CN111763296A - Modified acrylic resin and preparation method thereof - Google Patents
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
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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
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4063—Mixtures of compounds of group C08G18/62 with other macromolecular compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4081—Mixtures of compounds of group C08G18/64 with other macromolecular compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
- C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
- C08G18/622—Polymers of esters of alpha-beta ethylenically unsaturated carboxylic acids
- C08G18/6225—Polymers of esters of acrylic or methacrylic acid
- C08G18/6229—Polymers of hydroxy groups containing esters of acrylic or methacrylic acid with aliphatic polyalcohols
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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
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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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2150/00—Compositions for coatings
- C08G2150/90—Compositions for anticorrosive coatings
Abstract
The invention discloses a modified acrylic resin and a preparation method thereof, wherein the modified acrylic resin is prepared from the following main raw materials: the modified acrylic resin comprises hydroxy acrylic resin, isocyanate and polyaspartic acid ester, wherein the hydroxy acrylic resin comprises the following raw materials in percentage by weight: 28-32% of organic solvent, 40-51% of hard monomer, 3-7% of soft monomer, 10-12% of hydroxyl monomer and 4-5% of initiator. According to the invention, through introducing the polyaspartic acid ester, a hydroxyl group with low reaction activity on the original hydroxyl acrylic resin is replaced by a high-activity amino group, so that the reaction speed of the resin and a-NCO group in a curing agent is improved, the curing speed of a paint film is obviously accelerated, the drying time is shortened, the time interval for polishing the paint film is reduced, the baking process in the conventional production can be cancelled, the energy is saved, and in addition, the adhesive force, the chemical corrosion resistance and the aging resistance of the paint film are also improved.
Description
Technical Field
The invention relates to the technical field of resin synthesis, in particular to a modified acrylic resin and a preparation method thereof.
Background
The traditional hydroxyl acrylic resin is a high molecular polymer formed by copolymerizing acrylic ester, methacrylate ester and ethylene unsaturated monomers, and the acrylic resin with different performances and different occasions is synthesized by selecting monomers with different structures, then adjusting the monomer ratio and adopting different processes. The hydroxyl acrylic resin is a decorative raw material with high cost performance and wide application, and the prepared coating has the characteristic of wide adaptability and is widely applied to industries such as automobiles, household appliances, mobile phones and the like.
The hydroxyl group-OH in the hydroxyl resin formula and the-NCO group in the curing agent have the defects of slow reaction speed and overlong low-temperature reaction time in winter. The prior hydroxy acrylic resin coating generally adopts delayed curing time and increased baking procedures to solve the problem; this makes the construction process time longer, and the decoration spraying production efficiency is low, and the baking process then causes the waste of energy. The second method for improving the reaction speed of-OH and-NCO is to add tertiary amine and organic metal catalysts, but because the addition amount of the catalysts is relatively large, the catalysts are not connected to a molecular structure in a chemical bond mode, and the effect is limited, after the paint is cured into a film, the catalysts remain in a free form in the paint film, and the appearance and the weather resistance of the paint film are adversely affected. The third method is to select the kind of isocyanate, such as an aromatic isocyanate-based initiator like TDI trimer. Although the initiator has high reaction speed, the initiator has a great defect of poor weather resistance, easy yellowing of resin and limited application range.
Disclosure of Invention
The invention aims to provide a modified acrylic resin and a preparation method thereof, the modified acrylic resin solves the problem that the common hydroxyl acrylic resin is slow to dry, the modified acrylic resin obviously improves the curing speed on the basis of keeping the conventional performance, and the adhesive force, the chemical corrosion resistance and the aging resistance are also improved to a certain extent.
In order to achieve the purpose, the invention adopts the following technical scheme:
a modified acrylic resin is composed of the following main raw materials: hydroxyacrylic resins, isocyanates and polyaspartic esters;
the hydroxyl acrylic resin is prepared from the following raw materials in percentage by weight:
28-32% of organic solvent, 40-51% of hard monomer, 3-7% of soft monomer, 10-12% of hydroxyl monomer and 4-5% of initiator;
the molar ratio of the isocyanate to the hydroxyl monomer is 0.4-1.0, and the molar ratio of the polyaspartic ester to the isocyanate is 1-1.3.
The weight ratio of the isocyanate to the hydroxyl monomer is 0.4-1.7, and the weight ratio of the polyaspartic ester to the isocyanate is 0.5-2.0.
Preferably, the organic solvent is any one or more of butyl acetate, propylene glycol methyl ether acetate, xylene, sec-butyl acetate or ethyl acetate.
Preferably, the hard monomer is any one or more of methyl methacrylate, styrene or cyclohexyl methacrylate.
Preferably, the soft monomer is any one or more of butyl acrylate, ethyl acrylate or methyl acrylate.
Preferably, the hydroxyl monomer is any one or more of hydroxyethyl acrylate, hydroxyethyl methacrylate or hydroxypropyl methacrylate.
Preferably, the initiator is any one or more of di-tert-butyl peroxide, tert-butyl peroxybenzoate or di-tert-amyl peroxide.
Preferably, the isocyanate is IPDI or hexahydrotoluene diisocyanate.
Preferably, the polyaspartic acid ester has a solids content of greater than 95% and a viscosity of 0.2 to 0.5 Pa.s.
The preparation method of the modified acrylic resin comprises the following steps:
s1, synthesizing hydroxyl acrylic resin: heating an organic solvent to a reaction temperature, dropwise adding a mixture of a hard monomer, a soft monomer, a hydroxyl monomer and an initiator, and carrying out heat preservation reaction to obtain a hydroxyl acrylic resin as a first section of a prepolymer;
s2, synthesis of a urethane prepolymer: after cooling, adding a catalyst, dripping isocyanate, and then carrying out heat preservation reaction to obtain a urethane prepolymer as a prepolymer II section, wherein the reaction equation is as shown in formula 1 (in the formula, the reaction equation is from the main chain of the hydroxyl acrylic resin to the main chain of the hydroxyl acrylic resin):
s3, slowly adding the urethane prepolymer obtained in the step S2 into polyaspartic acid ester, and stirring and reacting at a controlled temperature to obtain the modified acrylic resin, wherein the reaction equation is as follows:
it is understood that in formula 1, under the action of the catalyst, the IPDI preferentially and selectively reacts the NCO group on the hexylene, and the C ═ N bond is opened to replace the hydrogen atom on the hydroxyl group.
Preferably, step S1 is performed under a protective atmosphere, and a protective gas is introduced to replace air before the temperature is raised.
Preferably, the weight average molecular weight of the hydroxyacrylic resin of step S1 is 1500-6000.
Preferably, the catalyst in step S2 is at least one of stannous octoate (abbreviated SO), dibutyltin dilaurate (abbreviated DBTDL) or triethylamine (abbreviated TEA).
Preferably, the reaction temperature in the step S1 is 150-170 ℃, and the heat preservation reaction time is 4-6 h.
Preferably, step S1 controls the mixture to be dripped within 2-6h, and step S2 controls the isocyanate to be dripped within 0-5 h.
Preferably, the temperature of the step S2 is reduced to 42-46 ℃, and the reaction time is kept for 1-2 h.
Preferably, the temperature-controlled reaction in step S3 is controlled at 0-35 deg.C for 0.5-1 h.
Has the advantages that:
1. according to the invention, through introducing polyaspartic acid ester, hydroxyl groups with low reaction activity on the original hydroxyl acrylic resin are replaced by high-activity amino groups, so that the reaction speed of-NCO groups in the resin and the curing agent is improved, the curing speed of a paint film is remarkably accelerated, and the drying time is shortened by more than 10 times;
2. according to the invention, by reducing the time interval between paint film polishing, the baking process required in the conventional production can be eliminated, and the energy is saved;
3. the adhesive force, the chemical corrosion resistance and the aging resistance of the paint film of the modified acrylic resin prepared by the invention are improved.
Drawings
The above and/or additional aspects and advantages of the present invention will become apparent and readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings of which:
FIG. 1 is a hardness test comparison chart of example 1, example 2 and a comparative example;
FIG. 2 is a comparative graph of adhesion tests of example 1, example 2 and comparative example.
Detailed Description
The present invention will be explained in more detail with reference to examples. The practice of the present invention is not limited to the following examples, and any modification or variation of the present invention is within the scope of the present invention.
A modified acrylic resin has a formula composition shown in Table 1:
TABLE 1
Example 1
A preparation method of modified acrylic resin comprises the following steps:
s1, firstly introducing nitrogen into a reaction kettle, adding 30kg of butyl acetate, heating to 160 ℃, dropwise adding a mixture of 17kg of methyl methacrylate, 24kg of styrene, 7kg of cyclohexyl methacrylate, 5kg of butyl acrylate, 12kg of hydroxyethyl acrylate and 5kg of di-tert-butyl peroxide into the reaction kettle at a constant speed within 6 hours, and preserving heat for 5 hours to obtain low-molecular-weight hydroxy acrylic resin as a first section of a prepolymer;
s2, introducing cooling water to reduce the temperature in the reaction kettle to 46 ℃, adding 0.005kg of metal organic catalyst stannous octoate, dropwise adding 20kg of IPDI into the reaction kettle at a constant speed within 5h, and keeping the temperature for 1h to obtain a urethane prepolymer serving as a second section of the prepolymer;
s3, adding 36kg of polyaspartic ester serving as a base material into another reaction kettle, selecting JH-8122 of Zhejiang Jinfeng new material science and technology limited, wherein the solid content is 96% and the viscosity is 0.2 Pa.s, keeping the temperature in the kettle below 30 ℃, slowly adding the carbamate prepolymer obtained in the step S2 while stirring, controlling the temperature in the adding process to be not more than 35 ℃, slowing down the adding speed of the materials if the temperature is raised under the condition of a cold water bath, stirring for 0.5h after the adding, and adjusting indexes by using a solvent to discharge to obtain a modified acrylic resin finished product.
Example 2
A preparation method of modified acrylic resin comprises the following steps:
s1, firstly introducing nitrogen into a reaction kettle, adding 30kg of butyl acetate, heating to 160 ℃, dropwise adding a mixture of 17kg of methyl methacrylate, 24kg of styrene, 7kg of cyclohexyl methacrylate, 5kg of butyl acrylate, 12kg of hydroxyethyl acrylate and 5kg of di-tert-butyl peroxide into the reaction kettle at a constant speed within 6 hours, and preserving heat for 5 hours to obtain low-molecular-weight hydroxy acrylic resin as a first section of a prepolymer;
s2, introducing cooling water to reduce the temperature in the reaction kettle to 46 ℃, adding 0.005kg of metal organic catalyst stannous octoate, dropwise adding 10kg of IPDI into the reaction kettle at a constant speed within 5h, and keeping the temperature for 1h to obtain a urethane prepolymer serving as a second section of the prepolymer;
s3, adding 18kg of polyaspartic ester serving as a base material into another reaction kettle, selecting JH-8122 of Zhejiang Jinfeng new material science and technology limited, wherein the solid content is 96 percent, the viscosity is 0.2 Pa.s, keeping the temperature in the kettle below 30 ℃, slowly adding the carbamate prepolymer obtained in the step S2 while stirring, controlling the temperature in the adding process to be not more than 35 ℃, slowing down the adding speed of the materials if the temperature is raised under the condition of a cold water bath, stirring for 0.5h after the adding, and adjusting indexes by using a solvent to discharge to obtain a modified acrylic resin finished product.
Comparative example (ordinary hydroxy acrylic resin)
The preparation method of the general hydroxyacrylic resin is step S1 of example 1.
The resins obtained in example 1, example 2 and comparative example were formulated into overprint varnishes according to the formulation given in Table 2 to give paint films 1, 2 and 3, respectively.
TABLE 2
Conventional performance testing of paint film 1, paint film 2 and paint film 3 the comparative examples are shown in table 3:
TABLE 3
As can be seen from Table 3, the surface drying time and the actual drying time of the paint film 1 and the paint film 2 are obviously reduced compared with those of the comparative example, which shows that the modified acrylic resin has a faster curing speed, other conventional properties are maintained, and the chemical corrosion resistance and the aging resistance are improved to a certain extent.
According to the GB T1730-2007 standard, the hardness of a paint film is tested by adopting a pendulum hardness tester according to set time, a graph is drawn by testing the hardness and the time as shown in figure 1, and it can be seen that the drying speed is obviously improved in the embodiment 1 and the embodiment 2, and the drying speed is improved by more than 10 times compared with that of a conventional product.
The paint films obtained in example 1, example 2 and comparative example were respectively coated on ABS and PC boards, and the adhesion tests were carried out on the ABS and PC boards according to GB1720-89, the adhesion being best rated 0 according to the standard, the results of the test are shown in FIG. 2, and the adhesion to PC boards can be seen from FIG. 2: example 1> example 2> comparative example, adhesion to ABS plaques: example 1> example 2> comparative example, which shows that the modified resin has obvious improvement on adhesion.
The above embodiments are only preferred embodiments of the present invention, and the embodiments of the present invention are not limited to the above embodiments, and any other changes, modifications, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. The modified acrylic resin is characterized by comprising the following main raw materials: hydroxyacrylic resins, isocyanates and polyaspartic esters;
the hydroxyl acrylic resin is prepared from the following raw materials in percentage by weight:
28-32% of organic solvent, 40-51% of hard monomer, 3-7% of soft monomer, 10-12% of hydroxyl monomer and 4-5% of initiator;
the weight ratio of the isocyanate to the hydroxyl monomer is 0.4-1.7, and the weight ratio of the polyaspartic ester to the isocyanate is 0.5-2.0.
2. The modified acrylic resin as claimed in claim 1, wherein the organic solvent is one or more selected from butyl acetate, propylene glycol methyl ether acetate, xylene, sec-butyl acetate and ethyl acetate.
3. The modified acrylic resin as claimed in claim 1, wherein the hard monomer is any one or more of methyl methacrylate, styrene and cyclohexyl methacrylate; the soft monomer is any one or more of butyl acrylate, ethyl acrylate and methyl acrylate.
4. The modified acrylic resin as claimed in claim 1, wherein the hydroxyl monomer is any one or more of hydroxyethyl acrylate, hydroxyethyl methacrylate and hydroxypropyl methacrylate; the initiator is any one or more of di-tert-butyl peroxide, tert-butyl peroxybenzoate and di-tert-amyl peroxide.
5. The modified acrylic resin of claim 1 wherein said isocyanate is IPDI or hexahydrotoluene diisocyanate.
6. The modified acrylic resin of claim 1 wherein said polyaspartic ester has a solids content of greater than 95% and a viscosity of 0.2 to 0.5 pa.s.
7. The method for producing a modified acrylic resin as claimed in any one of claims 1 to 6, comprising the steps of:
s1, synthesizing hydroxyl acrylic resin: heating an organic solvent to a reaction temperature, dropwise adding a mixture of a hard monomer, a soft monomer, a hydroxyl monomer and an initiator, and carrying out heat preservation reaction to obtain hydroxyl acrylic resin;
s2, synthesis of a urethane prepolymer: after cooling, adding a catalyst, then dropwise adding isocyanate, and then carrying out heat preservation reaction to obtain a carbamate prepolymer, wherein the reaction equation is as shown in formula 1:
s3, adding the urethane prepolymer obtained in the step S2 into polyaspartic acid ester, and performing temperature control reaction to obtain the modified acrylic resin, wherein the reaction equation is as shown in formula 2:
8. the method according to claim 7, wherein the catalyst in step S2 is at least one of stannous octoate, dibutyltin dilaurate or triethylamine.
9. The method as claimed in claim 7, wherein the reaction temperature in step S1 is 150 ℃ to 170 ℃, and the reaction time is 4-6 h.
10. The preparation method according to claim 7, wherein the temperature of step S2 is reduced to 42-46 ℃, and the reaction time is 1-2 h; the temperature of the temperature-controlled reaction in the step S3 is 0-35 ℃, and the time of the temperature-controlled reaction is 0.5-1 h.
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