CN108774456A - A kind of preparation method of photocuring rare-earth europium modified rosin acid composite polymer material - Google Patents
A kind of preparation method of photocuring rare-earth europium modified rosin acid composite polymer material Download PDFInfo
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- CN108774456A CN108774456A CN201810682826.9A CN201810682826A CN108774456A CN 108774456 A CN108774456 A CN 108774456A CN 201810682826 A CN201810682826 A CN 201810682826A CN 108774456 A CN108774456 A CN 108774456A
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- rosin acid
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/41—Preparation of salts of carboxylic acids
- C07C51/418—Preparation of metal complexes containing carboxylic acid moieties
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C61/00—Compounds having carboxyl groups bound to carbon atoms of rings other than six-membered aromatic rings
- C07C61/16—Unsaturated compounds
- C07C61/28—Unsaturated compounds polycyclic
- C07C61/29—Unsaturated compounds polycyclic having a carboxyl group bound to a condensed ring system
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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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2603/00—Systems containing at least three condensed rings
- C07C2603/02—Ortho- or ortho- and peri-condensed systems
- C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
- C07C2603/22—Ortho- or ortho- and peri-condensed systems containing three rings containing only six-membered rings
- C07C2603/26—Phenanthrenes; Hydrogenated phenanthrenes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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Abstract
Specifically composite polymer material is made through processing such as mixing, film forming, ultra-violet curings by rare earth rosin acid complex, three-functionality-degree aliphatic urethane acrylate, two degree of functionality aliphatic urethane acrylates, methyl acrylic ester reactive diluent, photoinitiator and levelling agent and stabilizer component in a kind of preparation method of photocuring rare-earth europium modified rosin acid composite polymer material.Preparation method of the present invention is simple, environmental-friendly, is suitble to industrial production；Rare earth rosin acid complex contains hydrogenation phenanthrene ring frame structure, imparts the excellent thermal stability of composite polymer material of the present invention, further improves its gloss, suppleness, hardness etc.；Composite polymer material has good fluorescence property, can send out the special red fluorescence of europium ion, excitation peak wave-length coverage is wider, in the near ultraviolet region of 300~400nm；Curing of coatings time of composite polymer material of the present invention is short, speed is fast, and properties of coating is good.
Description
Technical field
The present invention relates to a kind of preparation methods of photocuring rare-earth europium modified rosin acid composite polymer material, particularly belong to
High-molecular organic material technical field.
Technical background
Ultraviolet light（UV）Curing technology comes across in the 1960s, being the energy using ultraviolet light, causing has chemistry anti-
It is solid process to answer active liquid fast transition, is a kind of advanced surface treatment technology of material.UV materials due to
It is wide with applicability, efficient, the characteristics of energy conservation and environmental protection, so being widely used in production and living.
Rare earth element has unique outer electronic structure, determines it with various electronic shell arrangement and abundant electricity
Sub- energy level makes its rare earth compound show many unique physics and chemical property, thus is widely used in light, electricity, magnetic neck
Domain.When rare earth ion is combined to obtain rare earth compounding with organic ligand, it can be sensitized shining for rare earth ion, make up rare earth ion
In the defect that ultraviolet region absorptivity is small, luminous efficiency is not high, to promote the characteristic fluorescence of rare earth ion to emit.
The present invention selects research most wide, and the best europium element of fluorescence intensity is coordinated with rosin acid, then by synthesis
Orgnic RE complex is introduced into UV materials, to prepare the UV composite materials that europium is modified with rosin acid, material is made to have
There are rare earth and the exclusive characteristic of rosin acid.The compound UV high molecular materials of rare-earth europium have good mechanical property and thermal stability
Can, and the fluorescent characteristic with rare-earth europium, it can be applied to the fields such as luminescent material, fluorescent ink, photoelectric information.
Invention content
The purpose of the present invention is to provide a kind of preparation sides of photocuring rare-earth europium modified rosin acid composite polymer material
Method, rare earth compounding have hydrogenation phenanthrene nucleus structure, can under the irradiation of ultraviolet light containing rigid alkene ring and carbon-carbon double bond structure
Polymerisation is crosslinked with oligomer such as aliphatic urethane acrylates, crosslinked polymerized product has good compatibility,
And improve the performances such as photocureable coating hardness, suppleness.
A kind of preparation method of photocuring rare-earth europium modified rosin acid composite polymer material of the present invention includes rare earth rosin
Two step of preparation of the synthesis and photocuring rare-earth europium modified rosin acid composite polymer material of sour complex.
Step 1：The synthesis of rare earth rosin acid complex
In the ratio of 1mmol/10ml, europium oxide is dissolved in concentrated hydrochloric acid, heating water bath to clear transparent solutions continues to heat
Solution is evaporated afterwards, obtained white solid EuCl3∙6H2O uses 10ml absolute ethyl alcohols to dissolve again, and it is molten to obtain Europium chloride absolute ethyl alcohol
Liquid；
The molar ratio for controlling europium oxide and rosin acid is 1:3, equipped with thermometer, condenser pipe, dropping funel three-necked flask in,
3mmol rosin acids and 50ml absolute ethyl alcohols is added；Europium chloride ethanol solution is slowly dropped in three-necked flask, is then used
NaOH solution has a large amount of Precipitations when adjusting pH to 6-7, then is warming up to 55~85 DEG C, after the reaction was continued 1.5~3h, standing one
Night makes precipitation be precipitated completely；By after standing reaction product filtering, obtained crude product after suction filtration respectively with absolute ethyl alcohol, go
Ion water washing is subsequently placed in vacuum drying chamber and dries to constant weight, the rare earth rosin acid complex of pale yellow powder shape is made
（Eu2(ABA)3）；
Step 2：The preparation of photocuring rare-earth europium modified rosin acid composite polymer material
By mass percentage, 1%~10% rare earth rosin acid complex, 50%~65% three-functionality-degree aliphatic polyurethane third
Olefin(e) acid ester, 12%~16% two degree of functionality aliphatic urethane acrylates, 10%~30% methyl acrylic ester activity are dilute
Release agent, 1%~5% photoinitiator and 0.5%-3% levelling agents and stabilizer be mixed evenly, be applied to sheet glass, metal
On piece or ABS substrate, in the ultraviolet curing lamp of 400-800w power, ultra violet lamp 30s obtains rare earth under no nitrogen atmosphere
Europium modified rosin acid composite polymer material；
The photoinitiator is 1173（2- hydroxy-2-methyl propiophenones）.
The methyl acrylic ester reactive diluent is trimethylolpropane trimethacrylate（TMPTA）, hexylene glycol
Diacrylate（HDDA）Or neopentylglycol diacrylate（NPGDA）.
The levelling agent is BYK371.
The stabilizer is UV531.
Advantageous effect of the present invention：
1, rare earth rosin acid complex of the present invention has hydrogenation phenanthrene nucleus structure can be with polyurethane containing stiffening ring and carbon-carbon double bond
Under the irradiation of ultraviolet light cross-linking polymerization occurs for acrylate, reactive diluent, and it is multiple to impart rare-earth europium modified rosin acid
The excellent thermal stability of high molecular material is closed, the performances such as gloss, suppleness, the hardness of high molecular material are further improved.
2, by introducing rare earth rosin acid complex, keep rare-earth europium modified rosin acid composite polymer material of the present invention hard
Degree, flexibility etc. are strengthened, and film laser curing velocity is fast, and hardening time greatly shortens, thermal stability is improved, light
Cured coating film has fluorescent characteristic, can send out the special red fluorescence of europium ion, the maximum emission peak of europium ion is 618nm, most
Big excitation wavelength is 316nm, and excitation peak wave-length coverage is wider, the near ultraviolet region of 300~400nm.
3, present invention incorporates UV-curing technologies, utilize reproducible biological material rosin acid, the high score of preparation
Sub- material has many advantages, such as environmental protection, degradable, and preparation method is simple, easily operated, is suitble to industry clean manufacturing.
Description of the drawings
Fig. 1 is the fluorescence spectra of rare-earth europium modified rosin acid composite polymer material of the present invention.
Specific implementation mode
Embodiment 1
It is 1 in molar ratio by europium oxide, rosin acid:3 carry out quality weighing, and wherein europium oxide is 1mmol.It is molten to measure 10ml hydrochloric acid
Europium oxide is solved, heating water bath to clear transparent solutions, solution is evaporated to obtain white solid EuCl after continuing heating3∙6H2O is used
10ml absolute ethyl alcohols are dissolved for use, and Europium chloride ethanol solution is obtained.Equipped with thermometer, condenser pipe, dropping funel
Three-necked flask in 3mmol rosin acids and 50ml absolute ethyl alcohols is added, rare-earth chlorination europium ethanol solution is slowly added drop-wise to three
In mouth flask, adjusting pH to 6-7 with NaOH solution has a large amount of Precipitations, and temperature is increased to 85 DEG C after being added dropwise, is continued
1.5h is reacted, one night of standing makes precipitation be precipitated completely.Obtained crude product is filtered, is washed with absolute ethyl alcohol, deionized water more
It is secondary, it is subsequently placed in vacuum drying chamber and dries to constant weight, obtain pale yellow powder.
The preparation of rare earth high polymer coating：
Rare earth rosin acid complex 2%, three-functionality-degree urethane acrylate（B-305）60%, two degree of functionality polyurethane acroleic acids
Ester（B-270）15%, reactive diluent（Trimethylolpropane trimethacrylate）15%, photoinitiator 1173（2- hydroxy-2-methyls
Propiophenone）5%, ethyl acetate 3%, in proportion by rare earth compounding, urethane acrylate, reactive diluent, photoinitiator etc.
It is uniformly mixed, rare earth high polymer photocureable coating is made.
Coating is smearable on the glass substrate, and the ultraviolet lamp direct irradiation photocuring of 400w is used under the atmosphere of no nitrogen
Film forming, hardening time 30s, coating layer thickness are less than 1.2mm, and the pencil hardness of film is 6H, and adhesive force is 5 grades, water-fast, resistance to
Acid, alkali resistance test pass through, and paint film has excellent mechanical property and weatherability without falling off and breakage, has fluorescence
Characteristic can launch the special emission peak of rare-earth europium, send out feux rouges.
Embodiment 2
It is 1 in molar ratio by europium oxide, rosin acid:3 carry out quality weighing, and wherein europium oxide is 1mmol.It is molten to measure 10ml hydrochloric acid
Europium oxide is solved, heating water bath to clear transparent solutions, solution is evaporated to obtain white solid EuCl after continuing heating3∙6H2O is used
10ml absolute ethyl alcohols are dissolved for use, and Europium chloride ethanol solution is obtained.Equipped with thermometer, condenser pipe, dropping funel
Three-necked flask in 3mmol rosin acids and 50ml absolute ethyl alcohols is added, rare-earth chlorination europium ethanol solution is slowly added drop-wise to three
In mouth flask, adjusting pH to 6-7 with NaOH solution has a large amount of Precipitations, and temperature is increased to 85 DEG C after being added dropwise, is continued
1.5h is reacted, one night of standing makes precipitation be precipitated completely.Obtained crude product is filtered, is washed with absolute ethyl alcohol, deionized water more
It is secondary, it is subsequently placed in vacuum drying chamber and dries to constant weight, obtain pale yellow powder.
The preparation of rare earth high polymer coating：
Rare earth rosin acid complex 3%, three-functionality-degree urethane acrylate（B-305）56%, two degree of functionality polyurethane acroleic acids
Ester（B-270）14%, reactive diluent（Trimethylolpropane trimethacrylate）15%, photoinitiator 1173（2- hydroxy-2-methyls
Propiophenone）5%, ethyl acetate 7%, in proportion by rare earth compounding, urethane acrylate, reactive diluent, photoinitiator etc.
It is uniformly mixed, rare earth high polymer photocureable coating is made.
Coating is smearable on the glass substrate, and the ultraviolet lamp direct irradiation photocuring of 400w is used under the atmosphere of no nitrogen
Film forming, hardening time 34s, coating layer thickness are less than 1.2mm, and the pencil hardness of film is 6H, and adhesive force is 5 grades, water-fast, resistance to
Acid, alkali resistance test pass through, and paint film has excellent mechanical property and weatherability without falling off and breakage, has fluorescence
Characteristic can launch the special emission peak of rare-earth europium, send out feux rouges.
Claims (4)
1. a kind of preparation method of photocuring rare-earth europium modified rosin acid composite polymer material, it is characterised in that：The system
Preparation Method includes the preparation of the synthesis and photocuring rare-earth europium modified rosin acid composite polymer material of rare earth rosin acid complex
Two steps；
Step 1：The synthesis of rare earth rosin acid complex
In the ratio of 1mmol/10ml, europium oxide is dissolved in concentrated hydrochloric acid, heating water bath to clear transparent solutions continues to heat
Solution is evaporated afterwards, obtained white solid EuCl3∙6H2O uses 10ml absolute ethyl alcohols to dissolve again, and it is molten to obtain Europium chloride absolute ethyl alcohol
Liquid；
The molar ratio for controlling europium oxide and rosin acid is 1:3, equipped with thermometer, condenser pipe, dropping funel three-necked flask in,
3mmol rosin acids and 50ml absolute ethyl alcohols is added；Europium chloride ethanol solution is slowly dropped in three-necked flask, is then used
NaOH solution has a large amount of Precipitations when adjusting pH to 6-7, then is warming up to 55~85 DEG C, after the reaction was continued 1.5~3h, standing one
Night makes precipitation be precipitated completely；By after standing reaction product filtering, obtained crude product after suction filtration respectively with absolute ethyl alcohol, go
Ion water washing is subsequently placed in vacuum drying chamber and dries to constant weight, the rare earth rosin acid complex of pale yellow powder shape is made；
Step 2：The preparation of photocuring rare-earth europium modified rosin acid composite polymer material
By mass percentage, 1%~10% rare earth rosin acid complex, 50%~65% three-functionality-degree aliphatic polyurethane third
Olefin(e) acid ester, 12%~16% two degree of functionality aliphatic urethane acrylates, 10%~30% methyl acrylic ester activity are dilute
Release agent, 1%~5% photoinitiator and 0.5%-3% levelling agents and stabilizer be mixed evenly, be applied to sheet glass, metal
On piece or ABS substrate, in the ultraviolet curing lamp of 400-800w power, ultra violet lamp 30s obtains rare earth under no nitrogen atmosphere
Europium modified rosin acid composite polymer material；The photoinitiator is 1173.
2. a kind of preparation method of photocuring rare-earth europium modified rosin acid composite polymer material according to claim 1,
It is characterized in that：The methyl acrylic ester reactive diluent is trimethylolpropane trimethacrylate, hexylene glycol dipropyl
Olefin(e) acid ester or neopentylglycol diacrylate.
3. a kind of preparation method of photocuring rare-earth europium modified rosin acid composite polymer material according to claim 1,
It is characterized in that：The levelling agent is BYK371.
4. a kind of preparation method of photocuring rare-earth europium modified rosin acid composite polymer material according to claim 1,
It is characterized in that：The stabilizer is UV531.
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| CN201810682826.9A CN108774456B (en) | 2018-06-28 | 2018-06-28 | Preparation method of photocuring rare earth europium-modified abietic acid composite high polymer material |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111171059A (en) * | 2020-02-09 | 2020-05-19 | 中国林业科学研究院林产化学工业研究所 | Dehydroabietic acid and derivative-based europium ion fluorescent complex thereof and preparation method thereof |
| CN115403727A (en) * | 2021-05-28 | 2022-11-29 | 苏州科思迈新材料科技有限公司 | Polyurethane soft and hard segment adjustment and force-induced color change function integrated composite processing aid and preparation method thereof |
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| JP2002068900A (en) * | 2000-09-01 | 2002-03-08 | National Institute Of Advanced Industrial & Technology | Method of forming epitaxial thin film on surface of single crystal substrate |
| CN101250340A (en) * | 2008-04-03 | 2008-08-27 | 惠州市长润发涂料有限公司 | Ultraviolet light curing fingerprint resistant paint |
| CN102604529A (en) * | 2012-03-17 | 2012-07-25 | 常熟市方塔涂料化工有限公司 | Photocureable coating for anodization |
| CN103525293A (en) * | 2013-10-16 | 2014-01-22 | 惠州市凯辉化工有限公司 | Non-yellowing UV (Ultraviolet) gloss oil as well as preparation method thereof |
| CN104497851A (en) * | 2015-01-17 | 2015-04-08 | 南昌航空大学 | Ultraviolet cured rare earth polymer material and preparation method thereof |
-
2018
- 2018-06-28 CN CN201810682826.9A patent/CN108774456B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002068900A (en) * | 2000-09-01 | 2002-03-08 | National Institute Of Advanced Industrial & Technology | Method of forming epitaxial thin film on surface of single crystal substrate |
| CN101250340A (en) * | 2008-04-03 | 2008-08-27 | 惠州市长润发涂料有限公司 | Ultraviolet light curing fingerprint resistant paint |
| CN102604529A (en) * | 2012-03-17 | 2012-07-25 | 常熟市方塔涂料化工有限公司 | Photocureable coating for anodization |
| CN103525293A (en) * | 2013-10-16 | 2014-01-22 | 惠州市凯辉化工有限公司 | Non-yellowing UV (Ultraviolet) gloss oil as well as preparation method thereof |
| CN104497851A (en) * | 2015-01-17 | 2015-04-08 | 南昌航空大学 | Ultraviolet cured rare earth polymer material and preparation method thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111171059A (en) * | 2020-02-09 | 2020-05-19 | 中国林业科学研究院林产化学工业研究所 | Dehydroabietic acid and derivative-based europium ion fluorescent complex thereof and preparation method thereof |
| CN111171059B (en) * | 2020-02-09 | 2022-06-24 | 中国林业科学研究院林产化学工业研究所 | Dehydroabietic acid and derivative-based europium ion fluorescent complex thereof and preparation method thereof |
| CN115403727A (en) * | 2021-05-28 | 2022-11-29 | 苏州科思迈新材料科技有限公司 | Polyurethane soft and hard segment adjustment and force-induced color change function integrated composite processing aid and preparation method thereof |
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