CN113429524A - Film-forming resin for water-based floating-coating-free colored paint and preparation method thereof - Google Patents
Film-forming resin for water-based floating-coating-free colored paint and preparation method thereof Download PDFInfo
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- CN113429524A CN113429524A CN202110823550.3A CN202110823550A CN113429524A CN 113429524 A CN113429524 A CN 113429524A CN 202110823550 A CN202110823550 A CN 202110823550A CN 113429524 A CN113429524 A CN 113429524A
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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
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
- C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
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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
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/003—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
Abstract
The invention discloses a film-forming resin for water-based floating-free paint and a preparation method thereof, which comprises the steps of firstly synthesizing a high-softening-point modified acrylic resin prepolymer by a solution method, using a low-softening-point monomer and a hydrophilic cosolvent in a reaction kettle as dispersion liquid, and carrying out copolymerization between the low-softening-point monomer and grafting and interpenetrating with the high-softening-point modified acrylic resin prepolymer by an initiator and heating; and (3) adding a neutralizing agent to neutralize after the reaction is finished, removing part of the solvent in advance, adding an emulsifying agent to emulsify and disperse water, and continuously removing the organic solvent until the residue of the organic solvent is controlled to be below 15 percent of the total amount of the cosolvent to obtain the modified polyacrylate water dispersion. The resin prepared by the invention is used as film-forming resin for the floating-coating-free paint, the film-forming resin is a self-drying volatile system, a cross-linking agent is not needed, the cost is reduced, and inconvenience caused by the use process of the cross-linking agent is avoided.
Description
Technical Field
The invention relates to a film-forming resin for a waterborne floating-coating-free paint and a preparation method thereof.
Background
The mainstream scheme for coating automobile bodies at home and abroad is a three-coating system, namely, a cathode electrophoretic paint layer (also called an electrophoretic primer layer), a middle paint layer and a finish paint layer are sequentially coated on an automobile body material. The middle coating is an important coating, can fill up defects or marks on the surface of the electrophoretic primer layer, increases the adhesive force between the primer and the electrophoretic primer layer, and has better stone-impact resistance, surface smoothness and weather resistance.
With the progress of finish paint technology, the performance of the finish paint still reaches the performance of the original three coatings after the intermediate coating is omitted, so the intermediate coating-free coating process is widely applied.
The applicant filed a floating-coating-free glittering base coat for metal parts and a preparation method thereof on 29/11/2010 (application number 201010563534.7), and the floating-coating-free glittering base coat comprises the following components in parts by weight: 26-35 parts of polyester modified resin, 7-10 parts of amino resin, 3-8 parts of closed aliphatic polyisocyanate, 4-10 parts of functional resin, 8-15 parts of rheological control resin, 1-6 parts of coloring pigment, 0.5-8 parts of effect pigment, 3-10 parts of filler, 2-8 parts of light stabilizing auxiliary agent, 2-5 parts of dispersing agent, 0.1-2 parts of flatting agent, 3-10 parts of orientation auxiliary agent, 1-5 parts of anti-settling auxiliary agent and 20-40 parts of organic solvent.
Also, on 2/4/2015, an application of 'aqueous short process flash base color paint and a coating method thereof' (application number 201510057053.1) is filed, wherein the short process is a floating-coating-free process without floating coat, and the base color paint comprises a first aqueous short process flash base color paint and a second aqueous short process flash base color paint; the first-pass water-based short-process flashing base coat comprises a paint component and a curing agent.
Although the two technologies have excellent performance, a two-component system is involved, a curing agent needs to be used for crosslinking, the preparation of the two components in the coating process is consistent with the consumption in the application process so as to reduce unnecessary consumption, and the consumption of the two-component water-based system on a crosslinking agent is multiplied compared with the consumption of the traditional solvent-based system.
Disclosure of Invention
The invention aims to solve the technical problem of providing a film-forming resin for a water-based floating-coat-free paint and a preparation method thereof.
The technical scheme for realizing the aim of the invention is a preparation method of film-forming resin for water-based floating-coating-free paint, which comprises the following steps:
firstly, a solution method is adopted to synthesize a modified acrylic resin prepolymer with high softening point.
And secondly, using the low-softening-point monomers and the hydrophilic cosolvent in the reaction kettle as dispersion liquid, and performing copolymerization between the low-softening-point monomers and grafting and interpenetrating with the high-softening-point modified acrylic resin prepolymer through an initiator and heating.
Thirdly, adding a neutralizing agent for neutralization after the reaction is finished, removing part of the solvent in advance, then adding an emulsifying agent for emulsification and water dispersion, and then continuously removing the organic solvent until the residue of the organic solvent is controlled below 15 percent of the total amount of the cosolvent to obtain the modified polyacrylate water dispersion.
Injecting a proper amount of cosolvent into a reactor, starting stirring, heating to above 90 ℃, starting dropwise adding a mixture of a high-softening-point monomer, active siloxane and an initiator for 3-6 h, and continuously preserving heat for 3-6 h at 100-110 ℃; dropping a mixture of a low-softening-point monomer and an initiator in 3-6 h, keeping the temperature for 3-6 h, adding a neutralizer N, N-dimethylethanolamine for neutralization, and controlling the neutralization degree to be 90-95%; distilling under reduced pressure to remove organic solvent, adding emulsifier and stirring uniformly when the solvent removal amount reaches 60% of the total amount of the solvent, slowly adding water, rapidly stirring, emulsifying and dispersing water during the water addition process, continuously removing the organic solvent until the organic solvent residue is controlled below 15% of the total amount of the cosolvent, filtering, and packaging.
The cosolvent is a hydrophilic solvent with dissolving capacity for thermoplastic acrylic acid.
The high-softening-point monomer is a mixture of three or more of butyl methacrylate, methyl methacrylate, acrylonitrile, isobornyl methacrylate, isobornyl acrylate, methacrylic acid, acrylic acid and styrene.
The reactive siloxane is vinyl silicone.
The initiator is azo or peroxide.
Adding a hydrophilic cosolvent into a reactor filled with a prepolymer, dropwise adding a mixture of a low-softening-point monomer and an initiator, dropwise adding the mixture in 3-6 hours, and continuously preserving the temperature for 3-6 hours; and (4) dropwise adding and preserving heat, wherein the temperature is controlled to be 90-110 ℃.
The ratio of the total mass of the high-softening-point monomers to the total mass of the low-softening-point monomers is 80-95: 5-20.
Optionally, the low-softening-point monomer is a mixture of three or more of methyl methacrylate, butyl acrylate, ethyl acrylate, isooctyl acrylate, acrylic acid and styrene;
the initiator is azo or peroxide.
Preferably, in the third step, the neutralizer is N, N-dimethylethanolamine, and the neutralization degree is controlled to be 90-95%.
In the step (III), the emulsifier is anionic or nonionic.
In the third step, the cosolvent is properly supplemented with water in the process of evaporation to maintain the effective mass fraction of the resin within 50 +/-5%.
The invention has the positive effects that:
(1) when the resin is prepared, firstly, a solvent method is adopted to synthesize the high-softening-point acrylic prepolymer, then, a monomer mixture with a low softening point participates in the structural penetration of the high-softening-point oligomer, and then, copolymerization, neutralization, emulsifying by adding an emulsifier, water dispersion and solvent removal are carried out, so that the film-forming polymer of a self-crosslinking and single-component self-drying system is obtained. The resin prepared by the invention can be used as film-forming resin for the floating-coating-free paint, the film-forming resin is a self-drying volatile system, a cross-linking agent is not required for curing, the cost is reduced, and inconvenience caused by the use process of the cross-linking agent is avoided.
(2) The film-forming resin has strong practicability and can be widely used as a film-forming base material of water-based paint without painting. The colored paint prepared by using the film-forming resin has the functions of a middle coating paint and a base paint, and has excellent mechanical properties, dryness, stone impact resistance and medium resistance.
Drawings
FIG. 1 is a process flow diagram of the present invention.
Detailed Description
(example 1)
Referring to fig. 1, the preparation method of the film-forming resin for the waterborne floating-in-paint of the present embodiment comprises the following steps:
adding a hydrophilic cosolvent into a reactor with a heating and stirring device, starting stirring and heating, dropwise adding a mixture of a high-softening-point monomer, active siloxane and an initiator when the temperature is increased to 90-95 ℃, continuously preserving the temperature for 3-6 hours at 100-110 ℃ after dropwise adding is finished for 3-6 hours to obtain a hard monomer prepolymer, and then carrying out a pre-polymerization with a pre-polymerization A code.
The cosolvent is a hydrophilic solvent having a dissolving capacity for thermoplastic acrylic acid, such as one or more of ethylene glycol ethyl ether, ethylene glycol butyl ether, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol butyl ether, and the like, and in this embodiment, is propylene glycol methyl ether.
The reactive silicone is a vinyl silicone, such as KH-570 or A-151, having a vinyl silicone content of 0.5% to 5% (based on the reactive double bond monomer consumed by the final dispersion emulsion). The reactive silicone in this example is KH-570.
The high softening point monomer is selected from butyl methacrylate, methyl methacrylate, acrylonitrile, isobornyl methacrylate, isobornyl acrylate, methacrylic acid, acrylic acid and styrene, and is a mixture of 3 or more than 3 of the monomers.
The initiator may be azo type or peroxide, such as azobisisobutyronitrile, t-amyl peroxide, benzoyl peroxide, and in this embodiment benzoyl peroxide is used.
Specifically, in this embodiment, 50 parts of hydrophilic cosolvent is added into a reactor with a heating and stirring device, stirring and temperature rising are started, when the temperature rises to 90 ℃, a mixture containing 35 parts of methyl methacrylate, 1 part of acrylonitrile, 2.5 parts of methacrylic acid, 6.5 parts of butyl methacrylate, 4.5 parts of styrene, 0.5 part of KH-570 and 0.5 part of benzoyl peroxide is added dropwise, after the dropwise addition is completed for 3 hours, the temperature is kept at 100-110 ℃ for 4 hours to obtain a hard monomer prepolymer, and the mark of the prepolymer A is used later, and the softening point is controlled at 85-95 ℃.
② adding hydrophilic cosolvent and 1/3 of low-softening-point monomer into a reactor filled with prepolymer A, and uniformly stirring.
The low softening point monomer is selected from methyl methacrylate, butyl acrylate, ethyl acrylate, isooctyl acrylate, acrylic acid and styrene.
Specifically, 50 parts of propylene glycol methyl ether and 1/3 parts of a low-softening-point monomer (composed of 15 parts of butyl acrylate, 9 parts of isooctyl acrylate, 2.5 parts of acrylic acid, 6 parts of methyl methacrylate, 5 parts of butyl methacrylate, 5 parts of styrene and 7.5 parts of ethyl acrylate) are added into a reactor filled with prepolymer A and stirred uniformly.
After the temperature is raised to 90 ℃, the mixture of 0.5 part of benzoyl peroxide and the rest of the mixed monomer B is dripped in 3 hours, the temperature in the reactor is controlled to be 90-110 ℃ in the dripping process, and the temperature is kept for 4 hours at 90-110 ℃ after the dripping is finished.
The ratio of the total mass of the high-softening-point monomers to the total mass of the low-softening-point monomers is 80-95: 5-20, in this example 4: 1.
Thirdly, after the heat preservation is finished, adding 5.4 parts of organic base N, N-dimethylethanolamine into the reacted materials for neutralization, and controlling the neutralization degree to be 90-95 percent; after neutralization, the cosolvent is removed by reduced pressure distillation.
When the removal amount of the solvent reaches 60 percent of the total amount of the solvent, 1.5 parts of emulsifier sodium dodecyl benzene sulfonate is added into the material of the pre-removed cosolvent and is stirred uniformly, then 90 parts of water is slowly added (after about 20 minutes), and the material is quickly stirred, emulsified and dispersed in water in the water adding process.
The emulsifier is anionic emulsifier and nonionic emulsifier, such as OP series, sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, etc., in this embodiment sodium dodecyl benzene sulfonate.
Removing the residual organic solvent in the reactor by reduced pressure distillation after the material is dispersed in water until 90 percent of the cosolvent injected in the initial stage of the system is evaporated; properly supplementing water in the process of distilling off the cosolvent to maintain the mass effective component of the resin within 50 +/-5%; filtering after reduced pressure distillation to obtain the modified polyacrylate water dispersion, namely the film-forming resin for the waterborne floating-in-free paint, wherein the film-forming resin contains a small amount of cosolvent.
(example 2)
The preparation method of the film-forming resin for the waterborne floating-in-paint of the embodiment is the same as that of the embodiment 1 except that:
adding a hydrophilic cosolvent into a reactor with a heating and stirring device, starting stirring and heating, and dropwise adding a mixture containing 35 parts of methyl methacrylate, 1 part of isobornyl acrylate, 2.5 parts of acrylic acid, 6.5 parts of butyl methacrylate, 4.5 parts of styrene, 0.5 part of KH-570 and 0.5 part of benzoyl peroxide when the temperature is increased to 90 ℃.
In the second step, the mixed monomer B is composed of 24 parts of butyl acrylate, 2.5 parts of acrylic acid, 6 parts of methyl methacrylate, 5 parts of butyl methacrylate, 5 parts of styrene and 7.5 parts of ethyl acrylate.
(example 3)
The preparation method of the film-forming resin for the waterborne floating-in-paint of the embodiment is the same as that of the embodiment 1 except that:
in the first step, when the temperature is raised to 90 ℃, a mixture containing 35 parts of methyl methacrylate, 1 part of acrylonitrile, 2.5 parts of methacrylic acid, 6.5 parts of butyl methacrylate, 4.5 parts of styrene, 0.5 part of KH-570 and 0.5 part of benzoyl peroxide is dripped, and after the dripping is finished for 5 hours, the temperature is kept for 5 hours at 100-110 ℃ to obtain the hard monomer prepolymer.
In the second step, after the temperature is raised to 90 ℃, the mixture of 0.5 part of benzoyl peroxide and the rest of the mixed monomer B (2/3 of the mixed monomer B) is dripped in 5 hours, the temperature in the reactor is controlled to be about 100 ℃ plus or minus 10 ℃ in the dripping process, and the temperature is kept for 5 hours at 90-110 ℃ after the dripping is finished.
(Experimental example 1)
Comparative example: the aqueous dispersion prepared in one step was mixed and added dropwise in the same manner and at the same reaction temperature as in example 1.
The preparation method comprises the specific one-step mixing and dropwise adding preparation process that propylene glycol methyl ether is added into a reactor with a heating and stirring device, stirring and heating are started, when the temperature is increased to 90 ℃, a mixture of a high-softening-point monomer, active siloxane, a low-softening-point monomer (mixed monomer B) and an initiator is dropwise added, after dropwise adding is completed within 3-6 hours, heat preservation is continuously carried out for 3-6 hours at the temperature of 100-110 ℃.
(1) The modified polyacrylate of examples 1 to 3 and the aqueous dispersion of the comparative example were applied to a steel member coated with an electrophoretic primer layer according to the test requirements, and the test was carried out after air-drying at room temperature, and the results of the resin film property test were as follows:
(2) the modified polyacrylate of examples 1 to 3 and the aqueous dispersion of the comparative example were applied to ABS parts according to the test requirements, and after air-drying at room temperature, the resin film performance test results were as follows:
(4) the modified polyacrylate of examples 1 to 3 and the aqueous dispersion of the comparative example were applied to HIPS parts in proper amounts according to the test requirements, and after air-drying at room temperature, the resin film performance test results were as follows:
the modified polyacrylate water dispersion prepared by the invention is a single-component self-drying system, does not need to be crosslinked by an external crosslinking agent, and has the performance meeting the requirement of coating resin on vehicles; the modified polyacrylate water dispersion has good adhesion fastness on the surfaces of a metal electrophoretic paint layer and plastics such AS ABS, PVC, PS (HIPS), AS and the like.
Claims (10)
1. A preparation method of film-forming resin for water-based floating-coating-free paint is characterized by comprising the following steps:
firstly, synthesizing a high-softening-point modified acrylic resin prepolymer by a solution method;
using a low-softening-point monomer and a hydrophilic cosolvent in a reaction kettle as a dispersion liquid, and performing copolymerization between the low-softening-point monomer and a high-softening-point modified acrylic resin prepolymer for grafting and interpenetrating through an initiator and heating;
thirdly, adding a neutralizing agent for neutralization after the reaction is finished, removing part of the solvent in advance, then adding an emulsifying agent for emulsification and water dispersion, and then continuously removing the organic solvent until the residue of the organic solvent is controlled below 15 percent of the total amount of the cosolvent to obtain the modified polyacrylate water dispersion.
2. The method for preparing the film-forming resin for the waterborne floating-in-paint according to claim 1, wherein the method comprises the following steps:
adding a hydrophilic cosolvent into a reactor with a heating and stirring device, starting stirring and heating, dropwise adding a mixture of a high-softening-point monomer, active siloxane and an initiator when the temperature is raised to 90-95 ℃, after dropwise adding is completed within 3-6 hours, continuously preserving the temperature for 3-6 hours at 100-110 ℃ to obtain the high-softening-point modified acrylic resin prepolymer.
3. The method for preparing the film-forming resin for the waterborne floating-in-paint according to claim 2, wherein the method comprises the following steps: the ratio of the total mass of the high-softening-point monomers to the total mass of the low-softening-point monomers is 80-95: 5-20.
4. The method for preparing the film-forming resin for the waterborne floating-in-paint according to claim 2, wherein the method comprises the following steps:
the cosolvent is a hydrophilic solvent with dissolving capacity on thermoplastic acrylic acid;
the high-softening-point monomer is a mixture of three or more of butyl methacrylate, methyl methacrylate, acrylonitrile, isobornyl methacrylate, isobornyl acrylate, methacrylic acid, acrylic acid and styrene;
the active siloxane is vinyl silicone;
the initiator is azo or peroxide.
5. The method for preparing the film-forming resin for the waterborne floating-in-paint according to claim 1, wherein the method comprises the following steps:
adding a hydrophilic cosolvent into a reactor filled with a prepolymer, dropwise adding a mixture of a low-softening-point monomer and an initiator, dropwise adding the mixture in 3-6 hours, and continuously preserving the temperature for 3-6 hours; and (4) dropwise adding and preserving heat, wherein the temperature is controlled to be 90-110 ℃.
6. The method for preparing the film-forming resin for the waterborne floating-in-paint according to claim 5, wherein the method comprises the following steps:
the low-softening-point monomer is a mixture of three or more than three of methyl methacrylate, butyl acrylate, ethyl acrylate, isooctyl acrylate, acrylic acid and styrene;
the initiator is azo or peroxide.
7. The method for preparing the film-forming resin for the waterborne floating-in-paint according to claim 1, wherein the method comprises the following steps:
in the third step, the neutralizer is N, N-dimethylethanolamine, and the neutralization degree is controlled to be 90-95%.
8. The method for preparing the film-forming resin for the waterborne floating-in-paint according to claim 1, wherein the method comprises the following steps:
in the step (III), the emulsifier is anionic or nonionic.
9. The method for preparing the film-forming resin for the waterborne floating-in-paint according to claim 1, wherein the method comprises the following steps:
in the third step, the cosolvent is properly supplemented with water in the process of evaporation to maintain the effective mass fraction of the resin within 50 +/-5%.
10. A film-forming resin for an aqueous floating-on paint prepared by the process according to claim 1.
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| CN202110823550.3A CN113429524A (en) | 2021-07-21 | 2021-07-21 | Film-forming resin for water-based floating-coating-free colored paint and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115975485A (en) * | 2022-12-06 | 2023-04-18 | 常州市武进晨光金属涂料有限公司 | Water-based primer-topcoat coating |
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