parts of acrylic ester monomer, 8-25 parts of vinyl monomer, 15-28 parts of acrylic ester derivative monomer, 1-8 parts of organosilicon monomer and 0.5-3 parts of initiator in parts by mass to form a mixed solution A;
s2, taking 25-30 parts of reactive diluent, heating to 140-150 ℃, dropwise adding the mixed solution A prepared in the step S1, stirring and preserving heat after the dripping, cooling, adding 3-18 parts of isocyanate bridging agent, controlling the mass content of-NCO, and reacting to obtain prepolymer;
s3, adding 1-8 parts of neutralizing agent into the prepolymer prepared in the step S2, then adding 5-30 parts of water, reacting for 5-30 minutes, then adding 120-150 parts of water for dispersion, and finally filtering to obtain filtrate, thus obtaining the organosilicon modified hydroxyl polyacrylate dispersoid.
6. A silicone modified hydroxy polyacrylate dispersion prepared by the preparation process of any one of claims 1 to 5; the pH of the organosilicon modified hydroxy polyacrylate dispersoid is 7.5-8.5, the particle size is smaller than 120nm, the solid content is 42% -50%, the content of hydroxy is 3.7% -4.5%, and the content of small molecular alcohol is smaller than 0.15%.
7. Use of the silicone modified hydroxy polyacrylate dispersion according to claim 6 in polyurethane coatings.
8. An aqueous two-component polyurethane coating comprising an a-component comprising the silicone modified hydroxyl polyacrylate dispersion of claim 6 and a B-component comprising a curing agent.
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