CN112851596B - Oxazolidine-containing radiation-curable urethane (meth) acrylate and preparation method thereof - Google Patents
Oxazolidine-containing radiation-curable urethane (meth) acrylate and preparation method thereof Download PDFInfo
- Publication number
- CN112851596B CN112851596B CN202110133133.6A CN202110133133A CN112851596B CN 112851596 B CN112851596 B CN 112851596B CN 202110133133 A CN202110133133 A CN 202110133133A CN 112851596 B CN112851596 B CN 112851596B
- Authority
- CN
- China
- Prior art keywords
- oxazolidine
- diisocyanate
- reaction
- acrylate
- compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
- C07D263/02—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings
- C07D263/04—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
-
- 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
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
- C09D163/10—Epoxy resins modified by unsaturated compounds
Abstract
The invention discloses oxazolidine-containing radiation-curable urethane (methyl) acrylate and a preparation method thereof, and the oxazolidine-containing radiation-curable urethane (methyl) acrylateThe radiation curable urethane (meth) acrylate has the structural formula:
wherein R is 1 Is optionally C1-C4 alkyl, R 2 、R 3 And R 4 Are both hydrogen or optionally C 1 ‑C 4 Alkyl of R 5 Is a diisocyanate residue containing a C2-C6 aliphatic branch or an aliphatic ether chain, R 6 Is hydrogen or methyl. The compound adopts a modification mode of combining oxazolidine monohydric alcohol and urethane, so that the hardness, flexibility and adhesive force of the prepared photocuring material (paint, ink or adhesive) on a plastic substrate are improved; the preparation method is simple and easy to control, and the obtained product has high purity and good performance.
Description
Technical Field
The invention relates to oxazolidine-containing radiation-curable urethane (methyl) acrylate and a preparation method thereof, belonging to the technical field of photosensitive high polymer materials.
Background
The photocuring technology has the advantages of rapid curing, energy and time saving, low solvent release, low curing temperature, small equipment volume, low investment and the like, and the application field of the photocuring technology is developed from the initial wood coating to a plurality of industrial production fields such as plastic decoration, metal part coating, medical instruments, electronic components, information recording media, photosensitive printing, plastic materials, optical fibers and the like, and the photocuring technology mainly appears in the forms of UV coatings, UV printing inks, UV adhesives and the like.
The ultraviolet curing material consists of a photosensitive prepolymer (oligomer), an active dilution monomer, a photoinitiator and various addition additives (pigment, filler, defoaming agent and the like). The prepolymer is a base resin of an ultraviolet curing system and occupies a large proportion in the whole system. The reactive diluent is used to dilute the prepolymer to achieve the desired viscosity of the resin system. The prepolymer and reactive diluent monomer together generally account for more than 90% of the total curing system mass, with the reactive diluent monomer accounting for 40-60%. The prepolymer and the reactive diluent monomer play a decisive role in the performance of the whole system, such as hardness, adhesion, flexibility, durability, abrasion resistance, tensile strength, impact resistance, aging resistance and the like.
Polyurethane acrylate (PUA for short) is a relatively important photocuring oligomer (photocuring oligomer refers to oligomer which can be rapidly subjected to physical and chemical changes in a short time after being irradiated by ultraviolet rays and then is subjected to crosslinking curing), is applied to a wide extent and is second to epoxy acrylate, and is widely applied to the fields of photocuring coatings, printing inks, adhesives and the like. The synthesis process is simple and flexible, and the resin performance can be adjusted through molecular design, so that various performances such as flexibility, hardness, tolerance and the like can be designed and controlled in advance, and the resin has quite strong flexibility.
The molecules of the polyurethane acrylate (PUA) contain acrylic acid functional groups and urethane bonds, and the cured paint film/adhesive has the high wear resistance, adhesion, flexibility, high peel strength, excellent low-temperature resistance and excellent optical performance and weather resistance of the polyurethane, and is a radiation curing material with excellent comprehensive performance. However, polyurethane resins generally have high viscosity and are generally solid or semi-solid at room temperature, which causes great difficulties in both application and production.
Plastics are polymer materials which are widely applied in the current society, but the defects of poor scratch resistance, insufficient wear resistance and the like generally exist in plastic products, so the surface decoration and the strengthening of the plastic products are particularly important. The plastic surface is coated by adopting the paint, so that a good protection effect can be achieved, mechanical abrasion is prevented, and the scratch resistance is improved; can endow the surface of the plastic with various decorative effects, such as high light, matte, hammer marks and the like; and can bring many functional effects to plastics, such as electrostatic discharge, reflection resistance, fingerprint resistance and the like. The traditional dry solvent coating has the defects of easy volatilization of solvent, environmental pollution, low production efficiency, large occupied space of equipment, high energy consumption of baking equipment, easy deformation of plastic and the like, and the UV plastic coating can perfectly solve the problems of the solvent coating and is rapidly developed in recent years.
Unlike wood and paper, plastic is a non-absorbent substrate that cannot rely on penetration of the coating into the substrate to create various mechanical anchors for attachment purposes. Compared to metals, which are also non-absorbent substrates, plastics are "inert" materials, and there are few active sites on the surface that can react with the components of the coating, and the chemical bonds needed to achieve effective adhesion cannot be formed. Adhesion between the plastic and the UV coating is therefore rather difficult and usually only depends on the mutual adsorption between the coating and the plastic surface by very weak intermolecular forces. This requires that the UV plastic coatings must have a low surface tension and good wetting ability on the substrate.
The plastic part structure generally has certain complexity, can not use drenching coating, roller coat construction admittedly, and the spraying construction is adopted mostly, considers the viscosity problem especially, and this needs to reduce viscosity with a large amount of monomers, and when solidifying with epoxy acrylate and multi-functional monomer, the coating density increases along with the double bond consumption, has caused the volume shrinkage, produces the internal stress to lead to the adhesive force variation of cured film to the substrate. The novel functional radiation-curable urethane (methyl) acrylate which has small viscosity, small volume shrinkage and good flexibility and has better hardness of a cured coating film and better adhesive force to plastics has important significance for the application of radiation-curable materials on the surface of the plastics and also has important significance for the field of printing ink requiring low-viscosity acrylate resin, in particular the field of ink jet.
Disclosure of Invention
The invention provides oxazolidine-containing radiation-curable urethane (meth) acrylate and a preparation method thereof, and overcomes the defects that radiation-curable urethane acrylate in the prior art has high viscosity and cannot simultaneously ensure the adhesive force, hardness, flexibility and other comprehensive application properties of a coating film.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
an oxazolidine-containing radiation-curable urethane (meth) acrylate having the formula:
wherein R is 1 Is optionally C1-C4 alkyl, R 2 、R 3 And R 4 Are both hydrogen or optionally C 1 -C 4 Alkyl of R 5 Is a diisocyanate residue containing a C2-C6 aliphatic branch or an aliphatic ether chain, R 6 Is hydrogen or methyl.
The applicant finds out through research that: the oxazolidine urethane acrylate compound can greatly promote the adhesion between the UV plastic coating and the plastic surface, and obviously improve the adhesion between the UV plastic coating and the plastic surface; the oxazolidine urethane acrylate compound has the characteristics of low viscosity of 2000-6000m Pa.s, low volume shrinkage rate, adjustable flexibility and flexibility, and the prepared coating layer has high hardness, excellent chemical resistance and adhesive force, and excellent adhesive force and good adhesive property on plastics.
The preparation method of the oxazolidine-containing radiation-curable urethane (meth) acrylate comprises the following steps of sequentially connecting:
a. preparation of oxazolidine monoalcohol: using dihydric alcohol amine containing chain alkane and ketone compound or aldehyde compound (R) 2 H) reacting under the action of a first catalyst, and removing water generated in the reaction by using an azeotropic water-carrying agent to generate an oxazolidine monohydric alcohol intermediate product containing a substituent group;
b. preparation of terminal (meth) acryloyl group-containing isocyanate prepolymer: diisocyanate and a hydroxyl-containing terminal (methyl) acryloyl compound react at a raised temperature under the action of a second catalyst to prepare a prepolymer monomer containing isocyanate which is not completely reacted;
c. and (c) carrying out temperature reaction on the oxazolidine monohydric alcohol obtained in the step a and the pre-polymerized monomer obtained in the step b under the action of a second catalyst to obtain the oxazolidine radiation-curable urethane (meth) acrylate-containing compound.
The preparation method is simple and easy to control, and the obtained product has high purity and good performance, and the product obtained by the method has lower viscosity, low volume shrinkage, excellent adhesive force, adjustable flexibility and flexibility.
In order to give consideration to the comprehensive performance of the product and the cost of raw materials, in the step a, the alkane-containing glycol amine is diethanolamine or diethanolamine with hydroxy alpha position containing C1-C4 substituent, and further preferably, the alkane-containing glycol amine is diisopropanolamine, diethanolamine and dibutanolamine; the ketone compound is C3-C8 aliphatic ketone, and more preferably, the ketone compound is acetone or butanone; the aldehyde compound is C1-C4 aliphatic aldehyde, and more preferably, the aldehyde compound is acetaldehyde, 1-propionaldehyde and 1-butyraldehyde. The rigid cyclic urethane (meth) acrylate with multiple branched chains obtained by the reaction has adjustable flexibility and flexibility, good adhesion to plastics and better hardness of the surface of a coating film of a coating system.
In order to increase the product yield, the molar ratio of the ketone compound or the aldehyde compound to the alkane-containing glycol amine is 100 (100-130).
In order to ensure the catalytic efficiency, in the step a, the first catalyst is one or a mixture of two or more of sulfuric acid, sulfonic acid, methanesulfonic acid, ethylsulfonic acid, benzenesulfonic acid and p-toluenesulfonic acid in any ratio, more preferably sulfuric acid, methanesulfonic acid or p-toluenesulfonic acid, and still more preferably methanesulfonic acid; the first catalyst is used in a molar amount of 1 to 6% based on the moles of the alkane-containing glycol amine.
In order to improve the reaction efficiency, in the step a, the azeotropic water-carrying agent is one or a mixture of more than two of benzene, toluene, C5 alkane and C6 alkane in any ratio, more preferably toluene, n-pentane, n-hexane or cyclohexane, and more preferably cyclohexane; the mass consumption of the azeotropic water-carrying agent is 40-60% of the sum of the masses of the dihydric alcohol amine containing alkane and the ketone compound or the aldehyde compound. The water-carrying agent can ensure that the reaction is smoothly carried out at a lower temperature, does not influence the quality of a product, has better compatibility with the product, and is easy to remove.
In order to ensure the product yield, in the step a, the reaction is carried out for 6 to 16 hours under the condition that the temperature is 60 to 120 ℃.
In order to further improve the structural strength of the obtained product, in step b, the hydroxyl-containing terminal (meth) acryloyl compound is (meth) acrylic acid containing a C2-C6 aliphatic branch or aliphatic ether chain, and more preferably: one or a mixture of more than two of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate or diethylene glycol monoacrylate in any proportion.
The hydroxyl-containing terminal (meth) acryloyl compound may also be a ring-opening product of (meth) acrylic acid and epichlorohydrin, a ring-opening product of hydroxyethyl (meth) acrylate and phthalic anhydride reacted with epichlorohydrin (3-chloro-2-hydroxypropyl acrylate), and mixtures thereof.
The hydroxyl-containing terminal (meth) acryloyl compound is more preferably: hydroxyethyl acrylate, hydroxyethyl methacrylate, diethylene glycol monoacrylate or 3-chloro-2-hydroxypropyl acrylate; most preferably: hydroxyethyl acrylate or diethylene glycol monoacrylate.
In the step b, the diisocyanate may be an aliphatic, alicyclic or aromatic polyisocyanate, or may be others. In order to further improve the mechanical properties of the product, the diisocyanate is preferably one or a mixture of more than two of Toluene Diisocyanate (TDI), diphenylmethane diisocyanate (MDI), isophorone diisocyanate (IPDI), hexamethylene Diisocyanate (HDI), dicyclohexylmethane diisocyanate (hch) or cyclohexane diisocyanate (CHDI) in any ratio; further preferably, the diisocyanate is isophorone diisocyanate (IPDI) or hexamethylene-1,6-diisocyanate (HDI).
In order to improve the reaction efficiency, in the steps b and c, the second catalyst is one or a mixture of more than two of dibutyl tin dilaurate, stannous octoate, potassium octoate, cobalt octoate, bismuth octoate, zinc naphthenate, cobalt naphthenate, bismuth naphthenate, titanium octoate, titanium carboxylate, triethylene diamine or dimethylethanolamine in any proportion; in steps b and c, the amount of the second catalyst is 2 to 10 per thousand of the amount of the hydroxyl-containing terminal (meth) acryloyl compound.
In order to further improve the reaction efficiency, reduce side reactions and improve the purity of the product, preferably, the catalyst in steps b and c is dibutyltin dilaurate, bismuth octoate or bismuth naphthenate.
In order to effectively control the reaction and ensure the comprehensive performance of the product, in the steps b and c, a polymerization inhibitor is added in the temperature rising process, the polymerization inhibitor is one or a mixture of more than two of p-benzoquinone, hydroquinone, p-hydroxyanisole, copper dimethylamino diethylamino, copper dibutyl dithiocarbamate, 2,2,6,6-tetramethylpiperidine oxide or 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxygen free radical in any proportion, preferably, the polymerization inhibitor is p-hydroxyanisole or 2,2,6,6-tetramethylpiperidine oxide. In the steps b and c, the molar amount of the polymerization inhibitor is 0.5-5 per mill of the molar number of the oxazolidine monohydric alcohol.
More preferably, in steps b and c, the mass amount of the second catalyst is 1.8-2.2 times of the mass amount of the polymerization inhibitor.
In order to effectively control the reaction, the preparation method of the isocyanate prepolymer containing terminal (methyl) acryloyl in the step b comprises the following steps: mixing diisocyanate and a polymerization inhibitor, heating to 45-50 ℃, dripping a mixture of a hydroxyl-containing terminal (methyl) acryloyl compound and a second catalyst, heating to 55-60 ℃ after dripping is finished, reacting until the NCO value reaches a theoretical value, and stopping the reaction to obtain a prepolymer monomer containing isocyanate which is not completely reacted.
In order to effectively control the reaction, the step c is as follows: and c, mixing the oxazolidine monohydric alcohol obtained in the step a with a polymerization inhibitor, heating to 45-50 ℃, dropwise adding the mixture of the prepolymer monomer and the catalyst obtained in the step b, heating to 55-60 ℃ after dropwise adding, reacting until NCO is reduced to below 0.5, and stopping reaction to obtain the oxazolidine radiation-curable urethane (methyl) acrylate-containing compound.
To further ensure the product yield, the molar ratio of diisocyanate to terminal (meth) acryloyl compound in step b is 1 (0.95-1.05) and the molar ratio of oxazolidine monoalcohol to prepolymeric monomer in step c is 1 (1.9-2.1).
The oxazolidine-containing radiation-curable urethane (meth) acrylate can be applied to the fields of high polymer resins such as coatings, inks, adhesives and the like.
The prior art is referred to in the art for techniques not mentioned in the present invention.
The oxazolidine-containing radiation-curable urethane (meth) acrylate is an urethane acrylate with an oxazolidine ring structure, is a special monofunctional urethane acrylate applied to plastics, can also be applied to an ink-jet formula of ink, and has the characteristics of low viscosity of 2000-6000m Pa.s, low volume shrinkage, adjustable flexibility and flexibility; the prepared coating layer has higher hardness, excellent chemical resistance, excellent adhesive force to plastics and good adhesive property; the applicant finds that by introducing a tertiary amine group into the dihydric alcohol amine with a branched chain, the acrylic ester with the tertiary amine group can be used as an auxiliary initiator and is matched with hydrogen abstraction type free radical photoinitiators such as benzophenone, the photocuring rate can be improved, the influence of oxygen inhibition can be reduced, the surface curing of a photocuring material can be improved, and the photocuring efficiency can be improved; the design of the five-membered oxazole ring ensures that the acrylate has excellent adhesive force and good adhesive property to plastics, and the prepared photocureable coating has more excellent coating hardness, the flexibility and the flexibility of the monomer can be adjusted by the amount of branched chains, so that the prepared coating has good impact resistance and strong adhesive force; the ink-jet ink has excellent comprehensive performance and low viscosity, so that the ink-jet ink can be applied to ink-jet formulas, the preparation method is simple and easy to control, and the obtained product has high purity and good performance.
Detailed Description
For better understanding of the present invention, the following examples are given for further illustration of the present invention, but the present invention is not limited to the following examples.
Yield: the percentage of the mass of the product actually produced to the mass produced according to the theory of glycol amine.
Example 1
Preparation of cyclic oxazolidine monoalcohols from diisopropanolamine and acetone:
(134g, 1mol) diisopropanolamine, (75.4 g,1.3 mol) acetone, (4.11g, 30mmol) 70% methanesulfonic acid and 98.9g cyclohexane were charged into a 1000ml reaction flask equipped with electric stirring and a water-cooled reflux condenser, the flask was placed in a sand bath in a heating mantle, the temperature of the sand bath was controlled using a temperature controller connected to a thermocouple immersed in the sand bath, the contents of the flask were heated to 80 ℃ with stirring of the sand bath, the reaction temperature was maintained at 80 ℃ with continuous stirring for 10 hours, the water produced during the reaction was continuously distilled off by the cyclohexane solvent, the distilled cyclohexane and acetone were refluxed to the reaction flask to continue the reaction, excess acetone and cyclohexane solvent were distilled off from the reaction flask after the reaction was completed, and the remaining product cyclooxazolidine monool M1 weighed approximately 156.3g, a yield of 89.83%. Separating the obtained product with silica gel chromatographic column, and separating with final product 1 H-NMR nucleusThe magnetic field is analyzed by a magnetic analysis, 1 H-NMR is measured by a Bruker AV300 NMR nuclear magnetic resonance instrument, TMS is an internal standard reference, 1 H NMR(300MHz,CDCl 3 ) ppm:3.58 (s, 1H), 3.37-3.41 (m, 1H), 3.24-3.26 (m, 1H), 2.61-2.64 (m, 2H), 2.36-2.39 (m, 2H), 1.30 (s, 6H), 1.18 (d, 3H), 1.05 (d, 3H), hydrogen nuclear magnetic resonance (s, 1H) 1 H NMR) spectroscopic analysis the resulting product was presumed to be a cyclic oxazolidine monoalcohol as shown in formula I below.
Experiments prove that the reaction can be catalyzed by adopting sulfuric acid, sulfonic acid, ethylsulfonic acid, benzenesulfonic acid and p-toluenesulfonic acid instead of methanesulfonic acid in the embodiment.
Example 2
Preparation of cyclic oxazolidine monoalcohols from bis (4-hydroxypentyl) amine and 2-hexanone:
a1000 ml reaction flask equipped with an electric stirrer and a water-cooled reflux condenser was charged with (190g, 1mol) bis (4-hydroxypentyl) amine, (130g, 1.3 mol) 2-hexanone, (4.11g, 30mmol) 70% methanesulfonic acid and 147.5g cyclohexane, the flask was placed in a sand bath in a heating mantle, the temperature of the sand bath was controlled using a temperature controller connected to a thermocouple immersed in the sand bath, the contents of the flask were heated to 80 ℃ with stirring of the sand bath, the reaction temperature was maintained at 80 ℃ with continuous stirring for 10 hours, the water produced during the reaction was continuously taken up by distillation of the cyclohexane solvent, the distilled cyclohexane and hexanone refluxed to the reaction flask for further reaction, and after completion of the reaction, the excess hexanone and cyclohexane solvent were distilled out of the reaction flask to obtain the remaining product cyclic oxazolidine monool M2, which was weighed to about 238.8g, with a yield of 87.79%. Separating the obtained product with silica gel chromatographic column, and separating the final product 1 H-NMR nuclear magnetic analysis is carried out, 1 H-NMR is measured by a Bruker AV300 NMR nuclear magnetic resonance instrument, TMS is an internal standard reference, 1 H NMR(300MHz,CDCl 3 ) ppm:3.58 (s, 1H), 3.44-3.46 (m, 1H), 3.05-3.08 (m, 1H), 2.61-2.64 (m, 2H), 2.36-2.39 (m, 2H), 1.40-1.49 (m, 6H), 1.23-1.37 (m, 11H), 0.89-0.91 (t, 9H), hydrogen nuclear magnetic resonance (M, 9H) 1 H NMR) spectroscopic analysisThe product was determined to be a cyclic oxazolidine monoalcohol as shown in formula II below.
Example 3
Preparation of cyclic oxazolidine monoalcohols from diisopropanolamine and butanone:
(134g, 1mol) diisopropanolamine, (93.6 g,1.3 mol) butanone, (4.111g, 30mmol) 70% methanesulfonic acid and 105g cyclohexane were charged into a 1000ml reaction flask equipped with electric stirring and a water-cooled reflux condenser, the flask was placed in a sand bath in an electric mantle, the temperature of the sand bath was controlled using a temperature controller connected to a thermocouple immersed in the sand bath, the contents of the flask were heated to 80 ℃ with stirring of the sand bath, the reaction temperature was maintained at 80 ℃ with continuous stirring for 10 hours, the water produced during the reaction was continuously distilled off by the cyclohexane solvent, the distilled cyclohexane and butanone were refluxed to the reaction flask for further reaction, excess butanone and cyclohexane solvent were distilled off from the reaction flask, and the remaining product cyclic oxazolidine monool M3 weighed about 170.6g, yield 90.74%. Separating the obtained product with silica gel chromatographic column, and separating the final product 1 H-NMR nuclear magnetic analysis is carried out, 1 H-NMR is measured by a Bruker AV300 NMR nuclear magnetic resonance instrument, TMS is an internal standard reference, 1 H NMR(300MHz,CDCl 3 ) ppm:3.58 (s, 1H), 3.37-3.41 (m, 1H), 3.24-3.26 (m, 1H), 2.61-2.64 (m, 2H), 2.36-2.39 (m, 2H), 1.51-1.53 (q, 2H), 1.35 (s, 3H), 1.18 (d, 3H), 1.05 (d, 3H), 0.89-0.91 (t, 3H), hydrogen nuclear magnetic resonance (m, 1H) 1 H NMR) spectroscopic analysis the resulting product was presumed to be a cyclic oxazolidine monoalcohol represented by the following formula III.
Example 4
Preparation of cyclic oxazolidine monoalcohols from diethanolamine and acetaldehyde:
a mixture of (106g, 1mol) diethanolamine, (57.2g, 1.3mol) acetaldehyde, (4.11g, 30mmol) 70% methanesulfonic acid and 76g cyclohexane were charged into a 1000ml reaction flask equipped with an electric stirrer and a water-cooled reflux condenser, the flask was placed in a sand bath in a mantle, the temperature of the sand bath was controlled using a temperature controller connected to a thermocouple immersed in the sand bath, the contents of the flask were heated to 80 ℃ with stirring of the sand bath, the reaction temperature was maintained at 80 ℃ and stirring was continued for 8 hours, water produced during the reaction was continuously distilled off by the cyclohexane solvent, the distilled cyclohexane and acetaldehyde were refluxed to the reaction flask to continue the reaction, excess acetaldehyde and cyclohexane solvent were distilled off from the reaction flask, and the residual product cyclooxazolidine monool M4 weighed about 118.2g, with a yield of 89.55%. Separating the obtained product with silica gel chromatographic column, and separating the final product 1 H-NMR nuclear magnetic analysis is carried out, 1 H-NMR is measured by a Bruker AV300 NMR nuclear magnetic resonance instrument, TMS is an internal standard reference, 1 H NMR(300MHz,CDCl 3 ) ppm:4.14-4.16 (q, 1H), 3.65 (s, 1H), 2.52-3.62 (m, 4H), 2.47-2.59 (m, 4H), 1.25 (t, 3H) 1 H NMR) spectroscopic analysis the resulting product was presumed to be a cyclic oxazolidine monoalcohol represented by the following formula IV.
Example 5
Preparation of a Cyclic oxazolidine monoalcohol from bis (3-hydroxybutyl) amine and 1-propionaldehyde:
adding (162g, 1mol) bis (3-hydroxybutyl) amine, (75.4 g,1.3 mol) 1-propionaldehyde, (4.111g, 30mmol) 70% methanesulfonic acid and 113.5g cyclohexane into a 1000ml reaction flask equipped with an electric stirring and water-cooling reflux condenser, placing the flask in a sand bath in a heating jacket, controlling the temperature of the sand bath by using a temperature controller connected to a thermocouple immersed in the sand bath, heating the solution in the flask to 80 ℃ by using the stirring of the sand bath, continuously stirring for 8 hours while maintaining the reaction temperature at 80 ℃, continuously distilling and taking out the water generated in the reaction process by using a cyclohexane solvent, refluxing the distilled cyclohexane and propionaldehyde to the reaction flask for continuous reaction, and continuously reacting the excessive propionaldehyde and the cyclohexane after the reaction is finishedThe alkane solvent was distilled off the reaction flask to give the remaining product cyclic oxazolidine monoalcohol M5 weighing about 180.5g, 89.36% yield. Separating the obtained product with silica gel chromatographic column, and separating the final product 1 H-NMR nuclear magnetic analysis is carried out, 1 H-NMR is measured by a Bruker AV300 NMR nuclear magnetic resonance instrument, TMS is an internal standard reference, 1 H NMR(300MHz,CDCl 3 ) ppm 3.95-3.98 (m, 1H), 3.58 (s, 1H), 3.43-3.47 (m, 1H), 3.05-3.09 (m, 1H), 2.61-2.64 (m, 2H), 2.36-2.39 (m, 2H), 1.45-1.57 (m, 6H), 0.89-0.91 (t, 9H), hydrogen nuclear magnetic resonance (M, 9H) 1 H NMR) spectroscopic analysis the resulting product was presumed to be a cyclic oxazolidine monoalcohol represented by the following structural formula V.
Example 6
Preparation of a cyclic oxazolidine monoalcohol from bis (5-hydroxyhexyl) amine and 1-butyraldehyde:
(218g, 1mol) bis (5-hydroxyhexyl) amine, (93.6 g,1.3 mol) 1-butyraldehyde, (4.111g, 30mmol) 70% methanesulfonic acid and 147g cyclohexane were charged into a 1000ml reaction flask equipped with electric stirring and a water-cooled reflux condenser, the flask was placed in a sand bath in an electric heating mantle, the temperature of the sand bath was controlled using a temperature controller connected to a thermocouple immersed in the sand bath, the contents of the flask were heated to 80 ℃ with stirring of the sand bath, the reaction temperature was maintained at 80 ℃ with continuous stirring of 8h, the water of reaction formed during the reaction was continuously distilled off by the cyclohexane solvent, the distilled cyclohexane and butyraldehyde were refluxed to the reaction flask for further reaction, and the excess butyraldehyde and cyclohexane solvent were distilled off the reaction flask to give the remaining product cyclooxazolidine monool M6 weighing about 242.1g, with a yield of 89.01%. Separating the obtained product with silica gel chromatographic column, and separating with final product 1 H-NMR nuclear magnetic analysis is carried out, 1 H-NMR is measured by a Bruker AV300 NMR nuclear magnetic resonance instrument, TMS is an internal standard reference, 1 H NMR(300MHz,CDCl 3 ) ppm of 3.58 (s, 1H), 3.43-3.47 (m, 1H), 3.05-3.09 (m, 1H), 2.61-2.64 (m, 2H), 2.36-2.39 (m, 2H), 1.42-1.49 (m, 6H), 1.31-1.36 (m, 9H), 1.24-1.26 (m, 2H), 0.89-0.91 (t, 9H), hydrogen nuclear magnetic resonanceVibration ( 1 H NMR) spectroscopic analysis the resulting product was presumed to be a cyclic oxazolidine monoalcohol as shown in formula VI below.
Example 7:
isophorone diisocyanate (IPDI) (222g, 1mol) and 0.5g p-hydroxyanisole are added into a reaction device, the temperature is raised to 50 ℃, and a mixture of hydroxyethyl acrylate (116g, 1mol) and 1.01g dibutyltin dilaurate (DBTDL) serving as a catalyst is dripped; after dripping, the temperature is raised to 55 ℃, the NCO content in the system is detected by a di-n-butylamine method, and when the NCO content is less than 12.6 percent, the reaction is stopped, thus obtaining the pre-polymerization monomer (U1) containing the hydroxyethyl acrylate end group and the isocyanic acid radical reaction group.
Example 8:
hexamethylene-1,6-diisocyanate (HDI) (168g, 1mol) and 0.49g of p-hydroxyanisole were added to the reaction apparatus, the temperature was raised to 50 ℃ and a mixture of diethylene glycol monoacrylate (160g, 1mol) and 0.98g of dibutyltin dilaurate (DBTDL) as a catalyst was added dropwise. After dripping, the temperature is raised to 55 ℃, the NCO content in the system is detected by a di-n-butylamine method, and when the NCO content is less than 12.9 percent, the reaction is stopped, thus obtaining the pre-polymerization monomer (U2) containing the hydroxyethyl acrylate end group and the isocyanic acid radical reaction group.
Example 9:
hexamethylene-1,6-diisocyanate (HDI) (168g, 1mol), 0.5g of p-hydroxyanisole were added to the reaction apparatus, the temperature was raised to 50 ℃, and a mixture of 3-chloro-2-hydroxypropyl acrylate (164.6 g, 1mol) and 1.00g of dibutyltin dilaurate (DBTDL) as a catalyst was added dropwise. After dripping, the temperature is raised to 55 ℃, the NCO content in the system is detected by a di-n-butylamine method, and when the NCO content is less than 12.8 percent, the reaction is stopped, thus obtaining the pre-polymerization monomer (U3) containing the hydroxyethyl acrylate end group and the isocyanic acid radical reaction group.
Example 10:
adding 0.5g of p-hydroxyanisole and 871 g of intermediate product M1 (87g, 0.5 mol) prepared by the reaction in example 1 into a reaction device, heating to 55 ℃, adding a mixture of U1 prepolymer monomer (323.6 g, 1mol) synthesized in example 7 and 1.01g of catalyst dibutyltin dilaurate (DBTDL) into a dropwise adding device, gradually dropwise adding into the reaction device, detecting the NCO content in the system by a di-n-butylamine method, and stopping the reaction when the NCO value reaches below 0.5, thus obtaining oxazolidine urethane (meth) acrylate PUA1.
Example 11:
adding 0.5g of p-hydroxyanisole and 0.9g of the intermediate product M2 (136g and 0.5 mol) prepared by the reaction in the example 2 into a reaction device, heating to 55 ℃, adding a mixture of the U2 pre-polymerization monomer (329g and 1mol) synthesized in the example 8 and 0.98g of dibutyltin dilaurate (DBTDL) serving as a catalyst into a dropping device, gradually dropping into the reaction device, detecting the NCO content in the system by a di-n-butylamine method, and stopping the reaction when the NCO value reaches below 0.5, thus obtaining the oxazolidine monoalcohol urethane (meth) acrylate PUA2.
Example 12:
intermediate M3 (94g, 0.5 mol) prepared by the reaction of example 3 and 0.5g of p-hydroxyanisole were added to the reaction apparatus and the temperature was raised to 55 ℃. A mixture of the U3 prepolymer monomer (333.6 g, 1mol) synthesized in example 9 and 1.00g of dibutyltin dilaurate (DBTDL) as a catalyst was gradually dropped into a dropping device, the NCO content in the system was detected by the di-n-butylamine method, and the reaction was stopped when the NCO value reached 0.5 or less, thereby obtaining oxazolidine urethane (meth) acrylate PUA3.
Example 13:
intermediate M4 (66g, 0.5 mol) prepared by the reaction of example 4 and 0.5g of p-hydroxyanisole were added into a reaction apparatus, the temperature was raised to 55 ℃, a mixture of U1 prepolymer monomer (323.6 g, 1mol) synthesized in example 7 and 1.01g of dibutyltin dilaurate (DBTDL) as a catalyst was gradually dropped into the reaction apparatus, the NCO content in the system was detected by the di-n-butylamine method, and when the NCO value reached below 0.5 by the reaction, the reaction was stopped, thus obtaining oxazolidine urethane (meth) acrylate PUA4.
Example 14:
the intermediate M5 (101g, 0.5 mol) prepared by the reaction of example 5 and 0.5g of p-hydroxyanisole were added to a reaction apparatus, the temperature was raised to 55 ℃, a mixture of the U2 prepolymer monomer (329g, 1mol) synthesized in example 8 and 0.98g of dibutyltin dilaurate (DBTDL) as a catalyst was added to a dropwise addition apparatus and gradually dropped into the reaction apparatus, the NCO content in the system was detected by the di-n-butylamine method, and when the NCO value reached below 0.5 by the reaction, the reaction was stopped, thus obtaining oxazolidine urethane (meth) acrylate PUA5.
Example 15:
adding 0.5g of p-hydroxyanisole and 0.6g of intermediate product M6 (136g, 0.5 mol) prepared by the reaction in example 1 into a reaction device, heating to 55 ℃, adding a mixture of U3 pre-polymerization monomer (333.6 g,1 mol) synthesized in example 9 and 1.00g of catalyst dibutyltin dilaurate (DBTDL) into a dropwise adding device, gradually dropwise adding into the reaction device, detecting the NCO content in the system by a di-n-butylamine method, and stopping the reaction when the NCO value reaches below 0.5, thus obtaining oxazolidine urethane (meth) acrylate PUA6.
Experiments further prove that the catalysts in PUA1, PUA2, PUA3, PUA4, PUA5 and PUA6 obtained in examples 10 to 15 can also be used for carrying out the above reaction by replacing dibutyltin dilaurate with bismuth octoate, zinc naphthenate and bismuth naphthenate.
Table 1 below shows the results of the product performance tests, with reference to GB 9282 for the determination of color, GB/T17530.5-1998 for the determination of polymerization inhibitor and GB/T5561-1994 for the determination of viscosity.
Glass transition temperature measurement after the coating film was sufficiently cured, the glass transition temperature was measured by Differential Scanning Calorimetry (DSC).
TABLE 1 evaluation tables for the properties of the products obtained in examples 10 to 15
The product is mixed according to the following proportion and then is subjected to blade coating application performance evaluation:
30 parts of the products obtained in examples 10 to 15 are respectively mixed with kepatin Ruiyang PEA (bisphenol A epoxy acrylate (20% trimethylolpropane triacrylate TMPTA) RY1101A 80), 28 parts, 1,6 hexanediol diacrylate HDDAR206 (kepatin Ruiyang), 21 parts, TMPTA R302 (kepatin Ruiyang), 15 parts, initiators 184 and 4 parts, a flatting agent Eterslip and 0.8 part, defoaming agents BYK-052 and 0.2 part to prepare a coating according to the prior art, wherein the parts are mass parts, the performance of the obtained coating is tested, and the impact resistance of the coating is determined according to GB 1732-1979; paint film adhesion (ABS plastic substrates) determination reference GB 1720-1979; the hardness of the paint film is determined according to GB6739-1986; the solvent resistance and the wiping resistance of the paint film are determined by reference to GB/T23989-2009 (methyl ethyl ketone); the application properties of the resulting coating are shown in Table 2.
TABLE 2 application properties of examples 10 to 15
Claims (10)
1. An oxazolidine-containing radiation-curable urethane (meth) acrylate characterized by: the structural formula is as follows:
wherein R is 1 Is optionally C1-C4 alkyl, R 2 、R 3 And R 4 Are both hydrogen or optionally C 1 -C 4 Alkyl of R 5 Is a diisocyanate residue containing a C2-C6 aliphatic branch or an aliphatic ether chain, R 6 Is hydrogen or methyl.
2. A process for the preparation of oxazolidine-containing radiation-curable urethane (meth) acrylates according to claim 1, characterized in that: comprises the following steps that:
a. preparation of oxazolidine monoalcohol: reacting dihydric alcohol amine containing chain alkane with a ketone compound or an aldehyde compound under the action of a first catalyst, removing water generated by the reaction by adopting an azeotropic water-carrying agent, and reacting to generate an oxazolidine monohydric alcohol intermediate product containing a substituent group; the alkane-containing dihydric alcohol amine is diethanol amine or diethanol amine with hydroxy alpha position containing C1-C4 substituent groups; the ketone compound is C3-C8 aliphatic ketone; the aldehyde compound is C2-C4 fatty aldehyde;
b. preparation of terminal (meth) acryloyl group-containing isocyanate prepolymer: diisocyanate and a hydroxyl-containing terminal (methyl) acryloyl compound react at a raised temperature under the action of a second catalyst to prepare a prepolymer monomer containing isocyanate which is not completely reacted; the hydroxyl-containing terminal (methyl) acryloyl compound is one or a mixture of more than two of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, 3-chloro-2-hydroxypropyl acrylate or diethylene glycol monoacrylate in any proportion; the diisocyanate is one or a mixture of more than two of toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate or cyclohexane diisocyanate in any proportion;
c. and (c) carrying out temperature reaction on the oxazolidine monohydric alcohol obtained in the step a and the pre-polymerized monomer obtained in the step b under the action of a second catalyst to obtain the oxazolidine radiation-curable urethane (meth) acrylate-containing compound.
3. The method of claim 2, wherein: in the step a, the molar ratio of the ketone compound or the aldehyde compound to the alkane-containing dihydric alcohol amine is 100 (100-130).
4. The production method according to claim 2 or 3, characterized in that: in the step a, the first catalyst is one or a mixture of more than two of sulfuric acid, sulfonic acid, methanesulfonic acid, ethylsulfonic acid, benzenesulfonic acid or p-toluenesulfonic acid in any proportion, and the molar amount of the first catalyst is 1-6% of the molar amount of the alkane-containing glycol amine; the azeotropic water-carrying agent is one or a mixture of more than two of benzene, toluene, C5 alkane or C6 alkane in any proportion, and the mass consumption of the azeotropic water-carrying agent is 40-60% of the mass sum of the dihydric alcohol amine containing alkane and the ketone compound or the aldehyde compound.
5. The production method according to claim 2 or 3, characterized in that: in the step a, the reaction is performed for 6 to 16 hours under the condition that the temperature is 60 to 120 ℃.
6. The production method according to claim 2 or 3, characterized in that: in the step b, the molar ratio of the diisocyanate to the terminal (methyl) acryloyl compound is 1 (0.95-1.05); in step c, the molar ratio of oxazolidine monoalcohol to prepolymerized monomer is 1 (1.9-2.1).
7. The production method according to claim 2 or 3, characterized in that: in the step b, the hydroxyl-containing terminal (methyl) acryloyl compound is hydroxyethyl acrylate, hydroxyethyl methacrylate, diethylene glycol monoacrylate or 3-chloro-2-hydroxypropyl acrylate; the diisocyanate is isophorone diisocyanate or hexamethylene-1,6-diisocyanate.
8. The production method according to claim 2 or 3, characterized in that: in the steps b and c, the second catalyst is one or a mixture of more than two of dibutyltin dilaurate, stannous octoate, potassium octoate, cobalt octoate, bismuth octoate, zinc naphthenate, cobalt naphthenate, bismuth naphthenate, titanium octoate, titanium carboxylate, triethylene diamine or dimethylethanolamine in any proportion; in the steps b and c, the mass usage amount of the second catalyst is 2-10 per thousand of the mass of the hydroxyl-containing terminal (methyl) acryloyl compound.
9. The production method according to claim 2 or 3, characterized in that: in the steps b and c, in the temperature rising process, a polymerization inhibitor is added, and the polymerization inhibitor is one or a mixture of more than two of p-benzoquinone, hydroquinone, p-hydroxyanisole, copper dimethylamino diethylamino, copper dibutyl dithiocarbamate, 2,2,6,6-tetramethylpiperidine oxide or 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxygen free radical in any proportion; in the steps b and c, the molar amount of the polymerization inhibitor is 0.5-5 per mill of the molar number of the oxazolidine monohydric alcohol.
10. The method of claim 9, wherein: the preparation method of the isocyanate prepolymer containing terminal (methyl) acryloyl group in the step b comprises the following steps: mixing diisocyanate and a polymerization inhibitor, heating to 45-50 ℃, dripping a mixture of a hydroxyl-containing terminal (methyl) acryloyl compound and a second catalyst, heating to 55-60 ℃ after dripping is finished, reacting until the NCO value reaches a theoretical value, and stopping the reaction to obtain a prepolymer monomer containing isocyanate which is not completely reacted;
the step c is: and c, mixing the oxazolidine monohydric alcohol obtained in the step a with a polymerization inhibitor, heating to 45-50 ℃, dropwise adding the mixture of the prepolymer monomer and the catalyst obtained in the step b, heating to 55-60 ℃ after dropwise adding, reacting until NCO is reduced to below 0.5, and stopping reaction to obtain the oxazolidine radiation-curable urethane (methyl) acrylate-containing compound.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110133133.6A CN112851596B (en) | 2021-02-01 | 2021-02-01 | Oxazolidine-containing radiation-curable urethane (meth) acrylate and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110133133.6A CN112851596B (en) | 2021-02-01 | 2021-02-01 | Oxazolidine-containing radiation-curable urethane (meth) acrylate and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112851596A CN112851596A (en) | 2021-05-28 |
| CN112851596B true CN112851596B (en) | 2022-12-27 |
Family
ID=75987219
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110133133.6A Active CN112851596B (en) | 2021-02-01 | 2021-02-01 | Oxazolidine-containing radiation-curable urethane (meth) acrylate and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112851596B (en) |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104341368B (en) * | 2014-11-03 | 2017-01-25 | 江苏开磷瑞阳化工股份有限公司 | Oxazolidine metacrylic acid ester photo-curing monomer as well as preparation method and application of oxazolidine metacrylic acid ester photo-curing monomer |
| CN106750140B (en) * | 2016-12-08 | 2020-02-14 | 天津久日新材料股份有限公司 | Amine modified urethane acrylate photocuring resin and preparation method thereof |
| CN112266375B (en) * | 2020-11-09 | 2022-01-07 | 广东石油化工学院 | Xylitol-containing radiation-curable urethane (meth) acrylate compound and preparation method thereof |
-
2021
- 2021-02-01 CN CN202110133133.6A patent/CN112851596B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN112851596A (en) | 2021-05-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107759757B (en) | Preparation method of hyperbranched polyurethane acrylate and ultraviolet-curable coating | |
| TWI257932B (en) | Urethane (meth)acrylate oligomer, process for its production and photocurable composition | |
| US8048979B2 (en) | Process for synthesis of telechelic urethane acrylate UV curable pre-polymeric materials | |
| TW201011050A (en) | Curable composition containing a reactive (meth)acrylate polymer and a cured product thereof | |
| US20210017381A1 (en) | Curable compositions for use as adhesives having properties capable of being altered based on external stimuli and methods of making and using the same | |
| JPS601886B2 (en) | Method for producing acrylated urethane silicone reaction product | |
| CN110527032B (en) | Light-cured resin material and preparation method thereof | |
| CN114181370A (en) | Modified urethane acrylate photocuring oligomer and preparation method thereof | |
| JPS60197719A (en) | Production of curable resin | |
| JP2001278917A (en) | Composition | |
| CN112851596B (en) | Oxazolidine-containing radiation-curable urethane (meth) acrylate and preparation method thereof | |
| CN112266375B (en) | Xylitol-containing radiation-curable urethane (meth) acrylate compound and preparation method thereof | |
| CN107141440B (en) | Rigid ring modified organosilicon polyurethane acrylate water-based oligomer and preparation method thereof | |
| CN110922603B (en) | Photocuring resin modified by different chain segments and preparation method and application thereof | |
| JP4017055B2 (en) | (Meth) acrylic acid ester and resin composition using the same | |
| JP6425986B2 (en) | Urethane (meth) acrylate, active energy ray-curable urethane (meth) acrylate composition and cured product thereof | |
| WO2005014679A1 (en) | Photo-curable urethane-acrylate compounds | |
| JP4017056B2 (en) | (Meth) acrylic acid ester and resin composition using the same | |
| TW202024142A (en) | Resin and ink | |
| CN113817086B (en) | Bio-based light-cured resin composition and preparation method and application thereof | |
| KR100202091B1 (en) | Two functional reactive tertiary ammonium salt having good antiwearing property, method of preparation thereof and photocurable resin composition containing thereof | |
| JPS5974116A (en) | Production of radical-polymerizable prepolymer | |
| JP4245217B2 (en) | Novel (meth) acrylic acid ester and resin composition | |
| CN111960969B (en) | Asparagus resin modified UV resin, preparation method thereof and ultraviolet curing coating | |
| CN111100261B (en) | Hyperbranched polyurethane acrylate monomer, and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |