CN111978462A - High-reactivity hydroxyl acrylic resin and preparation method thereof - Google Patents
High-reactivity hydroxyl acrylic resin and preparation method thereof Download PDFInfo
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- CN111978462A CN111978462A CN202010899507.0A CN202010899507A CN111978462A CN 111978462 A CN111978462 A CN 111978462A CN 202010899507 A CN202010899507 A CN 202010899507A CN 111978462 A CN111978462 A CN 111978462A
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- 239000004925 Acrylic resin Substances 0.000 title claims abstract description 47
- 229920000178 Acrylic resin Polymers 0.000 title claims abstract description 47
- 125000002887 hydroxy group Chemical group [H]O* 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims description 17
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 46
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000003999 initiator Substances 0.000 claims abstract description 43
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 35
- VWYIWOYBERNXLX-KTKRTIGZSA-N Glycidyl oleate Chemical class CCCCCCCC\C=C/CCCCCCCC(=O)OCC1CO1 VWYIWOYBERNXLX-KTKRTIGZSA-N 0.000 claims abstract description 26
- 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 23
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 23
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 23
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000011347 resin Substances 0.000 claims abstract description 22
- 229920005989 resin Polymers 0.000 claims abstract description 22
- 239000012986 chain transfer agent Substances 0.000 claims abstract description 21
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 17
- 239000002994 raw material Substances 0.000 claims abstract description 17
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000010992 reflux Methods 0.000 claims abstract description 14
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 claims abstract description 13
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000010526 radical polymerization reaction Methods 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims description 45
- 238000002156 mixing Methods 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 18
- 238000007792 addition Methods 0.000 claims description 12
- 238000004321 preservation Methods 0.000 claims description 10
- 239000008199 coating composition Substances 0.000 claims description 9
- NKFIBMOQAPEKNZ-UHFFFAOYSA-N 5-amino-1h-indole-2-carboxylic acid Chemical group NC1=CC=C2NC(C(O)=O)=CC2=C1 NKFIBMOQAPEKNZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 150000004700 cobalt complex Chemical class 0.000 claims description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 5
- 229910052791 calcium Inorganic materials 0.000 claims description 5
- 239000011575 calcium Substances 0.000 claims description 5
- 239000012948 isocyanate Substances 0.000 claims description 5
- 150000002513 isocyanates Chemical class 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 230000009257 reactivity Effects 0.000 claims description 5
- 229910021581 Cobalt(III) chloride Inorganic materials 0.000 claims description 4
- IEKWPPTXWFKANS-UHFFFAOYSA-K trichlorocobalt Chemical compound Cl[Co](Cl)Cl IEKWPPTXWFKANS-UHFFFAOYSA-K 0.000 claims description 4
- FEWFXBUNENSNBQ-UHFFFAOYSA-N 2-hydroxyacrylic acid Chemical compound OC(=C)C(O)=O FEWFXBUNENSNBQ-UHFFFAOYSA-N 0.000 claims 1
- 239000003973 paint Substances 0.000 abstract description 14
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 239000000853 adhesive Substances 0.000 abstract description 3
- 230000001070 adhesive effect Effects 0.000 abstract description 3
- 238000001035 drying Methods 0.000 description 14
- 238000000576 coating method Methods 0.000 description 9
- 229910017052 cobalt Inorganic materials 0.000 description 8
- 239000010941 cobalt Substances 0.000 description 8
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 238000007599 discharging Methods 0.000 description 6
- 230000004913 activation Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 4
- 238000010276 construction Methods 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 230000036632 reaction speed Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000002966 varnish Substances 0.000 description 3
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- OZCWUNHGNVXCCO-UHFFFAOYSA-N oxiran-2-ylmethyl hydrogen carbonate Chemical group OC(=O)OCC1CO1 OZCWUNHGNVXCCO-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 206010052428 Wound Diseases 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- RSOILICUEWXSLA-UHFFFAOYSA-N bis(1,2,2,6,6-pentamethylpiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)N(C)C(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)N(C)C(C)(C)C1 RSOILICUEWXSLA-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000003473 lipid group Chemical group 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- UJRDRFZCRQNLJM-UHFFFAOYSA-N methyl 3-[3-(benzotriazol-2-yl)-5-tert-butyl-4-hydroxyphenyl]propanoate Chemical compound CC(C)(C)C1=CC(CCC(=O)OC)=CC(N2N=C3C=CC=CC3=N2)=C1O UJRDRFZCRQNLJM-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000008096 xylene 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
- C08F220/10—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
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
-
- 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
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)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a high-reactivity hydroxyl acrylic resin, which is prepared by the following raw materials through free radical polymerization under the conditions of nitrogen pressurization and reflux: methyl methacrylate, styrene, butyl methacrylate, deuterated glycidyl oleate, hydroxypropyl acrylate, acrylic acid, an initiator di-tert-butyl peroxide, a chain transfer agent dodecyl mercaptan and a polymerization medium mesitylene. The invention introduces the deuterated glycidyl oleate into the acrylic resin, improves the fluidity of the resin and the elasticity of a paint film, ensures that the acrylic resin has the advantages of low viscosity, weather resistance, high adhesive force, good glossiness and the like, can ensure that the prepared paint film is plump, has good developability and low fog-shadow value, and has better market prospect. By adjusting the formula and adopting the strategies of pressurization and high temperature, the use amount of the initiator in the resin is greatly reduced, the control of the production process and the production safety are facilitated, and the product quality is improved.
Description
Technical Field
The invention belongs to the field of polymers, and particularly relates to a high-reactivity hydroxyl acrylic resin and a preparation method thereof.
Background
The hydroxy acrylic resin is a novel acrylic resin prepared by taking hard monomers such as styrene, methyl methacrylate and the like, soft monomers such as ethyl acrylate and the like, and functional monomers containing hydroxyl such as hydroxyethyl acrylate and the like as raw materials and carrying out free radical polymerization under the action of a molecular chain regulator. The resin has the advantages of high solid content, low system viscosity and easy construction.
In addition, the resin is compounded with isocyanate and is cured to form a cross-linked network structure, so that the heat resistance, water resistance, weather resistance, hardness, adhesive force and other properties of the coating are obviously superior to those of common acrylic resin, the coating is widely applied to the fields of gas car coatings, wood coatings and the like, and becomes one of the fastest-developing resin varieties.
In the synthesis process of the hydroxy acrylic resin, an initiator of free radical polymerization is needed, and the dosage of the initiator is usually about 1.5-4 percent at present. The initiator not only affects the molecular weight and molecular weight distribution of the polymer, but also affects the properties of the acrylic resin. For example, unreacted initiator can oxidize the resin at high temperature to darken the color and affect the quality of the resin. The more initiator not only increases the cost, but also causes the reaction to be too fast, the reaction is not easy to control, unsafe factors on the production are increased, and the reaction time is prolonged. It also results in increased decomposition products, affects product durability and is prone to odor generation.
The reaction temperature is directly an important index parameter in the acrylic acid polymerization process, and directly influences various parameters and performances of acrylic acid, but generally, adjustment for reaching low temperature is easier, but more initiator needs to be introduced at low temperature, and the pressure on cost and quality is brought. Under certain conditions, the solid content and relative molecular mass of the resin can be increased and the viscosity can be reduced along with the increase of the reaction temperature. However, it is also pointed out in the prior art that when the temperature is above a certain point, for example 150 ℃, the conversion decreases as the temperature continues to increase.
Disclosure of Invention
The invention aims to provide a hydroxyl acrylic resin based on the prior art, wherein deuterated glycidyl oleate is introduced into the acrylic resin, and the large volume and the long lipid chain part containing double bonds improve the fluidity and paint film elasticity of the resin, so that the acrylic resin has better quality. The resin can improve the reactivity with an isocyanate curing agent, so that the resin has application advantages in coating.
The invention also aims to provide a preparation method of the hydroxy acrylic resin, which can prepare the hydroxy acrylic resin with excellent performance under the condition of greatly reducing the using amount of the initiator by adjusting the formula and adopting a pressurizing and high-temperature strategy.
The third object of the present invention is to provide a coating composition containing the above-mentioned hydroxyacrylic resin.
The object of the invention can be achieved by the following measures:
a hydroxyl acrylic resin with high reactivity is prepared by the following raw materials through free radical polymerization under the conditions of nitrogen pressurization and reflux: methyl methacrylate, styrene, butyl methacrylate, deuterated glycidyl oleate, hydroxypropyl acrylate, acrylic acid, an initiator di-tert-butyl peroxide, a chain transfer agent dodecyl mercaptan and a polymerization medium mesitylene.
In one technical scheme, the raw materials comprise the following components in parts by mass: 10-20 parts of methyl methacrylate, 10-20 parts of styrene, 20-40 parts of butyl methacrylate, 10-20 parts of deuterated glycidyl oleate, 10-25 parts of hydroxypropyl acrylate, 2-5 parts of acrylic acid, 0.5-1.5 parts of chain transfer agent dodecyl mercaptan, 0.2-1.0 part of initiator di-tert-butyl peroxide and 10-30 parts of polymerization medium mesitylene.
In another embodiment, the amount of methyl methacrylate may be controlled within the range of 15 to 20 parts.
In another technical scheme, the dosage of the styrene can be controlled within the range of 10-20 parts.
In another technical scheme, the amount of the butyl methacrylate can be controlled within the range of 20-35 parts.
In another technical scheme, the dosage of the deuterated glycidyl oleate can be controlled within the range of 15-20 parts.
In another embodiment, the amount of hydroxypropyl acrylate may be controlled within the range of 15-25 parts.
In another technical scheme, the dosage of the initiator di-tert-butyl peroxide can be controlled within the range of 0.2-0.8 part.
In another embodiment, the amount of mesitylene used as the polymerization medium can be controlled within the range of 15-30 parts.
In the present application, the amount of the initiator di-tert-butyl peroxide can be as low as 0.2 to 0.5 part.
The high-reactivity hydroxyl acrylic resin can be prepared by carrying out free radical polymerization on all raw materials in a reaction device under the conditions of nitrogen pressurization to absolute pressure of 0.12-0.5MPa and reflux.
Further, the high reactivity hydroxy acrylic resin of the present invention can be prepared by radical polymerization of the respective raw materials in a reaction apparatus under nitrogen pressure to absolute pressure of 0.2-0.3MPa and at temperature of 160-165 ℃.
The invention provides a preparation method of the hydroxyl acrylic resin with high reaction activity, which comprises the following steps: mixing deuterated glycidyl oleate and a polymerization medium in a reaction vessel, introducing nitrogen, pressurizing and heating to reflux, then uniformly mixing methyl methacrylate, styrene, butyl methacrylate, hydroxypropyl acrylate, acrylic acid, a chain transfer agent and a part of initiator, slowly adding the mixture into the reaction vessel, slowly adding the rest of initiator after the mixture is added, and carrying out heat preservation reaction to obtain the deuterated glycidyl oleate.
The preparation method can directly filter and discharge after the heat preservation reaction.
In the above preparation method, it is preferable that nitrogen is introduced to an absolute pressure of 0.12 to 0.5MPa and the reaction temperature is 160-165 ℃.
In the above preparation method, nitrogen gas is charged to an absolute pressure of 0.2 to 0.3 MPa.
The invention also discloses a coating composition which comprises the hydroxyl acrylic resin, the calcium drier, the cobalt complex and the isocyanate curing agent.
In a preferred embodiment, the calcium drier in the coating composition is calcium naphthenate, and the content of the calcium drier in the composition is 0.02 to 0.2 percent by mass; the cobalt complex in the coating composition is hexaammine cobalt trichloride, and the mass content of the cobalt complex in the composition is 0.005-0.05%.
Various pigments used in the prior art can be added to the coating composition.
Dispersing agents and leveling agents may be further added to the coating composition to further adjust the overall properties of the coating.
The resin prepared by the method can improve the reaction activity with an isocyanate curing agent, is further compounded with a calcium naphthenate drier and hexaammine cobalt trichloride in a coating composition, and can achieve the effect of quick drying of the coating in a proper activation period by adjusting the crosslinking reaction and improving the reaction speed and also adjusting the dryness of the resin.
The hydroxyl acrylic resin with high reactivity prepared by the invention has the characteristic of high solid content, the appearance of the hydroxyl acrylic resin is colorless transparent solution, the hydroxyl acrylic resin does not change after long-term storage (1-6 months), the solid content is 75 +/-4 percent, the viscosity is 1000-one-1200 mPa.s, and the acid value is less than 10mgKOH.g-1The fineness is below 5 μm.
The deuterated glycidyl oleate is introduced into the acrylic resin, the fluidity and paint film elasticity of the resin are improved by the large volume of the deuterated glycidyl oleate and the long fat chain part containing double bonds, so that the acrylic resin has the advantages of low viscosity, weather resistance, high adhesive force, good glossiness and the like, and the prepared paint film is plump, good in developing property, low in fog-shadow value and better in market prospect. By adjusting the formula and adopting the pressurizing and high-temperature strategies, the use amount of the initiator in the resin is greatly reduced, the production cost is saved, the control of the production process is facilitated, the production safety is improved, the decomposition products are reduced, and the product quality is improved.
Detailed Description
The present invention is further illustrated by the following examples, but the scope of the present invention is not limited to the following examples.
Example 1
The high-reactivity hydroxyl acrylic resin comprises the following raw materials: 16Kg of methyl methacrylate, 18Kg of styrene, 31Kg of butyl methacrylate, 16Kg of deuterated glycidyl oleate, 19Kg of hydroxypropyl acrylate, 3Kg of acrylic acid, 1Kg of chain transfer agent dodecyl mercaptan, 0.5Kg of initiator di-tert-butyl peroxide and 20Kg of polymerization medium mesitylene.
The preparation method comprises the following steps: mixing deuterated glycidyl oleate and a polymerization medium in a reaction vessel, introducing nitrogen, pressurizing to the absolute pressure of 0.25MPa, heating to 164-plus-165 ℃ for reflux, then uniformly mixing methyl methacrylate, styrene, butyl methacrylate, hydroxypropyl acrylate, acrylic acid, a chain transfer agent and part of an initiator, dropwise adding the mixture into the reaction vessel, dropwise adding the rest of the initiator after the mixture is added, carrying out heat preservation reaction after the mixture is added, filtering, and discharging.
Example 2
The high-reactivity hydroxyl acrylic resin comprises the following raw materials: 19Kg of methyl methacrylate, 11Kg of styrene, 25Kg of butyl methacrylate, 19Kg of deuterated glycidyl oleate, 22Kg of hydroxypropyl acrylate, 5Kg of acrylic acid, 1Kg of chain transfer agent dodecyl mercaptan, 0.4Kg of initiator di-tert-butyl peroxide and 20Kg of polymerization medium mesitylene.
The preparation method comprises the following steps: mixing deuterated glycidyl oleate and a polymerization medium in a reaction vessel, introducing nitrogen, pressurizing to an absolute pressure of 0.2MPa, heating to 163-plus-165 ℃ for reflux, then uniformly mixing methyl methacrylate, styrene, butyl methacrylate, hydroxypropyl acrylate, acrylic acid, a chain transfer agent and part of an initiator, dropwise adding the mixture into the reaction vessel, dropwise adding the rest of the initiator after the addition, carrying out heat preservation reaction after the addition, filtering, and discharging.
Example 3
The high-reactivity hydroxyl acrylic resin comprises the following raw materials: 17Kg of methyl methacrylate, 14Kg of styrene, 29Kg of butyl methacrylate, 18Kg of deuterated glycidyl oleate, 17Kg of hydroxypropyl acrylate, 4Kg of acrylic acid, 1Kg of chain transfer agent dodecyl mercaptan, 0.5Kg of initiator di-tert-butyl peroxide, and 20Kg of mesitylene as polymerization medium.
The preparation method comprises the following steps: mixing deuterated glycidyl oleate and a polymerization medium in a reaction vessel, introducing nitrogen, pressurizing to an absolute pressure of 0.3MPa, heating to 163-plus-165 ℃ for reflux, then uniformly mixing methyl methacrylate, styrene, butyl methacrylate, hydroxypropyl acrylate, acrylic acid, a chain transfer agent and part of an initiator, dropwise adding the mixture into the reaction vessel, dropwise adding the rest of the initiator after the addition, carrying out heat preservation reaction after the addition, filtering, and discharging.
Example 4
The high-reactivity hydroxyl acrylic resin comprises the following raw materials: 18Kg of methyl methacrylate, 17Kg of styrene, 30Kg of butyl methacrylate, 17Kg of deuterated glycidyl oleate, 24Kg of hydroxypropyl acrylate, 2Kg of acrylic acid, 1Kg of chain transfer agent dodecyl mercaptan, 0.7Kg of initiator di-tert-butyl peroxide and 20Kg of polymerization medium mesitylene.
The preparation method comprises the following steps: mixing deuterated glycidyl oleate and a polymerization medium in a reaction vessel, introducing nitrogen, pressurizing to an absolute pressure of 0.25MPa, heating to 163-plus-165 ℃ for reflux, then uniformly mixing methyl methacrylate, styrene, butyl methacrylate, hydroxypropyl acrylate, acrylic acid, a chain transfer agent and part of an initiator, dropwise adding the mixture into the reaction vessel, dropwise adding the rest of the initiator after the addition, carrying out heat preservation reaction after the addition, filtering, and discharging.
Comparative example 1
The hydroxyl acrylic resin comprises the following raw materials: 16Kg of methyl methacrylate, 18Kg of styrene, 31Kg of butyl methacrylate, 16Kg of glycidyl versatate, 19Kg of hydroxypropyl acrylate, 3Kg of acrylic acid, 1Kg of dodecyl mercaptan as chain transfer agent, 2Kg of di-tert-butyl peroxide as initiator and 20Kg of mesitylene as polymerization medium.
The preparation method comprises the following steps: mixing the tertiary carbonic acid glycidyl ester and a polymerization medium in a reaction container, introducing nitrogen, pressurizing to the absolute pressure of 0.25MPa, heating to the temperature of 164-plus-one 165 ℃ for reflux, then uniformly mixing methyl methacrylate, styrene, butyl methacrylate, hydroxypropyl acrylate, acrylic acid, a chain transfer agent and part of an initiator, dropwise adding the mixture into the reaction container, dropwise adding the rest of the initiator after the addition, carrying out heat preservation reaction after the addition, filtering, and discharging. The viscosity is more than 1500mPa.s, and the colorless transparent solution turns into yellowish after standing for a long time.
Comparative example 2
The hydroxyl acrylic resin comprises the following raw materials: 16Kg of methyl methacrylate, 18Kg of styrene, 31Kg of butyl methacrylate, 16Kg of glycidyl versatate, 19Kg of hydroxypropyl acrylate, 3Kg of acrylic acid, 1Kg of dodecyl mercaptan as chain transfer agent, 2Kg of di-tert-butyl peroxide as initiator and 20Kg of mesitylene as polymerization medium.
The preparation method comprises the following steps: mixing the tertiary carbonic acid glycidyl ester and a polymerization medium in a reaction container, heating to 164-165 ℃ for reflux, then uniformly mixing methyl methacrylate, styrene, butyl methacrylate, hydroxypropyl acrylate, acrylic acid, a chain transfer agent and part of an initiator, dropwise adding into the reaction container, dropwise adding the rest initiator after the addition, carrying out heat preservation reaction after the addition, filtering, and discharging. The viscosity is more than 2000mPa.s, and the colorless transparent solution turns into yellowish after standing for a long time.
Example 5
The hydroxy acrylic resins prepared in the above examples were formulated into high solids white topcoats according to the formulation of Table 1.
The preparation method comprises mixing part A, dispersing until the fineness is less than 10 μm, adding part B, and mixing. Adding part C before use, and mixing.
TABLE 1
The high solids white topcoats prepared in table 1 were tested for performance and the results are shown in table 2.
TABLE 2
The hydroxyl acrylic resin obtained in the comparative example 1 and the comparative example 2 is used for preparing the high-solid white finish paint by adopting the formula in the table 1, and the VOC of the hydroxyl acrylic resin are 420-450, and the spraying property of the hydroxyl acrylic resin and the VOC of the hydroxyl acrylic resin is lower than that of the hydroxyl acrylic resin in the example by adopting the method in the table 2. Wherein the paint film drying speed T3 of comparative example 1 is >15h, the gloss is 20 ° < 90; the paint film drying speed T3 of comparative example 2 was >14h, gloss 20 ° < 90. Therefore, the deuterated glycidyl oleate obviously improves the quality of the hydroxyl acrylic resin, is superior to the existing tertiary glycidyl versatate, and simultaneously, the quality of a paint film is further improved by using a small amount of the initiator.
Experiments show that after cobalt hexammine trichloride in table 1 of example 5 is removed, or after calcium naphthenate drier and cobalt hexammine trichloride are replaced by cobalt drier, under the condition that other conditions are not changed, the activation period of the paint is basically the same as that of the example, and the drying speed of a paint film is slowed by more than 25%, so that the compounding of the calcium naphthenate drier and the cobalt hexammine trichloride can adjust the crosslinking reaction and improve the reaction speed, and the drying of resin can be adjusted to enable the paint to achieve the effect of quick drying in a proper activation period.
Example 6
The hydroxy acrylic resins prepared in the above examples were formulated into quick-drying varnishes according to the formulation in Table 3.
The preparation method comprises the steps of mixing the component A, adding the mixed component B before use, and uniformly mixing.
TABLE 3
| Material(s) | weight/Kg |
| Component A | |
| Acrylic resin of examples 1 to 4 | 54 |
| Solvent(s) | 14 |
| BASF Tinuvin 1130 | 0.5 |
| BASF Tinuvin 292 | 0.5 |
| Byk chemical BYK-331 | 0.1 |
| Byk chemical BYK-358 | 0.2 |
| Metal drier-after dilution | 1.5 |
| Dinonyl DN-B60 calcium naphthenate siccator | 0.2 |
| Hexaammine cobalt trichloride | 0.02 |
| Component B | |
| Scientific wound curing agent Desmurder N3390 | 19.3 |
| Acetic acid butyl ester | 10.3 |
The performance test of each quick-drying varnish obtained is carried out, the construction viscosity of the coating No. 4 is about 16-18 seconds, the construction solid content is about 53 percent, the activation period (viscosity is doubled) is 2 hours, the spraying property is excellent, and the drying speed T3 is less than 90 minutes. 20 ℃ gloss is greater than 91, 60 ℃ gloss is greater than 96, and xylene drop resistance passes the 20min test.
The hydroxyacrylic resins obtained in comparative examples 1 and 2 were formulated into quick-drying varnishes using the formulation in Table 3, which were inferior to those of the examples in terms of sprayability, drying speed T3>5h, and gloss 60 ° < 94. Therefore, the deuterated glycidyl oleate obviously improves the quality of the hydroxyl acrylic resin, is superior to the existing tertiary glycidyl versatate, and simultaneously, the quality of a paint film is further improved by using a small amount of the initiator.
Experiments show that after the cobalt hexammine trichloride in the example table 3 is removed, or after the calcium naphthenate drier and the cobalt hexammine trichloride are replaced by cobalt driers, the drying speed of a paint film is slowed by more than 25% under the condition that other conditions are not changed, so that the compounding of the calcium naphthenate drier and the cobalt hexammine trichloride can adjust the crosslinking reaction and improve the reaction speed, and the coating can achieve the effect of quick drying in a proper activation period by adjusting the drying of resin.
Claims (10)
1. The high-reactivity hydroxyl acrylic resin is characterized by being prepared by carrying out free radical polymerization on the following raw materials under the conditions of nitrogen pressurization and reflux: methyl methacrylate, styrene, butyl methacrylate, deuterated glycidyl oleate, hydroxypropyl acrylate, acrylic acid, an initiator di-tert-butyl peroxide, a chain transfer agent dodecyl mercaptan and a polymerization medium mesitylene.
2. The high-reactivity hydroxy acrylic resin according to claim 1, which is characterized by comprising the following raw materials in parts by mass: 10-20 parts of methyl methacrylate, 10-20 parts of styrene, 20-40 parts of butyl methacrylate, 10-20 parts of deuterated glycidyl oleate, 10-25 parts of hydroxypropyl acrylate, 2-5 parts of acrylic acid, 0.5-1.5 parts of chain transfer agent dodecyl mercaptan, 0.2-1.0 part of initiator di-tert-butyl peroxide and 10-30 parts of polymerization medium mesitylene.
3. The high-reactivity hydroxy acrylic resin according to claim 2, which is characterized by comprising the following raw materials in parts by mass: 15-20 parts of methyl methacrylate, 10-20 parts of styrene, 20-35 parts of butyl methacrylate, 15-20 parts of deuterated glycidyl oleate, 15-25 parts of hydroxypropyl acrylate, 2-5 parts of acrylic acid, 0.5-1.5 parts of chain transfer agent dodecyl mercaptan, 0.2-0.8 part of initiator di-tert-butyl peroxide and 15-30 parts of polymerization medium mesitylene.
4. The high reactive hydroxy acrylic resin according to claim 1, wherein each raw material is obtained by radical polymerization under the conditions of pressurizing to an absolute pressure of 0.12 to 0.5MPa with nitrogen and refluxing in a reaction apparatus.
5. The high reactivity hydroxy acrylic resin as claimed in claim 4, wherein the raw materials are prepared by radical polymerization in a reaction apparatus under nitrogen pressure to absolute pressure of 0.2-0.3MPa and at temperature of 160-165 ℃.
6. The high-reactivity hydroxyacrylic resin according to claim 4, characterized in that it is prepared by the method comprising: mixing deuterated glycidyl oleate and a polymerization medium in a reaction vessel, introducing nitrogen, pressurizing and heating to reflux, then uniformly mixing methyl methacrylate, styrene, butyl methacrylate, hydroxypropyl acrylate, acrylic acid, a chain transfer agent and a part of initiator, slowly adding the mixture into the reaction vessel, slowly adding the rest of initiator after the mixture is added, and carrying out heat preservation reaction to obtain the deuterated glycidyl oleate.
7. The preparation method of high-reactivity hydroxyacrylic acid resin as claimed in claim 1, characterized in that deuterated glycidyl oleate is mixed with polymerization medium in a reaction vessel, then nitrogen is filled in for pressurization and temperature rise to reflux, then methyl methacrylate, styrene, butyl methacrylate, hydroxypropyl acrylate, acrylic acid, chain transfer agent and part of initiator are mixed uniformly and slowly added into the reaction vessel, after the addition, the rest of initiator is slowly added, after the addition, the heat preservation reaction is carried out, and after the reaction, filtration and discharge are carried out.
8. The method as set forth in claim 7, wherein nitrogen is introduced to an absolute pressure of 0.12-0.5MPa and the reaction temperature is 160-165 ℃.
9. A coating composition comprising the hydroxyacrylic resin of claim 1, a calcium drier, a cobalt complex and an isocyanate curing agent.
10. The coating composition according to claim 9, characterized in that the calcium drier is calcium naphthenate, which is present in the composition in an amount of 0.02 to 0.2% by mass; the cobalt complex is hexaammine cobalt trichloride, and the mass content of the cobalt complex in the composition is 0.005-0.05%.
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| CN110982007A (en) * | 2019-12-02 | 2020-04-10 | 上海保立佳新材料有限公司 | LED lamp emulsion and preparation method thereof |
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