CN105505183B - A kind of preparation method of high performance fluorine carbon coating - Google Patents
A kind of preparation method of high performance fluorine carbon coating Download PDFInfo
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- CN105505183B CN105505183B CN201510997912.5A CN201510997912A CN105505183B CN 105505183 B CN105505183 B CN 105505183B CN 201510997912 A CN201510997912 A CN 201510997912A CN 105505183 B CN105505183 B CN 105505183B
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
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- 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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/4269—Lactones
- C08G18/4277—Caprolactone and/or substituted caprolactone
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- 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
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- C08G18/40—High-molecular-weight compounds
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
- C08G18/6275—Polymers of halogen containing compounds having carbon-to-carbon double bonds; halogenated polymers of compounds having carbon-to-carbon double bonds
- C08G18/6279—Polymers of halogen containing compounds having carbon-to-carbon double bonds; halogenated polymers of compounds having carbon-to-carbon double bonds containing fluorine atoms
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- 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
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
- C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
- C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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Abstract
The present invention relates to a kind of preparation method of high performance fluorine carbon coating.The fluororine-carbon coating is made up of the component of first, second two, and wherein first component is made up of isocyanate-terminated polyol oligomer and anhydrous diluents A；Second component is made up of fluorocarbon resin, dispersant, inorganic filler, catalyst, anhydrous diluents；The mol ratio according to isocyanates and hydroxyl value of the component of first, second two is 0.6~1.5:1 carries out being mixed to get fluorocarbon coating.Wherein polyol oligomer includes PEPA and PPG, assign coating excellent mechanical property, good low temperature flexibility and hydrolytic resistance, reacted after isocyanate-terminated with fluorocarbon resin, by the soft segment and the distribution of isocyanates hard section rule of polyol oligomer and fluorocarbon resin formation in the coating, three-dimensional netted interpenetrating structure is formed.Made fluorocarbon coating has ageing-resistant, resistance to dust storm performance, can be applied to prepare the application type solar cell backboard used in ruthless area.
Description
Technical field
The present invention relates to a kind of preparation method of fluorocarbon coating, belong to material surface protection technique field.
Background technology
Nearly ten years, country has driven what is matched therewith in the development of new energy, building, machinery, automobile, railway etc.
The development of coatings industry, decoration is played by application to outdoor steel structure, aluminum curtain walls, wind power installation, solar cell backboard etc.
And protective effect, outer bound pair their erosion can be effectively resisted, is increased the service life.Some are large-scale, emphasis structural steelwork
Project design required corrosion-inhibiting coating durability up to 20 years, aluminium-plastic panel also require that 20 years it is colour-fast, carried on the back as solar cell module
The backboard of face protection materials is even more to require the service life up to 25 years.Fluorocarbon resin introduces the big fluorine element of electronegativity, fluorine carbon
Bond energy is strong, makes it have prominent resistance to ag(e)ing, corrosion-resistant and anti-stain characteristic, is especially suitable for making long-acting weather-resistant coating, especially
It is in dust storm overall situation more severe the Northwest.
Traditional fluorocarbon resin is linear structure, after isocyanate curing agent reaction, forms two dimensional surface network structure, applies
Layer adhesive force, the erosion performance of resistance to dust storm and mechanical strength be weaker, be subjected to 15 years or so will aging come off, for adapt to sunshine it is strong,
The more rugged environment condition such as dust storm is big, haze is more, the four seasons temperature difference is big from formulation for coating material, it is necessary to start with, increase coating crosslinking
Density, forms tridimensional network, while introducing flexible group improves the resistance to low temperature of coating, for increase coating to material
Protective effect and extension service life it is significant.
Patent CN102664204A is provided in a kind of application type solar cell backboard of new structure, its fluororine-carbon coating
Its wearability is improved by adding epoxy resin, epoxy resin causes coating abrasion performance to obtain greatly with the preferable compatibility of fluororesin
Width is improved, and is combined yet with their strand by physical force, and intensity is little, and the addition of epoxy resin, causes coating yellow
Become serious；Patent CN101792639A discloses a kind of wear-resisting scratch-resisting weather-proof polyurethane coating, and it mainly uses hydroxyl ester propylene
Acid resin, fluorocarbon resin and polyester resin add all kinds of nanometer inorganic fillers and are filled as matrix resin, afterwards and polyisocyanate
Cyanate curing agent reaction be made, it is adaptable to the top finishing of bullet train, automobile bus etc., wherein due to hydroxy acrylic acid with
Polyester resin introducing to a certain extent can weaken coating ageing-resistant performance, while nano-sized filler is to be filled in resin base
In body, both compatibilities are poor, the difficulties in dispersion in matrix resin, if processing is bad, can cause the drawbacks such as coating cracking；
Patent CN104194599A discloses a kind of fluorine carbon two-component coating of function admirable, and wherein first component is main by fluorine carbon poly urethane
Performed polymer, nanometer inorganic filler etc. are constituted, and component B is mainly made up of Hydroxylated acrylic resin, isocyanate curing agent, obtained
High crosslink density fluororine-carbon coating, with excellent wearability, but its manufacture craft is relative complex.
Therefore, it is necessary to invent, a kind of preparation technology is simple, and compatibility is good between each component, with excellent color inhibition, resistance to
The ultraviolet, erosion performance of resistance to dust storm, coating of the weatherability for 25 years, to meet the application type sun that ruthless area is used
Can battery back-sheet.
The content of the invention
The technical problem to be solved in the present invention is to overcome that of the prior art not enough there is provided a kind of high performance fluorine carbon coating
Preparation method.
To solve technical problem, solution of the invention is：A kind of preparation method of high performance fluorine carbon coating, including with
Lower step：
(1) 100 weight polyol oligomer, the antioxidant of 0~2.5 parts by weight, the acid of 0~0.5 parts by weight are hindered
After poly- agent is well mixed, it is dehydrated 2.5~4.5 hours under the conditions of 100~150 DEG C；Temperature is down to 45~95 DEG C, adds isocyanic acid
Ester curing agent and anhydrous diluents A insulation reactions 5~8 hours, then add catalyst A, after being well mixed, and are protected under vacuum condition
Hold 1~3 hour, first component (isocyanate-terminated polyol oligomer performed polymer) is made；Wherein, the OH of polyol oligomer
NCO mol ratios with isocyanate curing agent are 1:2.0~4.5, anhydrous diluents A and isocyanate curing agent quality phase
Consumption Deng, catalyst A is the 0~0.5% of isocyanate curing agent quality；
(2) fluorocarbon resin of 35~65 parts by weight is added into the diluent B of 20~35 parts by weight under agitation, then
Dispersant, the inorganic filler of 0~40 parts by weight of 0~1.6 parts by weight are added, it is pre-dispersed to be ground afterwards with sand mill, extremely
Grain fineness≤5 micron, add the catalyst B, the levelling agent of 0~0.5 parts by weight, 0~1.2 parts by weight of 0.1~1.5 parts by weight
Defoamer, the flatting silica of 0~5 parts by weight, after being well mixed, adjust viscosity, component B (fluorocarbon coating master is made in filtering
Agent)；
During coating, according in the NCO (NCO) in first component and component B institute's hydroxyl (OH) mole the ratio between
For 0.6~1.5：1.0 are matched；
The polyol oligomer is that one or both of PPG, PEPA are constituted according to any proportioning
Mixture, the PPG include polyoxypropylene polyol, polymer grafted polyether polyol, PolyTHF two
Alcohol homopolymerization, PolyTHF polyol, tetrahydrofuran-propylene oxide copolymer glycols, polyoxyethylated polyols；Polyester is more
First alcohol includes adipic acid system polyester-diol, aromatic polyester polyol, polycaprolactone polyol, polycarbonate polyol；As
It is preferred that, polyol oligomer degree of functionality can be 2 or 3, and molecular weight is 200~1300, and hydroxyl value is 100~700mgKOH/g, acid number
≤ 1.0mgKOH/g, moisture≤0.2%.
Further, described isocyanate curing agent is one of following or two kinds of mixing according to any proportioning composition
Thing：Hexamethylene diisocyanate (HDI) tripolymer, hexamethylene diisocyanate (HDI) biuret, the isocyanide of hexa-methylene two
Acid esters (HDI) addition product, IPDI (IPDI) tripolymer, IPDI (IPDI) addition
Thing.
Further, the fluorocarbon resin is by vinylidene type fluorocarbon resin, CTFE type fluorocarbon resin, tetrafluoro second
One or more in ene-type fluorocarbon resin constitute according to any proportioning, preferably, the hydroxyl value of fluorocarbon resin be 45~
60mgKOH/g, acid number is 2~12mgKOH/g, and solid content >=50%, Oil repellent is 20%~30%.
Further, the antioxidant is Hinered phenols antioxidant；The acid polymerization inhibitor is p-methyl benzenesulfonic acid；It is described to urge
Agent A or catalyst B are metallic catalyst, including zinc Isoocatanoate, stannous octoate, tin dilaurate dioctyl tin, oxidation only son
One or more mixtures according to any proportioning composition in Ji Xi, the isooctyl acid tin of monobutyl three, dibutyl tin laurate.
Further, described dispersant by the affinity groups containing pigment block copolymerization species dispersant, acrylic acid block
Copolymer analog dispersant, height branched structure polyesters dispersant, the dispersant of copolymer analog containing acidic-group, hydroxy functional group carboxylic
It is one or more according to any proportioning composition in esters of gallic acid dispersant.
Further, described levelling agent is by polyether siloxane copolymer class levelling agent, polyether-modified polysiloxane
It is one or more according to any proportioning composition in class levelling agent, polyacrylate levelling agent.
Further, the inorganic filler by titanium dioxide, carbon black, calcium carbonate, aluminum oxide, barium sulfate it is one or more according to
Any proportioning composition.
Further, the diluent A, diluent B are by toluene, dimethylbenzene, n-butyl acetate, propylene glycol monomethyl ether acetic acid
In ester, ethyl acetate, butyl acetate, ethylene glycol, methanol, n-butanol, butanone, MEK, cyclohexanone it is one or more according to
Any proportioning composition.
Further, the defoamer be polyoxyethylene polyoxypropylene pentaerythrite ether, polyoxyethylene polyoxy propyl alcohol amidogen ether,
Polypropylene glycerol aether, polyoxyethylene polyoxypropylene glycerin ether, the one or more of fluorine-carbon modified acrylic ester type are according to any
Proportioning composition.
Further, the flatting silica is silica, talcum powder one or both according to any proportioning composition.
The beneficial effects are mainly as follows：The invention provides a kind of preparation technology is relatively easy, between each component
The good fluorocarbon coating of compatibility, wherein polyol oligomer and long-chain fluorocarbon resin constitute soft segment, and isocyanates agent constitutes hard section,
Hydroxy-end capped polyol oligomer provides chain extension effect simultaneously, is distributed soft segment and hard section rule in the coating by reacting,
Coating crosslink density is improved, three-dimensional netted interpenetrating structure is formed.Wherein PEPA assign the excellent mechanical property of coating, it is resistance to
Hot and hardness, PPG assigns coating good low temperature flexibility and anti-hydrolytic performance, and it is excellent that fluorocarbon resin assigns coating
Different weatherability and corrosion resistance.Made fluorocarbon coating high-strength and high ductility height attachment is one kind in material surface protection field
The high-performance coating in face, can be applied to prepare the application type solar battery back used in the larger ruthless area of dust storm
Plate.
Embodiment
Below in conjunction with specific embodiment, the present invention is described further, but protection scope of the present invention is not limited to these
The content of specific embodiment and embodiment.
It should be noted that ripe production of the heretofore described height branched structure polyesters dispersant for this area
Product, " height " and non-limiting degree of grafting, height branched structure polyesters are technical term commonly used in the art, such as German Bick
The BYK2151 of Co., Ltd, 2152 etc..
Embodiment 1
A kind of high performance fluorine carbon coating, is made up of first and second liang of components.
The preparation of first component：By 1000g (3.04mol OH groups) PTMG-propylene oxide copolymer glycols (on
Hai Yiqing trade Co., Ltds) under the conditions of 150 DEG C, 15g Hinered phenols antioxidants 1076 are added as needed, and (Dongguan City, which converges, anticipates
Chemical materials Co., Ltd), add 5g p-methyl benzenesulfonic acid (Mike woods reagent) and be dehydrated 2.5 hours；Reaction temperature is down to 95 afterwards
DEG C, PTMG-propylene oxide copolymer glycols after dehydration add 2932g (9.12mol NCO groups) hexa-methylene two
Isocyanate trimer curing agent HT-90BS (Wanhua Chemical Group Co., Ltd.), 2932g anhydrous acetic acid butyl esters (Zhejiang
Chemical company) it is added sequentially in reactor, insulation reaction 8 hours, then vacuum is kept for 1 hour, is made isocyanate-terminated
PTMG-propylene oxide copolymerization performed polymer, obtain sealing standby after first component, cooling；
The preparation of component B：
200g butanone (Hangzhou chemical reagent Co., Ltd) is placed in container, 400g is sequentially added under stirring at low speed
(0.39mol OH groups) fluorocarbon resin ZHM-2 (east fluorination work), the wetting point of 6.5g affinity groups containing pigment polymer copolymerization body
Powder BYK-163 (German Bick Chemical Co., Ltd.), 230g titanium dioxides R793 (Luohe Xing Mao Tai Ye limited companies),
It is ground after 10g carbon blacks MA100 (Mitsubishi) is pre-dispersed with sand mill, to grain fineness≤5 micron, adds 11.5g
The isooctyl acid tin catalyst of monobutyl three (the far and near Chemical Co., Ltd. in Nantong), 2g polyester modification dimethyl silicone polymer levelling agents
BYK310 (German Bick Chemical Co., Ltd.), after being well mixed, adjusts viscosity, filtering is made second component, deposited in dry
It is stand-by in hermetically sealed can；
The preparation of high performance fluorine carbon coating：Before coating, by first component and component B according to mole the ratio between matched somebody with somebody for 0.6
Than being well mixed, fluorocarbon coating being made.
Embodiment 2
The preparation of first component：1000g (9.6mol OH groups) polycaprolactone polyol PCL303 (Japanese Daicel) are existed
Under the conditions of 100 DEG C, 5g Hinered phenols antioxidants 1076 (Dongguan City Hui Yi chemical materials Co., Ltd), dehydration are added as needed
3.5 hour；Reaction temperature is down to 75 DEG C afterwards, and 3717g (19.2mol are added in the polycaprolactone polyol PCL303 after dehydration
NCO group) hexamethylene diisocyanate trimer curing agent TKA100 (Asahi Chemical Corp), 18g tin dilaurates
The anhydrous positive butanone (Zhejiang chemical company) of dibutyl tin, 3717g is added sequentially to insulation reaction 6 hours, Ran Houzhen in reactor
Sky is kept for 2 hours, and isocyanate-terminated polycaprolactone polyol performed polymer is made, obtains sealing standby after first component, cooling；
The preparation of component B：
The anhydrous butanone of 230g (Hangzhou chemical reagent Co., Ltd) is placed in container, 400g is sequentially added under stirring at low speed
(0.46mol OH groups) fluorocarbon resin L101 (Huambo painting Co., Ltd), 16g affinity groups containing acid pigment high score
Sub- EVA class dispersant B YK111 (German Bi Ke chemical companies), 400g titanium dioxide r902s (Dupont), it is pre-dispersed after
It is ground with sand mill, to grain fineness≤5 micron, adds the polyether-modified poly organo siloxane levelling agents 505 of 2.2g (deep
Zhen Shi Wei Bo Chemical Co., Ltd.s), 8.2g stannous octoate catalysts (the far and near Chemical Co., Ltd. in Nantong) after being well mixed, are adjusted
Whole viscosity, filtering is made second component face slurry, deposited in stand-by in dry hermetically sealed can；
The preparation of high performance fluorine carbon coating：Before coating, by first component and component B according to mole the ratio between matched somebody with somebody for 1.5
Than being well mixed, fluorocarbon coating being made.
Embodiment 3
A kind of high performance fluorine carbon coating, is made up of first and second liang of components.
The preparation of first component：By 1000g PCDLs T5651 (1.96mol OH groups) (the firm chemical industry of Guangzhou sky
Science and Technology Ltd.) it is dehydrated 4.5 hours under the conditions of 130 DEG C；Reaction temperature is down to 45 DEG C afterwards, and the makrolon after dehydration is more
First alcohol T5651 adds 1557g (4.41mol NCO groups) different Buddhist isophorone diisocyanate trimer Z4470BA, and (Germany is visitd
Ear), 854g (4.41mol NCO groups) hexamethylene diisocyanate trimer curing agent TKA100 (Asahi Chemical Industry's chemistry strain formulas
Commercial firm), 2411g anhydrous ethyl acetates (Zhejiang chemical company) be added sequentially in reactor, insulation reaction 5 hours, Ran Houzhen
Sky is kept for 3 hours, and isocyanate-terminated PCDL performed polymer is made, obtains sealing standby after first component, cooling；
The preparation of component B：
350g anhydrous dimethyls benzene (Hangzhou chemical reagent Co., Ltd) is placed in container, sequentially added under stirring at low speed
650g (1.7molOH groups) fluorocarbon resin GK570 (Daikin), the polyester wetting dispersing agent BYK- of 16g highly branched structures
2151 (German Bick Chemical Co., Ltd.s), 160g carbon blacks (Dongguan City Ju Tai Chemical Co., Ltd.s), 60g calcium carbonate (Shanghai letter
Yun Yuan Chemical Co., Ltd.s) it is pre-dispersed after be ground with sand mill, to grain fineness≤5 micron, mend that 8g is polymer to disappear
Infusion BYK8801 (German Bick chemical company) adds 1g tin dilaurate dioctyl tins catalyst (Jin Tian raw materials Co., Ltd),
5g the copolymer levelling agent BYK4510 (German Bick Chemical Co., Ltd.) with acidic-group, 50g Degussa flatting silicas OK520
(the triumphant mattress chemical industry in Shanghai), after being well mixed, adjusts viscosity, filtering is made second component, deposited in stand-by in dry hermetically sealed can；
The preparation of high performance fluorine carbon coating：Before coating, by first component and component B according to mole the ratio between matched somebody with somebody for 1.0
Than being well mixed, fluorocarbon coating being made.A kind of high performance fluorine carbon coating, is made up of first and second liang of components.
Embodiment 4
A kind of high performance fluorine carbon coating, is made up of first and second liang of components.
The preparation of first component：It is prepared by first component：By 1000g (2.36mol OH groups) aromatic polyester polyol AK3080
(Foshan is with moral Chemical Co., Ltd.) adds (the Dongguan City remittance meaning chemical industry of 25g Hinered phenols antioxidants 1076 under the conditions of 105 DEG C
Materials Co., Ltd), it is dehydrated 2.5 hours；Reaction temperature is down to 55 DEG C afterwards, the aromatic polyester polyol AK3080 after dehydration
Add 2023g (6.08mol NCO groups) hexamethylene diisocyanate trimer curing agent HT-90BS (ten thousand magnificent chemical groups
Limited company), 2023g anhydrous acetic acids butyl ester (Zhejiang chemical company) be added sequentially in reactor, insulation reaction 8 is small
When, then vacuum is kept for 1 hour, and isocyanate-terminated PTMG-propylene oxide copolymerization performed polymer is made, first is obtained
Seal standby after component, cooling；
The preparation of component B：
200g propylene glycol methyl ether acetates (Hangzhou chemical reagent Co., Ltd) are placed in container, under stirring at low speed successively
Add 350g (0.37mol OH groups)) fluorocarbon resin SW-5570 (Shanghai Sheng Wei trade Co., Ltds), 2g wetting dispersing agents
BYK-163 (German Bick Chemical Co., Ltd.), it is pre-dispersed to be ground afterwards with sand mill, to grain fineness≤5 micron, mend
Plus 3g acrylate interpolymer levelling agents BYK350 (German Bick Chemical Co., Ltd.), (Nantong is far for 15g zinc Isoocatanoates catalyst
Near Chemical Co., Ltd.), the polymer defoamer BYK8801 of 12g (German Bick Chemical Co., Ltd.) after being well mixed, are adjusted
Whole viscosity, filtering is made component B face slurry, deposited in stand-by in dry hermetically sealed can；
The preparation of high performance fluorine carbon coating：Before coating, by first component and component B according to mole the ratio between matched somebody with somebody for 0.9
Than being well mixed, fluorocarbon coating being made.
Comparative example 1
The preparation of first component：By 1303g (6.08mol NCO groups) hexamethylene diisocyanate trimer curing agent
HT-90BS (Wanhua Chemical Group Co., Ltd.) is well mixed, mistake with 1303g anhydrous acetic acids butyl ester (Zhejiang chemical company)
Filter, is made first component, deposits in stand-by in dry hermetically sealed can.
The preparation of component B：It is same as Example 1；
The preparation of high performance fluorine carbon coating：Before coating, by first component and component B according to mole the ratio between matched somebody with somebody for 0.6
Than being well mixed, fluorocarbon coating being made.
Comparative example 2
The preparation of first component：1000g (9.6mol OH groups) polycaprolactone polyol PCL303 (Japanese Daicel) are existed
Under the conditions of 100 DEG C, 5g Hinered phenols antioxidants 1076 (Dongguan City Hui Yi chemical materials Co., Ltd), dehydration are added as needed
3.5 hour；Reaction temperature is down to 75 DEG C afterwards, and 1858g (9.6mol are added in the polycaprolactone polyol PCL303 after dehydration
NCO group) hexamethylene diisocyanate trimer curing agent TKA100 (Asahi Chemical Corp), the anhydrous fourths of 1858g
Ketone (Zhejiang chemical company) is added sequentially to insulation reaction 6 hours in reactor, and then vacuum is kept for 2 hours, and isocyanic acid is made
The polycaprolactone polyol performed polymer of ester end-blocking, obtains sealing standby after first component, cooling；
The preparation of component B：It is same as Example 2；
The preparation of high performance fluorine carbon coating：Before coating, by first component and component B according to mole the ratio between matched somebody with somebody for 0.6
Than being well mixed, fluorocarbon coating being made.
The preparation method of sample in the present embodiment is common technical means in the art, can specifically pass through the company of automation
Continuous shaping or batch process are coated uniformly on by gluing substrate surface, and coating dry film thickness is 5~60 microns, and solidification temperature is
145 DEG C~200 DEG C, hardening time is 2~30min.Can be structural steel, aluminium, poly terephthalic acid second by bonding substrates
Terephthalate substrate film, polybutylene terephthalate (PBT) basilar memebrane, PEN basilar memebrane, poly- naphthalenedicarboxylic acid fourth
Terephthalate substrate film, poly- 11 lactam group counterdie, nylon 12 basilar memebrane, polypropylene-base counterdie, polyvinyl counterdie,
Safety glass etc..
The coating prepared to fluorocarbon coating prepared by embodiment 1~4 and comparative example 1,2, and carry out performance detection and aging
Test is, it is necessary to which explanation, every related performance indicators of sample prepared by the coating obtained by above-described embodiment are under
State method of testing to be evaluated, evaluation result is listed in table 1.
1. coating hardness
According to GB/T6739《Hardness of film pencil determination method》The hardness of standard testing coating：By pencil with 0.5mm/s speed
Degree moves horizontally 3mm on sample and determines hardness, tests 5 times, according to there is cut situation, records hardness values.
2. method of testing reference standard GB/T 23988《Coating wearability determines knockout method》：Sample in advance 25 DEG C,
24h is placed under 50% humidity environment, is then tested, normal sand is highly fallen on the sample of 45° angle from 914mm, according to abrasion
Region, calculates knockout amount, and the wearability of testing sample is calculated by formula：In A=V/T, formula：A wearabilities, unit is to rise every micron
(L/ μm), V abrasive material usage amounts, unit is rises a L, and T is coating layer thickness, unit for μm.
3. wet and heat ageing resistant performance
Hydrothermal aging experiment is carried out by GB/T2423.3 test methods.
Experiment condition：+ 85 DEG C, relative humidity 85%.
Sample adhesive force is tested according to ISO-2409-2007 standards before and after experiment；To sample yellowness index (△
YI) according to national standard GB2409-80《Plastics yellow colour index test method》It is measured.
The performance parameter of fluororine-carbon coating sample made from table 1
In the preparation method of the fluorocarbon coating of embodiment 1~4, the polyol oligomer used is respectively PPG, gathered
Caprolactone polyol, polycarbonate polyol, aromatic polyester polyol prepare isocyanate-terminated prepolymer；In comparative example 1
It is normal experiment formula, using conventional solidified dose, polyol oligomer is not used and carries out performed polymer preparation；The polyalcohol of comparative example 2
Oligomer performed polymer is 1 according to the OH of polyol oligomer and the NCO mol ratios of isocyanate curing agent:1 prepares.The number in table
According to understanding that the fluororine-carbon coating of embodiment 1~4 can effectively improve the wearability of coating, hardness is high, and through burin-in process post yellowing
Index is relatively small, and ageing-resistant performance is excellent.It can be seen that the fluorocarbon coating that the present invention is provided has excellent weather-proof, resistance to knock-out capability
Can, it is a kind of high performance fluorine carbon coating, is a kind of to be used to prepare the application type that uses in the larger ruthless area of dust storm too
The high performance fluorine carbon coating of positive energy battery back-sheet.
Claims (10)
1. a kind of preparation method of high performance fluorine carbon coating, it is characterised in that comprise the following steps：
(1) by 100 weight polyol oligomer, the antioxidant of 0~2.5 parts by weight, 0~0.5 parts by weight acid polymerization inhibitor
After well mixed, it is dehydrated 2.5~4.5 hours under the conditions of 100~150 DEG C；Temperature is down to 45~95 DEG C, adds isocyanates and consolidates
Agent and anhydrous diluents A insulation reactions 5~8 hours, then add catalyst A, and after being well mixed, 1 is kept under vacuum condition
~3 hours, first component is made；Wherein, the NCO mol ratios of the OH of polyol oligomer and isocyanate curing agent are 1:2.0~
4.5, anhydrous diluents A are equal with the quality of isocyanate curing agent, and catalyst A consumption is isocyanate curing agent quality
0~0.5%；
(2) fluorocarbon resin of 35~65 parts by weight is added into the diluent B of 20~35 parts by weight under agitation, is added
The inorganic filler of the dispersant of 0~1.6 parts by weight, 0~40 parts by weight, it is pre-dispersed to be ground afterwards with sand mill, to particle
Fineness≤5 micron, add the catalyst B of 0.1~1.5 parts by weight, the levelling agent of 0~0.5 parts by weight, 0~1.2 parts by weight and disappear
The flatting silica of infusion, 0~5 parts by weight, after being well mixed, adjusts viscosity, component B is made in filtering；
During coating, according in the NCO and component B in first component institute's hydroxyl mole the ratio between be 0.6~1.5：1.0
Matched；
The polyol oligomer is one or both of PPG, PEPA according to the mixed of any proportioning composition
Compound, it is equal that the PPG includes polyoxypropylene polyol, polymer grafted polyether polyol, polytetrahydrofuran diol
Poly or poly tetrahydrofuran polyol, tetrahydrofuran-propylene oxide copolymer glycols, polyoxyethylated polyols；PEPA
Including adipic acid system polyester-diol, aromatic polyester polyol, polycaprolactone polyol, polycarbonate polyol.
2. a kind of preparation method of high performance fluorine carbon coating as claimed in claim 1, it is characterised in that：Described isocyanates
Curing agent is one of following or two kinds of mixtures according to any proportioning composition：Hexamethylene diisocyanate (HDI) tripolymer,
Hexamethylene diisocyanate (HDI) biuret, hexamethylene diisocyanate (HDI) addition product, isophorone diisocyanate
Ester (IPDI) tripolymer, IPDI (IPDI) addition product.
3. a kind of preparation method of high performance fluorine carbon coating as claimed in claim 1, it is characterised in that：The fluorocarbon resin by
In vinylidene type fluorocarbon resin, CTFE type fluorocarbon resin, tetrafluoroethene type fluorocarbon resin it is one or more according to
Any proportioning composition.
4. a kind of preparation method of high performance fluorine carbon coating as claimed in claim 1, it is characterised in that：The antioxidant be by
Hinder phenolic antioxidant；The acid polymerization inhibitor is p-methyl benzenesulfonic acid；The catalyst A and catalyst B are metallic catalyst, bag
Include zinc Isoocatanoate, stannous octoate, tin dilaurate dioctyl tin, monobutyltin oxide, the isooctyl acid tin of monobutyl three, tin dilaurate two
One or more mixtures according to any proportioning composition in butyl tin.
5. a kind of preparation method of high performance fluorine carbon coating as claimed in claim 1, it is characterised in that：Described dispersant by
Block copolymerization species dispersant, acrylic block copolymers class dispersant, the height branched structure polyester of the affinity groups containing pigment
In class dispersant, the dispersant of copolymer analog containing acidic-group, hydroxy functional group carboxylic acid esters dispersant it is one or more according to
Any proportioning composition.
6. a kind of preparation method of high performance fluorine carbon coating as claimed in claim 1, it is characterised in that：Described levelling agent by
In polyether siloxane copolymer class levelling agent, polyether-modified poly organo siloxane levelling agent, polyacrylate levelling agent
It is one or more to be constituted according to any proportioning.
7. a kind of preparation method of high performance fluorine carbon coating as claimed in claim 1, it is characterised in that：The inorganic filler by
Titanium dioxide, carbon black, calcium carbonate, aluminum oxide, barium sulfate are one or more to be constituted according to any proportioning.
8. a kind of preparation method of high performance fluorine carbon coating as claimed in claim 1, it is characterised in that：It is the diluent A, dilute
Agent B is released by toluene, dimethylbenzene, n-butyl acetate, propylene glycol methyl ether acetate, ethyl acetate, butyl acetate, ethylene glycol, first
It is one or more according to any proportioning composition in alcohol, n-butanol, butanone, MEK, cyclohexanone.
9. a kind of preparation method of high performance fluorine carbon coating as claimed in claim 1, it is characterised in that：The defoamer is poly-
Oxygen ethene polyoxypropylene pentaerythrite ether, polyoxyethylene polyoxy propyl alcohol amidogen ether, polypropylene glycerol aether, polyoxyethylene polyoxypropylene
Glycerin ether, the one or more of fluorine-carbon modified acrylic ester type constitute according to any proportioning.
10. a kind of preparation method of high performance fluorine carbon coating as claimed in claim 1, it is characterised in that：The flatting silica is
Silica, talcum powder one or both are constituted according to any proportioning.
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| CN106010414A (en) * | 2016-06-30 | 2016-10-12 | 杭州福斯特光伏材料股份有限公司 | High-cohesiveness fluorocarbon coating and application |
| CN106366791B (en) * | 2016-08-29 | 2018-11-09 | 苏州福斯特光伏材料有限公司 | A kind of backboard that can delay failure under dry wet alternating environment |
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| CN107629570A (en) * | 2017-09-24 | 2018-01-26 | 陈晨特 | A kind of ceramic sanitary appliance self-cleaning composition |
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| CN109354937B (en) * | 2018-09-26 | 2020-12-11 | 江苏省化工研究所有限公司 | Flexible curing agent for fluorocarbon coating and preparation method thereof |
| CN109505129A (en) * | 2018-11-07 | 2019-03-22 | 连云港纶洋单丝科技有限公司 | A kind of liquid gel resin and the method for preparing ultra-high molecular weight polyethylene fishline |
| CN109679418B (en) * | 2018-12-24 | 2021-04-09 | 山东一诺威聚氨酯股份有限公司 | Polyurethane elastomer for fluorocarbon paint and preparation method thereof |
| CN112680077A (en) * | 2019-10-17 | 2021-04-20 | 陈二孝 | Fluorocarbon paint for surface corrosion prevention of carbon steel product and preparation method thereof |
| CN113912819B (en) * | 2021-09-28 | 2023-01-31 | 广东粤港澳大湾区黄埔材料研究院 | Polyurethane material and preparation method and application thereof |
| CN116445071A (en) * | 2023-04-28 | 2023-07-18 | 中国铁道科学研究院集团有限公司金属及化学研究所 | Low-temperature-resistant flexible fluorocarbon coating and preparation method thereof |
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| US6881782B2 (en) * | 2002-11-06 | 2005-04-19 | 3M Innovative Properties Company | Latex paint compositions and coatings |
| CN1900183B (en) * | 2006-07-20 | 2010-10-06 | 上海申真企业发展有限公司 | Self cleaning fluorocarbon resin paint and its preparing method |
| CN101712842B (en) * | 2009-11-09 | 2013-10-16 | 深圳市广田环保涂料有限公司 | Adhesion and doodling prevention coating |
| CN102277048A (en) * | 2011-07-01 | 2011-12-14 | 中远关西涂料化工（天津）有限公司 | Self-cleaning polytetrafluoroethylene FEVE (fluoralkene alkyl vinyl ether or ester) coating and preparation method thereof |
| CN103952072B (en) * | 2014-05-15 | 2016-09-28 | 上海台安实业集团有限公司 | A kind of polyurethane water-proof paint and preparation method thereof |
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