CN109456441B - Acrylic resin and preparation method and application thereof - Google Patents
Acrylic resin and preparation method and application thereof Download PDFInfo
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- CN109456441B CN109456441B CN201811295156.1A CN201811295156A CN109456441B CN 109456441 B CN109456441 B CN 109456441B CN 201811295156 A CN201811295156 A CN 201811295156A CN 109456441 B CN109456441 B CN 109456441B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
Abstract
The invention discloses an acrylic resin, a preparation method and application thereof, wherein the acrylic resin comprises at least one structural unit (A), at least one structural unit (B), at least one structural unit (C) and at least one structural unit (D), and is obtained by carrying out solution polymerization and neutralization dispersion on ortho-hydroxyl type bridge ring structure acrylate and other acrylate monomers. In addition, the invention also provides a film-forming composition comprising the polyisocyanate and the acrylic resin and a two-component aqueous polyurethane coating comprising the film-forming composition or the acrylic resin, which form a compact network structure after curing and crosslinking, and the hydrophobic polycyclic aliphatic group containing a bridged ring structure endows a coating film with better water resistance and physical and mechanical properties.
Description
Technical Field
The invention relates to the field of polyurethane coatings, and particularly relates to an acrylic resin, and a preparation method and application thereof.
Background
The two-component solvent type polyurethane coating has the advantages of low film forming temperature, good wear resistance, high hardness, good chemical resistance and weather resistance and the like, and is widely used as industrial protection, wood furniture, automobile coating and the like.
The two-component waterborne polyurethane is composed of a hydroxyl component of a polymer with a molecular chain segment rich in hydroxyl and an isocyanate curing agent, wherein the isocyanate is used as a cross-linking agent and can react with the hydroxyl to form a cured cross-linked network structure, the hydroxyl component is used as a main body of the coating and plays a main role in the performance of the coating, the dispersibility of the curing agent in a water phase, the diffusion and the cross-linking in the film forming process and the final performance of the coating are influenced, and the structural composition of the hydroxyl component is adjusted to obtain the coatings with different performances.
A common hydroxyl component is a hydroxy acrylic resin, typically copolymerized from acrylate monomers. Most of the acrylate containing hydroxyl functional groups at present is aliphatic compounds, such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate and the like, but the monomers have high irritation, and the obtained water-dispersible hydroxy acrylic resin has the problems of poor polymerization stability, low hydroxyl content, poor stability, high Volatile Organic Compound (VOC) content, low solid content, poor emulsifying and dispersing performance on a curing agent and the like, and has the problems of poor water resistance and mechanical performance of a coating when being used for a water-based coating.
CN95196075 discloses an aqueous two-component polyurethane coating composition comprising: A) a water-dilutable polyacrylate resin having a hydroxyl value of 40 to 200mgKOH/g and an acid value of 20 to 100mgKOH/g, and B) a polyisocyanate component, the water-dilutable acrylate resin being obtained by polymerizing: at least one ester of (meth) acrylic acid and a cycloaliphatic C6-C10 alcohol, at least one monomer containing a hydroxyl group in addition to cyclohexyl methacrylate. When it is used as a clear coat over a primer, it causes only a small early dissolution of the underlying primer and shows good light/dark effect when viewed at different angles. At the same time, the resulting coatings should have good chemical resistance and good weatherability. However, the coating film of the coating is poor in water resistance and mechanical properties.
CN105925157A discloses a two-component waterborne polyurethane floor paint and a preparation method thereof, wherein the floor paint is composed of a component A and a component B, the component A contains a hydroxy acrylic emulsion, the hydroxy acrylic emulsion has a hydroxyl content of 1.2-1.5%, the component B contains self-emulsifying type poly-diisocyanate, the mass ratio of the component A to the component B is 6-10: 1, and the two-component waterborne polyurethane floor paint can be normally constructed under a low-temperature condition, has high hardness and good freeze-thaw stability, but has poor water resistance.
Preparation and performance of a two-component waterborne polyurethane coating, namely a mixed system of acrylic latex polyol and hydrophilic modified HDI trimer, Wu Sheng Hua et al, Anhui university of Industrial science (Nature science edition), volume 28, No. 2, discloses a preparation method of a two-component waterborne polyurethane coating, wherein the two-component waterborne polyurethane coating mainly comprises a waterborne hydroxyl component (A component) and a polyisocyanate component (B component). Acrylic latex polyol is used as a component A, hydrophilic modified HDI tripolymer is used as a component B, the acrylic latex polyol and the hydrophilic modified HDI tripolymer are mixed and cured to form a film, and the bi-component waterborne polyurethane film is obtained, the comprehensive performance of the bi-component waterborne polyurethane film is close to that of a corresponding bi-component solvent type polyurethane film, but the content of VOC (volatile organic compound) of the bi-component waterborne polyurethane film is low, the environmental protection requirement is met, and the mechanical property and.
Disclosure of Invention
In view of the disadvantages of the prior art, an object of the present invention is to provide an acrylic resin comprising at least one structural unit (a), at least one structural unit (B), at least one structural unit (C), and at least one structural unit (D);
the R is1Is hydrogen or methyl;
m is 0 or 1;
the R is2、R3、R4、R6And R8Each independently selected from hydrogen or methyl;
the R is5Is any one of C1-C12 straight chain or branched chain saturated alkyl;
the R is7Is composed of
N is any integer from 2 to 4;
said X+Is a quaternary ammonium salt cation including
Any one of them.
In the acrylic resin, the total number of the polymerized units is n0The number of the structural units (A) is n1The number of the structural units (B) is n2The number of the structural units (C) is n3The number of the structural units (D) is n4。
Since the number of the structural units of each polymer chain may be different, n here0、n1、n2、n3、n4Are averages.
N is0、n1、n2、n3、n4The following conditions are satisfied: n is more than or equal to 200≤100、1≤n1≤20、10≤n2≤60、0≤n3≤25、2≤n4≤20。
The acrylic resin may include structural units common in the prior art in addition to the structural units (a), (B), (C), and (D), and the present invention is not limited herein.
The bridged ring structure in the structural unit A enables the acrylic resin to simultaneously have hydrophilic hydroxyl groups and hydrophobic polycyclic alkyl groups, the hydroxyl groups have reactivity, the acrylic resin can further react with isocyanate to form a cross-linked network structure, the coating is endowed with better compactness, and the polycyclic alkyl groups endow the coating with better hydrophobic property, lower polymer shrinkage and excellent physical and mechanical properties after film forming.
Preferably, said n1/n00.01 to 0.20, for example, 0.02, 0.10, 0.15, 0.18, etc.
When the number of the structural units (A) accounts for 0.01-0.20 of the total number of the structural units, the acrylic resin shows the optimal suitable hydrophilic and hydrophobic properties and mechanical properties. When n is1/n0When the content of hydroxyl groups in the acrylic resin is too large, excessive cross-linked networks can be formed, so that the coating becomes brittle, the mechanical property is reduced, and the flexibility is reduced; when n is1/n0Too small, the properties of the structural unit (A) itself cannot be expressed.
Preferably, said n2/n00.10 to 0.60, for example, 0.2, 0.3, 0.4, 0.5, etc.
Preferably, said n3/n00 to 0.25, such as 0.1, 0.15, 0.2, etc.
Preferably, said n4/n00.02 to 0.20, for example 0.03. 0.1, 0.15, 0.18, etc.
The invention also aims to provide a preparation method of the acrylic resin, which comprises the following steps:
(1) the monomer is dissolved in a solvent, and solution polymerization is carried out to obtain an acrylate copolymer solution.
The monomer is o-hydroxyl type bridged ring structure acrylate
Alkyl acrylate or methacrylate
Hydroxyalkyl acrylate or hydroxyalkyl methacrylate
Acrylic acid or methacrylic acid
Any 1 or a combination of at least 2 of them.
In the monomer, the components of each compound can be proportioned according to the number of structural units in the target acrylic resin.
Exemplary, Compounds of the invention
The preparation method can refer to the prior patent CN201711339235.3, and specifically comprises the following steps:
(I) polycyclic olefins
Epoxidation reaction of (1):
adding a measured polycyclic olefin, a pH regulator and a solvent into a four-neck glass flask provided with a constant pressure dropping funnel, a thermometer and mechanical stirring, placing the flask into an ice-water mixed bath, starting stirring, uniformly mixing, keeping the temperature of the system at 5-15 ℃, controlling the pH value of the system at 3.5-5.5, dropping liquid at constant pressureAdding metered organic acid peroxide R into a funnel4And slowly dripping COOOH into the reaction system, keeping the reaction temperature not to exceed 25 ℃, and continuing to react for 1-2 hours after dripping.
Standing and layering the mixed solution after the reaction is finished, taking the lower organic layer solution, washing the lower organic layer solution to the pH value of 6.5-7.0, filtering, and evaporating the solvent to obtain an epoxidation product
(II) polycyclic aliphatic epoxides
The ring-opening esterification reaction of (a) to prepare a hydroxyl-containing acrylate compound;
adding a metered polycyclic aliphatic epoxide, (methyl) acrylic acid, a catalyst and a polymerization inhibitor into a four-neck glass flask provided with a mechanical stirrer, a thermometer and a condenser, starting stirring and heating, keeping the reaction temperature at 75-85 ℃, and reacting for 0.5-2.5 h, wherein the reaction end point is obtained when the acid value of the system is unchanged. The acrylic ester compound containing hydroxyl can be obtained by reduced pressure rectification.
Optionally, step (2) is performed after step (1): and carrying out neutralization reaction on the acrylate copolymer solution and dispersing the acrylate copolymer solution into a dispersion medium to obtain the acrylic resin.
The R is1、R2、R3、R4、R5、R6、R7And R8With the same limits as one of the purposes.
Four types of monomers as described above, each type of monomer can be based on the compound glass transition temperature (T)g) The optimum effect can be achieved by a single selection or a combination of multiple compounds, which is not limited by the present invention.
The o-hydroxyl type bridged ring structure acrylate copolymerization unit has a bridged ring-containing polycyclic alkyl structure, so that the monomers have the characteristics of relatively high polymerization speed, low polymer shrinkage and the like, and the hydroxyl groups on the polycyclic alkyl group endow the monomers with reactivity, for example, the monomers can react with isocyanate curing agents to form a crosslinked network structure.
The o-hydroxyl type bridge ring structure acrylic ester has high boiling point, low vapor pressure and weak smell, and can greatly improve the construction environment when preparing the water dispersible acrylic resin component.
Preferably, the solution polymerization reaction system in the step (1) comprises the following components in percentage by mass:
the mass ratios between the individual monomers can be converted according to the ratio of the number of the individual structural units defined as one of the objects of the invention, the conversion being known to the person skilled in the art.
Preferably, the mass percent of the solvent is 40.0-60.0 wt.%, e.g., 42 wt.%, 50 wt.%, 58 wt.%, etc.
Preferably, the mass percentage of the monomer is 34.0-55 wt.%, e.g., 35 wt.%, 40 wt.%, 45 wt.%, 48 wt.%, etc.
Preferably, the mass percentage of the initiator is 0.5-5.0 wt.%, e.g., 0.6 wt.%, 2.5 wt.%, 4.8 wt.%, etc.
Preferably, the mass percent of the chain transfer agent is 0.5-3.0 wt.%, e.g., 0.6 wt.%, 1.5 wt.%, 2.8 wt.%, etc.
Preferably, step (1) specifically comprises: adding a part of solvent into a reactor, heating to reflux the solvent, mixing the monomer, the rest of solvent, a part of initiator and a chain transfer agent according to the formula amount, adding the obtained mixed solution into the reactor, continuously maintaining the reflux temperature, adding the rest of initiator, continuously maintaining the reflux temperature, and terminating the reaction to obtain the acrylate copolymer solution.
Preferably, the mass of the part of the solvent is 50-70% of the total mass of the solvent, such as 52%, 60%, 68% and the like.
Preferably, the mass of the part of the initiator is 70-80% of the total mass of the initiator, such as 72%, 75%, 78%, etc.
Preferably, the mixed solution is added to the reaction system in the form of a dropwise addition.
Preferably, the dripping time is 3-6 h.
Preferably, the time for maintaining the reflux temperature is 0.5-2 h, such as 0.6h, 1h, 1.8h, and the like.
Preferably, the solvent includes any one or a combination of at least two of butylene glycol, 2-methoxypropanol, n-butanol, methoxybutanol, n-propanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, and butyl acetate.
Preferably, the chain transfer agent comprises any one or a combination of at least two of mercaptoethanol, mercaptopropionic acid, and dodecyl mercaptan.
Preferably, the initiator comprises any one or at least two of azodiisobutyronitrile, dibenzoyl peroxide, tert-butyl peroxybenzoate, dicumyl peroxide, tert-butyl peroxy-2-ethylhexanoate, di-tert-butyl peroxide and di-tert-amyl peroxide.
Preferably, the ortho-hydroxyl type bridged ring structure acrylate comprises any one or at least two of the following compounds in combination:
preferably, the solid content of the acrylic resin in the step (2) is 35-45%, such as 36%, 40%, 44% and the like.
Preferably, the neutralizing agent for the neutralization reaction comprises any one or a combination of at least two of 10-30% by mass of ammonia water, triethylamine, tripropylamine, tributylamine, N-dimethylethanolamine, N-diethylethanolamine, diethanolamine, triethanolamine, diisopropanolamine, N-dimethylisopropylamine and 2-amino-2-methyl-propanol.
Preferably, the molar weight ratio of the neutralizing agent to the carboxyl groups in the acrylate copolymer solution is 0.9 to 1.1:1, such as 0.95:1, 1.0:1, 1.05:1, and the like.
Preferably, the step (2) specifically comprises: and (2) reducing the temperature of the acrylate copolymer solution to 50-70 ℃, such as 55 ℃, 60 ℃, 65 ℃ and the like, adding a neutralizing agent, adjusting the pH value of the system, removing the organic solvent, keeping the temperature of the system at 30-40 ℃, such as 32 ℃, 35 ℃, 38 ℃ and the like, adding deionized water, and stirring to obtain the acrylic resin.
Preferably, the dispersion medium comprises deionized water.
Preferably, the method of removing the organic solvent comprises distillation under vacuum.
Preferably, the residual amount of the organic solvent is less than 3% before the removal of the organic solvent.
Preferably, the pH value is adjusted to 6.5-9.0, such as 6.6, 6.8, 6.9, etc.
Preferably, the neutralization reaction time is 10-30 min, such as 12min, 20min, 28min and the like.
Preferably, the stirring time is 0.5-1 h, such as 0.6h, 0.8h, 0.9h and the like.
It is a further object of the present invention to provide a film-forming composition comprising a polyisocyanate and an acrylic resin according to one of the objects of the present invention.
The acrylate has hydrophobic polycyclic alkyl and hydrophilic hydroxyl groups, and has appropriate hydrophilicity and reactivity when used for preparing water-dispersible hydroxy acrylic resin, excellent hydrophobicity when being cured into a film at a later stage, and excellent water resistance, physical and mechanical properties and the like of a coating film.
Preferably, the polyisocyanate includes any one or at least two combinations of a tetramethylphenyl diisocyanate/trihydroxypropane adduct, an HDI dimer, an HDI trimer and a polyisocyanate hydrophilic modification.
Preferably, the film-forming composition is applied to a coating.
Preferably, the coating comprises any one or at least two of automobile coating, woodware coating, industrial anticorrosive and antirust coating and plastic coating.
The fourth purpose of the invention is to provide a two-component waterborne polyurethane coating, which comprises the acrylic resin for one purpose of the invention; alternatively, the coating comprises the film-forming composition described in the third object of the present invention.
The o-hydroxyl bridged ring structure acrylate monomer for preparing the two-component waterborne polyurethane coating provided by the invention has oleophylic polycyclic aliphatic groups and hydrophilic hydroxyl groups, the hydrophilic hydroxyl groups and the oleophylic alicyclic groups of the compound show good compatibility in the preparation of the hydroxyl groups of the two-component waterborne polyurethane, the polymerization activity is high, the monomer residue is low, and the coating after film formation shows excellent properties such as weather resistance, water and oil resistance, impact resistance and the like.
The fifth purpose of the invention is to provide a using method of the two-component waterborne polyurethane coating, which comprises the following steps: the acrylic resin and the polyisocyanate are mixed in a molar ratio of hydroxyl group to isocyanate group of 1:1 to 1.6, for example, 1:1.2, 1:1.4, 1:1.5, etc.
Preferably, the method specifically comprises: mixing acrylic resin and polyisocyanate, adding a catalyst and a defoaming agent, and uniformly dispersing to obtain the double-component waterborne polyurethane coating.
Preferably, the amount of the catalyst added is 0.05-0.1% of the total mass of the acrylic resin and the polyisocyanate, such as 0.06%, 0.07%, 0.09% and the like.
Preferably, the amount of the defoamer added is 0.01-0.1% of the total mass of the acrylic resin and the polyisocyanate, such as 0.02%, 0.5%, 0.8% and the like.
Compared with the prior art, the invention has the following beneficial effects:
(1) the acrylic resin provided by the invention has lipophilic polycyclic aliphatic groups and hydrophilic hydroxyl groups, the hydrophilic hydroxyl groups and the lipophilic alicyclic groups of the compound show good compatibility in the preparation of the hydroxyl components of the two-component waterborne polyurethane, the polymerization activity is high, the monomer residue is low, the coating after film formation shows excellent properties such as weather resistance, water resistance, oil resistance and impact resistance, the adhesive force of the coating can reach 1-2 grades, the impact resistance is more than or equal to 50 kg-cm, only whitening occurs in a water resistance test, and the restoration can be realized.
(2) The o-hydroxyl type bridged ring structure acrylic ester used in the invention can be used as a special functional monomer to replace or partially replace the conventional (methyl) hydroxyalkyl acrylate, has high boiling point, low vapor pressure and weak odor, and can greatly improve the construction environment when preparing the water-dispersible acrylic resin component.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Preparation example 1
The acrylic resin 1 obtained in this preparation example was composed of the following structural units:
wherein n is1Is 10, n2Is 40, n3Is 15, n4Is 10, i.e. n1/n0Is 0.13.
The preparation method of the acrylic resin comprises the following steps:
(1) solution polymerization: 60 percent of the total amount of the propylene glycol monomethyl ether is put into a reactor provided with a stirring device, a condenser, a temperature control system and a monomer dripping device, the temperature is slowly increased to the boiling point of the solvent, and dripping is started after the reflux
Methyl methacrylate, butyl acrylate, 2-ethylhexyl methacrylate, hydroxyethyl methacrylate, acrylic acid, the remaining 40% of propylene glycol monomethyl ether,And (3) after the 75% tert-butyl peroxybenzoate and mercaptoethanol mixed solution is dripped within 5h, preserving the heat for 1h, supplementing the remaining 25% tert-butyl peroxybenzoate, preserving the heat for 1h, and stopping heating to obtain the hydroxyl acrylate copolymer solution.
(2) And (3) neutralization reaction: and (3) adding ammonia water with the mass concentration of 25% for neutralization after the temperature of the hydroxyl acrylate copolymer solution is reduced to 60 ℃, and reacting for 20 min. Followed by distillation under vacuum to evaporate the organic solvent to a residual content of less than 3%. And adding deionized water into the obtained product at 35 ℃, and violently stirring for 0.8h to obtain the water-dispersible hydroxyacrylic resin 1 with the solid content of 40%.
The solution polymerization reaction system comprises the following components in percentage by mass:
the mass ratio of the monomers is converted according to the number ratio of the above-mentioned structural units, and the conversion method is well known to those skilled in the art.
Preparation example 2
The difference from preparation example 1 is that n in the acrylic resin 21Is 1, n2Is 55, n3Is 25, n4Is 20, i.e. n1/n0Is 0.01.
Preparation example 3
The difference from preparation example 1 is that n in the acrylic resin 31Is 16, n2Is 40, n3Is 15, n4Is 10, i.e. n1/n0Is 0.2.
Preparation example 4
The difference from preparation example 1 is that n in the acrylic resin 41Is 1, n2Is 60, n3Is 25, n4Is 20, i.e. n1/n0Is 0.0094.
Preparation example 5
The difference from preparation example 1 is that n in acrylic resin 51Is 20, n2Is 40, n3Is 15, n4Is 10, i.e. n1/n0Is 0.24.
Preparation example 6
The difference from the preparation example 1 is that
Is replaced by
Will be provided with
Is replaced by
Acrylic resin 6 was obtained.
Preparation example 7
The difference from the preparation example 1 is that
Is replaced by
Acrylic resin 7 was obtained.
Preparation example 8
The difference from the preparation example 1 is that the solution polymerization reaction system for preparing the acrylic resin 8 comprises the following components in percentage by mass:
preparation example 9
The difference from the preparation example 1 is that the solution polymerization reaction system for preparing the acrylic resin 9 comprises the following components in percentage by mass:
preparation example 10
The difference from the preparation example 1 is that the solution polymerization reaction system for preparing the acrylic resin 10 comprises the following components in percentage by mass:
preparation example 11
The difference from the preparation example 1 is that the solution polymerization reaction system for preparing the acrylic resin 11 comprises the following components in percentage by mass:
preparation example 12
The difference from preparation example 1 is that the method for preparing acrylic resin 12 comprises the steps of:
(1) solution polymerization: 50 percent of the total amount of the propylene glycol monomethyl ether acetate is put into a reactor provided with a stirring device, a condenser, a temperature control system and a monomer dripping device, the temperature is slowly increased to the boiling point of the solvent, and dripping is started after the reflux
And (3) after the mixed solution of methyl methacrylate, butyl acrylate, 2-ethylhexyl methacrylate, hydroxyethyl methacrylate, acrylic acid, the remaining 50% of propylene glycol monomethyl ether acetate, 70% of di-tert-butyl peroxide and dodecyl mercaptan is dripped within 3h, keeping the temperature for 0.5h, supplementing the remaining 30% of di-tert-butyl peroxide, keeping the temperature for 0.5h, and stopping heating to obtain the hydroxyl acrylate copolymer solution.
(2) And (3) neutralization reaction: and adding N, N-dimethylethanolamine for neutralization after the temperature of the hydroxyl acrylate copolymer solution is reduced to 50 ℃, and reacting for 10 min. Followed by distillation under vacuum to evaporate the organic solvent to a residual content of less than 3%. And adding deionized water into the obtained product at 30 ℃, and violently stirring for 0.5h to obtain the water-dispersible hydroxyacrylic resin 12 with the solid content of 35%.
The solution polymerization reaction system comprises the following components in percentage by mass:
preparation example 13
The difference from preparation example 1 is that the method for preparing the acrylic resin 13 includes the steps of:
(1) solution polymerization: adding 70% of n-butanol into a reactor equipped with a stirring device, a condenser, a temperature control system and a monomer dripping device, slowly heating to the boiling point of the solvent, and dripping after refluxing
And (3) after the mixed solution of methyl methacrylate, butyl acrylate, 2-ethylhexyl methacrylate, hydroxyethyl methacrylate, acrylic acid, the rest 30% of n-butyl alcohol, 80% of di-tert-amyl peroxide and mercaptoethanol is dripped in 6 hours, preserving heat for 2 hours, supplementing the rest 20% of di-tert-amyl peroxide, preserving heat for 2 hours, and stopping heating to obtain the hydroxyl acrylate copolymer solution.
(2) And (3) neutralization reaction: and (3) adding triethylamine for neutralization after the temperature of the hydroxyl acrylate copolymer solution is reduced to 70 ℃, and reacting for 30 min. Followed by distillation under vacuum to evaporate the organic solvent to a residual content of less than 3%. And adding deionized water into the obtained product at 40 ℃, and stirring vigorously for 1h to obtain the water-dispersible hydroxyacrylic resin 13 with the solid content of 45%.
The solution polymerization reaction system comprises the following components in percentage by mass:
example 1
A method for using a two-component waterborne polyurethane coating comprises the following steps:
mixing acrylic resin 1 and HDI dimer according to the molar ratio of hydroxyl to isocyanate group of 1:1.3 to obtain a mixture, adding dibutyl tin dilaurate accounting for 0.08% of the mass of the mixture and polydimethylsiloxane (viscosity of 5000cP) accounting for 0.02% of the mass of the mixture, and uniformly dispersing to obtain the two-component waterborne polyurethane coating. After spraying, the coating can be solidified into a film at 40 ℃, and the performance of the coating is tested after two days.
Example 2
The difference from example 1 is that acrylic resin 1 was replaced with acrylic resin 2.
Example 3
The difference from example 1 is that acrylic resin 1 was replaced with acrylic resin 3.
Example 4
The difference from example 1 is that acrylic resin 1 was replaced with acrylic resin 4.
Example 5
The difference from example 1 is that acrylic resin 1 was replaced with acrylic resin 5.
Example 6
The difference from example 1 is that acrylic resin 1 was replaced with acrylic resin 6.
Example 7
The difference from example 1 is that acrylic resin 1 was replaced with acrylic resin 7.
Example 8
The difference from example 1 is that acrylic resin 1 was replaced with acrylic resin 8. .
Example 9
The difference from example 1 is that acrylic resin 1 was replaced with acrylic resin 9.
Example 10
The difference from example 1 is that acrylic resin 1 was replaced with acrylic resin 10.
Example 11
The difference from example 1 is that acrylic resin 1 was replaced with acrylic resin 11.
Example 12
The difference from example 1 is that acrylic resin 1 was replaced with acrylic resin 12.
Example 13
The difference from example 1 is that acrylic resin 1 was replaced with acrylic resin 13.
Example 14
The difference from example 1 is that acrylic resin 1 is mixed with HDI dimer in a hydroxyl to isocyanate molar ratio of 1:1.
Example 15
The difference from example 1 is that acrylic resin 1 was mixed with HDI dimer in a hydroxyl to isocyanate molar ratio of 1: 1.6.
Example 16
A method for using a two-component waterborne polyurethane coating comprises the following steps:
mixing acrylic resin 1 and HDI trimer according to the molar ratio of hydroxyl to isocyanate group of 1:1.3 to obtain a mixture, adding 0.05% of stannous octoate and 0.01% of polydimethylsiloxane (viscosity of 5000cP) in the mass of the mixture, and uniformly dispersing to obtain the double-component waterborne polyurethane coating. After spraying, the coating can be solidified into a film at 40 ℃, and the performance of the coating is tested after two days.
Example 17
Mixing acrylic resin 1 and HDI trimer according to the molar ratio of hydroxyl to isocyanate group of 1:1.3 to obtain a mixture, adding 0.1% of dibutyl tin dilaurate and 0.1% of polydimethylsiloxane (viscosity of 5000cP) in the mass of the mixture, and uniformly dispersing to obtain the double-component waterborne polyurethane coating. After spraying, the coating can be solidified into a film at 40 ℃, and the performance of the coating is tested after two days.
Comparative example 1
The difference from the embodiment 1 is that
Is replaced by
Will be provided with
Replacement was with hydroxyethyl methacrylate.
Comparative example 2
The difference from the embodiment 1 is that
Is replaced by
Will be provided with
Replaced with methyl methacrylate.
And (3) performance testing:
the impact resistance of the coating films was tested by means of a QCJ paint film impactor in accordance with GB/T1732-1993.
The coating hardness was measured by a QHQ type coating pencil scratch hardness tester in accordance with GB/T6739-.
The adhesion of the coating was tested by means of a QFZ-type paint film adhesion tester in accordance with GB/T1720-1979.
The water resistance of the coating was tested in accordance with GB/T1733-1993.
The tack-free time of the coating was tested by means of a QGC-type coating drying time tester in accordance with GB/T1722-1989.
The appearance of the coating was tested by visual inspection according to GB/T1722-.
The results of the performance tests of the examples and comparative examples are shown in table 1.
TABLE 1 summary of film coating performance tests
As can be seen from Table 1, by comparing examples 1 to 3, examples 6 to 17 with comparative examples 1 and 2, the two-component waterborne polyurethane prepared by the invention introduces a polymerization unit containing a bridged ring structure into the main chain of an acrylic resin, and the performances of adhesion, hardness, impact resistance and water resistance of a coating after curing and film forming are shown as follows: the adhesive force is grade 1 or grade 2, the pencil hardness is above grade B, the impact resistance is above 50kg cm, and the water resistance performance is qualified, namely, the introduced polymerization unit containing a bridged ring structure has a remarkable improvement effect on the performance of the two-component waterborne polyurethane.
Comparing example 1 with examples 2 to 5, it can be seen that when n is1/n0When the content of n is in the range of 0.01 to 0.20, the coating film exhibits the best performance1/n0When it is too small, the properties of the structural unit itself having a bridged ring structure cannot be expressed, so that the surface drying time becomes long, the pencil hardness becomes low, and when n is1/n0If the amount is too large, the amount of hydroxyl groups in the acrylic resin increases, an excessive crosslinked network is formed, and the hardness of the coating film can be increased, but the coating film becomes brittle and the impact resistance deteriorates.
The present invention is illustrated in detail by the examples described above, but the present invention is not limited to the details described above, i.e., it is not intended that the present invention be implemented by relying on the details described above. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (37)
1. An acrylic resin, characterized in that it comprises at least one structural unit (a), at least one structural unit (B), at least one structural unit (C) and at least one structural unit (D);
the R is1Is hydrogen or methyl;
m is 0 or 1;
the R is2、R3、R4、R6And R8Each independently selected from hydrogen or methyl;
the R is5Is any one of C1-C12 straight chain or branched chain saturated alkyl;
the R is7Is composed of
N is any integer from 2 to 4;
said X+Is quaternary ammonium salt positive ion;
in the acrylic resin, the total number of the polymerized units is n0The number of the structural units (A) is n1The number of the structural units (B) is n2The number of the structural units (C) is n3The number of the structural units (D) is n4；
N is0、n1、n2、n3、n4The following conditions are satisfied: n is more than or equal to 200≤100、1≤n1≤20、10≤n2≤60、0＜n3≤25、2≤n4≤20。
2. The acrylic resin as claimed in claim 1, wherein n is1/n00.01 to 0.20.
3. The acrylic resin as claimed in claim 1, wherein n is2/n00.10 to 0.60.
4. The acrylic resin as claimed in claim 1, wherein n is3/n00.1 to 0.25.
5. The acrylic resin as claimed in claim 1, wherein n is4/n00.02 to 0.20.
6. A method for preparing the acrylic resin according to any one of claims 1 to 5, comprising the steps of:
(1) dissolving a monomer in a solvent, and carrying out solution polymerization to obtain an acrylate copolymer solution;
the monomer is o-hydroxyl type bridged ring structure acrylate
Alkyl acrylate or methacrylate
Hydroxyalkyl acrylate or hydroxyalkyl methacrylate
Acrylic acid or methacrylic acid
Combinations of (a) and (b).
7. The production method according to claim 6, wherein step (2) is performed after step (1): carrying out neutralization reaction on the acrylate copolymer solution and dispersing the acrylate copolymer solution into a dispersion medium to obtain acrylic resin;
the R is1、R2、R3、R4、R5、R6、R7And R8Having the same limits as in claim 1.
8. The preparation method according to claim 6, wherein the solution polymerization reaction system in the step (1) comprises the following components in percentage by mass:
9. the preparation method according to claim 6, wherein the step (1) specifically comprises: adding a part of solvent into a reactor, heating to reflux the solvent, mixing the monomer, the rest of solvent, a part of initiator and a chain transfer agent according to the formula amount, adding the obtained mixed solution into the reactor, continuously maintaining the reflux temperature, adding the rest of initiator, continuously maintaining the reflux temperature, and terminating the reaction to obtain the acrylate copolymer solution.
10. The method according to claim 9, wherein the mass of the solvent is 50 to 70% of the total mass of the solvent.
11. The method according to claim 9, wherein the mass of the portion of the initiator is 70 to 80% of the total mass of the initiator.
12. The production method according to claim 9, wherein the mixed solution is added dropwise to the reaction system.
13. The preparation method according to claim 9, wherein the dropping time is 3 to 6 hours.
14. The method according to claim 9, wherein the reflux temperature is maintained for 0.5 to 2 hours.
15. The method according to claim 8, wherein the solvent includes any one or a combination of at least two of butylene glycol, 2-methoxypropanol, n-butanol, methoxybutanol, n-propanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, and butyl acetate.
16. The method according to claim 8, wherein the chain transfer agent comprises any one or a combination of at least two of mercaptoethanol, mercaptopropionic acid, and dodecyl mercaptan.
17. The method according to claim 8, wherein the initiator comprises any one or a combination of at least two of azobisisobutyronitrile, dibenzoyl peroxide, tert-butyl peroxybenzoate, dicumyl peroxide, tert-butyl peroxy-2-ethylhexanoate, di-tert-butyl peroxide and di-tert-amyl peroxide.
18. The method according to claim 6, wherein the ortho-hydroxyl type bridged ring structure acrylate comprises any one or a combination of at least two of the following compounds:
19. the preparation method according to claim 7, wherein the acrylic resin in the step (2) has a solid content of 35 to 45%.
20. The method according to claim 7, wherein the neutralizing agent for the neutralization reaction comprises any one or a combination of at least two of 10 to 30% by mass of ammonia, triethylamine, tripropylamine, tributylamine, N-dimethylethanolamine, N-diethylethanolamine, diethanolamine, triethanolamine, diisopropanolamine, N-dimethylisopropylamine and 2-amino-2-methyl-propanol.
21. The method according to claim 20, wherein the molar weight ratio of the neutralizing agent to the carboxyl groups in the acrylate copolymer solution is 0.9 to 1.1: 1.
22. The preparation method according to claim 7, wherein the step (2) specifically comprises: and (3) reducing the temperature of the acrylic ester copolymer solution to 50-70 ℃, adding a neutralizing agent, adjusting the pH value of the system, removing the organic solvent, keeping the temperature of the system at 30-40 ℃, adding deionized water, and stirring to obtain the acrylic resin.
23. The method of claim 7, wherein the dispersion medium comprises deionized water.
24. The method of claim 22, wherein the removing the organic solvent comprises distillation under vacuum.
25. The method according to claim 22, wherein the residual amount of the organic solvent is less than 3% before removing the organic solvent.
26. The method according to claim 22, wherein the pH is adjusted to 6.5 to 9.0.
27. The method according to claim 22, wherein the neutralization reaction time is 10 to 30 min.
28. The method of claim 22, wherein the stirring time is 0.5 to 1 hour.
29. A film-forming composition comprising a polyisocyanate and the acrylic resin of any one of claims 1-5.
30. The film-forming composition of claim 29, wherein the polyisocyanate comprises any one or a combination of at least two of a tetramethylphenyl diisocyanate/trihydroxypropane adduct, a HDI dimer, a HDI trimer and a hydrophilic modification of a polyisocyanate.
31. Use of a film-forming composition according to claim 29 in the application of a coating.
32. The use according to claim 31, wherein the coating comprises any one or a combination of at least two of an automotive coating, a wood coating, an industrial anticorrosive and antirust coating and a plastic coating.
33. A two-component aqueous polyurethane coating, characterized in that it comprises an acrylic resin according to any one of claims 1 to 5; alternatively, the coating comprises the film-forming composition of claim 29.
34. A method of using the two-component aqueous polyurethane coating of claim 33, comprising the steps of: mixing acrylic resin and polyisocyanate according to the molar ratio of hydroxyl to isocyanate of 1: 1-1.6.
35. Use according to claim 34, characterized in that it comprises in particular: mixing acrylic resin and polyisocyanate, adding a catalyst and a defoaming agent, and uniformly dispersing to obtain the double-component waterborne polyurethane coating.
36. The use method of claim 34, wherein the catalyst is added in an amount of 0.05-0.1% by mass based on the total mass of the acrylic resin and the polyisocyanate.
37. The use method of claim 34, wherein the amount of the antifoaming agent added is 0.01-0.1% of the total mass of the acrylic resin and the polyisocyanate.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5621019A (en) * | 1994-01-31 | 1997-04-15 | Nec Corporation | Monomer having vinyl group, polymer thereof and photosensitive resin including those |
| JPH103169A (en) * | 1996-06-18 | 1998-01-06 | Toshiba Corp | Photosensitive composition |
| US6030747A (en) * | 1997-03-07 | 2000-02-29 | Nec Corporation | Chemically amplified resist large in transparency and sensitivity to exposure light less than 248 nanometer wavelength and process of forming mask |
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| JP5593075B2 (en) * | 2010-01-13 | 2014-09-17 | 富士フイルム株式会社 | Pattern forming method, pattern, chemically amplified resist composition, and resist film |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5621019A (en) * | 1994-01-31 | 1997-04-15 | Nec Corporation | Monomer having vinyl group, polymer thereof and photosensitive resin including those |
| JPH103169A (en) * | 1996-06-18 | 1998-01-06 | Toshiba Corp | Photosensitive composition |
| US6030747A (en) * | 1997-03-07 | 2000-02-29 | Nec Corporation | Chemically amplified resist large in transparency and sensitivity to exposure light less than 248 nanometer wavelength and process of forming mask |
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