CN107892864B - A kind of polyether sulfone stain resistant coating - Google Patents
A kind of polyether sulfone stain resistant coating Download PDFInfo
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- CN107892864B CN107892864B CN201711272000.7A CN201711272000A CN107892864B CN 107892864 B CN107892864 B CN 107892864B CN 201711272000 A CN201711272000 A CN 201711272000A CN 107892864 B CN107892864 B CN 107892864B
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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
- C09D165/00—Coating compositions based on macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Coating compositions based on derivatives of such polymers
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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
- C09D181/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur, with or without nitrogen, oxygen, or carbon only; Coating compositions based on polysulfones; Coating compositions based on derivatives of such polymers
- C09D181/06—Polysulfones; Polyethersulfones
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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
- C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
- C09D5/1662—Synthetic film-forming substance
Abstract
The present invention relates to a kind of novel polyether sulfone stain resistant coating.The anti-pollution paint includes component A and polyether sulfone B, the component A arePolyether sulfone B is
Description
Technical field
The present invention relates to polymeric material fields, specifically, the present invention relates to a kind of paintings of novel polyether sulfone stain resistant
The purposes of material and its synthetic method and this resin in industrial aspect.
Background technique
High performance engineering plastics are the major class in special engineering plastics, in a broad sense high performance engineering plastics resin packet
Include polyether sulphone, poly(aryl ether ketone), poly (aryl ether sulfone ketone), polyethers phthalimide etc..Feature in its structure is that rouge is practically free of on main chain
Fat race group but be formed by connecting by phenyl ring, naphthalene nucleus, azacyclo- etc. by ether, sulfuryl, carbonyl etc., this design feature makes
This kind of high molecular material has temperature classification high, and thermal stability is good, and mechanical property is strong, and good stability of the dimension etc. is a series of excellent
Comprehensive performance, due to high performance engineering plastics resin temperature classification height with higher and excellent mechanical property, thus extensively
Applied to aviation, space flight, nuclear energy, military project, electronics, the high-tech areas such as precision instrument.This resinoid is because it is with very high simultaneously
Use value, and have irreplaceable role in special dimension.As polyether-ether-ketone (PEEK) in high molecular material resistance to spoke
It is best to penetrate performance, is applied to nuclear power industry；Again due to temperature resistant grade height, composite performance is good, is used in as high performance resin
The basis material of composite material.Polysulfones resinoid is the best engineering plastics of hot water resistance, is used for a long time in 100 degree of boiling water,
Performance gloss is constant, nontoxic, corrosion-resistant, high transparency, is used in the manufacture series of products such as Medical sterilizing utensil and food containers, can
See that high performance engineering plastics resin has broad application prospects.
Currently, many countries are developing not stanniferous self polishing copolymer antifouling paint in the world.The coating is using solvable
And hydrolyzable resin, as base-material, the cuprous oxide or other noxious materials for cooperating low toxicity are as anti-fouling agent.The coating is in sea
Under the action of water, paint vehicle outermost layer is hydrolyzed, and is generated small molecule, while releasing anti-fouling agent, is formed hydrophilic macromolecular chain.
When naval vessel is advanced with speed more than 15 sections, the water flow of seawater and the generation of hull interface will will lose the paint film erosion of coating
Fall, exposes new coating.So in cycles, fallen up to entire layer coating solution by erosion.Resin as substrate has perhaps
A variety of, what is mainly used has polyacrylic and polyester resin.2- thiocyanogen arsenic pyridine 1- oxide and oxidation can such as be used
It is cuprous or use 2- arsenic pyridine mercaptan 1- oxide and cuprous oxide for main component, rosin, chlorinated rubber, silica etc. is added
Antifouling paint is made.In addition document report, as base-material, Cu-Cr-Ba is added as hydrogenation catalyst and life using chlorination PVC
Object kills agent, and obtained coating has good anti-fouling effect.Using ethyl acrylate-cyclohexyl methacrylate-methyl-prop
Olefin(e) acid methoxy poly (ethylene glycol) (NK-EsterM-90G)-acrylic copolymer, copper acetate, Equacid SA13 (6,6- diformazans
Base -2- methyl -2- isobutyl base heptane carboxylic acid) made of automatic polishing copolymer mixed with cuprous oxide toxic agent and other additives,
Antifouling paint obtained still has good anti-pollution after using in the seawater 36 months.
Pollutant (such as aqueous oil pen, skin oil and fat etc.) has hydrophilic and lipophilic ingredients.Surface can influence anti-be stained with
One of an important factor for dirty coating property.Solid Surface Free Energy is smaller, is just less susceptible to be soaked by some liquid, otherwise also
So.Therefore, seek and prepare the solid table with low surface free energy to be the premise calls for preparing hydrophobic contamination resistant coating.People
By the discovery that studies for a long period of time, organic siliconresin and fluorine resin these two types are the extremely low materials of surface energy.Organic siliconresin due to
It makes the usual choosing for preparing low-surface-energy material with performances such as good hydro-oleophobicity, high-low temperature resistant, resistances to oxidation
It selects.Such as the F8261 (2- perfluoro hexyl ethyl triethoxysilane) of goldschmidt chemical corporation, the DowCorning2604 of Dow Corning Corporation
(2- perfluorooctylethyl group trimethoxy silane) and perfluoropolyether organosilicon handle glass, ceramics, can assign this kind of inorganic material
Good anti-stain characteristic energy.
Conventionally, fluorine resin has surface energy (low 10mN/m or so) more lower than organic siliconresin, because of fluorine
It is electronegativity highest (3.98), atomic polarizability minimum (0.557) in all elements, Van der Waals atomic radius minimum
The element of (0.135nm, dehydrogenation), fluorine atom and carbon atom can form very firm covalent bond, and therefore, perfluor alkane chain is unique
Molecular structure protect it by fluorine atom around, it is such as extremely low thus with the incomparable special performance of other materials
Surface energy, good hydro-oleophobicity, resistance to one time property, heat resistance, chemical stability etc., therefore, preferred fluorine resin is made
Standby contamination resistant coating.The product of Aerojet-Gerenal company, the U.S., a kind of polyether polyol with fluorinated side chain, through different
After the solidification of cyanic acid vinegar, there is low surface free energy, low-friction coefficient and low pollution release etc., be that one kind has the anti-of development prospect very much
Stain coating, but its wearability and bad.
Organosilicon contamination resistant coating is used widely in recent years, is quickly grown.Organic siliconresin be have it is highly cross-linked
The polymeric siloxane systems of structure.Because its excellent electrical insulating property, high-low temperature resistant type, water resistance, surface-active are applying due to the features such as
Material field is widely used.The critical surface tension of organic siliconresin in practical applications can significantly lower than other resins
As hydrophobic oleophobic, dirt-resistant material.It InternationlPaint company and takes the lead in being proposed Intersleek425 for 1996
Organosilicon contamination resistant coating, IP company are also proposed Intersleek757 organosilicon contamination resistant coating recently.The coating has good
The characteristics such as good dirt-resistant and drag reduction.Ippon company has invented a kind of with micro phase separation structure, cruel by organosilicon-acrylic acid
Contamination resistant coating made from copolymer resins: this coating is made of two or more incompatible resins, can form diameter on surface
For the granular raised structures of 10-20nm, there is good dirt-resistant effect.The organosilicon that synthesis Co., Ltd., Japan releases recently
Anti-fingerprint resin can form the granular raised structures that diameter is 80-100nm on surface, using its resin as matrix resin, be added
Into ultraviolet light curing formula, as long as 20-30wt% is added, coating has good anti-fingerprint, anti-skin oil and fat contamination.
But for now, the wearability of organosilicon contamination resistant coating is not significant, and organosilicon contamination resistant coating there is also with
Matrix adhesive force is poor, and recoatability is bad, and the cracking that easily becomes fragile, anti-to buy the disadvantages of dirty, anti-skin oil and fat performance is not lasting.
Ultraviolet-curing paint because efficiently, energy-saving and environmental protection, the advantages such as economy and the excellent resistance to marring of film, resistance toization
Learn property, light, it is plentiful the features such as, be widely used to the surface Lacquer finish of the consumption electronic products such as mobile phone, laptop.But this
A little products are easy the spots such as fingerprints, cosmetics, skin oil and fat or even ink marks, coffee in use, and are not easy clear
It removes.For aesthetic, hygienic, security needs, people are more and more denseer to the interest of UV-cured contamination resistant coating product.
Ultraviolet-curing paint is mainly by photo curable prepolymer, reactive diluent, photoinitiator and other auxiliary agents etc.
Composition.The different mechanism for causing monolithic entity polymerization according to photoinitiator, can be broadly divided into free radical for UV curing system
System and cationic system.Under uv radiation, photoinitiator generates living radical or cation, these living radicals or sun
Ion causes prepolymer and reactive diluent molecule carbon-carbon double bond or epoxy group etc. and carries out opening for free radical polymerization or cation
Cyclopolymerization reaction, so that liquid material crosslinking curing be made to form a film.
Polyether sulfone has the characteristics that raw material is easy to get and at low cost, but polymer surfaces tension is larger, and has low surface
Energy, good hydro-oleophobicity, weatherability, heat resistance, chemical stability etc., but its wearability is poor.
Therefore, it needs to develop one kind with good antifouling property, while having both good wear-resisting and performance coating.
Summary of the invention
In order to solve the above technical problems, present invention employs following technical proposals:
The present invention provides a kind of novel polyether sulfone stain resistant coating comprising component A and polyether sulfone B, wherein component A
Shown in following Formulas I:
Wherein,
Ar1It is independent to be selected from substituted or unsubstituted C5-10Arlydene takes containing 1-4 is heteroatomic in N, O and S
Generation or the sub- heterocycle of unsubstituted 5-10 member, or contain the 1-4 heteroatomic substituted or unsubstituted 5-10 members in N, O and S
Inferior heteroaryl；
Ar2It is independent to be selected from substituted or unsubstituted C5-10Arlydene takes containing 1-4 is heteroatomic in N, O and S
Generation or the sub- heterocycle of unsubstituted 5-10 member, or contain the 1-4 heteroatomic substituted or unsubstituted 5-10 members in N, O and S
Inferior heteroaryl；
D is independent to be selected from C5-10Arlydene contains 1-4 substituted or unsubstituted 5-10 heteroatomic in N, O and S
First Asia heterocycle, or contain 1-4 substituted or unsubstituted 5-10 member inferior heteroaryls heteroatomic in N, O and S；
R1And R2It is independent to be selected from substituted or unsubstituted C5Above alkyl, substituted or unsubstituted C5Above is halogenated
Alkyl, substituted or unsubstituted C5Above alkenyl, substituted or unsubstituted C5Above alkynyl, substituted or unsubstituted C5With
On naphthenic base；Preferably, R1And R2It is independent to be selected from substituted or unsubstituted C5-10Alkyl, substituted or unsubstituted C5-10Halogen
Substituted alkyl, substituted or unsubstituted C5-10Alkenyl, substituted or unsubstituted C5-10Alkynyl, substituted or unsubstituted C5-10Naphthenic base；
N is 10~1000；
The M of the polymerw=2.0~3.9 × 106, Mn=2.6~6.6 × 105, molecular weight distribution index is 3~15；
Polyether sulfone B is shown in following Formulas I:
Wherein,
A, B and c is independent selected from chemical bond, arlydene, sub- heterocycle or inferior heteroaryl；
M is 100~1000.
It is substituted described in wherein, refer to corresponding group by halogen, NH2、OH、C1-6Alkyl, C2-6Alkenyl, C2-6Alkynes
Base, C3-10Naphthenic base, C6-10Aryl contains one or more of 1-4 5-10 unit's heteroaryls heteroatomic in N, O and S
It is replaced；
The inferior heteroaryl is selected from substituted or unsubstituted pyridyl group, benzo pyridyl group, pyrimidine radicals, benzo pyrimidine radicals, miaow
Oxazoline base, imidazolidinyl, isothiazole alkyl, isoxazolidinyl, morpholinyl, thienyl, benzothienyl, oxazolidinyl, piperidines
Base, piperazinyl, pyrrolidinyl, pyrazolidinyl, quininuclidinyl, thiazolidinyl, tetrahydrofuran base, trioxane base, trithiane base, three
Piperazine base, THP trtrahydropyranyl, thio-morpholinyl or thiamorpholinyl.
The arlydene is selected from substituted or unsubstituted benzene, naphthalene, anthracene or phenanthrene.
Preferably, the component A is selected from following polymer:
Polyether sulfone (polyethersulfone, PES) resin is a kind of transparent, amber, non-crystalline thermoplasticity
Special engineering plastics.Polyether sulfone molecule is the linear polymeric for being interconnected by ether and sulfuryl and phenyl and being constituted.Polyether sulfone
The big resonance system that in strand there is the flexibility of ether, the rigidity of phenyl ring and sulfuryl and total unit to be formed simultaneously,
The quite stable gas polyethersulfone resin heat resistance of entire molecule is high, can be used continuously 20 years at 180 DEG C, use at 200 DEG C
2-3, other thermoplastic engineering plastics can not in contrast, the dimensional stability and solvent resistance of its product also than other polysulfones
Resinoid is high, can not only process film forming, can also be processed into all kinds of profiles, synthetic fibers, composite material, metal and ceramic material
Expect substitute etc..Polyether sulfone is succeeded in developing first within 1972 by chemical company, empire, Britain (ICI), and with Victrex commodity
The trade mark is sold in all over the world.After 1992, UCC company, the U.S., E.I.Du Pont Company, BASF Corp. of Germany, SUMITOMO CHEMICAL chemistry are public
Also there is commodity release in department etc. in succession, and the maximum manufacturer of polyethersulfone resin is BASF Corp. of Germany at present, and trade names are
UltrasonE.Domestic Fudan University, Changchun applied chemistry study institute, Jilin University, Dalian University of Science & Engineering and Xuzhou engineering plastics factory
Existing a small amount of test manufacture kind.Polyether sulfone product type on domestic and international market mainly has glass-fiber reinforced polyethersulfone resin
(SGN3030R, SGN2020R, SGN2030R, SGP2020R, SGP2021R), fibre reinforced polyethersulfone resin (EXS-1) are sliding
Expect grade polyethersulfone resin (SGF2030, SGF2040, FO-10D).Polyether sulfone has good heat resistance, anti-flammability, creep resistance
With the performances such as chemical resistance.
Preferably, polyether sulfone B is selected from following polymer:
Astrel(3M Corp.)、720P(ICI)、200P(ICI)、Udel(Union Carbide)、Radel(Union
Carbide)、
As known to those skilled in the art, the novel polyether sulfone stain resistant coating, further include filler, pigment or
Solvent.
Wherein, the novel polyether sulfone stain resistant coating, component A is 20~50 parts by weight, polyether sulfone group is divided into 30
~50 parts by weight, remaining is suitable filler, pigment or solvent.
The present invention also provides a kind of polymer that can be used for coating, shown in formula I:
Wherein,
Ar1It is independent to be selected from substituted or unsubstituted C5-10Arlydene takes containing 1-4 is heteroatomic in N, O and S
Generation or the sub- heterocycle of unsubstituted 5-10 member, or contain the 1-4 heteroatomic substituted or unsubstituted 5-10 members in N, O and S
Inferior heteroaryl；
Ar2It is independent to be selected from substituted or unsubstituted C5-10Arlydene takes containing 1-4 is heteroatomic in N, O and S
Generation or the sub- heterocycle of unsubstituted 5-10 member, or contain the 1-4 heteroatomic substituted or unsubstituted 5-10 members in N, O and S
Inferior heteroaryl；
D is independent to be selected from C5-10Arlydene contains 1-4 substituted or unsubstituted 5-10 heteroatomic in N, O and S
First Asia heterocycle, or contain 1-4 substituted or unsubstituted 5-10 member inferior heteroaryls heteroatomic in N, O and S；
R1And R2It is independent to be selected from substituted or unsubstituted C5Above alkyl, substituted or unsubstituted C5Above is halogenated
Alkyl, substituted or unsubstituted C5Above alkenyl, substituted or unsubstituted C5Above alkynyl, substituted or unsubstituted C5With
On naphthenic base；Preferably, R1It is independent selected from substituted or unsubstituted C with R25-10Alkyl, substituted or unsubstituted C5-10Halogen
Substituted alkyl, substituted or unsubstituted C5-10Alkenyl, substituted or unsubstituted C5-10Alkynyl, substituted or unsubstituted C5-10Naphthenic base；
N is 10~1000；
The M of the polymerw=2.0~3.9 × 106, Mn=2.6~6.6 × 105, molecular weight distribution index is 3~15；
Preferably, wherein described is substituted, refer to corresponding group by halogen, NH2、OH、C1-6Alkyl, C2-6Alkene
Base, C2-6Alkynyl, C3-10Naphthenic base, C6-10Aryl contains one in 1-4 5-10 unit's heteroaryls heteroatomic in N, O and S
It is a or multiple replaced；
Preferably, it is phonetic to be selected from substituted or unsubstituted pyridyl group, benzo pyridyl group, pyrimidine radicals, benzo for the inferior heteroaryl
Piperidinyl, imidazolinyl, imidazolidinyl, isothiazole alkyl, isoxazolidinyl, morpholinyl, thienyl, benzothienyl, oxazolidine
Base, piperidyl, piperazinyl, pyrrolidinyl, pyrazolidinyl, quininuclidinyl, thiazolidinyl, tetrahydrofuran base, trioxane base, three thiophenes
Alkyl, triazine radical, THP trtrahydropyranyl, thio-morpholinyl or thiamorpholinyl；
Preferably, the arlydene is selected from substituted or unsubstituted benzene, naphthalene, anthracene or phenanthrene.
More preferable following polymer:
Formulas I polymer of the present invention can be used for industrial use.
The term " substituted " used herein refers to any one or more hydrogen atoms on specified atom or group
Replaced with the specified group of selection, on condition that being no more than the general chemical valence of specified atom.When substituent group be oxygen or ketone (i.e.=
0), then 2 hydrogen atoms on atom are substituted.Ketone substituent group is not present in fragrant segment.If replaced without other explanations
Base is named to division center.For example, it is to be understood that when (naphthenic base) alkyl is possible substituent group, the substituent group to center
The tie point of structure is in moieties.Ring double bond used herein is formed at two double bonds closed between annular atom
(such as C=C, C=N or N=N).
The combination of substituent group and/or variable is allowed, and only generates stable compound or useful synthesis when these are combined
Intermediate.When stable compound or rock-steady structure implies that the compound is separated with useful purity from reaction mixture
Be it is sufficiently stable, therewith prepare form effective therapeutic reagent.Preferably, the compound does not include N- halogen, S at present
(O)2H or S (O) H base.
Term " aryl " is referred in monocycle or Bicyclic alkyl that loop section has 6 to 12 carbon atoms, such as phenyl
And naphthalene, it each can be substituted.
Term " heteroaryl " refer to replace and non-substituted fragrant 5 or 6 unit monocycle group, 9- or 10- membered bicyclic group, and
11 to 14 membered tricyclic groups have at least one hetero atom (O, S or N) at least one ring, described excellent containing heteroatomic ring
Choosing has 1,2 or 3 hetero atom in O, S and N.Each ring containing heteroatomic heteroaryl can contain one or two oxygen or
Sulphur atom and/or by 1 to 4 nitrogen-atoms, on condition that heteroatomic sum is 4 or less in each ring, and each ring has extremely
A few carbon atom.Carbon atom can only be contained by completing bicyclic and three cyclic groups fused rings, and can be saturation, fractional saturation or
It is unsaturated.Nitrogen and sulphur atom can be optionally oxidized and nitrogen-atoms can be optionally quaternized.Bicyclic or tricyclic heteroaryl must wrap
At least one full aromatic rings is included, the other fused rings of nitrogen can be armaticity or nonaromatic.Heteroaryl can be in any of any ring
Using being connected on nitrogen or carbon atom.When chemical valence allows, if other rings are naphthenic base or heterocycle, in addition optionally with
=O (oxygen) replaces.
Exemplary monocyclic heteroaryl includes pyrrole radicals, pyrazolyl, pyrazolinyl, imidazole radicals, oxazolyl, isoxazolyl, thiophene
Oxazolyl, thiadiazolyl group, furyl, thienyl, oxadiazoles base, pyridyl group, pyrazinyl, pyrimidine radicals, pyridazinyl, triazine radical and its class
Like object.
Exemplary bicyclic heteroaryl include indyl, benzothiazolyl, benzodioxole base, benzoxazolyl,
Benzothienyl, quinolyl, tetrahydro isoquinolyl, isoquinolyl, benzimidazolyl, benzopyranyl, indolizine base, benzo furan
It mutters base, chromone base, cumarin base, benzopyranyl, cinnoline base, quinoxalinyl, indazolyl, pyrrolopyridinyl, fluorinated pyridine
Base, dihydro-iso indolyl, tetrahydric quinoline group and the like.
It is preferred that coating composition of the present invention also includes one or more fillers, pigment or solvent.
The example of suitable filler is barium sulfate, calcium sulfate, calcium carbonate, silica or silicate (such as talcum, feldspar and porcelain
Soil), lead plaster paste/thin slice, bentonite or other clays.Some fillers may have thixotropic effect to coating composition.Based on painting
The total weight of feed composition, filler can be 0~20 parts by weight.
Whether pigment can select addition as needed, the example of suitable pigments is Black Rouge and titanium dioxide, additive amount
For 0~5 parts by weight.
Suitable solvent include aromatic hydrocarbons, alcohol, ketone, ester and above-mentioned solvent each other or the mixture with aliphatic hydrocarbon.For with making environment
Used solvent is minimized on face, it is advantageous to use the solution compatible with coating technology used being concentrated as far as possible.Solvent
Amount be added as needed by those skilled in the art, additive amount be 20~80 parts by weight.
The present invention provides polymer shown in a kind of Formulas I, have long chain hydrocarbon groups in the molecular structure, enhance wear-resisting
Performance.Its reason may be, the introducings of long chain hydrocarbon groups so that material crosslink density becomes larger after solidification, enhance between molecule
Active force, improve the hardness and wearability of material molecule.
Embodiment
Below by embodiment, the invention will be further described.It should be understood that the method for the embodiment of the present invention
It is only used for illustrating the present invention, rather than limiting the invention, to preparation side of the invention under concept thereof of the invention
The simple modifications of method belong to the scope of protection of present invention.Unless otherwise instructed, all raw materials for being used in embodiment and
Solvent is commercially available analysis net product.
Prepare embodiment:
Embodiment 1:
(1) in the reaction vessel, compound 1 (300mmol) and the concentrated sulfuric acid (300ml) is added, NBS is added portionwise in stirring
(1mol), being protected from light to reaction terminates, and reactant is slowly poured into ice water, filters, and successively uses sodium bicarbonate aqueous solution, water
Filter residue is washed with methanol.It is recrystallized after filter residue and drying with DMSO, obtains the compound 2 of yellow solid, yield: 15%.1HNMR
(DMSO): δ 7.71 (d, J=6.0Hz, 1H), 7.36-7.38 (m, 5H), 7.29 (d, J=6.0Hz, 1H), 5.84 (s, 1H)
(2) in the reaction vessel, compound 2 (100mmol) is added, 200mL ethyl alcohol is added and is dissolved, it will under stirring
(200mmol) sodium borohydride is dissolved in 20mL ethanol solution, is added drop-wise in reaction flask under ice bath, 60min is dripped off.Room temperature reaction is extremely
Reaction is completed, and filtering, solid is washed with water 3 times, is dissolved filter cake with the water of washing solid, and ethyl acetate extracts 3 times × 50mL,
Merge organic phase, is evaporated under reduced pressure, it is dry, compound as white solid 3 is obtained, without being further purified, is directly used in anti-in next step
It answers.1HNMR (DMSO): δ 7.40 (d, J=6.0Hz, 1H), 7.35-7.38 (m, 5H), 6.93 (d, J=6.0Hz, 1H), 5.20
(s, 1H), 5.11 (d, J=7.2Hz, 1H), 4.89 (s, 1H) .4.85-4.88 (m, 2H)
(3) in the reaction vessel, compound 3 (60mmol), sodium hydroxide (200mmol) and DMF 150mL, heating is added
To 50 DEG C, stirring, addition bromoethane (200mmol) continues stirring to be terminated to reaction, and reactant is poured into water, methylene chloride extraction
It takes, washes, magnesium sulfate dries, filters, and ethyl acetate and petroleum ether recrystallize to obtain compound as white solid 4, yield: 79%.1HNMR (DMSO): δ 7.40 (d, J=6.4Hz, 1H), 7.32-7.39 (m, 5H), 7.14 (d, J=6.4Hz, 1H), 5.08 (d, J
=7.2Hz, 1H), 4.52-4.58 (m, 2H), 3.80-3.91 (m, 4H), 1.15-1.21 (m, 6H)
(4) under nitrogen protection, in the reaction vessel, compound 4 (50mmol), Ni (dppp) Cl is added2(0.5mmol)、
C well prepared in advance is added dropwise under ice bath in anhydrous tetrahydro furan 200mL6H13The THF solution of MgBr (150mmol).It is added dropwise to complete
Afterwards, overnight, the NH of saturation is added in room temperature reaction4Cl, n-hexane extraction, magnesium sulfate are dry.With ethyl acetate and petroleum ether
(VEthyl acetate∶VPetroleum ether=1: 3) carrying out column chromatography for eluant, eluent, obtain the compound 5 of colourless liquid, yield 65%.1HNMR (DMSO):
δ 7.52 (d, J=6.4Hz, 1H), 7.34-7.37 (m, 5H), 6.91 (d, J=6.4Hz, 1H), 5.36 (d, J=7.6Hz, 1H),
4.48-4.56 (m, 2H), 3.85-3.93 (m, 4H), 2.53-2.58 (m, 4H), 1.52-1.59 (m, 4H), 1.31-1.29 (m,
12H), 1.14-1.19 (m, 6H), 0.84-0.90 (m, 6H)
(5) in the reaction vessel, compound 5 (50mmol), Isosorbide-5-Nitrae-dioxane (150mL) is added, stirring is protected from light, ice
Bath is lower to be added dropwise fuming nitric aicd (80mL).It flows back after being added dropwise to complete, until reaction terminates, reactant is poured into water, methylene chloride extraction
It takes, washes, anhydrous magnesium sulfate dries, filters, and is evaporated under reduced pressure, and recrystallize with dichloromethane obtains faint yellow solid compound 6, yield:
85%.1HNMR (DMSO): δ 7.49 (d, J=6.4Hz, 1H), 7.33-7.36 (m, 5H), 6.90 (d, J=6.4Hz, 1H),
5.82 (s, 1H), 2.51-2.57 (m, 4H), 1.53-1.60 (m, 4H), 1.31-1.29 (m, 12H), 0.83-0.90 (m, 6H)
(6) in the reaction vessel, compound 6 (100mmol) is added, 3,6- bis- bromo- 1,2- phenylenediamines (150mmol), second
Sour 50mL and tetrahydrofuran 15mL, stirring are heated to 60 DEG C, and TLC monitoring reaction is completed.Reactant is poured into water, is filtered, filter
Slag is recrystallized with acetic acid/tetrahydrofuran mixed solution, obtains compound as white solid 7, yield: 76%.1HNMR (DMSO): δ 7.80
(d, J=7.2Hz, 2H), 7.34-7.38 (m, 5H), 7.09 (d, J=6.4Hz, 1H), 6.93 (d, J=6.4Hz, 1H), 6.28
(s, 1H), 2.49-2.56 (m, 4H), 1.52-1.60 (m, 4H), 1.30-1.29 (m, 12H), 0.83-0.89 (m, 6H)
(7) under nitrogen protection, compound 7 (30mmol) is added in the reaction vessel, 2- (tributyl tin) is added under ice bath
Pyrimidine (80mmol) adds triphenylphosphine palladium chloride (0.18g, 0.5mmol) and anhydrous tetrahydro furan 200mL, heating stirring
Terminate to reaction, reactant is poured into water, ethyl acetate extraction is washed, and magnesium sulfate dries, filters, and is evaporated under reduced pressure, dichloromethane
Alkane recrystallizes to obtain compound as white solid 8, yield: 88%.1HNMR (DMSO): δ 8.90 (d, J=7.6Hz, 4H), 8.07 (d, J
=7.2Hz, 2H), 7.30-7.39 (m, 7H), 7.10 (d, J=6.4Hz, 1H), 6.91 (d, J=6.4Hz, 1H), 6.30 (s,
1H), 2.50-2.56 (m, 4H), 1.51-1.60 (m, 4H), 1.30-1.29 (m, 12H), 0.84-0.90 (m, 6H)
(8) in the reaction vessel, compound 8 (30mmol) is added, tetrahydrofuran 200mL is slowly added under stirring
NBS70mmol, overnight.After reaction, reactant being poured into water, methylene chloride extraction, washing, magnesium sulfate dries, filters,
Vacuum distillation, recrystallizes to obtain brown solid compound 9, yield: 19% with petrol ether/ethyl acetate.1HNMR (DMSO): δ 8.83
(d, J=7.2Hz, 2H), 8.08 (d, J=7.2Hz, 2H), 7.32-7.39 (m, 7H), 7.08 (d, J=6.4Hz, 1H), 6.89
(d, J=6.4Hz, 1H), 6.29 (s, 1H), 2.51-2.57 (m, 4H), 1.50-1.61 (m, 4H), 1.31-1.29 (m, 12H),
0.850.91 (m, 6H)
(9) under nitrogen protection, Isosorbide-5-Nitrae two (tin trimethyl) benzene (15mmol), compound 9 are added in the reaction vessel
(15mmol)、Pd2(dba)3(0.015mmol)、P(o-tol)3(0.02mmol) and toluene 100mL, is protected from light, at 100 DEG C of heating
Reaction 72 hours.It is separately added into tin trimethyl benzene (0.2g) and bromobenzene (0.2g) sealing end, then reacts 10 hours and terminates to reaction,
It is cooled to room temperature, in methyl alcohol by reaction solution precipitating, is successively stripped with methanol, acetone, recrystallize with dichloromethane obtains Huang
Color solid, yield: 70%.
The M of the polymerw=2.5 × 106, Mn=4.6 × 105, molecular weight distribution index 5.4.
1HNMR (DMSO): δ 8.75 (d, J=7.2Hz, 2H), 8.08 (d, J=7.2Hz, 2H), 7.60 (d, J=7.2Hz,
2H), 7.29-7.40 (m, 6H), 7.11-7.18 (m, 4H), 6.89 (d, J=6.4Hz, 1H), 6.27 (s, 1H), 2.52-2.60
(m, 4H), 1.52-1.60 (m, 4H), 1.31-1.29 (m, 12H), 0.85-0.91 (m, 6H)
Following polymer are prepared according to the similar method of embodiment 1, according to the difference for preparing polymer architecture, selection is corresponding
Raw material, such as by C6H13MgBr replaces with C respectively7H15MgBr and C8H17Isosorbide-5-Nitrae-two (tin trimethyl) benzene is replaced with 1 by MgBr,
5- bis- (tin trimethyl) pyridine.
Embodiment 2:
Mw=2.1 × 106, Mn=3.6 × 105, molecular weight distribution index 5.8
1HNMR (DMSO):
1HNMR (DMSO): δ 8.74 (d, J=7.2Hz, 2H), 8.06 (d, J=7.2Hz, 2H), 7.76 (d, J=7.2Hz,
1H), 7.65 (d, J=7.2Hz, 1H), 7.29-7.40 (m, 5H), 7.12 (d, J=6.4Hz, 1H), 6.88 (d, J=6.4Hz,
1H), 6.29 (s, 1H), 2.51-2.60 (m, 4H), 1.53-1.61 (m, 4H), 1.30-1.25 (m, 12H), 0.85-0.90 (m,
6H).
Embodiment 3:
Mw=3.0 × 106, Mn=4.1 × 105, molecular weight distribution index 7.3
1HNMR (DMSO): δ 8.76 (d, J=7.2Hz, 2H), 8.09 (d, J=7.2Hz, 2H), 7.61 (d, J=7.2Hz,
2H), 7.23-7.40 (m, 6H), 7.12-7.18 (m, 4H), 6.86 (d, J=6.4Hz, 1H), 6.25 (s, 1H), 2.51-2.60
(m, 4H), 1.52-1.61 (m, 4H), 1.35-1.28 (m, 14H), 0.85-0.91 (m, 6H)
Embodiment 4:
Mw=3.7 × 106, Mn=6.0 × 105, molecular weight distribution index 6.2
1HNMR (DMSO): δ 8.79 (d, J=7.2Hz, 2H), 8.06 (d, J=7.2Hz, 2H), 7.60 (d, J=7.2Hz,
2H), 7.22-7.40 (m, 6H), 7.10-7.18 (m, 4H), 6.83 (d, J=6.4Hz, 1H), 6.27 (s, 1H), 2.50-2.59
(m, 4H), 1.52-1.61 (m, 4H), 1.37-1.27 (m, 16H), 0.83-0.90 (m, 6H)
Performance test:
Antifouling property test:
It mixes according to following table component, and suitably heats, add suitable acetone, prepare coating, be coated on commercially available Ma Kou
On iron plate material, high-temperature maturing condition: cymel 303,150 DEG C × 30 minutes；Ripening at low temperature condition: N3390,60 DEG C × 30 points
Clock, room temperature 3 days；
| Sample | Composition |
| Sample 1 | Astrel (3M Corp.), 5g | - |
| Sample 2 | 1 polymer of embodiment, 5g | Astrel (3M Corp.), 5g |
| Sample 3 | 2 polymer of embodiment, 5g | Astrel (3M Corp.), 5g |
| Sample 4 | 3 polymer of embodiment, 5g | Astrel (3M Corp.), 5g |
| Sample 5 | 4 polymer of embodiment, 5g | Astrel (3M Corp.), 5g |
Anti-pollution test data is as follows:
Surface cleanness rank: 1- is optimal；2- is excellent；In 3-；4- is poor；5- is very poor.
Wear-resisting property test:
It is tested according to GB/T 1768-2006 the method:
Instrument: JM-V paint film abrasion test instrument (Shanghai modern environment)
Substrate: the cold-rolled steel sheet of Q195, plate is smooth not to be deformed, and 100mm × 100mm, center is provided with diameter and is
The hole of 6.35mm, acetone clean the surface, drying.
Sample 1-5 is coated on commercially available tinplate plate, high-temperature maturing condition: cymel 303,150 DEG C × 30 minutes；
Ripening at low temperature condition: N3390,60 DEG C × 30 minutes, room temperature 3 days；
Wearability test data are as follows:
| Sample | Sample 1 | Sample 2 | Sample 3 | Sample 4 | Sample 5 |
From the above, it is seen that not only there is good anti-pollution after herein described coating is due to being added Formulas I polymer
Performance, while having both excellent abrasion resistance.
Claims (12)
1. a kind of polyether sulfone stain resistant coating, it is characterised in that including component A and polyether sulfone B, wherein component A is with following Formulas I
It is shown:
Wherein,
Ar1It is independent to be selected from substituted or unsubstituted C5-10Arlydene, containing 1-4 in N, O and S heteroatomic substitution or
The unsubstituted sub- heterocycle of 5-10 member, or it is sub- miscellaneous containing a substituted or unsubstituted 5-10 member heteroatomic in N, O and S of 1-4
Aryl；
Ar2It is independent to be selected from substituted or unsubstituted C5-10Arlydene, containing 1-4 in N, O and S heteroatomic substitution or
The unsubstituted sub- heterocycle of 5-10 member, or it is sub- miscellaneous containing a substituted or unsubstituted 5-10 member heteroatomic in N, O and S of 1-4
Aryl；
D is independent to be selected from C5-10Arlydene contains the 1-4 heteroatomic substituted or unsubstituted 5-10 member Asias in N, O and S
Heterocycle, or contain 1-4 substituted or unsubstituted 5-10 member inferior heteroaryls heteroatomic in N, O and S；
R1And R2It is independent to be selected from substituted or unsubstituted C5Above alkyl, substituted or unsubstituted C5Above halogenated alkyl,
Substituted or unsubstituted C5Above alkenyl, substituted or unsubstituted C5Above alkynyl, substituted or unsubstituted C5Above ring
Alkyl；
N is 10~1000；
Mw=2.0~3.9 × 10 of the component A6, Mn=2.6~6.6 × 105, molecular weight distribution index is 3~15；
Polyether sulfone B is shown in following formula:
A, B and C is independent selected from chemical bond, arlydene, sub- heterocycle or inferior heteroaryl；
M is 100~1000.
2. polyether sulfone stain resistant coating according to claim 1, it is characterised in that: R1And R2It is independent selected from replace or
Unsubstituted C5-10Alkyl, substituted or unsubstituted C5-10Halogenated alkyl, substituted or unsubstituted C5-10Alkenyl, substitution do not take
The C in generation5-10Alkynyl, substituted or unsubstituted C5-10Naphthenic base.
3. polyether sulfone stain resistant coating according to claim 1, it is characterised in that: it is substituted described in wherein, refer to
It is corresponding group by halogen, NH2、OH、C1-6Alkyl, C2-6Alkenyl, C2-6Alkynyl, C3-10Naphthenic base, C6-10Aryl contains 1-4
Replaced one or more of a 5-10 unit's heteroaryl heteroatomic in N, O and S；
The inferior heteroaryl is selected from substituted or unsubstituted pyridyl group, benzo pyridyl group, pyrimidine radicals, benzo pyrimidine radicals, imidazoline
Base, imidazolidinyl, isothiazole alkyl, isoxazolidinyl, morpholinyl, thienyl, benzothienyl, oxazolidinyl, piperidyl, piperazine
Piperazine base, pyrrolidinyl, pyrazolidinyl, quininuclidinyl, thiazolidinyl, tetrahydrofuran base, trioxane base, trithiane base, triazine radical,
THP trtrahydropyranyl, thio-morpholinyl or thiamorpholinyl.
4. polyether sulfone stain resistant coating according to claim 1 or 2, it is characterised in that: the arlydene, which is selected from, to be replaced
Or unsubstituted benzene, naphthalene, anthracene or phenanthrene.
5. polyether sulfone stain resistant coating according to claim 4, it is characterised in that the component A is selected from following polymerizations
Object:
6. polyether sulfone stain resistant coating according to claim 4, it is characterised in that the polyether sulfone B is selected from following polymerizations
Object:
, Union Carbide company production Radel,
7. polyether sulfone stain resistant coating according to claim 4, it is characterised in that further include filler, pigment or solvent.
8. polyether sulfone stain resistant coating according to claim 7, it is characterised in that component A is 20~50 parts by weight, gathers
Ether sulfone B is 30~50 parts by weight, remaining is suitable filler, pigment or solvent.
9. a kind of polymer that can be used for coating, it is characterised in that as shown in following Formulas I:
Wherein,
Ar1It is independent to be selected from substituted or unsubstituted C5-10Arlydene, containing 1-4 in N, O and S heteroatomic substitution or
The unsubstituted sub- heterocycle of 5-10 member, or it is sub- miscellaneous containing a substituted or unsubstituted 5-10 member heteroatomic in N, O and S of 1-4
Aryl；
Ar2It is independent to be selected from substituted or unsubstituted C5-10Arlydene, containing 1-4 in N, O and S heteroatomic substitution or
The unsubstituted sub- heterocycle of 5-10 member, or it is sub- miscellaneous containing a substituted or unsubstituted 5-10 member heteroatomic in N, O and S of 1-4
Aryl；
D is independent to be selected from C5-10Arlydene contains the 1-4 heteroatomic substituted or unsubstituted 5-10 member Asias in N, O and S
Heterocycle, or contain 1-4 substituted or unsubstituted 5-10 member inferior heteroaryls heteroatomic in N, O and S；
Mw=2.0~3.9 × 10 of the component A6, Mn=2.6~6.6 × 105, molecular weight distribution index is 3~15；
R1And R2It is independent to be selected from substituted or unsubstituted C5Above alkyl, substituted or unsubstituted C5Above halogenated alkyl,
Substituted or unsubstituted C5Above alkenyl, substituted or unsubstituted C5Above alkynyl, substituted or unsubstituted C5Above ring
Alkyl；
N is 10~1000.
10. polymer according to claim 9, which is characterized in that R1 and R2 is independent to be selected from substituted or unsubstituted C5-10
Alkyl, substituted or unsubstituted C5-10Halogenated alkyl, substituted or unsubstituted C5-10Alkenyl, substituted or unsubstituted C5-10Alkynyl,
Substituted or unsubstituted C5-10Naphthenic base；It is substituted described in wherein, refer to corresponding group by halogen, NH2、OH、C1-6Alkane
Base, C2-6Alkenyl, C2-6Alkynyl, C3-10Naphthenic base, C6-10Aryl contains 1-4 5-10 member heteroaryls heteroatomic in N, O and S
Replaced one or more of base；
The inferior heteroaryl is selected from substituted or unsubstituted pyridyl group, benzo pyridyl group, pyrimidine radicals, benzo pyrimidine radicals, imidazoline
Base, imidazolidinyl, isothiazole alkyl, isoxazolidinyl, morpholinyl, thienyl, benzothienyl, oxazolidinyl, piperidyl, piperazine
Piperazine base, pyrrolidinyl, pyrazolidinyl, quininuclidinyl, thiazolidinyl, tetrahydrofuran base, trioxane base, trithiane base, triazine radical,
THP trtrahydropyranyl, thio-morpholinyl or thiamorpholinyl；The arlydene is selected from substituted or unsubstituted benzene, naphthalene, anthracene or phenanthrene.
11. polymer according to claim 9 is selected from following polymer:
12. the polymer of claim 9 or 11 is in the purposes of industrial aspect.
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