CN112795300B - UV coating and preparation method thereof - Google Patents
UV coating and preparation method thereof Download PDFInfo
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- CN112795300B CN112795300B CN202011615426.XA CN202011615426A CN112795300B CN 112795300 B CN112795300 B CN 112795300B CN 202011615426 A CN202011615426 A CN 202011615426A CN 112795300 B CN112795300 B CN 112795300B
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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
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
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Abstract
The invention relates to the field of coatings, in particular to a UV coating and a preparation method thereof, wherein the preparation raw materials of the coating comprise, by weight, 45-60 parts of N-alkyl maleimide modified polyurethane acrylate, 10-35 parts of acrylate monomer and 0.05-1 part of initiator. The UV coating initiator has low dosage and low smell, and reaches A in French VOC labels+And (4) standard.
Description
Technical Field
The invention relates to the field of coatings, in particular to a UV coating and a preparation method thereof.
Background
The UV coating, namely the ultraviolet curing coating, is applied to the furniture and floor industries at first, and has the advantages of high curing speed, low energy consumption, low pollution and the like. With the increasing development of coating technology, UV coatings are gradually applied to materials such as plastics, paper, wood, metal, leather and the like, and become an important choice for decorative coatings in many industries.
Coatings are closely related to our lives. However, the traditional UV coating can release harmful substances such as formaldehyde, benzene series, volatile organic compounds, heavy metals and the like in the construction process, and has adverse effects on the environment and human bodies.
Disclosure of Invention
In view of the problems in the prior art, the first aspect of the present invention provides a UV coating, which is prepared from 45-60 parts by weight of N-alkyl maleimide-modified urethane acrylate, 10-35 parts by weight of acrylate monomer, and 0.05-1 part by weight of initiator.
As a preferred embodiment of the present invention, the acrylate monomer is an ethoxylated acrylate monomer.
In a preferred embodiment of the present invention, the ethoxylated acrylate monomer is selected from one or more of ethoxylated trimethylolpropane triacrylate, ethoxylated pentaerythritol triacrylate, and ethoxylated hydroxyethyl bisphenol a diacrylate.
As a preferred technical solution of the present invention, the ethoxylated acrylate monomer is a mercapto-modified ethoxylated acrylate monomer.
As a preferable technical scheme of the invention, the raw materials for preparing the N-alkyl maleimide modified polyurethane acrylate comprise polyester polyol, polyisocyanate, hydroxyl acrylate monomer and N-alkyl maleimide, wherein the content of functional groups in the polyester polyol and the polyisocyanate N (-OH): n (-NCO) ═ 1: (1.5-2).
As a preferable technical scheme of the invention, the polyester polyol is selected from one or more of polyester glycol adipate, polycarbonate glycol and polycaprolactone glycol.
As a preferable technical scheme of the invention, the weight average molecular weight of the polycaprolactone diol is 2000-6000.
As a preferred embodiment of the present invention, the weight average molecular weight of the polycarbonate diol is 2000-4000.
In a preferred embodiment of the present invention, the polyisocyanate is selected from one or more of hexamethylene diisocyanate trimer, isophorone diisocyanate, HDI biuret polyisocyanate, and IPDI trimer adduct.
The second aspect of the present invention provides a method for preparing the UV paint, which comprises: mixing the N-alkyl maleimide modified polyurethane acrylate, the acrylate monomer and the initiator to obtain the acrylic acid modified polyurethane acrylate.
Compared with the prior art, the invention has the following beneficial effects:
(1) in the application, N-alkyl maleimide modified urethane acrylate and sulfhydryl modified ethoxylated acrylate monomer are main components, and are applied to a photocuring coating system to enable the specific high-efficiency odor-removing effect of UV coating through multiple-effect modification and mutual synergistic effect: according to the UV coating, N-alkyl maleimide and a branched monosulfur bond with electron transfer and high-efficiency co-initiation effects are introduced by carrying out molecular structure design on N-alkyl maleimide modified polyurethane acrylate and a mercapto modified ethoxylated acrylate monomer, so that a photoinitiator can be initiated to generate a free radical under ultralow concentration and further initiate a double bond reaction in macromolecules, the photo-initiation efficiency is greatly improved, fragments quenching the free radical are reduced, and the high-efficiency co-initiation odor-free effect is realized; the thiol-modified ethoxylated acrylate monomer forms a branched structure containing a plurality of monosulfur bonds by utilizing the targeted addition reaction of thiol and unsaturated double bonds, so that the monomer can effectively block the formation of oxygen free radicals in the air to improve the curing efficiency, and meanwhile, the ethoxy in a molecular chain segment has a good anti-oxygen polymerization inhibition effect; the synergistic effect of the two different chain structures greatly reduces initiator fragment residues and realizes high-efficiency odor-free initiation-promoting effect.
(2) The N-alkyl maleimide modified polyurethane acrylate can participate in initiation reaction to replace partial photoinitiator, so that the use amount of the photoinitiator in a formula system is reduced, and the average photoinitiator dosage in the technical scheme can be lower than 1 wt% and is far lower than the initiator dosage of 3-5 wt% in coating products in the market.
(3) The UV coating has low odor and reaches A in French VOC labels+And (4) standard.
Detailed Description
The present invention is illustrated by the following specific embodiments, but is not limited to the specific examples given below.
The first aspect of the invention provides a UV coating, which is prepared from 45-60 parts by weight of N-alkyl maleimide modified polyurethane acrylate, 10-35 parts by weight of acrylate monomer and 0.05-1 part by weight of initiator.
In one embodiment, the preparation raw materials of the UV coating further comprise 10-35 parts of light-cured monomer, 0-20 parts of powder and 1-5 parts of auxiliary agent by weight.
In one embodiment, the raw materials for preparing the UV coating comprise, by weight, 45-60 parts of N-alkyl maleimide modified polyurethane acrylate, 10-35 parts of acrylate monomer, 0.1-1 part of initiator, 10-35 parts of photo-curing monomer, 0-20 parts of powder and 1-5 parts of auxiliary agent.
In a preferred embodiment, the raw materials for preparing the UV coating comprise 50 parts by weight of N-alkyl maleimide modified polyurethane acrylate, 22 parts by weight of acrylate monomer, 0.6 part by weight of initiator, 14.4 parts by weight of photo-curing monomer, 10 parts by weight of powder and 3 parts by weight of auxiliary agent.
N-alkyl maleimidesModified urethane acrylates
In one embodiment, the raw materials for preparing the N-alkyl maleimide modified polyurethane acrylate comprise polyester polyol, polyisocyanate, hydroxyl acrylate monomer and N-alkyl maleimide.
In one embodiment, the polyester polyol is reacted with a polyisocyanate having a functional group content n (-OH): n (-NCO) ═ 1: (1.5-2).
Preferably, the content of functional groups n (-NCO) in the polyester polyol and polyisocyanate is: n (-OH) ═ 1.8: 1.
in this application n is the amount of substance.
In one embodiment, the polyester polyol is selected from one or more of a polyester adipate diol, a polycarbonate diol, and a polycaprolactone diol.
Preferably, the polyester polyol is polycarbonate diol and/or polycaprolactone diol.
Preferably, the weight average molecular weight of the polycaprolactone diol is 2000-6000.
Preferably, the polycarbonate diol has a weight average molecular weight of 2000-4000.
In one embodiment, the polyisocyanate is selected from one or more of hexamethylene diisocyanate trimer, isophorone diisocyanate, HDI biuret polyisocyanate, IPDI trimer adduct.
The polycarbonate diol and polycaprolactone diol described herein are not particularly limited and may be routinely selected by those skilled in the art based on the description herein.
In one embodiment, the N-alkyl maleimide contains a hydroxyl group.
The hydroxyl group-containing N-alkylmaleimide of the present invention is not particularly limited, and those skilled in the art can make routine selections based on the description in the present application.
Preferably, the N-alkyl maleimide is N- (2-hydroxyethyl) maleimide.
In one embodiment, the method for preparing the N-alkyl maleimide-modified urethane acrylate comprises the following steps:
(1) mixing polyester polyol and polyisocyanate, adding a catalyst I, and reacting at the temperature of 75-90 ℃ for 2-3h to obtain a prepolymer I;
(2) slowly adding N-alkyl maleimide into the prepolymer I for dissolving, adding a catalyst I after the dissolving is finished, and reacting at the temperature of 70-80 ℃ for 2-3h to obtain a prepolymer II;
(3) adding a polymerization inhibitor I, then adding a hydroxyl acrylate monomer into the prepolymer II, and reacting for 2-3h at the temperature of 75-90 ℃ to obtain the prepolymer.
Preferably, the content of functional groups N (-NCO) in the prepolymer I and the N-alkyl maleimide is: n (-OH) ═ 3-4: 1; more preferably, the content of functional groups N (-NCO) in the prepolymer I and the N-alkyl maleimide is: n (-OH) ═ 3.5: 1.
preferably, the content of functional groups n (-NCO) in the prepolymer II and the hydroxyl acrylate monomer is: n (-OH) ═ 1: (1.05-1.1).
Examples of the catalyst I of the present invention include a tertiary amine catalyst, an organotin catalyst, an organobismuth catalyst, and anhydrous zinc acetate.
Preferably, the catalyst I is organic bismuth and/or anhydrous zinc acetate.
The amount of catalyst I used in the present application is not particularly limited and can be routinely selected by those skilled in the art.
Preferably, the polymerization inhibitor I accounts for 0.1-0.2 wt% of the prepolymer II.
Preferably, the polymerization inhibitor I is selected from one or more of hydroquinone, p-methoxyphenol, p-phenetole, p-tert-butylcatechol and di-tert-amylhydroquinone.
Polymerization inhibitor I is not particularly limited in the present application, and those skilled in the art can make routine selections based on the description in the present application.
In a preferred embodiment, the method for preparing the N-alkyl maleimide-modified urethane acrylate comprises the following steps:
(1) mixing polyester polyol and polyisocyanate, adding a catalyst I, and reacting at 82 ℃ for 2.5 hours to obtain a prepolymer I;
(2) slowly adding N-alkyl maleimide into the prepolymer I for dissolving, adding a catalyst I after the dissolving is finished, and reacting at the temperature of 75 ℃ for 2.6 hours to obtain a prepolymer II;
(3) adding a polymerization inhibitor I, then adding a hydroxyl acrylate monomer into the prepolymer II, and reacting for 2.5 hours at the temperature of 84 ℃ to obtain the prepolymer.
Acrylate monomer
In one embodiment, the acrylate monomer is an ethoxylated acrylate monomer.
Preferably, the ethoxylated acrylate monomer is selected from one or more of ethoxylated trihydroxypropane triacrylate, ethoxylated pentaerythritol triacrylate, and ethoxylated hydroxyethyl bisphenol A diacrylate.
The ethoxylated acrylate monomer is not particularly limited in this application and may be selected by those skilled in the art in accordance with the disclosure herein.
In one embodiment, the ethoxylated acrylate monomer is a mercapto-modified ethoxylated acrylate monomer.
In one embodiment, the repeating units of ethoxy groups in the ethoxylated acrylate monomer are from 3 to 20.
In one embodiment, the method of making the mercapto-modified ethoxylated acrylate monomer comprises: mixing the ethoxylated acrylate monomer and the polymerization inhibitor II, dropwise adding a multi-sulfhydryl compound, reacting at the temperature of 20-35 ℃ for 5-6h, heating to 45-60 ℃, and preserving heat for 2-3h to obtain the acrylate copolymer.
In a preferred embodiment, the method of preparing the mercapto-modified ethoxylated acrylate monomer comprises: adding an ethoxylated acrylate monomer and a polymerization inhibitor II into a reaction bottle, uniformly stirring in an ice-water bath, then dropwise adding a multi-sulfhydryl compound, and controlling the temperature at 28 ℃ to react for 5.5 hours; then heating to 50 ℃ and preserving the heat for 3h to obtain the product.
Preferably, the ethoxylated acrylate monomer accounts for 65-80% of the total weight of the ethoxylated acrylate monomer, the polymerization inhibitor II and the multi-mercapto compound; more preferably, the ethoxylated acrylate monomer accounts for 72% of the total weight of the ethoxylated acrylate monomer, polymerization inhibitor II and the polythiol compound.
Preferably, the polymerization inhibitor II accounts for 0.05-1% of the total weight of the ethoxylated acrylate monomer, the polymerization inhibitor II and the multi-sulfhydryl compound; more preferably, the polymerization inhibitor II accounts for 0.1% of the total weight of the ethoxylated acrylate monomer, the polymerization inhibitor II and the polythiol compound.
In one embodiment, the polymerization inhibitor II is selected from one or more of hydroquinone, p-methoxyphenol, p-hydroxy phene, p-tert-butylcatechol, and di-tert-amylhydroquinone.
The polymerization inhibitor II is not particularly limited and may be selected by those skilled in the art in accordance with the description of the present application.
Preferably, the multi-sulfhydryl compound accounts for 20-35% of the total weight of the ethoxylated acrylate monomer, the polymerization inhibitor II and the multi-sulfhydryl compound; more preferably, the multi-mercapto compound accounts for 28% of the total weight of the ethoxylated acrylate monomer, polymerization inhibitor II and the multi-mercapto compound.
Preferably, the polymercapto compound is trimethylolpropane tris (3-mercaptopropionate) and/or pentaerythritol tetrakis-3-mercaptopropionate.
All selected monomers in the application are selected from monomers without toluene reaction.
Initiator
The initiator described herein is not particularly limited and can be routinely selected by one skilled in the art.
Examples of the initiator in the present application include initiator 184, initiator TPO, initiator ITX, initiator 907 and the like.
Photo-curing monomer
The photocurable monomer described herein is not particularly limited and may be conventionally selected by those skilled in the art.
Powder material
The powder described herein is not particularly limited and may be routinely selected by those skilled in the art.
Examples of the powder include graphene, glass fiber, nano silica, boron nitride, and ceramic fiber.
Auxiliary agent
The auxiliaries described herein are not particularly limited and can be routinely selected by those skilled in the art.
Examples of the auxiliary agent include a leveling agent, a leveling control agent, a wetting agent, a dispersing agent, a defoaming agent, an oil repellent agent, and an anti-tack agent.
The second aspect of the present invention provides a method for preparing the UV paint, which comprises: mixing the N-alkyl maleimide modified polyurethane acrylate, the acrylate monomer and the initiator to obtain the acrylic acid modified polyurethane acrylate.
In one embodiment, the method of preparing the UV coating includes: mixing the N-alkyl maleimide modified polyurethane acrylate, the acrylate monomer, the initiator, the photo-curing monomer, the powder and the auxiliary agent to obtain the high-performance polyurethane acrylate.
Examples
Hereinafter, the present invention will be described in more detail by way of examples, but it should be understood that these examples are merely illustrative and not restrictive. The starting materials used in the examples which follow are all commercially available unless otherwise stated.
Example 1
The embodiment 1 of the invention provides a UV coating, which comprises the following raw materials in parts by weight: 50 parts of N-alkyl maleimide modified polyurethane acrylate, 20 parts of acrylate monomer, 0.5 part of initiator, 20 parts of light curing monomer, 5 parts of powder and 5 parts of auxiliary agent.
The preparation method of the N-alkyl maleimide modified polyurethane acrylate specifically comprises the following steps:
(1) mixing polyester polyol and polyisocyanate, adding a catalyst I, and reacting at 82 ℃ for 2.5 hours to obtain a prepolymer I;
(2) slowly adding N-alkyl maleimide into the prepolymer I for dissolving, adding a catalyst I after the dissolving is finished, and reacting at the temperature of 75 ℃ for 2.6 hours to obtain a prepolymer II;
(3) adding a polymerization inhibitor I, then adding a hydroxyl acrylate monomer into the prepolymer II, and reacting for 2.5 hours at the temperature of 84 ℃ to obtain the prepolymer.
The polyester polyol is polycarbonate dihydric alcohol, and the weight average molecular weight is 2000; the polyisocyanate is hexamethylene diisocyanate trimer; the molar ratio of the polyester polyol to the functional groups in the polyisocyanate, n (-NCO), to n (-OH), 1.5: 1; the N-alkyl maleimide is N- (2-hydroxyethyl) maleimide; the molar ratio N (-NCO) of the prepolymer I to the functional groups in the N-alkyl maleimide is as follows: n (-OH) ═ 3: 1; the molar ratio n (-NCO) of the prepolymer II to the functional groups in the hydroxyl acrylate monomer is as follows: n (-OH) ═ 1: 1.05; the catalyst I is anhydrous zinc acetate; the polymerization inhibitor I is hydroquinone.
The acrylate monomer is a sulfhydryl modified ethoxylated acrylate monomer.
The preparation method of the sulfhydryl modified ethoxylated acrylate monomer comprises the following steps: adding an ethoxylated acrylate monomer and a polymerization inhibitor II into a reaction bottle, uniformly stirring in an ice-water bath, then dropwise adding a multi-sulfhydryl compound, and controlling the temperature at 28 ℃ to react for 5.5 hours; then heating to 50 ℃ and preserving the heat for 3h to obtain the product.
The ethoxylated acrylate monomer is ethoxylated trihydroxy propane triacrylate; the repeating unit of the ethoxy is 3; the ethoxylated acrylate monomer accounts for 65 percent of the total weight of the ethoxylated acrylate monomer, the polymerization inhibitor II and the multi-sulfhydryl compound; the polymerization inhibitor II accounts for 0.05 percent of the total weight of the ethoxylated acrylate monomer, the polymerization inhibitor II and the multi-sulfhydryl compound; the polymerization inhibitor II is hydroquinone; the multi-sulfhydryl compound accounts for 20 percent of the total weight of the ethoxylated acrylate monomer, the polymerization inhibitor II and the multi-sulfhydryl compound; the multi-mercapto compound is trimethylolpropane tris (3-mercaptopropionate).
The initiator is an initiator 184; the light curing monomer is tripropylene glycol diacrylate; the powder is graphene; the assistant is a leveling agent, and is German BYK 410.
The preparation method of the UV coating comprises the following steps of; mixing the N-alkyl maleimide polyurethane acrylate, the acrylate monomer, the initiator, the photo-curing monomer, the powder and the auxiliary agent to obtain the high-performance polyurethane acrylate.
Example 2
The embodiment 2 of the invention provides a UV coating, which comprises the following raw materials in parts by weight: 60 parts of N-alkyl maleimide modified polyurethane acrylate, 25 parts of acrylate monomer, 0.1 part of initiator, 10 parts of light curing monomer, 4 parts of powder and 1 part of auxiliary agent.
The preparation method of the N-alkyl maleimide modified polyurethane acrylate specifically comprises the following steps:
(1) mixing polyester polyol and polyisocyanate, adding a catalyst I, and reacting at 82 ℃ for 2.5 hours to obtain a prepolymer I;
(2) slowly adding N-alkyl maleimide into the prepolymer I for dissolving, adding a catalyst I after the dissolving is finished, and reacting at the temperature of 75 ℃ for 2.6 hours to obtain a prepolymer II;
(3) adding a polymerization inhibitor I, then adding a hydroxyl acrylate monomer into the prepolymer II, and reacting for 2.5 hours at the temperature of 84 ℃ to obtain the prepolymer.
The polyester polyol is polycarbonate dihydric alcohol, and the weight average molecular weight is 2000; the polyisocyanate is hexamethylene diisocyanate trimer; the molar ratio of the polyester polyol to the functional groups in the polyisocyanate, n (-NCO), to n (-OH) ═ 2: 1; the N-alkyl maleimide is N- (2-hydroxyethyl) maleimide; the molar ratio N (-NCO) of the prepolymer I to the functional groups in the N-alkyl maleimide is as follows: n (-OH) ═ 4: 1; the molar ratio n (-NCO) of the prepolymer II to the functional groups in the hydroxyl acrylate monomer is as follows: n (-OH) ═ 1: 1.1; the catalyst I is anhydrous zinc acetate; the polymerization inhibitor I is hydroquinone.
The acrylate monomer is a sulfhydryl modified ethoxylated acrylate monomer.
The preparation method of the sulfhydryl modified ethoxylated acrylate monomer comprises the following steps: adding an ethoxylated acrylate monomer and a polymerization inhibitor II into a reaction bottle, uniformly stirring in an ice-water bath, then dropwise adding a multi-sulfhydryl compound, and controlling the temperature at 28 ℃ to react for 5.5 hours; then heating to 50 ℃ and preserving the heat for 3h to obtain the product.
The ethoxylated acrylate monomer is ethoxylated trihydroxy propane triacrylate; the repeating unit of the ethoxy is 3; the ethoxylated acrylate monomer accounts for 80% of the total weight of the ethoxylated acrylate monomer, the polymerization inhibitor II and the multi-mercapto compound; the polymerization inhibitor II accounts for 0.2 percent of the total weight of the ethoxylated acrylate monomer, the polymerization inhibitor II and the multi-sulfhydryl compound; the polymerization inhibitor II is hydroquinone; the multi-sulfhydryl compound accounts for 35 percent of the total weight of the ethoxylated acrylate monomer, the polymerization inhibitor II and the multi-sulfhydryl compound; the multi-mercapto compound is trimethylolpropane tris (3-mercaptopropionate).
The initiator is an initiator 184; the light curing monomer is tripropylene glycol diacrylate; the powder is graphene; the assistant is a leveling agent, and is German BYK 410.
The preparation method of the UV coating comprises the following steps of; mixing the N-alkyl maleimide modified polyurethane acrylate, the acrylate monomer, the initiator, the photo-curing monomer, the powder and the auxiliary agent to obtain the high-performance polyurethane acrylate.
Example 3
The embodiment 3 of the invention provides a UV coating, which comprises the following raw materials in parts by weight: 50 parts of N-alkyl maleimide modified polyurethane acrylate, 22 parts of acrylate monomer, 0.6 part of initiator, 14.4 parts of light curing monomer, 10 parts of powder and 3 parts of auxiliary agent.
The preparation method of the N-alkyl maleimide modified polyurethane acrylate specifically comprises the following steps:
(1) mixing polyester polyol and polyisocyanate, adding a catalyst I, and reacting at 82 ℃ for 2.5 hours to obtain a prepolymer I;
(2) slowly adding N-alkyl maleimide into the prepolymer I for dissolving, adding a catalyst I after the dissolving is finished, and reacting at the temperature of 75 ℃ for 2.6 hours to obtain a prepolymer II;
(3) adding a polymerization inhibitor I, then adding a hydroxyl acrylate monomer into the prepolymer II, and reacting for 2.5 hours at the temperature of 84 ℃ to obtain the prepolymer.
The polyester polyol is polycarbonate dihydric alcohol, and the weight average molecular weight is 2000; the polyisocyanate is hexamethylene diisocyanate trimer; the molar ratio of the polyester polyol to the functional groups in the polyisocyanate, n (-NCO), to n (-OH), 1.8: 1; the N-alkyl maleimide is N- (2-hydroxyethyl) maleimide; the molar ratio N (-NCO) of the prepolymer I to the functional groups in the N-alkyl maleimide is as follows: n (-OH) ═ 3.5: 1; the molar ratio n (-NCO) of the prepolymer II to the functional groups in the hydroxyl acrylate monomer is as follows: n (-OH) ═ 1: 1.1; the catalyst I is anhydrous zinc acetate; the polymerization inhibitor I is hydroquinone.
The acrylate monomer is a sulfhydryl modified ethoxylated acrylate monomer.
The preparation method of the sulfhydryl modified ethoxylated acrylate monomer comprises the following steps: adding an ethoxylated acrylate monomer and a polymerization inhibitor II into a reaction bottle, uniformly stirring in an ice-water bath, then dropwise adding a multi-sulfhydryl compound, and controlling the temperature at 28 ℃ to react for 5.5 hours; then heating to 50 ℃ and preserving the heat for 3h to obtain the product.
The ethoxylated acrylate monomer is ethoxylated trihydroxy propane triacrylate; the repeating unit of the ethoxy is 3; the ethoxylated acrylate monomer accounts for 72 percent of the total weight of the ethoxylated acrylate monomer, the polymerization inhibitor II and the multi-sulfhydryl compound; the polymerization inhibitor II accounts for 0.1 percent of the total weight of the ethoxylated acrylate monomer, the polymerization inhibitor II and the multi-sulfhydryl compound; the polymerization inhibitor II is hydroquinone; the weight of the multi-sulfhydryl compound accounts for 28 percent of the total weight of the ethoxylated acrylate monomer, the polymerization inhibitor II and the multi-sulfhydryl compound; the multi-mercapto compound is trimethylolpropane tris (3-mercaptopropionate).
The initiator is an initiator 184; the light curing monomer is tripropylene glycol diacrylate; the powder is graphene; the assistant is a leveling agent, and is German BYK 410.
The preparation method of the UV coating comprises the following steps of; mixing the N-alkyl maleimide modified polyurethane acrylate, the acrylate monomer, the initiator, the photo-curing monomer, the powder and the auxiliary agent to obtain the high-performance polyurethane acrylate.
Example 4
Embodiment 4 of the present invention provides a UV coating, which comprises the following specific preparation raw materials, by weight: 50 parts of urethane acrylate, 22 parts of acrylate monomer, 2.3 parts of initiator, 14.4 parts of light curing monomer, 10 parts of powder and 3 parts of auxiliary agent.
The preparation method of the polyurethane acrylate specifically comprises the following steps:
(1) mixing polyester polyol and polyisocyanate, adding a catalyst I, and reacting at 82 ℃ for 2.5 hours to obtain a prepolymer I;
(2) adding a polymerization inhibitor I, then adding a hydroxyl acrylate monomer into the prepolymer I, and reacting for 2.5 hours at the temperature of 84 ℃ to obtain the prepolymer.
The polyester polyol is polycarbonate dihydric alcohol, and the weight average molecular weight is 2000; the polyisocyanate is hexamethylene diisocyanate trimer; the molar ratio n (-NCO) of the polyester polyol to the functional groups in the polyisocyanate: n (-OH) ═ 1.8: 1; the molar ratio n (-NCO) of the prepolymer I to the functional groups in the hydroxyl acrylate monomer is as follows: n (-OH) ═ 1: 1.1; the catalyst I is anhydrous zinc acetate; the polymerization inhibitor I is hydroquinone.
The acrylate monomer is a sulfhydryl modified ethoxylated acrylate monomer.
The preparation method of the sulfhydryl modified ethoxylated acrylate monomer comprises the following steps: adding an ethoxylated acrylate monomer and a polymerization inhibitor II into a reaction bottle, uniformly stirring in an ice-water bath, then dropwise adding a multi-sulfhydryl compound, and controlling the temperature at 28 ℃ to react for 5.5 hours; then heating to 50 ℃ and preserving the heat for 3h to obtain the product.
The ethoxylated acrylate monomer is ethoxylated trihydroxy propane triacrylate; the repeating unit of the ethoxy is 3; the ethoxylated acrylate monomer accounts for 72 percent of the total weight of the ethoxylated acrylate monomer, the polymerization inhibitor II and the multi-sulfhydryl compound; the polymerization inhibitor II accounts for 0.1 percent of the total weight of the ethoxylated acrylate monomer, the polymerization inhibitor II and the multi-sulfhydryl compound; the polymerization inhibitor II is hydroquinone; the weight of the multi-sulfhydryl compound accounts for 28 percent of the total weight of the ethoxylated acrylate monomer, the polymerization inhibitor II and the multi-sulfhydryl compound; the multi-mercapto compound is trimethylolpropane tris (3-mercaptopropionate).
The initiator is an initiator 184; the light curing monomer is tripropylene glycol diacrylate; the powder is graphene; the assistant is a leveling agent, and is German BYK 410.
The preparation method of the UV coating comprises the following steps: mixing urethane acrylate, an acrylate monomer, an initiator, a photocuring monomer, powder and an auxiliary agent to obtain the acrylic resin.
Example 5
Embodiment 5 of the present invention provides a UV coating, which is prepared from the following raw materials, by weight: 50 parts of N-alkyl maleimide modified polyurethane acrylate, 22 parts of acrylate monomer, 2 parts of initiator, 14.4 parts of light curing monomer, 10 parts of powder and 3 parts of auxiliary agent.
The preparation method of the N-alkyl maleimide modified polyurethane acrylate specifically comprises the following steps:
(1) mixing polyester polyol and polyisocyanate, adding a catalyst I, and reacting at 82 ℃ for 2.5 hours to obtain a prepolymer I;
(2) slowly adding N-alkyl maleimide into the prepolymer I for dissolving, adding a catalyst I after the dissolving is finished, and reacting at the temperature of 75 ℃ for 2.6 hours to obtain a prepolymer II;
(3) adding a polymerization inhibitor I, then adding a hydroxyl acrylate monomer into the prepolymer II, and reacting for 2.5 hours at the temperature of 84 ℃ to obtain the prepolymer.
The polyester polyol is polycarbonate dihydric alcohol, and the weight average molecular weight is 2000; the polyisocyanate is hexamethylene diisocyanate trimer; the molar ratio of the polyester polyol to the functional groups in the polyisocyanate, n (-NCO), to n (-OH), 1.8: 1; the N-alkyl maleimide is N- (2-hydroxyethyl) maleimide; the molar ratio N (-NCO) of the prepolymer I to the functional groups in the N-alkyl maleimide is as follows: n (-OH) ═ 3.5: 1; the molar ratio n (-NCO) of the prepolymer II to the functional groups in the hydroxyl acrylate monomer is as follows: n (-OH) ═ 1: 1.1; the catalyst I is anhydrous zinc acetate; the polymerization inhibitor I is hydroquinone.
The acrylate monomer is ethoxylated trihydroxy propane triacrylate; the repeating unit of the ethoxy group is 3.
The preparation method of the UV coating comprises the following steps of; mixing the N-alkyl maleimide modified polyurethane acrylate, the acrylate monomer, the initiator, the photo-curing monomer, the powder and the auxiliary agent to obtain the high-performance polyurethane acrylate.
Example 6
Embodiment 6 of the present invention provides a UV coating, which comprises the following specific preparation raw materials, by weight: 50 parts of N-alkyl maleimide modified polyurethane acrylate, 22 parts of acrylate monomer, 2 parts of initiator, 14.4 parts of light curing monomer, 10 parts of powder and 3 parts of auxiliary agent.
The preparation method of the N-alkyl maleimide modified polyurethane acrylate specifically comprises the following steps:
(1) mixing polyester polyol and polyisocyanate, adding a catalyst I, and reacting at 82 ℃ for 2.5 hours to obtain a prepolymer I;
(2) slowly adding N-alkyl maleimide into the prepolymer I for dissolving, adding a catalyst I after the dissolving is finished, and reacting at the temperature of 75 ℃ for 2.6 hours to obtain a prepolymer II;
(3) adding a polymerization inhibitor I, then adding a hydroxyl acrylate monomer into the prepolymer II, and reacting for 2.5 hours at the temperature of 84 ℃ to obtain the prepolymer.
The polyester polyol is polycarbonate dihydric alcohol, and the weight average molecular weight is 2000; the polyisocyanate is hexamethylene diisocyanate trimer; the molar ratio of the polyester polyol to the functional groups in the polyisocyanate, n (-NCO), to n (-OH), 1.8: 1; the N-alkyl maleimide is N- (2-hydroxyethyl) maleimide; the molar ratio N (-NCO) of the prepolymer I to the functional groups in the N-alkyl maleimide is as follows: n (-OH) ═ 3.5: 1; the molar ratio n (-NCO) of the prepolymer II to the functional groups in the hydroxyl acrylate monomer is as follows: n (-OH) ═ 1: 1.1; the catalyst I is anhydrous zinc acetate; the polymerization inhibitor I is hydroquinone.
The acrylate monomer is trihydroxy propane triacrylate.
The preparation method of the UV coating comprises the following steps of; mixing the N-alkyl maleimide modified polyurethane acrylate, the acrylate monomer, the initiator, the photo-curing monomer, the powder and the auxiliary agent to obtain the high-performance polyurethane acrylate.
Performance evaluation
And (3) odor test: the odors of the UV paints obtained in examples 1 to 6 were measured and ranked to obtain numbers 1 to 6, the number size indicating the size of the odor of the UV paint, the larger the odor, and the later the ranking, the larger the number.
TABLE 1
| Odor test | |
| Example 1 | 2 |
| Example 2 | 3 |
| Example 3 | 1 |
| Example 4 | 6 |
| Example 5 | 4 |
| Example 6 | 5 |
The foregoing examples are merely illustrative and serve to explain some of the features of the method of the present invention. The appended claims are intended to claim as broad a scope as is contemplated, and the examples presented herein are merely illustrative of selected implementations in accordance with all possible combinations of examples. Accordingly, it is applicants' intention that the appended claims are not to be limited by the choice of examples illustrating features of the invention. Also, where numerical ranges are used in the claims, subranges therein are included, and variations in these ranges are also to be construed as possible being covered by the appended claims.
Claims (7)
1. The UV coating is characterized in that the preparation raw materials comprise, by weight, 45-60 parts of N-alkyl maleimide modified polyurethane acrylate, 10-35 parts of acrylate monomer and 0.05-1 part of initiator; the preparation raw materials of the N-alkyl maleimide modified polyurethane acrylate comprise polyester polyol, polyisocyanate, hydroxyl acrylate monomer and N-alkyl maleimide, wherein the content of functional groups N (-OH) in the polyester polyol and the polyisocyanate is as follows: n (-NCO) ═ 1: (1.5-2); the N-alkyl maleimide contains a hydroxyl group; the acrylate monomer is an ethoxylated acrylate monomer, the ethoxylated acrylate monomer is a mercapto-modified ethoxylated acrylate monomer, and the repeating unit of the ethoxy group is 3-20;
the preparation method of the N-alkyl maleimide modified polyurethane acrylate comprises the following steps:
(1) mixing polyester polyol and polyisocyanate, adding a catalyst I, and reacting at the temperature of 75-90 ℃ for 2-3h to obtain a prepolymer I;
(2) slowly adding N-alkyl maleimide into the prepolymer I for dissolving, adding a catalyst I after the dissolving is finished, and reacting at the temperature of 70-80 ℃ for 2-3h to obtain a prepolymer II;
(3) adding a polymerization inhibitor I, then adding a hydroxyl acrylate monomer into the prepolymer II, and reacting for 2-3h at the temperature of 75-90 ℃ to obtain the prepolymer.
2. The UV coating of claim 1, wherein the ethoxylated acrylate monomer is selected from one or more of ethoxylated trimethylolpropane triacrylate, ethoxylated pentaerythritol triacrylate, and ethoxylated hydroxyethyl bisphenol A diacrylate.
3. The UV coating of claim 1, wherein the polyester polyol is selected from one or more of a polyester glycol adipate, a polycarbonate glycol, and a polycaprolactone glycol.
4. The UV coating of claim 3, wherein the polycaprolactone diol has a weight average molecular weight of 2000-6000.
5. The UV coating of claim 3, wherein the polycarbonate diol has a weight average molecular weight of 2000-4000.
6. UV coating according to any of claims 1 to 5, characterized in that the polyisocyanate is selected from one or more of hexamethylene diisocyanate trimer, isophorone diisocyanate, HDI biuret polyisocyanate, IPDI trimer adduct.
7. A method for preparing the UV paint according to any one of claims 1 to 5, characterized in that it comprises: mixing the N-alkyl maleimide modified polyurethane acrylate, the acrylate monomer and the initiator to obtain the acrylic acid modified polyurethane acrylate.
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