CN114181370A - Modified urethane acrylate photocuring oligomer and preparation method thereof - Google Patents
Modified urethane acrylate photocuring oligomer and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/675—Low-molecular-weight compounds
- C08G18/679—Acetylenic compounds
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- 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
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
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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
Abstract
The invention discloses a modified urethane acrylate photocuring oligomer and a preparation method thereof, wherein the oligomer has a structure shown in a formula (I):
wherein R is1Represents an alkylene oxide adduct having a molar mass of 300 to 2000g/mol and containing an unsaturated carbon-carbon triple bond; r2Represents methyl or methylene mono-or polysubstituted aromatic group or straight-chain or branched alkane or cycloalkane containing 6 to 13 carbon atoms; r3Represents a linear or branched alkyl carboxylate containing 2 to 3 carbon atoms or a quaternary tricarboxylate containing 2 to 3 unsaturated carbon-carbon double bonds; r4Represents a hydrogen atom or a methyl group; r5To representA hydrogen atom or a methyl group. The modified polyurethane acrylate oligomer has the characteristic of low viscosity, can improve the performance of a photocuring product in the use process, and also has the good functions of defoaming, wetting, leveling and the like.
Description
Technical Field
The invention relates to the technical field of fine chemical engineering, in particular to a modified urethane acrylate photocuring oligomer and a preparation method thereof.
Background
UV/EB curing refers to rapid polymerization, crosslinking, curing and molding of a liquid material with chemical activity initiated by ultraviolet light or visible light or electron beams, and belongs to an advanced material surface treatment technology. In the photocurable material, the oligomer is one of the photocurable materials, and has a group capable of undergoing a photocuring reaction such as a carbon-carbon unsaturated double bond.
The ultraviolet light curing urethane acrylate oligomer is a feasible substitute for the thermal curing of a urethane prepolymer, has the advantages of reducing use and energy consumption cost, eliminating VOCs in a coating, having a low viscosity effect formed in an application process and the like, belongs to a green industrial product, and can be used for curing coatings, adhesives, sealants, printing ink and the like. The urethane acrylate oligomer is based on an isocyanate-terminated polyurethane prepolymer; the polyurethane acrylate oligomer can be synthesized by two-step reaction of polyisocyanate, long-chain diol and acrylic hydroxy ester.
Due to the composition of the urethane acrylate oligomer, such as: in addition to the selection of various structures, the chemical flexibility of the polyisocyanate and the long-chain diol is also diversified, so that various types of urethane acrylate oligomers can be synthesized through molecular design to meet the actual requirements. Japanese patent JP4879560B2 discloses an ethylenically unsaturated group-containing isocyanate compound formed by esterification of a dihydroxyamine inorganic acid salt compound formed from a dihydroxyamine compound and an inorganic acid with a carboxylic acid chloride, followed by N-acylation reaction under the action of phosgene and finally dehydrochlorination in the presence of a basic nitrogen compound. This material is reacted with a polyol to give a urethane (meth) acrylate oligomer. Chinese patent CN102633984B discloses a urethane acrylate oligomer obtained by the reaction of acetone-dissolved dibutyltin dilaurate, a semi-adduct of a mixture of a hydroxy ester diisocyanate and a phosphate ester diisocyanate, and a synthesized neopolyol. European patent EP3039048B1 discloses a coating composition containing a water-dispersible urethane acrylate oligomer that can be used for a variety of substances.
The acetylene glycol surfactant is a nonionic surfactant having advantages of good wettability and dispersibility, low foamability and defoaming property, low toxicity, etc., and is generally called as an aag (advanced acrylic glycol) surfactant according to the molecular structure characteristics thereof because it has an alkynyl group, a polar group hydroxyl group and a nonpolar group hydrocarbon group. It is considered that the AAG-type surfactant is a surfactant having a branched structure, and the applicability thereof is improved by devising different numbers of ethoxy groups and/or propoxy groups in the molecular structure, such as hydrophilicity, low surface tension, etc. U.S. Pat. No. 5,5650543 discloses ethoxylated acetylenic diol adducts having low dynamic surface tension, which may be used alone or in combination with other surfactants in waterborne coatings. U.S. Pat. No. 6,686,4395 discloses ethoxylated/propoxylated acetylenic diol adducts obtained from one of 2,4,7, 9-tetramethyl-5-decyne-4, 7-diol, 2,5,8, 11-tetramethyl-6-dodecyne-5, 8-diol by reacting the ethoxylated acetylenic diol adduct with propylene oxide using a trialkylamine catalyst. The material is particularly suitable for one of the compositions of paint, ink, fountain solution and the like of an aqueous system. Also used in the above system are acetylenyl diol ethylene oxide/propylene oxide adducts disclosed in taiwan patent TWI245977B that utilize propylene oxide as a capping unit. Chinese patent CN102304029A discloses a method for synthesizing an adduct of alkynediol and ethylene oxide, and designs a method for realizing low-cost preparation of the adduct of alkynediol and ethylene oxide with different chain lengths under normal pressure conditions aiming at the defects of high-pressure reaction. Chinese patent CN110982056A discloses an alkynediol block polyether, which is a composite catalyst composed of an alkyl metal catalyst and an organic base catalyst, so that the color of the synthesized alkynediol block polyether is light, and the problem that the traditional synthesis process of the alkynediol block polyether needs aftertreatment due to dark color is solved. In addition, Qijieyong et al developed a novel high-efficiency surfactant butynediol ethoxylate trisiloxane through gas chromatography-mass spectrometry research, and the substance was synthesized by hydrosilylation reaction of heptamethyltrisiloxane and butynediol ethoxylate, and the advantages of an organosilicon surfactant and an alkynediol surfactant were inherited (printing and dyeing auxiliary, 2016,33(10): 57-60.).
According to the prior art, no urethane acrylate oligomer modified by an alkylene oxide adduct of alkynediol is seen at home and abroad. Common modification methods of urethane acrylate oligomer include introduction of fluorine chain, silicon chain, amine group, polyester and the like. Chinese patent CN102993404B discloses a photosensitive fluorosilicone block urethane acrylate oligomer for leather finishing agent, which is synthesized by four steps, wherein a fluorine-containing substance is introduced in the first step of reaction and a silicon-containing substance is introduced in the second step of reaction. Yuenther et al have independently developed a polyester urethane acrylate oligomer as a base resin for use in ultraviolet curable coatings (coating industry, 2014,44(3): 54-59.). Chinese patent CN106519182A discloses an organosilicon modified urethane acrylate oligomer and a preparation method thereof, wherein the method comprises the steps of reacting organosilicon polyol with diisocyanate compound, and then carrying out end capping by hydroxyl acrylate, and the organosilicon modified urethane acrylate oligomer can be used in the field of special release coatings. Chinese patent CN107325246B discloses an amino-containing modified polyurethane acrylate oligomer which can be used for photo-curing digital jet printing, wherein an amino group is introduced by using a bifunctional hydroxyl extended chain containing a tertiary amino group, wherein the bifunctional hydroxyl extended chain accounts for 5-50% of the mole number of aliphatic diisocyanate.
The oligomers have a common phenomenon that the oligomers have a large molecular weight and a high viscosity, and in addition to the essential components of the photocurable composition, an appropriate amount of additives such as an antifoaming agent and a wetting agent is required to be added in the actual use process. Especially, the defoaming agent is mainly used for eliminating a large amount of bubbles generated in the process. If the defoaming agent is not added, the bubbles in the paint film contain oxygen, which can prevent photopolymerization and affect the construction, and the use amount of the photoinitiator is increased, so that on one hand, the cost is increased, and on the other hand, the performances of the paint film, such as yellowing resistance, and the like, are negatively affected. The defoaming agents used for photocurable resins are relatively expensive, especially those with photoactivity, and the non-photoactivity can cause problems with applicability such as color migration.
Aiming at the defects that the oligomer has high viscosity, an additional defoaming agent needs to be added in practical application, and the problems of color migration, cost increase and the like caused by improper selection of the defoaming agent, the invention develops the modified urethane acrylate photocuring oligomer which is very suitable for being applied to the fields of photocuring paint, printing ink and the like.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide a modified urethane acrylate photocuring oligomer and a preparation method thereof; the modified polyurethane acrylate oligomer has the characteristic of low viscosity, can improve the performance of a photocuring product in the use process, and also has the good functions of defoaming, wetting, leveling and the like.
In order to achieve the technical purpose and achieve the technical effect, the invention is realized by the following technical scheme:
the invention provides a modified urethane acrylate photocuring oligomer, which has a structure shown in a formula (I):
wherein R is1Represents an alkylene oxide adduct having a molar mass of 300 to 2000g/mol and containing an unsaturated carbon-carbon triple bond; r2Represents methyl or methylene mono-or polysubstituted aromatic group or straight-chain or branched alkane or cycloalkane containing 6 to 13 carbon atoms; r3Represents a linear or branched alkyl carboxylate containing 2 to 3 carbon atoms or a quaternary tricarboxylate containing 2 to 3 unsaturated carbon-carbon double bonds; r4Represents a hydrogen atom or a methyl group; r5Represents a hydrogen atom or a methyl group.
Further, the modified urethane acrylate photocuring oligomer is prepared by the following reaction:
(a) an alkylene oxide adduct of an acetylenic diol having a molar mass of 300 to 2000g/mol, having an unsaturated carbon-carbon triple bond, and having at least one group capable of reacting with an isocyanate;
(b) at least one diisocyanate; and
(c) at least one hydroxy acrylate.
Further, the alkylene oxide adduct of an acetylenic diol is an ethoxylated acetylenic diol having the structure shown in formula (ii):
wherein, R is6、R7、R8And R9Respectively represent a straight chain or a saturated alkyl group containing one or more branched chains and having 1 to 8 carbon atoms; r6、R7、R8And R9May be the same or different; m and n are integers of 0-35, and m + n is more than or equal to 1 and less than or equal to 35; more preferably, m and n are integers of 0-20, and m + n is more than or equal to 1 and less than or equal to 20.
Preferably, the ethoxylated acetylenic diol has a structural formula as shown in formula (III), formula (IV) or formula (V):
the ethoxylated acetylenic diols of formula (V) are commercially available
440, wherein m + n is 35.
Preferably, the diisocyanate is selected from toluene diisocyanate, xylene methane diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate or dicyclohexylmethane diisocyanate.
Preferably, the hydroxy acrylate is selected from the group consisting of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, trimethylolpropane diacrylate and pentaerythritol triacrylate.
The invention further provides a preparation method of the modified urethane acrylate photocuring oligomer, which comprises the following steps:
(1) sequentially adding diisocyanate, a catalyst and a polymerization inhibitor into a reactor, and optionally adding a certain amount of diluent, controlling the reaction temperature to be 30-70 ℃, slowly dropwise adding hydroxyl acrylate for reaction, wherein the reaction time is 0.5-2 h;
(2) controlling the reaction temperature to be 70-120 ℃, and slowly dripping the alkynediol alkylene oxide adduct into the reactor for 1-2 h; and after the reaction is finished, cooling to obtain the modified urethane acrylate photocuring oligomer.
Preferably, the catalyst is selected from at least one of triethanolamine, triethylene diamine, dibutyltin laurate, stannous octoate and lead naphthenate; the polymerization inhibitor is selected from at least one of hydroquinone, p-hydroxyanisole, o-methyl hydroquinone, phenothiazine, di-tert-butyl hydroquinone, copper sulfate and copper acetate; the diluent is at least one selected from the group consisting of tripropylene glycol diacrylate, dipropylene glycol diacrylate, hexanediol diacrylate and trimethylolpropane triacrylate.
Further, the mass ratio of the diisocyanate to the hydroxyl acrylate to the alkyne diol alkylene oxide adduct is 1: (0.2-2): (0.5-2.5).
Further, the adding amount of the polymerization inhibitor is 0.1-1% by mass relative to the total mass of the diisocyanate, the hydroxyl acrylate and the alkynediol alkylene oxide adduct; the addition amount of the catalyst is 0.01-0.2% by mass relative to the total mass of the diisocyanate, the hydroxyl acrylate and the alkyne diol alkylene oxide adduct; the amount of the diluent added is 20 to 50% by mass based on the total mass of the diisocyanate, the hydroxy acrylate and the acetylene glycol epoxy adduct.
Furthermore, the reaction temperature in the step (1) is 40-55 ℃; the reaction temperature in the step (2) is 70-100 ℃.
The invention has the beneficial effects that:
according to the invention, the alkylene oxide adduct of aliphatic diol which has unsaturated carbon-carbon triple bonds and at least one isocyanate reactive group is used as one of raw materials for preparing the modified urethane acrylate photocuring oligomer, so that the unsaturated carbon-carbon triple bonds can be introduced into the oligomer, and the synthesized modified urethane acrylate oligomer has the characteristic of low viscosity, and can improve the fluidity, the easiness in spraying, the permeability with a base material and the like after being applied to photocuring paint, ink, an adhesive and the like; moreover, the alkylene oxide adduct of the aliphatic diol can ensure that the obtained modified urethane acrylate photocuring oligomer has better functions of defoaming, wetting, leveling and the like, so that additives such as a defoaming agent, a wetting agent and the like are not required to be additionally added during use, the production cost can be reduced, the problems of color migration, paint film yellowing and the like can be avoided, and the performance of the photocuring product is improved; the cured film formed by the modified urethane acrylate photocuring oligomer has better hardness, glossiness and adhesive force.
Detailed description of the invention
The technical solutions in the present invention will be described clearly and completely with reference to specific embodiments, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a modified urethane acrylate photocuring oligomer, which has a structure shown in a formula (I):
wherein R is1Represents an alkylene oxide adduct having a molar mass of 300 to 2000g/mol and containing an unsaturated carbon-carbon triple bond;R2represents methyl or methylene mono-or polysubstituted aromatic group or straight-chain or branched alkane or cycloalkane containing 6 to 13 carbon atoms; r3Represents a linear or branched alkyl carboxylate containing 2 to 3 carbon atoms or a quaternary tricarboxylate containing 2 to 3 unsaturated carbon-carbon double bonds; r4Represents a hydrogen atom or a methyl group; r5Represents a hydrogen atom or a methyl group.
The modified urethane acrylate photocuring oligomer is prepared by the following reaction:
(a) an alkylene oxide adduct of an acetylenic diol having a molar mass of 300 to 2000g/mol, having an unsaturated carbon-carbon triple bond, and having at least one group capable of reacting with an isocyanate;
(b) at least one diisocyanate; and
(c) at least one hydroxy acrylate.
Wherein the alkylene oxide adduct of an acetylenic diol is preferably an ethoxylated acetylenic diol having the structure shown in formula (II):
wherein, R is6、R7、R8And R9Respectively represent a straight chain or a saturated alkyl group containing one or more branched chains and having 1 to 8 carbon atoms; r6、R7、R8And R9May be the same or different; m and n are integers of 0-35, and m + n is more than or equal to 1 and less than or equal to 35; more preferably, m and n are integers of 0-20, and m + n is more than or equal to 1 and less than or equal to 20.
Further, the above-mentioned ethoxylated acetylenic diol may preferably be a compound represented by the formula (III), the formula (IV) or the formula (V):
the ethoxylated acetylenic diols of formula (V) are commercially available
440, wherein m + n is 35.
The diisocyanate is preferably toluene diisocyanate, xylene methane diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate or dicyclohexylmethane diisocyanate.
Among them, the hydroxyl acrylate is preferably hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, trimethylolpropane diacrylate or pentaerythritol triacrylate.
The preparation method of the modified urethane acrylate photocuring oligomer comprises the following steps:
(1) sequentially adding diisocyanate, a catalyst, a polymerization inhibitor and optionally a diluent into a reactor, controlling the reaction temperature to be 30-70 ℃, and slowly dropwise adding hydroxy acrylate for reaction for 0.5-2 h; the reaction temperature in the step (1) can be further preferably 40-55 ℃;
(2) controlling the reaction temperature to be 70-120 ℃, and slowly dripping the alkynediol alkylene oxide adduct into the reactor for 1-2 h; after the reaction is finished, cooling to obtain the modified urethane acrylate photocuring oligomer; the reaction temperature in the step (2) may be more preferably 70 to 100 ℃.
Wherein the catalyst is at least one selected from triethanolamine, triethylene diamine, dibutyltin laurate, stannous octoate and lead naphthenate; the polymerization inhibitor is at least one selected from hydroquinone, p-hydroxyanisole, o-methyl hydroquinone, phenothiazine, di-tert-butyl hydroquinone, copper sulfate and copper acetate; the diluent is at least one selected from the group consisting of tripropylene glycol diacrylate, dipropylene glycol diacrylate, hexanediol diacrylate, and trimethylolpropane triacrylate.
Wherein the mass ratio of diisocyanate, acrylic acid hydroxy ester and alkyne diol alkylene oxide adduct is 1: (0.2-2): (0.5-2.5).
The adding amount of the polymerization inhibitor is 0.1 to 1 percent of the total mass of the diisocyanate, the hydroxyl acrylate and the alkynediol alkylene oxide adduct; the addition amount of the catalyst is 0.01-0.2 percent of the total mass of the diisocyanate, the acrylic hydroxyl ester and the alkyne diol alkylene oxide adduct; the addition amount of the diluent is 20 to 50 percent of the total mass of the diisocyanate, the hydroxyl acrylate and the alkyne diol epoxy adduct.
The present invention will be described in further detail with reference to specific examples.
Example 1
The modified urethane acrylate photocuring oligomer is synthesized by toluene diisocyanate, hydroxyethyl acrylate and 2,4,7, 9-tetramethyl-5-decyne-4, 7-diol ethylene oxide adduct (m + n ═ 10).
348 parts of toluene diisocyanate, 2 parts of hydroquinone and 1 part of stannous octoate are added into a reactor, the mixture is stirred and heated to 55 ℃, 232 parts of hydroxyethyl acrylate is slowly dripped, the mixture is continuously reacted for 1 hour after the dripping is finished, then the temperature is raised to 100 ℃, 640 parts of 2,4,7, 9-tetramethyl-5-decyne-4, 7-glycol ethylene oxide adduct is slowly dripped, the reaction is continuously performed for 2 hours after the dripping is finished, and the mixture is cooled and discharged after the reaction is finished.
Example 2
The urethane acrylate photocurable oligomer was synthesized using dicyclohexylmethane diisocyanate, hydroxyethyl acrylate, and 2,3,5,8,10, 11-hexamethyl-5-decyne-4, 7-diol ethylene oxide adduct (m + n ═ 10).
Adding 525 parts of dicyclohexylmethane diisocyanate, 2 parts of di-tert-butylhydroquinone and 1 part of dibutyltin laurate into a reactor, stirring and heating to 50 ℃, slowly dropwise adding 232 parts of hydroxyethyl acrylate, continuously reacting for 1 hour after dropwise adding is finished, then heating to 90 ℃, slowly dropwise adding 694 parts of 2,3,5,8,10, 11-hexamethyl-5-decyne-4, 7-diol ethylene oxide adduct (m + n is 10), continuously reacting for 1 hour after dropwise adding is finished, namely, cooling and discharging.
Example 3
The urethane acrylate photocuring oligomer was synthesized from isophorone diisocyanate, hydroxyethyl acrylate, and 2,4,7, 9-tetramethyl-5-decyne-4, 7-diol ethylene oxide adduct (m + n ═ 3.5).
Adding 445 parts of isophorone diisocyanate, 2 parts of hydroquinone and 1 part of stannous octoate into a reactor, stirring and heating to 55 ℃, slowly dropwise adding 232 parts of hydroxyethyl acrylate, continuously reacting for 1 hour after dropwise adding is finished, then heating to 100 ℃, slowly dropwise adding 380 parts of 2,4,7, 9-tetramethyl-5-decyne-4, 7-diol ethylene oxide adduct (m + n is 3.5), continuously reacting for 2 hours after dropwise adding is finished, and cooling and discharging.
Example 4
The urethane acrylate photocurable oligomer was synthesized using xylylene diisocyanate, hydroxyethyl acrylate, and 2,5,8, 11-tetramethyl-5-decyne-4, 7-diol ethylene oxide adduct (m + n ═ 3.5).
376 parts of xylylene diisocyanate, 2 parts of phenothiazine and 1 part of triethanolamine are added into a reactor, the mixture is stirred and heated to 40 ℃, 232 parts of hydroxyethyl acrylate is slowly dripped, the reaction is continued for 1 hour after the dripping is finished, then the temperature is raised to 70 ℃, 380 parts of 2,4,7, 9-tetramethyl-5-decyne-4, 7-diol ethylene oxide adduct (m + n is 3.5) is slowly dripped, the reaction is continued for 2 hours after the dripping is finished, and the mixture is cooled and discharged.
Example 5
The urethane acrylate photocurable oligomer was synthesized using xylene methane diisocyanate, hydroxyethyl acrylate, and 2,5,8, 11-tetramethyl-5-decyne-4, 7-diol ethylene oxide adduct (m + n ═ 20).
500.5 parts of xylene methane diisocyanate, 2 parts of p-hydroxyanisole and 1 part of triethylene diamine are added into a reactor, the mixture is stirred and heated to 40 ℃, 232 parts of hydroxyethyl acrylate is slowly dripped, the reaction is continued for 0.5h after the dripping is finished, then the temperature is raised to 70 ℃, 1080 parts of 2,4,7, 9-tetramethyl-5-decyne-4, 7-diol ethylene oxide adduct (m + n is 20) is slowly dripped, the reaction is continued for 2h after the dripping is finished, and the mixture is cooled and discharged.
Example 6
The urethane acrylate photocurable oligomer was synthesized from xylene methane diisocyanate, pentaerythritol triacrylate, and 2,5,8, 11-tetramethyl-5-decyne-4, 7-diol ethylene oxide adduct (m + n ═ 20).
500.5 parts of xylene methane diisocyanate, 2 parts of p-hydroxyanisole and 1 part of triethylene diamine are added into a reactor, the mixture is stirred and heated to 50 ℃, 597 parts of pentaerythritol triacrylate is slowly dripped, the reaction is continued for 0.5h after the dripping is finished, then the temperature is raised to 70 ℃, 1080 parts of 2,4,7, 9-tetramethyl-5-decyne-4, 7-diol ethylene oxide adduct (m + n is 20) is slowly dripped, the reaction is continued for 2h after the dripping is finished, and the product is cooled and discharged after the reaction is finished.
Example 7
The urethane acrylate photocuring oligomer was synthesized from isophorone diisocyanate, pentaerythritol triacrylate, and 2,4,7, 9-tetramethyl-5-decyne-4, 7-diol ethylene oxide adduct (m + n ═ 10).
Adding 445 parts of isophorone diisocyanate, 2 parts of hydroquinone and 1 part of stannous octoate into a reactor, stirring and heating to 55 ℃, slowly dropwise adding 597 parts of pentaerythritol triacrylate, continuously reacting for 1h after dropwise adding is finished, then heating to 100 ℃, slowly dropwise adding 640 parts of 2,4,7, 9-tetramethyl-5-decyne-4, 7-diol ethylene oxide adduct (m + n ═ 10), continuously reacting for 2h after dropwise adding is finished, namely, cooling and discharging.
Example 8
The urethane acrylate photocurable oligomer was synthesized using dicyclohexylmethane diisocyanate, pentaerythritol triacrylate, and 2,3,5,8,10, 11-hexamethyl-5-decyne-4, 7-diol ethylene oxide adduct (m + n ═ 20).
Adding 525 parts of dicyclohexylmethane diisocyanate, 2 parts of di-tert-butylhydroquinone and 1 part of dibutyltin laurate into a reactor, stirring and heating to 50 ℃, slowly dropwise adding 597 parts of pentaerythritol triacrylate, continuously reacting for 1 hour after the dropwise addition is finished, then heating to 90 ℃, slowly dropwise adding 1134 parts of 2,3,5,8,10, 11-hexamethyl-5-decyne-4, 7-diol ethylene oxide adduct (m + n is 20), continuously reacting for 1 hour after the dropwise addition is finished, namely, cooling and discharging.
Example 9
The urethane acrylate photocurable oligomer was synthesized from xylylene diisocyanate, pentaerythritol triacrylate, and 2,5,8, 11-tetramethyl-5-decyne-4, 7-diol ethylene oxide adduct (m + n ═ 3.5).
376 parts of xylylene diisocyanate, 2 parts of phenothiazine and 1 part of triethanolamine are added into a reactor, the mixture is stirred and heated to 40 ℃, 597 parts of pentaerythritol triacrylate is slowly dropped, the reaction is continued for 1 hour after the dropping is finished, then the temperature is raised to 70 ℃, 380 parts of 2,5,8, 11-tetramethyl-5-decyne-4, 7-diol ethylene oxide adduct (m + n is 3.5) is slowly dropped, the reaction is continued for 2 hours after the dropping is finished, and the product is cooled and discharged.
Example 10
The urethane acrylate photocurable oligomer was synthesized from hexamethylene diisocyanate, pentaerythritol triacrylate, and 2,5,8, 11-tetramethyl-5-decyne-4, 7-diol ethylene oxide adduct (m + n ═ 3.5).
336 parts of hexamethylene diisocyanate, 2 parts of o-methyl hydroquinone and 1 part of dibutyltin laurate are added into a reactor, the mixture is stirred and heated to 40 ℃, 597 parts of pentaerythritol triacrylate is slowly dripped, the mixture reacts for 1 hour after the dripping is finished, then the temperature is raised to 70 ℃, 380 parts of 2,5,8, 11-tetramethyl-5-decyne-4, 7-diol ethylene oxide adduct (m + n is 3.5) is slowly dripped, the reaction is continued for 2 hours after the dripping is finished, and the mixture is cooled and discharged.
Performance testing of modified urethane acrylate oligomer cured films
According to a known method, 65% of the modified urethane acrylate oligomer obtained in examples 1 to 10 is mixed with 5% of a photoinitiator and 30% of different diluents, and the mixture is photocured to form a cured film; wherein the diluent is selected from HDDA (1, 6-hexanediol diacrylate), DPGDA (dipropylene glycol diacrylate) and TPGDA (tripropylene glycol diacrylate).
Measuring the glossiness of the cured film by using a BGD516/3 intelligent gloss meter according to a method specified by the national standard GB/T9754-2007 determination of 20 DEG, 60 DEG and 85 DEG specular gloss of paint films of colored paints and varnishes containing no metal pigments; testing the pencil hardness of the cured film according to a specified method of the national standard GB/T6739 & 2006 paint and varnish pencil method for determining the paint film hardness; the adhesion of the cured films was tested according to the method specified in the national standard GB/T9286-1998 test for the marking of paint and varnish films.
Table 1 below shows the types of diluents and the results of the performance tests of the cured films formed in examples 1 to 10.
TABLE 1
| Test items | Kind of diluent | Gloss of | Hardness of | Adhesion force |
| Example 1 | 30％HDDA | 95.9 | 2B | PVC upper 2 level |
| Example 2 | 30％DPGDA | 95.0 | 2B | PVC upper 0 grade |
| Example 3 | 30％HDDA | 94.8 | HB | PVC upper 0 grade |
| Example 4 | 30％TPGDA | 96.2 | HB | PVC upper 0 grade |
| Example 5 | 30％HDDA | 93.4 | H | PVC upper 1 level |
| Example 6 | 30％HDDA | 95.6 | H | PVC upper 0 grade |
| Example 7 | 30％HDDA | 94.3 | HB | PVC upper 0 grade |
| Example 8 | 30％DPGDA | 94.6 | 3B | PVC upper 0 grade |
| Example 9 | 30％TPGDA | 93.5 | B | PVC upper 1 level |
| Example 10 | 30％TPGDA | 94.8 | HB | PVC upper 0 grade |
As can be seen from Table 1, the cured film formed by using the modified urethane acrylate oligomer of the present invention has good hardness and gloss, and has good adhesion to PVC; moreover, after the oligomer is compounded with the diluent and the initiator, the oligomer can be automatically and quickly defoamed without using the measures of centrifugation, heating and the like.
The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications and equivalents made by the contents of the present invention or directly or indirectly applied to other related technical fields are included in the scope of the present invention.
Claims (10)
1. A modified urethane acrylate photocurable oligomer, characterized in that the oligomer has the structure shown in formula (I):
wherein R is1Representing having a molar mass of 300 to 2000g/mol and containing unsaturated carbonAlkylene oxide adducts of carbon triple bonds; r2Represents methyl or methylene mono-or polysubstituted aromatic group or straight-chain or branched alkane or cycloalkane containing 6 to 13 carbon atoms; r3Represents a linear or branched alkyl carboxylate containing 2 to 3 carbon atoms or a quaternary tricarboxylate containing 2 to 3 unsaturated carbon-carbon double bonds; r4Represents a hydrogen atom or a methyl group; r5Represents a hydrogen atom or a methyl group.
2. The modified urethane acrylate photocurable oligomer of claim 1, wherein the oligomer is prepared by reacting:
(a) an alkylene oxide adduct of an acetylenic diol having a molar mass of 300 to 2000g/mol, having an unsaturated carbon-carbon triple bond, and having at least one group capable of reacting with an isocyanate;
(b) at least one diisocyanate; and
(c) at least one hydroxy acrylate.
3. The modified urethane acrylate photocurable oligomer of claim 2, wherein the alkylene oxide adduct of an acetylenic diol is an ethoxylated acetylenic diol having the structure shown in formula (ii):
wherein, R is6、R7、R8And R9Respectively represent a straight chain or a saturated alkyl group containing one or more branched chains and having 1 to 8 carbon atoms; r6、R7、R8And R9May be the same or different; m and n are integers of 0-35, and m + n is more than or equal to 1 and less than or equal to 35.
4. The modified urethane acrylate photocurable oligomer of claim 2, wherein the diisocyanate is selected from the group consisting of toluene diisocyanate, xylene methane diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate and dicyclohexylmethane diisocyanate.
5. The modified urethane acrylate photocurable oligomer of claim 2, wherein said hydroxy acrylate is selected from the group consisting of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, trimethylolpropane diacrylate and pentaerythritol triacrylate.
6. A method for preparing the modified urethane acrylate photocurable oligomer as set forth in any one of claims 1 to 5, which comprises the steps of:
(1) sequentially adding diisocyanate, a catalyst and a polymerization inhibitor into a reactor, controlling the reaction temperature to be 30-70 ℃, and slowly dropwise adding acrylic hydroxy ester for reaction, wherein the reaction time is 0.5-2 h;
(2) controlling the reaction temperature to be 70-120 ℃, and slowly dripping the alkynediol alkylene oxide adduct into the reactor for 1-2 h; and after the reaction is finished, cooling to obtain the modified urethane acrylate photocuring oligomer.
7. The method for preparing the modified urethane acrylate photocuring oligomer according to claim 6, wherein the catalyst is at least one selected from triethanolamine, triethylenediamine, dibutyltin laurate, stannous octoate and lead naphthenate; the polymerization inhibitor is selected from at least one of hydroquinone, p-hydroxyanisole, o-methyl hydroquinone, phenothiazine, di-tert-butyl hydroquinone, copper sulfate and copper acetate.
8. The method for preparing the modified urethane acrylate photocured oligomer according to claim 6, wherein the mass ratio of the diisocyanate to the hydroxyl acrylate to the acetylenic diol alkylene oxide adduct is 1: (0.2-2): (0.5-2.5).
9. The method for preparing the modified urethane acrylate photocuring oligomer according to claim 6, wherein the addition amount of the polymerization inhibitor is 0.1-1% of the total mass of the diisocyanate, the hydroxyl acrylate and the alkynediol alkylene oxide adduct; the addition amount of the catalyst is 0.01-0.2% of the total mass of the diisocyanate, the hydroxyl acrylate and the alkyne diol alkylene oxide adduct.
10. The method for preparing the modified urethane acrylate photocured oligomer according to claim 6, wherein the reaction temperature in the step (1) is 40-55 ℃; the reaction temperature in the step (2) is 70-100 ℃.
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