CN108586699A - The antifouling anti-graffiti auxiliary agent of one kind and its application - Google Patents
The antifouling anti-graffiti auxiliary agent of one kind and its application Download PDFInfo
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- CN108586699A CN108586699A CN201810384315.9A CN201810384315A CN108586699A CN 108586699 A CN108586699 A CN 108586699A CN 201810384315 A CN201810384315 A CN 201810384315A CN 108586699 A CN108586699 A CN 108586699A
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- auxiliary agent
- antifouling anti
- graffiti
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- graffiti auxiliary
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- 0 CCC*1C(*(C)C*(C)C=NCCC*(C)(O*(C)(C)C)O[Si](C)(C)OC)=*1 Chemical compound CCC*1C(*(C)C*(C)C=NCCC*(C)(O*(C)(C)C)O[Si](C)(C)OC)=*1 0.000 description 2
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
- C08G18/673—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen containing two or more acrylate or alkylacrylate ester groups
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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
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
- C09D5/1637—Macromolecular compounds
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
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Abstract
The invention discloses a kind of antifouling anti-graffiti auxiliary agent and its applications, the auxiliary agent on the basis of perfluoropolyether group by introducing the groups such as organopolysiloxane segment, multiple photocuring active groups and CO NH, and it is combined by specific nitrogen-atoms, so that auxiliary agent has good intermiscibility and adhesive force with UV paint films, perfluoropolyether segment relocation site can be made more thorough, the antifouling property and wear-resisting property of UV coating are improved, is applied：Its application in antifouling anti-graffiti UV photocureable coating.
Description
Technical field
The invention belongs to polymeric material field more particularly to the auxiliary agents of UV photocureable coating, and in particular to Yi Zhongfang
Dirty anti-graffiti auxiliary agent and its application.
Background technology
UV photocureable coating has curing rate fast, saves the energy, volatile organic compounds (VOC) is free of, to environment
Pollute small, cured product performance is good, the advantages that being suitable for high-speed automated production, is the main substitute of traditional coating, more next
More paid attention to by coating circle.However, containing a large amount of carbonyl isopolarity functional group since UV coating is formed by paint film, cause
The anti-scribble poor performance of anti-pollution of paint film.Antifouling, the anti-sticking and antigraffiti properties for improving existing UV coating coating surface are always to apply
The hot and difficult issue for expecting research, is particularly applied to the 3C coating and display on the surfaces such as computer, communication and consumer electronics
With the rigidity-increasing dope of the optics film surface such as touch screen, also it is useful for the low-surface-energies such as anti-doodling paint of prevention city psoriasis and applies
Material.Technically, the hydrophobic oleophobic function of material surface is realized, there are mainly two types of approach, first, being added in material surface
Low-surface energy substance, mainly Organic fluoride and organosilicon；Second is that building coarse structure in material surface.It is to grind without doubt
Study carefully and add a kind of efficient anti-pollution auxiliary agent in existing formulation for coating material, the other performance without changing original coating is a kind of fast
Prompt, efficient and practical method.
Perfluoropolyether (PFPE) is a kind of fluorine of safety and environmental protection without containing environment cumulative bad chemical compositions such as PFOA, PFCS
Source.It is poor with other hydrocarbon component intermiscibilities in coating, floats on the surface of paint film in film forming procedure in meeting, reduces the surface of paint film
Can, finally realize the functions such as grease proofing, waterproof and dustproof.Chinese invention patent CN106220839A discloses a kind of holo-fluorine polyester
Anti-graffiti auxiliary agent and preparation method thereof, structural formula is as follows：
Wherein, n is natural number and 2≤n≤30；X is R1N(R2)-or-HN-
R2, R1、R2The respectively substituent group containing polyurethane structural, and alcoholic extract hydroxyl group is contained in the end of X.But this compound mainly contains
The groups such as polyurethane structural, alcoholic extract hydroxyl group are dfficult to apply in UV photocureable coating, the poor compatibility in UV photocureable coating,
It is difficult to play its antifouling anti-graffiti function.
For another example patent of invention CN2005800145739 discloses a kind of perfluoropolyether-modified acrylic acid with antifouling effect
Ester, the compound of this patent disclosure is applied to after coating, and for coating in UV Light Curings occur, the oxygen in air can be to solid
Change and generate oxygen inhibition effect, and the adhesive force and compatibility of this compound and paint film are all poor, and then can using in product
In journey occur perfluoropolyether be constantly detached from coating surface, eventually lead to paint film anti-pollution function durability be deteriorated, though therefore its
Certain antifouling wearability is so realized, but effect is still undesirable.
Invention content
The technical problem to be solved by the present invention is to overcome the deficiencies of the prior art and provide a kind of antifouling anti-graffiti auxiliary agent,
It can be applied in UV photocureable coating, and realize antifouling antigraffiti properties steady in a long-term, and wearability is good.
The present invention also provides a kind of antifouling anti-graffiti UV photocureable coating.
In order to solve the above technical problems, a kind of technical solution that the present invention uses is as follows：
A kind of antifouling anti-graffiti auxiliary agent, the antifouling anti-graffiti auxiliary agent have the following structure general formula：
Wherein, RfFor perfluoro polyether acyl group；
RSiFor organopolysiloxane radicals, tertiary N atom and silicon atom one of on the organopolysiloxane radicals
It is connected directly or is indirectly connected；
RAFor the organic group containing photocuring active group He-CO-NH-, wherein the photocuring active group has
It is multiple；
X is the organic group containing secondary amino group, nitrogen-atoms and the perfluoro polyether acyl of the X by the secondary amino group
Group is connected.
Some preferred aspects according to the present invention, the perfluoro polyether acyl group are one in group as follows
Kind or a variety of combinations：
Wherein, 50 >=a >=2；
Wherein, 50 >=b >=2；
Wherein, 50 >=c >=2,50 >=d >=2；
Wherein, 50 >=e >=2,50 >=f >=2.
Some preferred aspects according to the present invention, the photocuring active group are unsubstituted acrylate-functional groups
And/or C1-10Alkyl-substituted acrylate-functional groups.The structural formula of acrylate-functional groups is CH2=CHCOO, alkyl take
The acrylate-functional groups in generation can be CH2=C (CH3)COO、CH2=C (CH2CH3)COO、CH2=C (CH2CH2CH3)COO、
CH2=C (CH2CH2CH2CH3) COO etc..
Some preferred aspects according to the present invention, the photocuring active group have at least three and are located at the RA's
End.
Some preferred aspects according to the present invention, the RAPass through the carbon and tertiary N atom phase on one of them-CO-NH-
Even.
Some preferred aspects according to the present invention, the RAFor：
-CO-NH-R2-NH-COO-R3Or-CO-NH-R4-N(CO-NH-R5-NH-COO-R6)2, wherein
The R2To be selected fromR7For-NH-
CO-O-R8- O-CO-NH-, the R8To be selected from C1-10Alkylidene ,-(CH2CH2O)r2-CH2 CH2-、-(CH2CH2CH2O)r3-
CH2CH2CH2-、-(CH2CH2CH2CH2O)r4-CH2CH2 CH2CH2-、-(O-(CH2)4-O-CO-(CH2)4-CO)t-O-(CH2)4In
One or more combinations, r1, r2, r3, r4, t separately be selected from positive integer；It is highly preferred that C1-10Alkylidene can
Think-CH2-、-CH2CH2-、-CH2CH2CH2-、-CH2CH2CH2CH2-、 -CH2CH2CH2CH2CH2-、-
CH2CH2CH2CH2CH2CH2-、-CH(CH3)CH2-、-C(CH3) 2CH2-；R1, r2, r3, r4, t are separately in 1-100
Integer.Some specific aspects according to the present invention, r1, r2, r3, r4, t separately integer in 1-20.
R4、R5Separately it is selected from C1-20Alkylidene group；Specifically, R4、R5Separately it is selected from C1-10Asia
Alkyl group.Some specific aspects according to the present invention, R4、R5Separately it is selected from-CH2-、-CH2CH2-、-
CH2CH2CH2-、-CH2CH2CH2CH2-、-CH2CH2CH2CH2CH2-、 -CH2CH2CH2CH2CH2CH2-、-CH(CH3)CH2-、-C
(CH3)2CH2In one kind.
R3、R6Separately it is selected from：-(CH2)j-C(CH2OOC-CH=CH2)3, or,
-(CH2)k-C(CH2OOC-CH=CH2)2-CH2-O-CH2-C(CH2OOC-CH=CH2)3, wherein j, k are independently
Ground is selected from positive integer.It is highly preferred that j, k separately integer in 1-100.Specific side more according to the present invention
Face, j, k separately integer in 1-20.
In the present invention,It can be connected with other groups at position shown in indicating.
Some preferred aspects according to the present invention, the organopolysiloxane radicals are (CH3)3 Si-O-Si(CH3)(O-
(Si(CH3)2-O)g-Si(CH3)3)-R9, wherein R9For C1-20Alkylidene group, 20 >=g >=4.It is highly preferred that R9For
C1-10Alkylidene group.Some specific aspects according to the present invention, R9Can be-CH2-、-CH2CH2-、-CH2CH2CH2-、-
CH2CH2CH2CH2-、 -CH2CH2CH2CH2CH2-、-CH2CH2CH2CH2CH2CH2-、-CH(CH3)CH2-、-C(CH3) 2CH2-。
Some preferred aspects according to the present invention, the X are-R10- NH-, wherein R10For C1-20Alkylidene group.More
Preferably, R10For C1-10Alkylidene group.Some specific aspects according to the present invention, R10Can be-CH2-、-CH2CH2-、-
CH2CH2CH2-、-CH2CH2CH2CH2-、 -CH2CH2CH2CH2CH2-、-CH2CH2CH2CH2CH2CH2-、-CH(CH3)CH2-、-C
(CH3) 2CH2-。
More according to the present invention specific and preferred aspect, the antifouling anti-graffiti auxiliary agent are in following structural formula
One kind：
Formula I -1,
Wherein, 50 >=a >=2,20 >=g >=3, PTHF represent polytetrahydrofuran ether glycol molecule segment；
Formula I -2,
Wherein, 50 >=a >=2,20 >=g >=3；
Formula I -3,
Wherein, 50 >=a >=2,20 >=g >=3；
Formula I -4,
Wherein, 50 >=a >=2,20 >=g >=3,20 >=t >=2；
Formula I -5,
Wherein, 50 >=a >=2,20 >=g >=3；
Formula I -6,
Wherein, 50 >=a >=2,20 >=g >=3；
Formula I -7,
Wherein, 50 >=a >=2,20 >=g >=3,20 >=t >=2.
Another technical solution provided by the invention：A kind of antifouling anti-graffiti UV photocureable coating, raw material contain above-mentioned institute
The antifouling anti-graffiti auxiliary agent stated.
Due to the implementation of above-mentioned technical proposal, the present invention has the following advantages that compared with prior art：
The materials compatibility of antifouling anti-graffiti auxiliary agent provided by the invention and UV photocureable coating is good, the migration in paint film
Property it is strong, can make the perfluoropolyether group contained in auxiliary agent during coating forms a film quickly and thoroughly migrate to paint film
Surface and reach excellent antifouling anti-graffiti and other effects, while can also realize it is stronger with the adhesive force of paint film, in product
It will not fall off during use, and then ensure that steady in a long-term antifouling anti-graffiti and other effects of paint film, wearability is more preferable.
Description of the drawings
Fig. 1 is the nuclear-magnetism H of the PFPE-1 of embodiment 11NMR analysis of spectra.
Specific implementation mode
The preparation method of the antifouling anti-graffiti auxiliary agent of the present invention, the preparation method include the following steps：
1) it will be hydrolyzed simultaneously containing the alkoxy silane coupling agent of primary amino group and secondary amino group, head product obtained, then first
Polycondensation reaction is occurred into for gained head product and siloxanes ring body, organosilicon end capping agent in the presence of catalyst, generates amido silicon oil production
Object 1；
2) so that amido silicon oil product 1 prepared by step 1) is carried out amidation process with per-fluoro polyether compound, generate product
2；
3) in the presence of the second catalyst, in the presence of polymerization inhibitor, make isocyanate compound and hydroxyl third in a solvent
Enoic acid ester compounds react, and generate product 3；
4) product 3 prepared by step 3) is added in the product 2 prepared to step 2), reaction generates described antifouling anti-graffiti
Auxiliary agent.
The preparation method of the antifouling anti-graffiti auxiliary agent of the present invention is simple, easy to operate, and reaction condition is mild, preparation process peace
Entirely, environmentally friendly.
Some preferred aspects according to the present invention, the alkoxy silane coupling agent containing primary amino group and secondary amino group simultaneously
Can be N- (β-aminoethyl)-γ-aminopropyltriethoxies dimethoxysilanes and/or N- (β-aminoethyl)-γ-aminopropyltriethoxies two
Ethoxysilane.
Some preferred aspects according to the present invention in step 1), make the hydrolysis be carried out in desalted water.
Some preferred aspects according to the present invention, first catalyst are basic catalyst, the basic catalyst choosing
From one or more combinations in potassium hydroxide, sodium hydroxide and tetramethylammonium hydroxide.
Some preferred aspects according to the present invention, the siloxanes ring body are selected from octamethylcy-clotetrasiloxane, hexamethyl
One or more combinations in cyclotrisiloxane and decamethylcyclopentaandoxane.
Some preferred aspects according to the present invention, the organosilicon end capping agent are hexamethyldisiloxane, three silicon of prestox
One or more combinations in oxygen alkane and decamethyl tetrasiloxane.
Some preferred aspects according to the present invention, in step 1), the hydrolysis carries out at 10 DEG C~200 DEG C, when reaction
Between be 1~12 hour.It is highly preferred that in step 1), the hydrolysis carries out at 10 DEG C~100 DEG C, and the reaction time is 2~8 small
When.
Some preferred aspects according to the present invention, in step 1), the polycondensation reaction carries out at 10 DEG C~200 DEG C, instead
It is 1~12 hour between seasonable.It is highly preferred that in step 1), the polycondensation reaction carries out at 80 DEG C~200 DEG C, the reaction time
It is 2~8 hours.
Some preferred aspects according to the present invention make the amidation process of step 2) (such as can be in protective gas
For nitrogen etc.) in the presence of carry out.
The general structure of some preferred aspects according to the present invention, the per-fluoro polyether compound is RfOR11, wherein R11
For C1-10Alkyl.Some specific aspects according to the present invention, R11Can be-CH3、-CH2CH3、 -CH2CH2CH3、-
CH2CH2CH2CH3、-CH2CH2CH2CH2CH3、-CH2CH2CH2CH2CH2CH3、-CH(CH3)CH3Or-C (CH3)2CH3。
Some preferred aspects according to the present invention, in step 2), make the amidation process at 50 DEG C~200 DEG C into
Row, reaction time are 1~12 hour.It is highly preferred that in step 2), the amidation process is made to be carried out at 50 DEG C~150 DEG C,
Reaction time is 3~12 hours.It is further preferred that in step 2), make the amidation process at 50 DEG C~120 DEG C into
Row, reaction time are 3~10 hours.
Some preferred aspects according to the present invention, second catalyst can be choose triethylamine, butyl tetra titanate,
Dibutyltin dilaurate, stannous octoate, one kind in two (dodecyl sulphur) dibutyl tins and dibutyltin diacetate or
A variety of combinations.
Some preferred aspects according to the present invention, the polymerization inhibitor are selected from hydroquinone, 1,4-benzoquinone, methylnaphthohydroquinone, right
Hydroxyanisol, 2- tert-butyl hydroquinone and 2, one or more combinations in 5- di-tert-butyl hydroquinones.
Some preferred aspects according to the present invention, in step 3), the solvent is selected from ethyl acetate, ethyl ester propyl, second
One or more combinations in acid butyl ester, pentyl acetate, butanone, methyl butyl ketone and methyl iso-butyl ketone (MIBK).
Some preferred aspects according to the present invention, the isocyanate compound be selected from isophorone diisocyanate and
Its tripolymer, toluene di-isocyanate(TDI) and its dimer, tripolymer, hexamethylene diisocyanate and its dimer, tripolymer,
One or more combinations in dicyclohexyl methyl hydride diisocyanate.Can also be above-mentioned isocyanates reacts with dihydric alcohol
Product, wherein the dihydric alcohol is selected from polytetrahydrofuran ether glycol, polyethylene glycol, polypropylene glycol, polyethylene glycol the third two
One or more combinations in alcohol copolymer.When the isocyanate compound is reacting for above-mentioned isocyanates and dihydric alcohol
When product, the specific implementation mode of step 3) is：First make above-mentioned isocyanates anti-in the presence of the second catalyst with dihydric alcohol
The performed polymer product that NCO is blocked should be generated, and (for convenience of description, referred to as step a) adds polymerization inhibitor and hydroxy acrylic acid esterification
Object is closed, (for convenience of description, referred to as step b), generation contain NCO and the product of acrylate-functional groups 3 for reaction.
Some preferred aspects according to the present invention, the hydroxy acrylic acid ester compounds can be hydroxy-ethyl acrylate, first
Base hydroxy-ethyl acrylate, hydroxypropyl acrylate, hydroxy propyl methacrylate, hy-droxybutyl, methacrylate, season
One or more combinations of penta tetrol triacrylate, dipentaerythritol tetraacrylate etc..
Some preferred aspects according to the present invention in step 3), make the reaction be carried out at 20~150 DEG C, when reaction
Between be 1~12 hour.
Some preferred aspects according to the present invention, in step 3), when the isocyanate compound is above-mentioned isocyanates
When with the reaction product of dihydric alcohol, step a is made to be carried out at 60~150 DEG C.
Some preferred aspects according to the present invention, in step 3), when the isocyanate compound is above-mentioned isocyanates
When with the reaction product of dihydric alcohol, step b is made to be carried out at 20~80 DEG C.
Some preferred aspects according to the present invention in step 4), make the reaction be carried out at 0 DEG C~80 DEG C, when reaction
Between be 2~12 hours.
Some specific aspects according to the present invention, the embodiment of step 4) are：In the product 2 prepared to step 2) slowly
Product 3 prepared by step 3) is instilled, reaction.
Antifouling anti-graffiti UV photocureable coating provided by the invention, in terms of parts by weight, composition of raw materials includes：
Wherein, the UV living oligomers can choose unsaturated polyester resin, the ring containing acrylate-functional groups
Oxygen resin, the polyester resin containing acrylate-functional groups, contains acrylic acid at the polyurethane resin containing acrylate-functional groups
One or more groups in the polyethers of ester functional group and polydiorganosiloxanewith resin containing acrylate-functional groups etc.
It closes.
It is mono- that the UV reactive diluents can choose single functionality UV monomers, bifunctionality UV monomers and 3 degree of functionality UV
One or more combinations in body etc..Some routine UV monomers in the prior art are chosen, are not specifically limited herein.
The UV paint solvents can choose ethyl alcohol, isopropanol, normal propyl alcohol, ethyl acetate, ethyl ester propyl, acetic acid fourth
One or more combinations in ester, pentyl acetate, butanone, methyl ethyl ketone, methyl butyl ketone and methyl iso-butyl ketone (MIBK) etc.,
It can be needed not add according to practice of construction.
The photoinitiator can choose 2- hydroxy-2-methyl -1- phenylacetones, 1- hydroxycyclohexyl phenyl ketones,
2- methyl -2- (4- morpholinyls) -1- [4- (methyl mercapto) phenyl] -1- acetone, the oxidation of 2,4,6- trimethylbenzoy-diphenies
Phosphine, 2,4,6- trimethylbenzoyl phenyls phosphinic acid ethyl ester, 2- dimethylamino -2- benzyls -1- [4- (4- morpholinyls) phenyl] -
One or more combinations in 1- butanone, 2- hydroxy-2-methyls -1- [4- (2- hydroxyl-oxethyls) phenyl] -1- acetone etc..
According to actual operation requirements, to avoid the generation of VOC, retarder thinner that from can using；Appropriate, mesh can also be added
Be reduce coating viscosity, improve workability.
In the present invention, raw material described in whole can not have by commercially available and/or take known means and be prepared
When being illustrated, it is satisfied by the requirement of standard chemical products.
Said program is described further below in conjunction with specific embodiment；It should be understood that these embodiments are for illustrating
The basic principles, principal features and advantages of the present invention, and the present invention is not by the scope limitation of following embodiment；It is used in embodiment
Implementation condition further adjustment can be done according to specific requirement, the implementation condition being not specified is usually the item in routine experiment
Part.
Embodiment 1
The present embodiment provides a kind of antifouling anti-graffiti auxiliary agent 1# samples (PFPE-1), the structural formula of PFPE-1 is as follows：
Wherein, a=11, g=8, PTHF represent polytetrahydrofuran ether glycol molecule segment.
The preparation method of PFPE-1 is as follows：
N- (β-aminoethyl)-γ-aminopropyltriethoxy dimethoxysilane 21g and desalted water are added in the three-necked flask of 1L
20g, stirs hydrolysis 5 hours under the conditions of 50 DEG C, slowly opens negative pressure and is dehydrated the dry silane low-boiling-point substance of acquisition；It adds
Potassium hydroxide powder (0.02g), octamethylcy-clotetrasiloxane (60g) and hexamethyldisiloxane (16.2g), are to slowly warm up to
130 DEG C, it is 4 hours to be stirred to react the time, most obtains dry amido silicon oil through vacuum removal low-boiling-point substance technique afterwards；It is protected in nitrogen
(200g, structural formula is as follows, wherein R for addition perfluoropolyether methanol ester in above-mentioned product under shieldfChoose hexafluoropropylene oxide
Polymerized unit, Taicang Zhonghua Environmental Protection Medical Co., Ltd. provide), 80 DEG C are to slowly warm up to, the reaction time is 8 hours, is obtained complete
Perfluoroalkyl polyether modified amino silicon oil.
Dibutyltindilaurylmercaptide cinnamic acid tin (8g) is added in the three-necked flask of 1L, isophorone diisocyanate (44g), gathers
Tetrahydrofuran ether glycol (100g, molecular weight are 1000g/mol) and butyl acetate (200g), are to slowly warm up under nitrogen protection
80 DEG C, it is 2 hours to be stirred to react, and obtains isocyanate prepolymer；Reaction system is cooled to 50 DEG C, and polymerization inhibitor para hydroxybenzene is added
Methyl ether (1g) is slowly added to pentaerythritol triacrylate (31g) under agitation, obtains the acroleic acid esterification containing NCO
Object is closed, then adds solvent acetic acid butyl ester (900g)；Controlling reaction temperature is 10 DEG C, under agitation slowly drips above-mentioned product
Enter in perfluoropolyether-modified amido silicon oil, the reaction time is 4 hours, and sampling carries out the peaks infrared spectrum analysis NCO and disappears, to reaction
Product at reduced pressure removes solvent, and antifouling anti-graffiti auxiliary agent PFPE-1 is made.
Involved raw material perfluoropolyether methanol ester R in preparation methodfOCH3Middle RfStructure be：
Wherein, a=11.
Nuclear-magnetism H is carried out to product PFPE-1 compounds1NMR is analyzed, the H of PFPE-11NMR analysis results as shown in Figure 1, by
Known to Fig. 1：Mixed and disorderly chemical shift peak within the scope of 0ppm~0.2ppm belongs to silicon onychostroma in dimethyl silicone polymer side group
The absorption peak of son；Mixed and disorderly chemical shift peak within the scope of 1.0ppm~2.0ppm belongs among polytetrahydrofuran ether glycol two
Proton uptake peak on methylene and isophorone Molecular Ring；Mixed and disorderly chemical shift peak ownership within the scope of 2.5ppm~3.7ppm
In dimethyl silicone polymer side chain is poly- and isophorone Molecular Ring on be connected with urea groups (or amide groups and urethane bond)
Be connected in the absorption peak and tetrahydrofuran ether glycol segment of methylene with oxygen atom the proton uptake peaks of two methylene；
Mixed and disorderly chemical shift peak within the scope of 4.0ppm~4.2ppm belong in polytetrahydrofuran ether glycol with urethane bond phase
The absorption peak of methylene even and the absorption peak of the methylene on pentaerythrite；Occur in the range of 5.5~6.5ppm
Chemical shift of proton peak in double bond in acrylate structural, it was demonstrated that acrylate-functional groups have been successfully introduced on strand.
Embodiment 2
The present embodiment provides a kind of antifouling anti-graffiti auxiliary agent 2# samples (PFPE-2).
According to the step and technique shown in embodiment 1, polytetrahydrofuran ether glycol molecular weight is changed to 2000g/mol,
Quality is changed to 200g, and solvent acetic acid butyl ester quality is changed to 1150g, remaining condition and quality are same as Example 1, is made
Antifouling anti-graffiti auxiliary agent 2# samples (PFPE-2).
Embodiment 3
The present embodiment provides a kind of antifouling anti-graffiti auxiliary agent 3# samples (PFPE-3).
N- (β-aminoethyl)-γ-aminopropyltriethoxy dimethoxysilane 21g and desalted water are added in the three-necked flask of 1L
20g, stirs hydrolysis 5 hours under the conditions of 50 DEG C, slowly opens negative pressure and is dehydrated the dry silane low-boiling-point substance of acquisition；It adds
Potassium hydroxide powder (0.02g), octamethylcy-clotetrasiloxane (60g) and hexamethyldisiloxane (16.2g), are to slowly warm up to
130 DEG C, it is 4 hours to be stirred to react the time, most obtains dry amido silicon oil through vacuum removal low-boiling-point substance technique afterwards；It is protected in nitrogen
(200g, structural formula is as follows, wherein R for addition perfluoropolyether methanol ester in above-mentioned product under shieldfChoose hexafluoropropylene oxide
Polymerized unit, Taicang Zhonghua Environmental Protection Medical Co., Ltd. provide), 80 DEG C are to slowly warm up to, the reaction time is 8 hours, is obtained complete
Perfluoroalkyl polyether modified amino silicon oil.
Isophorone diisocyanate (44g), p-hydroxyanisole (1g), dibutyl tin are added in the three-necked flask of 1L
Tin dilaurate tin (8g) and butyl acetate (200g), are to slowly warm up to 80 DEG C under nitrogen protection, under agitation will be above-mentioned
Product is slowly dropped into pentaerythritol triacrylate (31g), and it is 2 hours to react, and obtains the acrylate compounds containing NCO,
Solvent acetic acid butyl ester (600g) is added again；Controlling reaction temperature is 10 DEG C, is under agitation slowly dropped into above-mentioned product entirely
In perfluoroalkyl polyether modified amino silicon oil, the reaction time is 4 hours, and sampling carries out the peaks infrared spectrum analysis NCO and disappears, to reaction product
Antifouling anti-graffiti auxiliary agent PFPE-3 is made in removed under reduced pressure solvent.
Involved raw material perfluoropolyether methanol ester R in preparation methodfOCH3Middle RfStructure be：
Wherein, a=11；
The structural formula of product PFPE-3 is as follows：
Wherein, a=11, g=8.
Comparative example 1
This comparative example provides a kind of antifouling anti-graffiti auxiliary agent 4# samples (PFPE-4).
Perfluoropolyether methanol ester (100g, specification are identical as example 1) and ethylaminoethanol are added in the three-necked flask of 1L
(10g, specification are identical as example 1) is to slowly warm up to 80 DEG C, and the reaction time is 8 hours, and sampling infrared analysis measures the red of ester bond
Outer absorption peak (1792cm-1) disappear, amido bond absorption peak (1712cm-1) occur；Reaction product crude product is stirred with absolute methanol
Mix cleaning, stratification takes lower liquid, repetition 3 times, the de- low boiling drying of decompression, acquisition perfluoropolyether acylamino- second at 80 DEG C
Alcohol sterling；Hexafluoro dimethylbenzene (200g), p-hydroxyanisole (0.2g) and acryloyl chloride (4.5g) are added, is stirred at 50 DEG C
Reaction 2 hours depressurizes and takes off low-boiling-point substance, and drying finally obtains antifouling anti-graffiti auxiliary agent 4# samples (PFPE-4), and structural formula is as follows
It is shown.
Wherein, a=11.
Comparative example 2
This comparative example provides a kind of antifouling anti-graffiti auxiliary agent 5# samples (PFPE-5).
Perfluoropolyether methanol ester (100g, specification are identical as example 1) and ethylaminoethanol are added in the three-necked flask of 1L
(10g, specification are identical as example 1) is to slowly warm up to 80 DEG C, and the reaction time is 8 hours, and sampling infrared analysis measures the red of ester bond
Outer absorption peak (1792cm-1) disappear, amido bond absorption peak (1712cm-1) occur；Reaction product crude product is stirred with absolute methanol
Mix cleaning, stratification takes lower liquid, repeats 3 times, is depressurized at 80 DEG C and takes off low-boiling-point substance, dry, acquisition perfluoropolyether acyl ammonia
Base ethyl alcohol sterling；Add hexafluoro dimethylbenzene (200g), p-hydroxyanisole (0.2g) and isocyanates ethyl acrylate
(7.0g) is stirred to react 2 hours at 50 DEG C, and sampling infrared analysis measures NCO and disappears, and finally obtains antifouling anti-graffiti auxiliary agent 5#
Sample (PFPE-5), structural formula is as follows.
Wherein, a=11.
The preparation of coating
Compounding is carried out according to formula (each component additive amount is in parts by weight) shown in table 1 and prepares UV coating, then will be applied
Material is sprayed on makrolon (PC) plastic paint test board, the first levelling 5min at room temperature of paint film, then is placed in 80 DEG C of baking ovens
3min is toasted, is finally placed in RW-UVA201-20 type UV photo solidification machines and is cured, condition of cure is light source power 2kw, defeated
2.5 ms/min of transmission rate.In table, EB264 represents the three-functionality-degree aliphatic urethane acrylate of Qing Te companies production
EBECRYL 264, TPGDA represent tri (propylene glycol) diacrylate, and TMPTA represents trimethylolpropane trimethacrylate,
MEK represents methyl ethyl ketone, and UV184 represents 1- hydroxycyclohexyl phenyl ketones (photoinitiator, technical grade, the macro safe chemical industry of Jingjiang
Co., Ltd provides).
The performance test of paint film
Anti- scribble property evaluation：It scribbles and is dried at room temperature for 4 hours in coating surface using capable oiliness black marking pen
Afterwards, the spot of coating surface is wiped with dry paper handkerchief, whether there are spots for observation coating surface.Classification mark is carried out according to following standard
Show：
1 grade：Expression can be easy to wipe spot, and without any residual inside paint film；
2 grades：Expression can wipe spot, but relatively elaborate, and without any residual inside paint film；
3 grades：Expression can wipe spot, but have the ink marks of infiltration inside paint film；
4 grades：Expression cannot wipe spot.
Contact angle test method：Test piece without any abrasion is placed in contact angle instrument (model：DSA30, German Ke Lvshi
Co., Ltd provides) on, using deionized water and dodecane as tested media, test droplets volume is 4 μ L, record 3 dropping liquids drop
Contact angle values, and take the arithmetic mean of instantaneous value of 3 test datas.
Rub durability evaluation：Test piece is fixed on wear-resistant tester to (ESIDA-NM-002, the easy generation in Shenzhen reach instrument
Equipment Co., Ltd provides), bundle polypropylene non-woven fabric (model on contact head friction probe：B95, the auspicious industrial material of Jiangxi sky
Expect Co., Ltd)；Probe top applies 500g test loads, test trip 20mm, 10 beats/min of sample speed；Wear testing into
Row after twenty minutes, stops experiment, and the contact angle on surface is lost.
It is anti-scribble property, contact angle, rub durability test result referring to table 1.
Table 1 is the formula and the performance test results of coating
It is compared by coating sample S1, S2, S3, S4, S5, S6, S7 and blank sample coating S8, it can be seen that in coating
PFPE is introduced in formula can be obviously improved antigraffiti properties, and the paint film for being not introduced into PFPE does not have pollution resistance, oleic acid that can paint
Film surface is sprawled completely, and permanent pen prepared Chinese ink can pollute paint film and cannot wipe；Compared with S6 and S7, S1, S2, S3,
Contact angle with higher water and oleic acid after the coating surface abrasion of S4 and S5, this is because coating S1, S2, S3, S4 and S5
In introduce 3 acrylate UV photocurings active function groups and polysiloxanes segment, with coating ontology have higher phase
Dissolubility and adhesive force make coating have higher wear-resisting property, and keep perfluoropolyether segment relocation site more thorough, are greatly promoted
Antifouling antigraffiti properties；It is found simultaneously by the comparison of coating sample S1, S2 and S3, the anti-scribble of PFPE base anti-pollutions helps in paint film
The increase of agent content contributes to the promotion of antifouling property, but increase rate is with the variation unobvious of content, it was demonstrated that when coating is matched
The content of the anti-scribble auxiliary agent of PFPE bases anti-pollution reaches a certain level rear pollution resistance and improves unobvious in side.Experimental result explanation：This
Good intermiscibility and adhesive force can be had with UV paint films by inventing the antifouling anti-graffiti auxiliary agent provided, can make perfluoropolyether segment
Relocation site is more thorough, therefore adds its paint film with good antifouling property and wear-resisting property.
The present invention is described in detail above, its object is to allow the personage for being familiar with this field technology that can understand this
The content of invention is simultaneously implemented, and it is not intended to limit the scope of the present invention, and the present invention is not limited to above-mentioned implementations
, equivalent change or modification made by all Spirit Essences according to the present invention should be covered by the protection scope of the present invention.
Claims (10)
1. a kind of antifouling anti-graffiti auxiliary agent, which is characterized in that the antifouling anti-graffiti auxiliary agent has the following structure general formula：
Wherein, RfFor perfluoro polyether acyl group；
RSiFor organopolysiloxane radicals, tertiary N atom and silicon atom one of on the organopolysiloxane radicals are direct
It is connected or is indirectly connected；
RAFor the organic group containing photocuring active group He-CO-NH-, wherein the photocuring active group has multiple；
X is the organic group containing secondary amino group, nitrogen-atoms and the perfluoro polyether acyl group of the X by the secondary amino group
It is connected.
2. antifouling anti-graffiti auxiliary agent according to claim 1, which is characterized in that the perfluoro polyether acyl group be selected from
One or more combinations in group as follows：
Wherein, 50 >=a >=2；
Wherein, 50 >=b >=2；
Wherein, 50 >=c >=2,50 >=d >=2；
Wherein, 50 >=e >=2,50 >=f >=2.
3. antifouling anti-graffiti auxiliary agent according to claim 1, which is characterized in that the photocuring active group is unsubstituted
Acrylate-functional groups and/or C1-10Alkyl-substituted acrylate-functional groups.
4. antifouling anti-graffiti auxiliary agent according to claim 1 or 3, which is characterized in that the photocuring active group has
At least three and be located at the RAEnd.
5. antifouling anti-graffiti auxiliary agent according to claim 1, which is characterized in that the RAPass through the carbon on the-CO-NH-
It is connected with tertiary N atom.
6. antifouling anti-graffiti auxiliary agent according to claim 1, which is characterized in that the RAFor：
-CO-NH-R2-NH-COO-R3Or-CO-NH-R4-N(CO-NH-R5-NH-COO-R6)2, wherein
The R2To be selected fromR7For-NH-CO-O-
R8- O-CO-NH-, the R8To be selected from C1-10Alkylidene ,-(CH2CH2O)r2-CH2CH2-、-(CH2CH2CH2O)r3-
CH2CH2CH2-、-(CH2CH2CH2CH2O)r4-CH2CH2CH2CH2-、-(O-(CH2)4-O-CO-(CH2)4-CO)t-O-(CH2)4In
One or more combinations, r1, r2, r3, r4, t separately be selected from positive integer；
R4、R5Separately it is selected from C1-20Alkylidene group；
R3、R6Separately it is selected from：-(CH2)j-C(CH2OOC-CH=CH2)3, or,
-(CH2)k-C(CH2OOC-CH=CH2)2-CH2-O-CH2-C(CH2OOC-CH=CH2)3, wherein j, k are separately selected
From positive integer.
7. antifouling anti-graffiti auxiliary agent according to claim 1, which is characterized in that the organopolysiloxane radicals are
(CH3)3Si-O-Si(CH3)(O-(Si(CH3)2-O)g-Si(CH3)3)-R9, wherein R9For C1-20Alkylidene group, 20 >=g
≥4。
8. antifouling anti-graffiti auxiliary agent according to claim 1, which is characterized in that the X is-R10- NH-, wherein R10For
C1-20Alkylidene group.
9. antifouling anti-graffiti auxiliary agent according to claim 1, which is characterized in that the antifouling anti-graffiti auxiliary agent is selected from such as
One kind in lower structure formula：
Wherein, 50 >=a >=2,20 >=g >=3, PTHF represent polytetrahydrofuran ether glycol molecule segment；
Wherein, 50 >=a >=2,20 >=g >=3；
Wherein, 50 >=a >=2,20 >=g >=3；
Wherein, 50 >=a >=2,20 >=g >=3,20 >=t >=2；
Wherein, 50 >=a >=2,20 >=g >=3；
Wherein, 50 >=a >=2,20 >=g >=3；
Wherein, 50 >=a >=2,20 >=g >=3,20 >=t >=2.
10. a kind of antifouling anti-graffiti UV photocureable coating, which is characterized in that its raw material contains any one of claim 1-9 power
Profit requires the antifouling anti-graffiti auxiliary agent.
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