CN108774456B - Preparation method of photocuring rare earth europium-modified abietic acid composite high polymer material - Google Patents
Preparation method of photocuring rare earth europium-modified abietic acid composite high polymer material Download PDFInfo
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- CN108774456B CN108774456B CN201810682826.9A CN201810682826A CN108774456B CN 108774456 B CN108774456 B CN 108774456B CN 201810682826 A CN201810682826 A CN 201810682826A CN 108774456 B CN108774456 B CN 108774456B
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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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
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- C07C2603/22—Ortho- or ortho- and peri-condensed systems containing three rings containing only six-membered rings
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Abstract
A preparation method of a photocuring rare earth europium-modified abietic acid composite high polymer material is characterized by mixing rare earth abietic acid complex, trifunctional aliphatic polyurethane acrylate, bifunctional aliphatic polyurethane acrylate, methacrylate reactive diluent, photoinitiator, leveling agent and stabilizer, forming a film, performing ultraviolet curing and the like to prepare the composite high polymer material. The preparation method is simple, environment-friendly and suitable for industrial production; the rare earth abietic acid complex contains a hydrogenated phenanthrene ring framework structure, so that the composite high polymer material disclosed by the invention is endowed with excellent thermal stability, and the luster, the flexibility, the hardness and the like of the composite high polymer material are improved; the composite polymer material has good fluorescence property, can emit special red fluorescence of europium ions, has a wide excitation peak wavelength range and is in a near ultraviolet region of 300-400 nm; the composite polymer material has short coating curing time, high speed and good coating comprehensive performance.
Description
Technical Field
The invention relates to a preparation method of a photocuring rare earth europium-modified abietic acid composite high polymer material, and particularly belongs to the technical field of organic high polymer materials.
Technical Field
Ultraviolet (UV) curing technology appeared in the 60's of the 20 th century, and it is an advanced material surface treatment technology that uses UV light as an energy source to initiate the process of rapidly converting a liquid substance with chemical reaction activity into a solid substance. The UV material has the characteristics of wide applicability, high efficiency, energy conservation and environmental protection, so the UV material is widely applied in production and life.
The rare earth element has a unique outer electronic structure, determines that the rare earth element has various electronic layer arrangements and rich electronic energy levels, and enables the rare earth compound to show a plurality of unique physical and chemical properties, thereby being widely applied to the fields of light, electricity and magnetism. When the rare earth ions are combined with the organic ligand to obtain the rare earth complex, the luminescence of the rare earth ions can be sensitized, and the defects of small light absorption coefficient and low luminous efficiency of the rare earth ions in an ultraviolet region are overcome, so that the characteristic fluorescence emission of the rare earth ions is promoted.
The europium element which is most widely researched and has the best fluorescence intensity is selected to be coordinated with the abietic acid, and then the synthesized rare earth europium organic complex is introduced into the UV material, so that the europium and abietic acid modified UV composite material is prepared, and the material has the unique characteristics of rare earth and abietic acid. The rare earth europium composite UV high polymer material has good mechanical property and thermal stability, has the fluorescence characteristic of rare earth europium, and can be applied to the fields of luminescent materials, fluorescent ink, photoelectric information and the like.
Disclosure of Invention
The invention aims to provide a preparation method of a photocuring rare earth europium-modified abietic acid composite high polymer material, wherein a rare earth complex has a hydrogenated phenanthrene core structure and contains a rigid alkene ring and a carbon-carbon double bond structure, and can perform a crosslinking polymerization reaction with oligomers such as aliphatic polyurethane acrylate and the like under the irradiation of ultraviolet light, and a crosslinking polymerization product has good compatibility and the performances of the photocuring coating such as hardness, flexibility and the like are improved.
The preparation method of the photocuring rare earth europium-modified abietic acid composite high polymer material comprises two steps of synthesizing a rare earth abietic acid complex and preparing the photocuring rare earth europium-modified abietic acid composite high polymer material.
Step 1: synthesis of rare earth abietic acid complex
Dissolving europium oxide in concentrated hydrochloric acid according to the proportion of 1mmol/10ml, heating in a water bath until the solution is clear and transparent, continuously heating, and evaporating to dryness to obtain a white solid EuCl3 & 6H2O, and dissolving with 10ml of absolute ethyl alcohol to obtain a europium chloride absolute ethyl alcohol solution;
controlling the molar ratio of europium oxide to abietic acid to be 1:3, and adding 3mmol of abietic acid and 50ml of absolute ethyl alcohol into a three-neck flask provided with a thermometer, a condenser tube and a dropping funnel; slowly dripping europium chloride absolute ethyl alcohol solution into a three-neck flask, and then usingWhen the pH value of the NaOH solution is adjusted to 6-7, a large amount of precipitate is separated out, the temperature is increased to 55-85 ℃, the reaction is continued for 1.5-3 h, and then the mixture is kept stand for one night to completely separate out the precipitate; filtering the reaction product after standing, washing the obtained crude product with absolute ethyl alcohol and deionized water after suction filtration, and then placing the crude product in a vacuum drying oven to dry the crude product to constant weight to obtain a light yellow powdery rare earth abietic acid complex (Eu)2(ABA)3)；
Step 2: preparation of photocuring rare earth europium modified abietic acid composite high polymer material
According to the mass percentage, 1-10% of rare earth abietic acid complex, 50-65% of tri-functionality aliphatic urethane acrylate, 12-16% of di-functionality aliphatic urethane acrylate, 10-30% of methacrylate reactive diluent, 1-5% of photoinitiator, 0.5-3% of flatting agent and stabilizer are mixed and stirred uniformly, coated on a glass sheet, a metal sheet or an ABS base material, and irradiated by an ultraviolet lamp for 30s under the environment of a nitrogen-free atmosphere in an ultraviolet curing lamp with the power of 400 plus 800W to obtain the rare earth europium modified abietic acid composite polymer material;
the photoinitiator is 1173 (2-hydroxy-2-methyl propiophenone).
The methacrylate reactive diluent is trimethylolpropane triacrylate (TMPTA), hexanediol diacrylate (HDDA) or neopentyl glycol diacrylate (NPGDA).
The leveling agent is BYK 371.
The stabilizer is UV 531.
The invention has the beneficial effects that:
1. the rare earth abietic acid complex has a hydrogenated phenanthrene core structure, contains a rigid ring and a carbon-carbon double bond, can perform a cross-linking polymerization reaction with urethane acrylate and an active diluent under the irradiation of ultraviolet light, endows the rare earth europium modified abietic acid composite high polymer material with excellent thermal stability, and also improves the properties of the high polymer material such as luster, flexibility, hardness and the like.
2. By introducing the rare earth abietic acid complex, the rare earth europium modified abietic acid composite polymer material has the advantages of enhanced hardness, flexibility and the like, high photocuring speed of a coated film, greatly shortened curing time and improved thermal stability, and the photocured coated film has the fluorescent characteristic and can emit special red fluorescence of europium ions, the maximum emission peak of the europium ions is 618nm, the maximum excitation wavelength is 316nm, the range of the excitation peak wavelength is wider, and the near ultraviolet region is 300-400 nm.
3. The invention combines the ultraviolet curing technology, utilizes the renewable biomass material abietic acid, and the prepared high polymer material has the advantages of environmental protection, degradability and the like, and the preparation method is simple, easy to operate and suitable for industrial clean production.
Drawings
FIG. 1 is a fluorescence spectrum of a rare earth europium-modified abietic acid composite polymer material of the invention.
Detailed Description
Example 1
Europium oxide and abietic acid are weighed according to the molar ratio of 1:3, wherein the europium oxide is 1 mmol. Measuring 10ml hydrochloric acid to dissolve europium oxide, heating in water bath to obtain clear and transparent solution, continuously heating, and evaporating the solution to dryness to obtain white solid EuCl3·6H2And O, dissolving the europium chloride in 10ml of absolute ethanol for later use to obtain an absolute ethanol solution of the europium chloride. Adding 3mmol of abietic acid and 50ml of absolute ethanol into a three-neck flask provided with a thermometer, a condenser tube and a dropping funnel, slowly dropwise adding a rare earth europium chloride ethanol solution into the three-neck flask, adjusting the pH value to 6-7 with a NaOH solution to separate out a large amount of precipitate, raising the temperature to 85 ℃ after the dropwise adding is finished, continuing to react for 1.5h, and standing overnight to completely separate out the precipitate. And (3) carrying out suction filtration on the obtained crude product, washing the crude product for multiple times by using absolute ethyl alcohol and deionized water, and then placing the crude product in a vacuum drying oven to be dried to constant weight to obtain light yellow powder.
Preparing the rare earth high-molecular paint:
2% of rare earth abietic acid complex, 60% of trifunctional polyurethane acrylate (B-305), 15% of bifunctional polyurethane acrylate (B-270), 15% of reactive diluent (trimethylolpropane triacrylate), 5% of photoinitiator 1173 (2-hydroxy-2-methyl propiophenone) and 3% of ethyl acetate, and uniformly mixing the rare earth complex, the polyurethane acrylate, the reactive diluent, the photoinitiator and the like according to a proportion to prepare the rare earth high polymer photocuring coating.
The coating can be coated on a glass substrate, a 400W ultraviolet lamp is adopted to directly irradiate light to be cured into a film in a nitrogen-free atmosphere, the curing time is 30s, the thickness of the coating is less than 1.2mm, the pencil hardness of the film is 6H, the adhesive force is 5 grades, the water resistance, acid resistance and alkali resistance tests are passed, the film is free of falling and damage, the coating has excellent mechanical property and weather resistance, has a fluorescent characteristic, and can emit a special emission peak of rare earth europium to emit red light.
Example 2
Europium oxide and abietic acid are weighed according to the molar ratio of 1:3, wherein the europium oxide is 1 mmol. Measuring 10ml hydrochloric acid to dissolve europium oxide, heating in water bath to obtain clear and transparent solution, continuously heating, and evaporating the solution to dryness to obtain white solid EuCl3·6H2And O, dissolving the europium chloride in 10ml of absolute ethanol for later use to obtain an absolute ethanol solution of the europium chloride. Adding 3mmol of abietic acid and 50ml of absolute ethanol into a three-neck flask provided with a thermometer, a condenser tube and a dropping funnel, slowly dropwise adding a rare earth europium chloride ethanol solution into the three-neck flask, adjusting the pH value to 6-7 with a NaOH solution to separate out a large amount of precipitate, raising the temperature to 85 ℃ after the dropwise adding is finished, continuing to react for 1.5h, and standing overnight to completely separate out the precipitate. And (3) carrying out suction filtration on the obtained crude product, washing the crude product for multiple times by using absolute ethyl alcohol and deionized water, and then placing the crude product in a vacuum drying oven to be dried to constant weight to obtain light yellow powder.
Preparing the rare earth high-molecular paint:
3% of rare earth abietic acid complex, 56% of trifunctional polyurethane acrylate (B-305), 14% of bifunctional polyurethane acrylate (B-270), 15% of reactive diluent (trimethylolpropane triacrylate), 5% of photoinitiator 1173 (2-hydroxy-2-methyl propiophenone) and 7% of ethyl acetate, and uniformly mixing the rare earth complex, the polyurethane acrylate, the reactive diluent, the photoinitiator and the like according to a proportion to prepare the rare earth high polymer photocuring coating.
The coating can be coated on a glass substrate, a 400W ultraviolet lamp is adopted to directly irradiate light to be cured into a film in a nitrogen-free atmosphere, the curing time is 34s, the thickness of the coating is less than 1.2mm, the pencil hardness of the film is 6H, the adhesive force is 5 grades, the water resistance, acid resistance and alkali resistance tests are passed, the film is free of falling and damage, the coating has excellent mechanical property and weather resistance, has a fluorescent characteristic, and can emit a special emission peak of rare earth europium to emit red light.
Claims (3)
1. A preparation method of a photocuring rare earth europium-modified abietic acid composite high polymer material is characterized by comprising the following steps of: the preparation method comprises two steps of synthesis of rare earth abietic acid complex and preparation of photocuring rare earth europium-modified abietic acid composite high polymer material;
step 1: synthesis of rare earth abietic acid complex
Dissolving europium oxide in concentrated hydrochloric acid according to the proportion of 1mmol/10ml, heating in a water bath until the solution is clear and transparent, continuously heating, and evaporating to dryness to obtain a white solid EuCl3 & 6H2O, and dissolving with 10ml of absolute ethyl alcohol to obtain a europium chloride absolute ethyl alcohol solution;
controlling the molar ratio of europium oxide to abietic acid to be 1:3, and adding 3mmol of abietic acid and 50ml of absolute ethyl alcohol into a three-neck flask provided with a thermometer, a condenser tube and a dropping funnel; slowly dropwise adding an anhydrous alcohol solution of europium chloride into a three-neck flask, then regulating the pH value to 6-7 by using a NaOH solution to separate out a large amount of precipitate, heating to 55-85 ℃, continuously reacting for 1.5-3 h, and standing overnight to completely separate out the precipitate; filtering the reaction product after standing, washing the obtained crude product with absolute ethyl alcohol and deionized water after suction filtration, and then placing the crude product in a vacuum drying oven to dry the crude product to constant weight to prepare a light yellow powdery rare earth abietic acid complex;
step 2: preparation of photocuring rare earth europium modified abietic acid composite high polymer material
According to the mass percentage, 1-10% of rare earth abietic acid complex, 50-65% of tri-functionality aliphatic urethane acrylate, 12-16% of di-functionality aliphatic urethane acrylate, 10-30% of methacrylate reactive diluent, 1-5% of photoinitiator, 0.5-3% of flatting agent and stabilizer are mixed and stirred uniformly, coated on a glass sheet, a metal sheet or an ABS base material, and irradiated by an ultraviolet lamp for 30s under the environment of a nitrogen-free atmosphere in an ultraviolet curing lamp with the power of 400 plus 800W to obtain the rare earth europium modified abietic acid composite polymer material; said photoinitiator is 1173; the methacrylate reactive diluent is trimethylolpropane triacrylate, hexanediol diacrylate or neopentyl glycol diacrylate.
2. The method for preparing the photocuring rare earth europium-modified abietic acid composite polymer material according to claim 1, wherein the method comprises the following steps: the leveling agent is BYK 371.
3. The method for preparing the photocuring rare earth europium-modified abietic acid composite polymer material according to claim 1, wherein the method comprises the following steps: the stabilizer is UV 531.
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