CN106590310B - A kind of anti-ultraviolet paint having self-repair function, preparation method and application - Google Patents
A kind of anti-ultraviolet paint having self-repair function, preparation method and application Download PDFInfo
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- CN106590310B CN106590310B CN201710092246.XA CN201710092246A CN106590310B CN 106590310 B CN106590310 B CN 106590310B CN 201710092246 A CN201710092246 A CN 201710092246A CN 106590310 B CN106590310 B CN 106590310B
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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
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/02—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to polysaccharides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/544—Silicon-containing compounds containing nitrogen
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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
- C09D5/32—Radiation-absorbing paints
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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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
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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
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- Life Sciences & Earth Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
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Abstract
The present invention relates to a kind of anti-ultraviolet paints and preparation method thereof, belong to functional polymer material field.The coating is copolymerized to obtain by the function monomer containing host-guest inclusion and polymerizable object functional group, polymeric matrix monomer；The function monomer is mainly made by cyclodextrin modified ultraviolet absorbing agent and guest materials；The polymeric matrix monomer is coating matrix material；The ultraviolet absorbing agent is linked together with coating matrix material by the supermolecular mechanism power of cyclodextrin host-guest inclusion.The anti-ultraviolet paint can be used for the surface coated in base material, form coating in substrate material surface after solvent volatilizes.The coating can absorb 90% or more ultraviolet light, to prevent the sample aging of protection, in the scratch that its surface is manufactured with scalpel, can disappear after pure water is added dropwise in scratch surface.
Description
Technical field
The present invention relates to a kind of anti-ultraviolet paints and preparation method thereof, and in particular to a kind of to have the anti-of self-repair function
Ultraviolet light coating, preparation method and its application, belong to functional polymer material field.
Background technique
Material inevitably will receive the irradiation of daylight in use, and the higher ultraviolet light of energy can accelerated material in daylight
Aging, greatly shorten the service life of material.Research shows that: most organic material, such as most polymer materials,
By the accumulation of UV energy photooxidation and light degradation can occur for woodwork, deteriorate to the performances such as generate discoloration, become fragile
Phenomenon (Zayat et al., Chem Soc Rev 2007,36,1270；Nespurek et al.,J Optoelect Adv
Mater 2005,7,1157.).It is to protect at present that on material product surface, coating, which can be absorbed or shield the coating material of ultraviolet light,
Protect the most effective approach that organic material supports anti-light aging.
Make general coating that there is the specific function for absorbing or shielding ultraviolet light, it is general ultraviolet using being added into coating matrix
The approach of light absorbers.Common ultraviolet absorbing agent can be divided into organic uvioresistant additive and inorganic uvioresistant additive
Two classes (Ma et al., Nanoscale Res Lett 2016,11,1.).But there is move at any time for both additives
The problem of advection is lost.More importantly: current existing ultraviolet resistant once meets with mechanical damage and (is such as scratched or generates
Scratch), uvioresistant function can substantially weaken.Even this is because small damage and gap, can also make ultraviolet light from
Incident material surface at coating damage greatly accelerates the local ageing of material, the defect of forming material, and deteriorates entire material in turn
The performance of material.
By nature life entity can with self-healing its wound behavior of being wound inspiration, in recent years, the system of self-repair material
Standby research has been a great concern (Hia et al., Polym Rev 2016,56,225.).Scientists are based on embedding and are cured
Mixture (Trask et al., J R Soc Interface 2007,4,363.), introduce dynamic covalent bond (Wei et al.,
Adv Funct Mater 2015,25,1352.) or supramolecular chemistry (Nakahata et al., Macromol Rapid
Comm 2016,37,86.) the methods of devise number of types of self-repair material.Wherein, also include can selfreparing anticorrosion
Coating and super-hydrophobic coat (Samadzadeh et al., Prog Org Coatings, 2010,68,159；Li et al.,
Angew Chem 2010,122,6265).But the coating material for being provided simultaneously with uvioresistant ability and self-healing properties yet there are no
Report.
Summary of the invention
In order to solve, current anti-ultraviolet paint middle-ultraviolet lamp absorbent is easy to run off and coating does not have self-healing properties
Problem, the invention proposes a kind of anti-ultraviolet paints and preparation method thereof for having self-repair function, and the coating is successful
Applied to protection base material.
To achieve the above object, the invention adopts the following technical scheme:
A kind of anti-ultraviolet paint having self-repair function, by the function containing host-guest inclusion and polymerizable object functional group
Energy monomer, polymeric matrix monomer are copolymerized to obtain；The function monomer is mainly by cyclodextrin modified ultraviolet absorbing agent and visitor
Body material is made；The polymeric matrix monomer is coating matrix material；The ultraviolet absorbing agent and coating matrix material are logical
The supermolecular mechanism power for crossing cyclodextrin host-guest inclusion links together.
Above-mentioned cyclodextrin modified ultraviolet absorbing agent is ultraviolet absorbing agent main body.The ultraviolet absorbing agent main body master
To be made by following raw materials: mass ratio is the cyclodextrin and ultraviolet absorbing agent of 0.1~10:1.
Above-mentioned function monomer is made by following raw materials: the guest materials of ultraviolet absorbing agent main body and 1.5~40 equivalents, with
And it can dissolve or the good solvent of fine dispersion ultraviolet absorbing agent subject and object material.
The mass ratio of above-mentioned function monomer and coating matrix material is 0.05~0.5:1.
The present invention also provides the preparation methods of the above-mentioned anti-ultraviolet paint for having self-repair function, including following step
It is rapid:
(1) it ultraviolet absorbing agent subject preparation: utilizes and is chemically or physically modified cyclodextrin modified in ultraviolet absorbing agent
On, cyclodextrin modified ultraviolet absorbing agent, i.e. ultraviolet absorbing agent main body is made；The cyclodextrin and ultraviolet absorbing agent
Mass ratio is 0.1~10:1；
(2) prepared by function monomer: in a solvent by ultraviolet absorbing agent main body ultrasonic disperse made from step (1), being added
The guest materials of 1.5~40 equivalents stirs at room temperature obtains assembly afterwards for 24 hours, this assembly is function monomer；
(3) polymerization prepares coating: function monomer made from step (2) being distributed in polymer solvent, coating matrix is added
Material and initiator carry out copolyreaction, obtain sol form anti-ultraviolet paint；The dosage of the function monomer is the coating
The 5%-50%wt of basis material monomer.
The ultraviolet absorbing agent refers to organic uv absorbers and/or inorganic ultraviolet absorbent, and referring to can be absorbed
The organic matter and/or inorganic matter of ultraviolet light, including but not limited to benzophenone and its derivative, group amine derivant, benzoic acid
Phenyl ester derivative and/or titanium dioxide, silica, zinc oxide.
The cyclodextrin refers to the cyclic oligosaccharide containing 6 or more glucopyranose molecules and/or its derivative.
The coating matrix material refers to acrylic ester monomer, epoxy monomer or isocyanates monomer.
The guest materials refer in molecule containing the first functional group for being included with cyclodextrin and with coating matrix material
The second functional group of polymerization reaction occurs for material；First functional group included with cyclodextrin, including but not limited to two cyclopentadienyls
Iron, adamantane or polyphenol functional group, the second functional group that polymerization reaction occurs with coating matrix material, including but not limited to
Such as double bond, epoxy or isocyanate functional group.The guest materials can be used while have aforementioned first functional group and the second official
The monomer molecule that can be rolled into a ball, can also will be respectively provided with the single or multiple molecule of functional group that can be included with cyclodextrin and have
The modified monomer material that the single or multiple molecule of functional group that polymerization reaction can occur are prepared by mixing into is as modified guest materials.
Solvent in the step (2) includes but is not limited to water, ethyl alcohol, tetrahydrofuran, dimethyl sulfoxide, N, N- dimethyl
The mixed solution of formamide or above-mentioned solvent；For that can dissolve simultaneously or the solvent of fine dispersion subject and object material, dosage
For that can be completely dissolved or fine dispersion subject and object material.
The temperature of above-mentioned steps (3) described copolyreaction is 10~190 DEG C, and the time of copolyreaction is 1~48 hour.
Above-mentioned steps (3) described polymer solvent includes but is not limited to water, ethyl alcohol, tetrahydrofuran, dimethyl sulfoxide, N, N- bis-
The mixed solution of methylformamide or above-mentioned solvent；For that can dissolve simultaneously or fine dispersion function monomer and coating matrix material
Solvent.
Above-mentioned steps (3) described initiator refers to the initiator that can cause free radical polymerization or ring-opening polymerisation, including but unlimited
In azo-initiator, peroxide initiator, oxidation-reduction initiator or cationic initiator；When containing in guest materials
When can trigger the functional group of double bond free radical polymerization or ring-opening polymerisation, initiator can not be individually added, at this point, the initiation
Agent is guest materials contained in function monomer.
The sol form anti-ultraviolet paint being prepared using the method for the invention can be coated in the table of base material
Face forms coating in substrate material surface after it is volatilized.The coating can absorb 95% ultraviolet light；It performs the operation on its surface
Knife manufactures scratch, 20 μ L pure water is added dropwise on scratch surface, scratch can disappear after 15min.
Detailed description of the invention
Fig. 1 is that anti-ultraviolet paint (embodiment 1) protection for having self-repair function adds with unprotected PVC sample item
Appearance after fast aging compares photo, and a is initial sample in figure, and b is shielded sample, and c is unprotected sample.
Fig. 2 is that the anti-ultraviolet paint (embodiment 5) for having self-repair function forms selfreparing front and back comparison diagram after coating.
Fig. 3 is that the anti-ultraviolet paint (embodiment 5) for having self-repair function forms the solid uv drs after coating
Spectrogram.
Specific embodiment
Technical solution of the present invention is described further below by way of example.
Table 1 is that Examples 1 to 5 has each reactant and dosage in the anti-ultraviolet paint preparation process of self-repair function
Table.
The material usage sheet of 1 Examples 1 to 5 of table
Embodiment 1
Ultraviolet absorbing agent subject preparation: the beta-cyclodextrin (β-CD) by 1g titanium dioxide ultrasonic disperse in 500mL is water-soluble
In liquid (20g/L), reaction irradiation 48h, is then centrifuged for being separated off unreacted dioxy at ultraviolet lamp (36W, λ=254nm)
Change titanium particle, is lyophilized after being washed with water 3 times to get to the ultraviolet absorbing agent main body T-CD for being modified with cyclodextrin；
Guest materials preparation: hydroxyethyl meth acrylate (HEMA) (15mmol), tripropyl amine (TPA) (23mmol) are dissolved in
In 200mL anhydrous methylene chloride (0-5 DEG C), the methylene chloride being then added dropwise dissolved with 3.7g adamantane formyl chloride (18.6mmol) is molten
Liquid continues to stand overnight after stirring 5h, and suction filtration obtains light yellow liquid.Successively with HCl (1mol/L), NaOH (1mol/L), steaming
Distilled water washing, retains supernatant, is dried, filtered with anhydrous sodium sulfate, removes solvent, obtaining lurid solid is object material
Expect HEMA-Ad；
Function monomer (assembly) preparation: by 212mg T-CD ultrasonic disperse into 6mL pure water, 10mg HEMA-Ad is added
(~20eq.) it is stirred at room temperature and is lyophilized afterwards for 24 hours up to assembly powder；
Polymerization prepares coating: by obtained assembly powder (200mg) ultrasonic disperse into 6mL dehydrated alcohol, being added
0.4mL HEMA and 5mg AIBN polymerize 12h under the conditions of 55 DEG C to obtain the final product.
Coating application: by obtained applying coating on PVC sample item, coating, the coating are formed in 30min at room temperature
95% ultraviolet light can be absorbed, for 24 hours with high-pressure sodium lamp (500W) irradiation, by contrast, shielded sample and initial sample are basic
Unanimously, unprotected sample has obvious aging rice seed, as shown in Figure 1；Scratch is manufactured with scalpel on its surface, in scratch table
20 μ L pure water are added dropwise in face, and selfreparing can be completed in 15min, and scratch disappears.
Embodiment 2
Ultraviolet absorbing agent subject preparation: 5g SiO215g 3- amino is added in the ultrasonic disperse 30min in 100mL toluene
Propyl-triethoxysilicane (APES), flow back under the conditions of 115 DEG C 6h, filters (polycarbonate membrane, 0.22 μm) after having reacted, uses first
Benzene washs completely, is dried in vacuo at room temperature after filtering for 24 hours up to APES-SiO2；2g APES-SiO2It is scattered in 50mL dimethyl methyl
In amide (DMF), it will be added dissolved with the DMF solution of 0.25g beta cyclodextrin-p-methyl benzenesulfonic acid ester (β-CD-Ts), and be warming up to 60 DEG C,
In N2Protection is lower to stir 7h, stands overnight at room temperature, collects product and uses DMF, acetone washing respectively, is drying to obtain in air
Ultraviolet absorbing agent main body Si-CD；
Guest materials preparation: hydroxyethyl meth acrylate (HEMA) (15mmol), tripropyl amine (TPA) (23mmol) are dissolved in
In 200mL anhydrous methylene chloride (0-5 DEG C), the methylene chloride being then added dropwise dissolved with 3.7g adamantane formyl chloride (18.6mmol) is molten
Liquid continues to stand overnight after stirring 5h, and suction filtration obtains light yellow liquid.Successively with HCl (1mol/L), NaOH (1mol/L), steaming
Distilled water washing, retains supernatant, is dried, filtered with anhydrous sodium sulfate, removes solvent, obtaining lurid solid is object material
Expect HEMA-Ad；
Function monomer (assembly) preparation: by 212mg Si-CD ultrasonic disperse into 6mL pure water, 10mg HEMA- is added
Ad (~20eq.), which is stirred at room temperature, to be lyophilized afterwards for 24 hours up to assembly powder；
Polymerization prepares coating: obtained 200mg assembly powder ultrasonic being distributed in 6mL DMSO, 2mL propylene is added
Acid butyl ester and 5mg azobisisoheptonitrile (AVBN) polymerize 12h under the conditions of 55 DEG C to obtain the final product.
Coating application: by obtained applying coating on polyethylene specimen item, forming coating at room temperature in 30min, should
95% ultraviolet light can be absorbed in coating, for 24 hours with high-pressure sodium lamp (500W) irradiation, by contrast, shielded sample and initial sample
It is almost the same, and unprotected sample has obvious aging rice seed；Scratch is manufactured with scalpel on its surface, is added dropwise on scratch surface
Selfreparing can be completed in 20 μ L pure water, 15min, and scratch disappears.
Embodiment 3
Ultraviolet absorbing agent subject preparation: 15g α-CD is dissolved in 100g 65wt%ZnCl2In aqueous solution, stirred under the conditions of 80 DEG C
(500r/min) is mixed, 15wt%NaOH solution is added dropwise and adjusts pH to 8.4, continues to be centrifugated after stirring 30min, product is used
Milli-Q water obtains ultraviolet absorbing agent main body ZnO-CD；
Guest materials: guest materials select have can reactive functionality amino P-aminoazobenzene (Azo-NH2)；
Function monomer (assembly) preparation: main body ZnO-CD 300mg ultrasonic disperse obtained is water-soluble to 10mL DMSO
In liquid (DMSO/ water=9:1), Azo-NH is added2(~15eq.) it is stirred at room temperature for 24 hours, assembling liquid solution is made；
Polymerization prepares coating and application: 1g basis material --- bisphenol-A ring being added into 10mL assembling liquid solution (330mg)
The DMSO solution of oxygen resin, quickly ultrasound removes bubble after mixing, and coated on wood sample item, combined polymerization solidifies at 40 DEG C
Coating is formed in 30 hours, which can be absorbed 95% ultraviolet light, for 24 hours, by contrast, be protected with high-pressure sodium lamp (500W) irradiation
The sample of shield and initial sample are almost the same, and unprotected sample has obvious aging rice seed；It is manufactured on its surface with scalpel
20 μ L pure water are added dropwise on scratch surface in scratch, and selfreparing can be completed in 15min, and scratch disappears.
Embodiment 4
Ultraviolet absorbing agent subject preparation: by the β-CD (CMCD) of 1g carboxylated and 150.0mg 4,4'- diamino hexichol
Ketone (DBPO) is dissolved in the anhydrous n,N-Dimethylformamide of 10mL (DMF), at 260.0mg dicyclohexylcarbodiimide (DCC)
It is reacted at room temperature under catalyst for 24 hours afterwards with acetone repeated precipitation 3 times up to ultraviolet absorbing agent main body CD-DBPO；
Guest materials preparation: 2.0g ferrocenecarboxylic acid (Fc-COOH) and 0.13g 4-dimethylaminopyridine (DMAP) are weighed
It is dissolved in 30mL anhydrous tetrahydro furan (THF), is subsequently added into 1.5mL tetrahydroxy butyl acrylate (HBMA), is stirred in ice bath
After 10min be added dropwise the DCC containing 2.7g anhydrous THF solution, react at room temperature for 24 hours, filter off insoluble matter, after being spin-dried for silicagel column into
Row purifying (ethyl acetate: petroleum ether=1:20), obtains guest materials Fc-HBMA；
Function monomer (assembly) preparation: by 106mg CD-DBPO ultrasonic disperse into 6mL DMF, 24mg is added
HEMA-Ad (~2eq.), which is stirred at room temperature, to be lyophilized afterwards for 24 hours up to assembly powder；
Polymerization prepares coating: by obtained assembly powder 96mg ultrasonic disperse into 6mL DMF, 1.8mL HBMA is added
With 5mg AIBN, it polymerize 12h under the conditions of 55 DEG C to obtain the final product.
Coating application: by obtained applying coating on PVC sample item, coating, the coating are formed in 30min at room temperature
96% ultraviolet light can be absorbed, for 24 hours with high-pressure sodium lamp (500W) irradiation, by contrast, shielded sample and initial sample are basic
Unanimously, unprotected sample has obvious aging rice seed；Scratch is manufactured with scalpel on its surface, 20 μ L are added dropwise on scratch surface
Selfreparing can be completed in pure water, 15min, and scratch disappears.
Embodiment 5
Ultraviolet absorbing agent subject preparation: ultraviolet absorbing agent has inorganic ultraviolet absorbent ZnO-CD and organic uv
Two kinds of absorbent CD-DBPO.Preparation method is shown in embodiment 3 and embodiment 4 respectively；
Guest materials is Fc-HBMA, and preparation method is shown in embodiment 4；
Function monomer (assembly) preparation: by 150mg CD-DBPO and 150mgZnO-CD, ultrasonic disperse is pure to 6mL simultaneously
In water, in 10mLDMSO aqueous solution in (DMSO/ water=9:1), addition Fc-HBMA (~15eq.) is stirred at room temperature to be made for 24 hours
Assemble liquid solution；
Coating preparation and application: 2.4mL HBMA, 1mL ethyl acrylate are added into 10mL assembling liquid solution (300mg)
With 5mg dibenzoyl peroxide BPO, it polymerize 12h under the conditions of 70 DEG C to obtain the final product.By obtained applying coating on wood sample item
Coating is formed, which can be absorbed 95% ultraviolet light, for 24 hours with high-pressure sodium lamp (500W) irradiation, and by contrast, shielded sample
It is almost the same with initial sample, and unprotected sample has obvious aging rice seed；Scratch is manufactured with scalpel on its surface, is being drawn
20 μ L pure water are added dropwise in trace surface, and selfreparing can be completed in 15min, and scratch disappears, as shown in Figure 2 and Figure 3.
Claims (5)
1. a kind of anti-ultraviolet paint for having self-repair function, it is characterised in that: by containing host-guest inclusion and polymerizable object
Function monomer, the polymeric matrix monomer of functional group are copolymerized to obtain；The function monomer is mainly by cyclodextrin modified ultraviolet light
Absorbent and guest materials are made；The polymeric matrix monomer is coating matrix material；The ultraviolet absorbing agent and coating
Basis material is linked together by the supermolecular mechanism power of cyclodextrin host-guest inclusion；The function monomer and coating matrix material
The mass ratio of material is 0.05~0.5:1；The function monomer is mainly made by following raw materials: cyclodextrin modified ultraviolet radiation absorption
The guest materials of agent and 1.5~40 equivalents；The cyclodextrin modified ultraviolet absorbing agent is mainly made by following raw materials: quality
Than the cyclodextrin and ultraviolet absorbing agent for 0.1~10:1；Containing being included with cyclodextrin in the guest materials molecule
First functional group and the second functional group that polymerization reaction occurs with coating matrix material；The coating matrix material be HEMA,
HBMA, ethyl acrylate, butyl acrylate or bisphenol A epoxide resin；First functional group is ferrocene, adamantane or azo
Benzene functional group, the second functional group are double bond, amino or isocyanate functional group.
2. a kind of anti-ultraviolet paint for having self-repair function according to claim 1, it is characterised in that: described ultraviolet
Light absorbers are organic uv absorbers and/or inorganic ultraviolet absorbent.
3. a kind of anti-ultraviolet paint for having self-repair function according to claim 1 or 2, it is characterised in that: described
Cyclodextrin is the cyclic oligosaccharide or/and its derivative of the glucopyranose molecules containing 6 or more.
4. a kind of preparation method of anti-ultraviolet paint for having self-repair function described in claim 1, which is characterized in that packet
Include following steps:
(1) it ultraviolet absorbing agent subject preparation: using being chemically or physically modified by cyclodextrin modified on ultraviolet absorbing agent, makes
Obtain cyclodextrin modified ultraviolet absorbing agent, i.e. ultraviolet absorbing agent main body；The quality of the cyclodextrin and ultraviolet absorbing agent
Than for 0.1~10:1；
(2) prepared by function monomer: in a solvent by ultraviolet absorbing agent main body ultrasonic disperse made from step (1), addition 1.5~
The guest materials of 40 equivalents stirs at room temperature obtains assembly afterwards for 24 hours, this assembly is function monomer；The guest materials molecule
In the second function containing the first functional group for being included with cyclodextrin and with coating matrix material generation polymerization reaction
Group；First functional group is ferrocene, adamantane or azobenzene functional group, and the second functional group is double bond, amino or different
Cyanate functional group,
(3) polymerization prepares coating: function monomer made from step (2) being distributed in polymer solvent, coating matrix material is added
It is carried out copolyreaction 1-48 hours with initiator, obtains sol form anti-ultraviolet paint；The coating matrix material be HEMA,
HBMA, ethyl acrylate, butyl acrylate or bisphenol A epoxide resin；The dosage of the function monomer is the coating matrix material
The 5%-50%wt of material list body.
5. a kind of application of anti-ultraviolet paint for having self-repair function according to claim 1, it is characterised in that: institute
Different base material surface formation protective coating can be coated in by obtaining coating, which can reach in the absorptivity of ultraviolet region
To 95%；After substrate material surface forms coating, the mechanical damage on surface can be automatically repaired with the help of water.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710092246.XA CN106590310B (en) | 2017-02-21 | 2017-02-21 | A kind of anti-ultraviolet paint having self-repair function, preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710092246.XA CN106590310B (en) | 2017-02-21 | 2017-02-21 | A kind of anti-ultraviolet paint having self-repair function, preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106590310A CN106590310A (en) | 2017-04-26 |
| CN106590310B true CN106590310B (en) | 2019-04-19 |
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| CN107955098A (en) * | 2017-12-01 | 2018-04-24 | 广东电网有限责任公司电力科学研究院 | A kind of elastomer and preparation method thereof |
| CN109134951A (en) * | 2018-08-28 | 2019-01-04 | 广东电网有限责任公司 | A kind of self-healing cable outer sheath material, preparation method and its method for coating |
| CN109181453A (en) * | 2018-09-27 | 2019-01-11 | 广东电网有限责任公司 | A kind of ultraviolet shielded coating of self-healing and preparation method thereof |
| CN109694479B (en) * | 2018-12-29 | 2021-05-28 | 广东工业大学 | Supermolecular material and host-guest self-assembly hydrogel and preparation method thereof |
| CN111117263A (en) * | 2019-12-30 | 2020-05-08 | 武汉华星光电半导体显示技术有限公司 | Polyimide composite, preparation method and application thereof |
| CN111303713A (en) * | 2020-04-27 | 2020-06-19 | 成都新柯力化工科技有限公司 | Ultraviolet light aging resistant environment-friendly coating and preparation method thereof |
| CN113698535A (en) * | 2020-05-21 | 2021-11-26 | 江苏百赛飞生物科技有限公司 | Polymer, composition, coating thereof and product |
| CN113603823B (en) * | 2021-09-10 | 2022-05-03 | 广东电网有限责任公司 | Anti-ultraviolet repair material and preparation method and application thereof |
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