CN116217782A - High-flexibility acrylic resin for powder coating and preparation method thereof - Google Patents
High-flexibility acrylic resin for powder coating and preparation method thereof Download PDFInfo
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- CN116217782A CN116217782A CN202211736504.0A CN202211736504A CN116217782A CN 116217782 A CN116217782 A CN 116217782A CN 202211736504 A CN202211736504 A CN 202211736504A CN 116217782 A CN116217782 A CN 116217782A
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- 238000000576 coating method Methods 0.000 title claims abstract description 44
- 239000011248 coating agent Substances 0.000 title claims abstract description 42
- 239000004925 Acrylic resin Substances 0.000 title claims abstract description 37
- 229920000178 Acrylic resin Polymers 0.000 title claims abstract description 37
- 239000000843 powder Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title description 12
- 239000002904 solvent Substances 0.000 claims abstract description 22
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 20
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 20
- GJBXIPOYHVMPQJ-UHFFFAOYSA-N hexadecane-1,16-diol Chemical compound OCCCCCCCCCCCCCCCCO GJBXIPOYHVMPQJ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 17
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims abstract description 16
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims abstract description 16
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims abstract description 9
- FOTKYAAJKYLFFN-UHFFFAOYSA-N decane-1,10-diol Chemical compound OCCCCCCCCCCO FOTKYAAJKYLFFN-UHFFFAOYSA-N 0.000 claims abstract description 9
- 230000003197 catalytic effect Effects 0.000 claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims description 32
- 238000006243 chemical reaction Methods 0.000 claims description 30
- 239000000463 material Substances 0.000 claims description 23
- XLLIQLLCWZCATF-UHFFFAOYSA-N 2-methoxyethyl acetate Chemical group COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 claims description 16
- 239000002994 raw material Substances 0.000 claims description 16
- 239000004593 Epoxy Substances 0.000 claims description 15
- 238000005886 esterification reaction Methods 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 12
- 230000032050 esterification Effects 0.000 claims description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 9
- 239000007806 chemical reaction intermediate Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 238000005070 sampling Methods 0.000 claims description 8
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 7
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical group C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 7
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 7
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 7
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical group CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 229910000831 Steel Inorganic materials 0.000 claims description 5
- 238000006116 polymerization reaction Methods 0.000 claims description 5
- 239000010959 steel Substances 0.000 claims description 5
- 239000008096 xylene Substances 0.000 claims description 5
- 238000009835 boiling Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000000178 monomer Substances 0.000 claims description 4
- 239000011541 reaction mixture Substances 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 3
- 239000002685 polymerization catalyst Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 3
- 230000035484 reaction time Effects 0.000 claims 1
- 238000005336 cracking Methods 0.000 abstract description 3
- 230000009477 glass transition Effects 0.000 abstract description 3
- 238000003541 multi-stage reaction Methods 0.000 abstract description 3
- 238000007711 solidification Methods 0.000 abstract description 3
- 230000008023 solidification Effects 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 10
- 239000002245 particle Substances 0.000 description 6
- 239000012467 final product Substances 0.000 description 5
- 229920000728 polyester Polymers 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- TVIDDXQYHWJXFK-UHFFFAOYSA-N dodecanedioic acid Chemical compound OC(=O)CCCCCCCCCCC(O)=O TVIDDXQYHWJXFK-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 239000005028 tinplate Substances 0.000 description 2
- QFGCFKJIPBRJGM-UHFFFAOYSA-N 12-[(2-methylpropan-2-yl)oxy]-12-oxododecanoic acid Chemical compound CC(C)(C)OC(=O)CCCCCCCCCCC(O)=O QFGCFKJIPBRJGM-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
Classifications
-
- 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
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
-
- 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
- C09D133/00—Coating compositions based on homopolymers or 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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
-
- 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
- C09D5/03—Powdery paints
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Paints Or Removers (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention relates to a high-flexibility acrylic resin for powder coating, which is prepared by stepwise reaction of acrylic acid, 1, 10-decanediol, 1, 16-hexadecanediol, butyl methacrylate, methyl methacrylate and glycidyl methacrylate under the conditions of a catalytic system, a water-carrying agent and a solvent. The product prepared by the invention introduces flexible chain segment structures with different lengths, so that the prepared coating film has good flexibility, low glass transition temperature and good fluidity during solidification, the problems of brittleness and easy cracking of the conventional acrylic resin coating film can be better solved, and the leveling grade can reach more than 7 grades.
Description
Technical Field
The invention relates to the field of powder coatings, in particular to a high-flexibility acrylic resin, a preparation method thereof and application thereof in the powder coating.
Background
The existing powder coating of acrylic resin for finishing paint in the fields of automobiles, hardware and the like has the advantages of weather resistance, water resistance, good transparency and the like, does not volatilize solvent, and gradually replaces the traditional solvent type coating, however, common acrylic resin is formed by copolymerizing methyl methacrylate, styrene, glycidyl methacrylate and the like, and has poor toughness and insufficient impact resistance due to high functionality and overlarge chain segment hardness, and can generally only reach 30-50cm impact, and the coating film cracks due to external force or collision of foreign objects such as small stones in the running process, thereby bringing defects to application performance.
Aiming at the problems of the conventional acrylic resin at present, the invention provides the high-flexibility acrylic resin for the powder coating, which is mainly prepared by stepwise reaction of acrylic acid, 1, 10-decanediol, 1, 16-hexadecanediol, butyl methacrylate, methyl methacrylate and glycidyl methacrylate under the conditions of a catalytic system, a water carrying agent and a solvent. The product prepared by the invention introduces flexible chain segment structures with different lengths, so that the prepared coating film has good flexibility, low glass transition temperature and good fluidity in curing, the problems of brittleness and easy cracking of the conventional acrylic resin coating film can be better solved, and the leveling grade can reach more than 7 grades.
Disclosure of Invention
The invention relates to a high-flexibility acrylic resin, a preparation method thereof and application thereof in powder coating.
A high-flexibility acrylic resin is prepared from acrylic acid, 1, 10-decanediol, 1, 16-hexadecanediol, butyl methacrylate, methyl methacrylate and glycidyl methacrylate through stepwise reaction under the conditions of catalytic system, water-carrying agent and solvent.
The high-flexibility acrylic resin comprises the following raw materials in parts by mole:
the raw materials also comprise a catalytic system, wherein the catalytic system comprises a catalyst A and a catalyst B, and the catalyst A is an esterification catalyst; the catalyst B is a polymerization catalyst.
Further, the catalyst A is tetrabutyl titanate, and the dosage is 0.2-0.8 percent (preferably 0.5 percent) of the dosage of the acrylic acid by mass; the catalyst B is benzoyl peroxide or di-tert-butyl peroxide, and the dosage is 1-2% of the mass dosage of the glycidyl methacrylate.
Further, the water-carrying agent is dimethylbenzene; the solvent is ethylene glycol methyl ether acetate.
The preparation method of the high-flexibility acrylic resin comprises the following steps:
A. respectively adding the acrylic acid, the 1, 10-decanediol, the 1, 16-hexadecane diol, the water-carrying agent and the catalyst A into a reaction kettle, connecting the reaction kettle with an esterification water separator, uniformly stirring, and heating to the boiling point temperature of the water-carrying agent for esterification water-carrying reaction;
B. sampling and detecting the hydroxyl value of the mixture in the reaction kettle, and when the hydroxyl value reaches 2mgKOH/g or below, considering that the esterification reaction is basically completed, starting a vacuum system at the moment, and decompressing and removing excessive unreacted acrylic acid at 130-133 ℃;
C. after no obvious material is distilled off (for example, less than 1 drop in 30 seconds), releasing vacuum to obtain a reaction intermediate, and adding 1/2 formula amount of solvent at the moment to fully stir so as to dissolve the solvent into a homogeneous phase;
D. adding the rest solvent, the formula amount of butyl methacrylate, methyl methacrylate, glycidyl methacrylate and the catalyst B into a high-level tank, stirring uniformly at normal temperature, and then beginning to drop into a reaction kettle in the step C to perform full polymerization reaction with the reaction intermediate obtained in the step C;
E. after all materials in the overhead tank are dripped, continuing to react at 130-133 ℃ in a heat preservation way;
F. sampling and detecting Tg and epoxy equivalent of the reaction mixture, stopping the reaction when the epoxy equivalent reaches 440-490g/mol and the Tg reaches 42-50 ℃, starting a vacuum system, decompressing and removing the solvent and a small amount of unreacted monomer raw materials in the reaction system, and finally controlling the temperature to 170-175 ℃;
G. after no obvious material is distilled (for example, less than 1 drop in 30 seconds), the vacuum is released, meanwhile, the material is discharged at high temperature, and the material is crushed after being rapidly cooled by a steel belt, so that the product is obtained.
Preferably, in the step B, the vacuum degree is controlled to be between-0.095 Mpa and-0.097 Mpa; in the step D, the dripping time is controlled to be 4-6 hours; in the step E, the reaction is carried out for 1 to 2 hours under the heat preservation condition; in the step F, the vacuum degree is controlled to be between-0.097 and-0.099 Mpa; in the step G, the materials are crushed after being rapidly cooled by a steel belt, and then the product is obtained.
The invention also relates to the application of the high-flexibility acrylic resin or the high-flexibility acrylic resin obtained by the preparation method in powder coating.
For example, a highly flexible acrylic resin for powder coating, the raw material composition comprising, in parts by mole:
the catalyst A is tetrabutyl titanate; the dosage is 0.5% of the mass dosage of the acrylic acid;
the catalyst B is benzoyl peroxide or di-tert-butyl peroxide, and the dosage is 1-2% of the mass dosage of the glycidyl methacrylate.
For example, the preparation method of the high-flexibility acrylic resin comprises the following steps:
A. respectively adding the acrylic acid, the 1, 10-decanediol, the 1, 16-hexadecane diol, the water-carrying agent xylene and the catalyst A into a reaction kettle, connecting the reaction kettle with an esterification water distributor, uniformly stirring, and heating to the boiling point temperature of the water-carrying agent xylene for esterification water-carrying reaction;
B. sampling and detecting the hydroxyl value of the mixture in the reaction kettle, and when the hydroxyl value reaches 2mgKOH/g or below, considering that the esterification reaction is basically completed, starting a vacuum system at the moment, decompressing and removing excessive unreacted acrylic acid at 130-133 ℃, wherein the vacuum degree is controlled to be-0.095 Mpa to-0.097 Mpa;
C. after no obvious material is distilled (less than 1 drop in 30 s), releasing vacuum to obtain a reaction intermediate, and adding 1/2 formula amount of solvent ethylene glycol methyl ether acetate at the moment to fully stir so as to dissolve the solvent ethylene glycol methyl ether acetate into a homogeneous phase;
D. adding the rest ethylene glycol methyl ether acetate, the formula amount of butyl methacrylate, methyl methacrylate, glycidyl methacrylate and the catalyst B into a high-level tank, uniformly stirring at normal temperature, then beginning to drop into a reaction kettle in the step C, and performing full polymerization reaction with the reaction intermediate obtained in the step C, wherein the drop time is controlled to be 4-6h;
E. after all materials in the overhead tank are dripped, continuing to react at 130-133 ℃ for 1-2h;
F. sampling and detecting Tg and epoxy equivalent of the reaction mixture, stopping the reaction when the epoxy equivalent reaches 440-490g/mol and the Tg reaches 42-50 ℃, decompressing and removing the solvent and a small amount of unreacted monomer raw materials in the reaction system, controlling the vacuum degree at-0.097-0.099 Mpa, and finally controlling the temperature at 170-175 ℃;
G. and after no obvious material is distilled (less than 1 drop in 30 s), releasing vacuum, discharging at high temperature, and crushing the material after quick cooling by a steel belt to obtain the product.
The product is white transparent particles with the epoxy equivalent weight of 440-490g/mol and the Tg of 42-50 ℃.
The polyester powder coating is prepared by mixing the acrylic resin obtained by the method with assistants such as dodecanedioic acid, a leveling agent, a degassing agent and the like.
The preparation method of the paint coating comprises the following steps: mixing the materials uniformly according to the formula of the polyester powder coating, extruding, tabletting and crushing by a double-screw extruder, and crushing and sieving the tablets (for example, 150-180 meshes) to prepare the powder coating; the powder coating is sprayed on the tinplate base material after surface treatment by adopting an electrostatic spray gun, and is sprayed with a certain thickness (for example, 60-80 mu m) and cured (for example, 170 ℃/20min condition) to obtain the powder coating film.
The invention has the beneficial effects that:
the product prepared by the invention introduces flexible chain segment structures with different lengths, so that the prepared coating film has good flexibility, low glass transition temperature and good fluidity during solidification, the problems of brittleness and easy cracking of the conventional acrylic resin coating film can be better solved, and the leveling grade can reach more than 7 grades.
Detailed Description
For the purposes of promoting an understanding of the invention, reference will now be made in detail to various exemplary embodiments of the invention, which should not be considered as limiting the invention in any way, but rather as describing in more detail certain aspects, features and embodiments of the invention.
The raw materials are all common commercial raw materials.
Example 1
The high-flexibility acrylic resin for the powder coating comprises the following raw materials in parts by mole:
the catalyst A is tetrabutyl titanate, and the dosage is 0.5% of the mass dosage of acrylic acid;
the catalyst B is benzoyl peroxide, and the dosage is 1.2 percent of the mass dosage of the glycidyl methacrylate.
The preparation method comprises the following steps:
A. respectively adding the acrylic acid, the 1, 10-decanediol, the 1, 16-hexadecane diol, the water-carrying agent xylene and the catalyst A into a reaction kettle, connecting the reaction kettle with an esterification water distributor, uniformly stirring, and heating to the boiling point temperature of the water-carrying agent xylene for esterification water-carrying reaction;
B. sampling and detecting the hydroxyl value of the mixture in the reaction kettle, and when the hydroxyl value reaches 2mgKOH/g, considering that the esterification reaction is basically completed, starting a vacuum system at the moment, decompressing and removing excessive unreacted acrylic acid at 133 ℃, wherein the vacuum degree is controlled at-0.097 Mpa;
C. after no obvious material is distilled (less than 1 drop in 30 s), releasing vacuum to obtain a reaction intermediate, and adding 1/2 formula amount of solvent ethylene glycol methyl ether acetate at the moment to fully stir so as to dissolve the solvent ethylene glycol methyl ether acetate into a homogeneous phase;
D. adding the rest ethylene glycol methyl ether acetate, the formula amount of butyl methacrylate, methyl methacrylate, glycidyl methacrylate and the catalyst B into a high-level tank, uniformly stirring at normal temperature, then beginning to dropwise add into the reaction kettle in the step C, and performing full polymerization reaction with the reaction intermediate obtained in the step C, wherein the dropwise adding time is controlled to be 6 hours;
E. after all materials in the overhead tank are dripped, continuing to react at 133 ℃ for 2 hours;
F. sampling and detecting Tg and epoxy equivalent of the reaction mixture, stopping the reaction when the Tg and the epoxy equivalent reach the expected values, decompressing and removing the solvent and a small amount of unreacted monomer raw materials in the reaction system, controlling the vacuum degree at-0.097 Mpa, and finally controlling the temperature at 175 ℃;
G. and after no obvious material is distilled (less than 1 drop in 30 s), releasing vacuum, discharging at high temperature, and crushing the material after quick cooling by a steel belt to obtain the product.
The final product prepared was white transparent particles in appearance, epoxy equivalent 459g/mol, tg 43 ℃.
Example 2
The high-flexibility acrylic resin for the powder coating comprises the following raw materials in parts by mole:
the catalyst A is tetrabutyl titanate, and the dosage is 0.5% of the mass dosage of acrylic acid;
the catalyst B is benzoyl peroxide or di-tert-butyl peroxide, and the dosage is 2% of the mass dosage of the glycidyl methacrylate.
The preparation method is the same as in example 1.
The final product prepared had the appearance of white transparent particles with an epoxy equivalent of 481g/mol and a Tg of 49 ℃.
Example 3
The high-flexibility acrylic resin for the powder coating comprises the following raw materials in parts by mole:
the catalyst A is tetrabutyl titanate, and the dosage is 0.5% of the mass dosage of acrylic acid;
the catalyst B is benzoyl peroxide or di-tert-butyl peroxide, and the dosage is 1.5 percent of the mass dosage of the glycidyl methacrylate.
The preparation method is the same as in example 1.
The final product prepared was white transparent particles in appearance, epoxy equivalent 445g/mol, tg 45 ℃.
Example 4
The high-flexibility acrylic resin for the powder coating comprises the following raw materials in parts by mole:
the catalyst A is tetrabutyl titanate, and the dosage is 0.5% of the mass dosage of acrylic acid;
the catalyst B is benzoyl peroxide or di-tert-butyl peroxide, and the dosage is 2% of the mass dosage of the glycidyl methacrylate.
The preparation method is the same as in example 1.
The final product prepared had the appearance of white transparent particles with an epoxy equivalent of 453g/mol and a Tg of 46 ℃.
Comparative example 1
The procedure of example 1 was followed except that acrylic acid, 1, 10-decanediol and 1, 16-hexadecane diol were not added, and the polymerization was carried out in accordance with the procedure of the experiment, whereby the final product had the appearance of white transparent particles, an epoxy equivalent of 278 g/mol, tg of 59℃and wherein the dodecanedioic acid in the formulation of the powder coating board was adjusted from 200 parts to 350 parts, the others being unchanged.
Comparative example 2
A commercially available acrylic resin, having an epoxy equivalent of 495 g/mol, tg of 55deg.C, model K7581, was purchased from Liuan Jiegui Kogyo New Material Co.
Application example
The polyester powder coating comprises the following components in parts by weight:
preparing a paint coating: according to the formula of the polyester powder coating, all materials are uniformly mixed, extruded by a double-screw extruder, pressed into tablets, crushed, and crushed and sieved (150-180 meshes) to prepare the powder coating. The powder coating is sprayed on the tinplate base material after surface treatment by adopting an electrostatic spray gun, the spraying thickness is 60-80 mu m, and the powder coating film is obtained after 170 ℃/20 mit solidification.
The determination of the hydroxyl equivalent is carried out according to the method of GB/T27807-2011 curing agent for polyester powder coating. The coating index detection is carried out according to GB/T21776-2008 'inspection standard guidelines for powder coating and coating thereof', the adhesion grade is carried out according to GB/T9286-1998 'drawing experiments for color paint and varnish film', and the leveling grade is according to PCI leveling grading standard.
The acrylic resins obtained in the above examples and comparative examples were prepared into coatings according to the coating formulations provided in the present invention described above, and then tested for coating properties, the results of which are shown in table 1 below.
Table 1 comparison of properties after coating of the products of examples and comparative examples
From the comparison of the data in table 1 above, it can be seen that: the product of the invention has excellent comprehensive properties such as coating appearance, impact resistance, gloss, adhesive force, leveling grade and the like; in particular, the shock resistance and the leveling property are far better than those of common domestic acrylic resin products, and the method has better industrialization prospect.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. And obvious variations or modifications thereof are contemplated as falling within the scope of the present invention.
Claims (10)
1. The high-flexibility acrylic resin is characterized in that raw materials comprising acrylic acid, 1, 10-decanediol, 1, 16-hexadecanediol, butyl methacrylate, methyl methacrylate and glycidyl methacrylate are used for gradual reaction under the conditions of a catalytic system, a water-carrying agent and a solvent.
2. The highly flexible acrylic resin according to claim 1, wherein the raw material composition comprises, in parts by mole:
the raw materials also comprise a catalytic system, wherein the catalytic system comprises a catalyst A and a catalyst B, and the catalyst A is an esterification catalyst; the catalyst B is a polymerization catalyst.
3. A highly flexible acrylic resin according to claim 2, wherein the catalyst a is tetrabutyl titanate in an amount of 0.2 to 0.8% based on the mass of acrylic acid; the catalyst B is benzoyl peroxide or di-tert-butyl peroxide, and the dosage is 1-2% of the mass dosage of the glycidyl methacrylate.
4. A highly flexible acrylic resin according to claim 2 or 3, wherein the water-carrying agent is xylene.
5. A highly flexible acrylic resin according to claim 2 or 3, wherein the solvent is ethylene glycol methyl ether acetate.
6. A method for producing a highly flexible acrylic resin according to claim 1 to 5, comprising the steps of:
A. respectively adding the acrylic acid, the 1, 10-decanediol, the 1, 16-hexadecane diol, the water-carrying agent and the catalyst A into a reaction kettle, connecting the reaction kettle with an esterification water separator, uniformly stirring, and heating to the boiling point temperature of the water-carrying agent for esterification water-carrying reaction;
B. sampling and detecting the hydroxyl value of the mixture in the reaction kettle, starting a vacuum system when the hydroxyl value reaches 2mgKOH/g or less, and decompressing and removing excessive unreacted acrylic acid at 130-133 ℃;
C. after no obvious material is distilled off, releasing vacuum to obtain a reaction intermediate, and adding 1/2 formula amount of solvent at the moment to fully stir so as to dissolve the solvent into homogeneous phase;
D. adding the rest solvent, the formula amount of butyl methacrylate, methyl methacrylate, glycidyl methacrylate and the catalyst B into a high-level tank, stirring uniformly at normal temperature, then beginning to drop into a reaction kettle in the step C, and carrying out polymerization reaction with a reaction intermediate obtained in the step C;
E. after all materials in the overhead tank are dripped, continuing to react at 130-133 ℃ in a heat preservation way;
F. sampling and detecting Tg and epoxy equivalent of the reaction mixture, stopping the reaction when the epoxy equivalent reaches 440-490g/mol and the Tg reaches 42-50 ℃, starting a vacuum system, decompressing and removing the solvent and a small amount of unreacted monomer raw materials in the reaction system, and finally controlling the temperature to 170-175 ℃;
G. and after no obvious material is distilled, releasing vacuum, discharging at the same time, cooling and crushing the material to obtain the product.
7. The method of claim 6, wherein the vacuum degree in the step B is controlled to be-0.095 MPa to-0.097 MPa.
8. The method for producing a highly flexible acrylic resin according to claim 6, wherein in step D, the dropping time is controlled to be 4 to 6 hours; in the step E, the reaction time is kept for 1-2h.
9. The method of producing a highly flexible acrylic resin according to claim 6, wherein in the step F, the vacuum degree is controlled to be-0.097 to-0.099 MPa; in the step G, the materials are crushed after being rapidly cooled by a steel belt, and then the product is obtained.
10. Use of the highly flexible acrylic resin according to claims 1 to 5 or the highly flexible acrylic resin obtained by the production method according to claims 6 to 9 in powder coating.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211736504.0A CN116217782A (en) | 2022-12-31 | 2022-12-31 | High-flexibility acrylic resin for powder coating and preparation method thereof |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1362906A (en) * | 1971-03-30 | 1974-08-07 | Ciba Geigy Ag | Polyacrylate compounds process for their production and use thereof |
| CN102686680A (en) * | 2009-12-28 | 2012-09-19 | 三菱丽阳株式会社 | Method for producing resin dispersion for antifouling coating |
| CN110845656A (en) * | 2019-11-21 | 2020-02-28 | 万华化学集团股份有限公司 | Hydroxyl acrylic emulsion and preparation method and application thereof |
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- 2022-12-31 CN CN202211736504.0A patent/CN116217782A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1362906A (en) * | 1971-03-30 | 1974-08-07 | Ciba Geigy Ag | Polyacrylate compounds process for their production and use thereof |
| CN102686680A (en) * | 2009-12-28 | 2012-09-19 | 三菱丽阳株式会社 | Method for producing resin dispersion for antifouling coating |
| CN110845656A (en) * | 2019-11-21 | 2020-02-28 | 万华化学集团股份有限公司 | Hydroxyl acrylic emulsion and preparation method and application thereof |
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