CN110527430A - A kind of modified polyvinylidene fluoride fluorocarbon coating and preparation method thereof - Google Patents
A kind of modified polyvinylidene fluoride fluorocarbon coating and preparation method thereof Download PDFInfo
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- CN110527430A CN110527430A CN201910790741.7A CN201910790741A CN110527430A CN 110527430 A CN110527430 A CN 110527430A CN 201910790741 A CN201910790741 A CN 201910790741A CN 110527430 A CN110527430 A CN 110527430A
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
- C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C08G81/024—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G
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- C09D187/00—Coating compositions based on unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
- C09D187/005—Block or graft polymers not provided for in groups C09D101/00 - C09D185/04
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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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 invention discloses a kind of modified polyvinylidene fluoride fluorocarbon coatings, it includes modified polyvinylidene fluoride resin dispersion liquid,, including 30~45 parts of polyvinylidene fluoride resin, 5~15 parts of modifying agent, 0.5~1.5 part of initiator, 35~60 parts of solvent based on parts by weight of raw materials, the modifying agent is that 1:0.5~1.5 form by polyethyleneglycol maleate and polyethylene glycol methacrylate-styrene polymer ratio by weight for it.The present invention is innovatively from the angle of MOLECULE DESIGN, it selects polyethyleneglycol maleate and polyethylene glycol methacrylate-styrene polymer is modifying agent, make polyvinylidene fluoride resin that there is hydrophilic side switch, resin matrix is modified as to have amphiphilic fluorocarbon modified resin by the strong-hydrophobicity of pure PVDF resin, and using modified polyvinylidene fluoride resin dispersion liquid as main film forming matter, obtains comprehensive performance and match in excellence or beauty the water-solubility modifying polyvinylidene fluoride fluorocarbon coating of existing solvent type fluorocarbon coating.
Description
Technical field
The present invention relates to paint field, in particular to a kind of polyvinylidene fluoride fluorocarbon coating and preparation method thereof.
Background technique
Fluororesin refers to the high-molecular compound on the carbon atom of main chain or side chain containing fluorine atom, polyvinylidene fluoride tree
Rouge (PVDF) is the resin matrix for preparing polyvinylidene fluoride fluorocarbon coating.The fluorine carbon key that the maximum fluorine of electronegativity is formed has excellent
Fastness and symmetry more, so that polyvinylidene fluoride fluorocarbon coating has excellent performance, such as resistant to chemical etching, oxytolerant
Change, high mechanical strength and toughness, the against weather of brilliance etc., application field is extensive.However traditional polyvinylidene fluoride fluorine
Carbon coating is mostly organic solvent class coating and powdery paints, and the polyvinylidene fluoride fluorocarbon coating of organic solvent type is in preparation process
With the VOC that can volatilize in solidification process, environmental-protecting performance is poor；It is severe to there is the warm condition of solidification in powder polyvinylidene fluoride fluorocarbon coating
The disadvantages of at quarter, difficulty of construction is big, these all limit the practical application of polyvinylidene fluoride fluorocarbon coating.
Low the VOC even developing policy of the environmental protection coating material of VOC free have been responded by aqueous fluorocarbon coating made of medium of water,
It is not only suitable for market development and the upgrading of coating industry, has more been in response to serious hope of the people to " green coating ".However, due to fluorine
The electronegativity of atom is strong, and the interaction force between fluorine atom is spirally distributed fluorine atom on C-C chain, makes molecule
It is easy to be completely filled up by the gap between two carbon atoms of attack on main chain, so as to form the knot of High level of stereoselectivity shielding
Structure, most of destructiveness group is difficult to enter, so that polyvinylidene fluoride resin has weatherability outstanding and excellent synthesis
Performance.But also just because of the high electronegativity of F atom on polyvinylidene fluoride resin, and result in polyvinylidene fluoride F resin
Surface tension is low, hydrophily is poor.So the water-solubility modifying of polyvinylidene fluoride resin becomes polyvinylidene fluoride fluorine carbon
The key technology difficulty of coating Water-borne modification exploitation.
Summary of the invention
It is an object of the invention to above-mentioned the deficiencies in the prior art, provide a kind of modified polyvinylidene fluoride fluorocarbon coating and
Preparation method.
The technical solution used in the present invention is: a kind of modified polyvinylidene fluoride fluorocarbon coating comprising modified polyvinilidene
Fluoride resin dispersion liquid, including 30~45 parts of polyvinylidene fluoride resin, modifying agent 5~15 based on parts by weight of raw materials
Part, 0.5~1.5 part of initiator, 35~60 parts of solvent, the modifying agent is by polyethyleneglycol maleate and polyethylene glycol methyl
Acrylate ratio by weight is the composition of 1:0.5~1.5.
Specifically, the polyethyleneglycol maleate and polyethylene glycol methacrylate-styrene polymer of special ratios are grafted by the present invention
It is modified on to polyvinylidene fluoride strand, makes polyvinylidene fluoride resin that there is hydrophilic side switch, by resin matrix
It is modified as that there is amphiphilic fluorocarbon modified resin by the strong-hydrophobicity of pure PVDF resin, is keeping resin excellent steady to reach
The purpose of the compatibility of polyvinylidene fluoride resin and water is significantly improved while qualitative.It finds in the course of the research, poly- second two
Comprehensive performance of the ratio of alcohol list maleate and polyethylene glycol methacrylate-styrene polymer to modified polyvinylidene fluoride resin coating film
It is particularly important, it only just can guarantee that modified polyvinylidene fluoride resin has after later period film forming in suitable proportional region
There is good water-compatible on the basis of good mechanical property.
As a further improvement of the foregoing solution, initiator described in step 2) is by two isobutyl of stannous chloride and N- nitroso
Amine is that 1:2.5~3.5 mix in mass ratio.Specifically, stannous chloride has catalytic action, with two isobutyl of N- nitroso
Amine may advantageously facilitate polymerizeing for polyvinylidene fluoride resin and modifying agent by the compound initiation system that specific mass ratio is constituted
Reaction.
As a further improvement of the foregoing solution, solvent described in step 5) is by 1,1,3- 3-methyl cyclohexanol ketenes and NMP
It is mixed by volume for 1:1~2.Specifically, the specific composition of solvent is molten in raising polyvinylidene fluoride resin as far as possible
The usage amount for poisoning organic solvent is reduced under the premise of solution performance.
As a further improvement of the foregoing solution, the preparation method of the modified polyvinylidene fluoride resin dispersion liquid includes
Following steps:
1) polyvinylidene fluoride resin powder is sufficiently dissolved into nmp solution, modifying agent is added and mixing is uniformly dispersed；
2) initiator is added in nitrogen atmosphere, is dispersed with stirring at room temperature uniformly；
3) 85~95 DEG C are heated to, 15~30h is stirred to react, removes nitrogen atmosphere, deionized water is added, it is thick to obtain precipitating
Product；
4) crude product vacuum filter will be precipitated into filter cake, dissolved with nmp solution, the mixed solution of again with methanol and petroleum ether
Precipitating, filtering, vacuum filtration, obtain modified polyvinylidene fluoride copolymer；
5) modified polyvinylidene fluoride copolymer and solvent mixing are uniformly dispersed in ice-water bath, are obtained modified poly-
Vinylidene fluoride resin dispersion liquid.
As a further improvement of the foregoing solution, the matter of modified polyvinylidene fluoride copolymer described in step 5) and solvent
Amount is than being 1:0.5~1.5.Specifically, when the mass ratio of modified polyvinylidene fluoride copolymer and solvent is in suitable range
When, the modified polyvinylidene fluoride copolymer just has good dissolubility energy in the fluorocarbon coating composition system.
As a further improvement of the foregoing solution, the modified polyvinylidene fluoride fluorocarbon coating based on parts by weight of raw materials including
40~70 parts of modified polyvinylidene fluoride resin dispersion liquid, 10~35 parts of pigments and fillers, 5~15 parts of auxiliary agent, helps 2~7 parts of curing agent
5~20 parts of solvent, 5~25 parts of deionized water.
As a further improvement of the foregoing solution, the curing agent is cyanate compound, is such as selected from isophorone two
Isocyanate trimer (HDI) or isophorone diisocyanate (IPDI).
As a further improvement of the foregoing solution, the pigments and fillers be selected from organic modification montmonrillonite, rutile type titanium white,
At least one of ultrafine mica powder.
As a further improvement of the foregoing solution, the auxiliary agent include wetting dispersing agent, it is coalescing agent, levelling agent, mould proof
Algaecide, defoaming agent and pH adjusting agent.Specifically, the wetting dispersing agent selects polyurethane-type high-molecular compound such as BYK-
163,2~7 parts by weight；The coalescing agent be decylene glycol ester, 1~5 part by weight；The levelling agent selects fluorine richness
Acrylic acid levelling agent, 1~5 part by weight；The fungusproof anti-corrosion agent selects isothiazolinone compound, such as CIT (5- chloro- 2
- 3 ketone of -4 isothiazoline of methyl) and MIT (2-methyl-4-isothiazolin-3-one) at least one, 0.5~2 part by weight；
The defoaming agent is organosilicon or mineral oil antifoam agent, and 0.1~2 part by weight, the pH adjusting agent selects ethanol amine, with weight
0~7 part of meter.
As a further improvement of the foregoing solution, the cosolvent be dipropylene glycol methyl ether and dipropylene at least
One kind, when selecting its mixture, the volume ratio of the dipropylene glycol methyl ether and dipropylene is 1:0.5~1.5.
A kind of preparation method of modified polyvinylidene fluoride fluorocarbon coating as described above comprising following processing step:
1) pigments and fillers, curing agent, auxiliary agent, cosolvent and deionized water are mixed, is stirred with the speed of 1500~2000rpm
8~15min, then 10~25min is stirred with the speed of 2500~3000rpm, obtain white mill base；
2) white mill base is mixed with modified polyvinylidene fluoride resin dispersion liquid, is stirred under 1500~2000rpm speed
15~25min is mixed, pH=8~9 are adjusted, it is ground, obtain modified polyvinylidene fluoride fluorocarbon coating finished product.
The beneficial effects of the present invention are: the present invention selects polyethyleneglycol horse innovatively from the angle of MOLECULE DESIGN
Coming acid esters and polyethylene glycol methacrylate-styrene polymer is modifying agent, and polyethylene glycol is prepared using Transfer Radical Polymerization
The polyvinylidene fluoride resin dispersion liquid of single maleate and polyethylene glycol methacrylate-styrene polymer graft modification makes to gather inclined difluoro second
Olefine resin has hydrophilic side switch, and resin matrix is modified as having amphiphilic modification by the strong-hydrophobicity of pure PVDF resin
Fluorocarbon resin, and using modified polyvinylidene fluoride resin dispersion liquid as main film forming matter, acquisition comprehensive performance matches in excellence or beauty existing molten
The water-solubility modifying polyvinylidene fluoride fluorocarbon coating of dosage form fluorocarbon coating.
Specific embodiment
The present invention is specifically described below with reference to embodiment, in order to technical field personnel to of the invention
Understand.It is necessary to it is emphasized that embodiment is only intended to, the present invention will be further described herein, should not be understood as to this
The limitation of invention protection scope, fields person skilled in the art, the non-intrinsically safe that the present invention is made according to foregoing invention content
The modifications and adaptations of property, should still fall within protection scope of the present invention.Mentioned raw materials following simultaneously are unspecified, are
Commercial product；The processing step or preparation method not referred in detail be processing step known to a person skilled in the art or
Preparation method.
Embodiment 1
Modified polyvinylidene fluoride resin dispersion liquid raw material components are based on parts by weight of raw materials including gathering inclined two in the present embodiment
30 parts of fluoroethylene resin, 10 parts of modifying agent, 1 part of initiator, 35 parts of solvent, wherein the modifying agent is by polyethyleneglycol maleic acid
Ester and polyethylene glycol methacrylate-styrene polymer ratio by weight mix for 1:1.5, and the initiator is by stannous chloride and N-
Nitroso di-iso-butylmanice mixes in mass ratio for 1:2.5, and the solvent presses body by 1,1,3- 3-methyl cyclohexanol ketenes and NMP
Product ratio mixes for 1:2.
Modified polyvinylidene fluoride fluorocarbon coating raw material components are based on parts by weight of raw materials including modified polyvinilidene in the present embodiment
70 parts of fluoride resin dispersion liquid, 3 parts of curing agent, 15 parts of pigments and fillers, 15 parts of auxiliary agent, 10 parts of cosolvent, 20 parts of deionized water,
Wherein the curing agent is HDI, and the pigments and fillers are ultra-fine by 5 parts of organic modification montmonrillonites, 5 parts of rutile type titanium whites and 5 parts
Mica powder composition, the auxiliary agent is by 3 parts of BYK-163 wetting dispersing agents, 3 parts of decylene glycol ester coalescing agents, 4 parts of fluorin modified crylic acids
Levelling agent, 1 part of MIT fungusproof anti-corrosion agent, 1 part of organic silicon defoamer and 3 parts of ethanol amine pH adjusting agent compositions, the cosolvent is by 5
Part dipropylene glycol methyl ether and 5 parts of dipropylenes compositions.
The preparation method of modified polyvinylidene fluoride resin dispersion liquid:
1) polyvinylidene fluoride resin powder is sufficiently dissolved into 50 parts of nmp solution by formula ratio, stirs and heats
System is cooled to room temperature to 50 DEG C of sufficiently dissolutions, polyethyleneglycol maleate and polyethylene glycol methacrylate-styrene polymer is added simultaneously
Mixing is uniformly dispersed；
2) initiator is added in nitrogen atmosphere, stirs 30min at room temperature and is uniformly dispersed；
3) 90 DEG C are heated to, 20h is stirred to react, removes nitrogen atmosphere, deionized water is added, obtains precipitating crude product；
4) crude product vacuum filter will be precipitated into filter cake, dissolved with nmp solution, the mixed solution of again with methanol and petroleum ether
Precipitating is filtered, 48h is filtered by vacuum, and modified polyvinylidene fluoride copolymer is obtained；
5) by modified polyvinylidene fluoride copolymer and by 1,1,3- 3-methyl cyclohexanol ketenes and N- methyl in ice-water bath
The solvent mixing that pyrrolidones mixes is uniformly dispersed, and obtains 1 modified polyvinylidene fluoride resin dispersion liquid of embodiment.
The preparation method of modified polyvinylidene fluoride fluorocarbon coating:
1) pigments and fillers, curing agent, auxiliary agent, cosolvent and deionized water are mixed by formula ratio, is stirred with the speed of 2000rpm
10min is mixed, then 15min is stirred with the speed of 2500rpm, obtains white mill base；
2) white mill base is mixed with the modified polyvinylidene fluoride resin dispersion liquid of formula ratio, under 1500rpm speed
20min is stirred, pH=8~9 are adjusted, it is ground, obtain 1 modified polyvinylidene fluoride fluorocarbon coating finished product of embodiment.
Embodiment 2
Modified polyvinylidene fluoride resin dispersion liquid raw material components are based on parts by weight of raw materials including gathering inclined two in the present embodiment
30 parts of fluoroethylene resin, 10 parts of modifying agent, 1 part of initiator, 35 parts of solvent, wherein the modifying agent is by polyethyleneglycol maleic acid
Ester and polyethylene glycol methacrylate-styrene polymer ratio by weight mix for 1:0.5, and the initiator is by stannous chloride and N-
Nitroso di-iso-butylmanice mixes in mass ratio for 1:3.5, and the solvent presses body by 1,1,3- 3-methyl cyclohexanol ketenes and NMP
Product ratio mixes for 1:1.5.
Modified polyvinylidene fluoride fluorocarbon coating raw material components are based on parts by weight of raw materials including modified polyvinilidene in the present embodiment
60 parts of fluoride resin dispersion liquid, 7 parts of curing agent, 15 parts of pigments and fillers, 15 parts of auxiliary agent, 15 parts of cosolvent, 25 parts of deionized water,
Wherein the curing agent is HDI, and the pigments and fillers are made of 10 parts of organic modification montmonrillonites and 5 parts of rutile type titanium whites, institute
Auxiliary agent is stated by 5 parts of BYK-163 wetting dispersing agents, 3 parts of decylene glycol ester coalescing agents, 2 parts of fluorin modified crylic acid levelling agents, 1 part of MIT
Fungusproof anti-corrosion agent, 1 part of organic silicon defoamer and 3 parts of ethanol amine pH adjusting agent compositions, the cosolvent is by 5 parts of dipropylene glycol methyl ethers
It is formed with 10 parts of dipropylenes.
The preparation method of modified polyvinylidene fluoride resin dispersion liquid:
1) polyvinylidene fluoride resin powder is sufficiently dissolved into 50 parts of nmp solution by formula ratio, stirs and heats
System is cooled to room temperature to 50 DEG C of sufficiently dissolutions, polyethyleneglycol maleate and polyethylene glycol methacrylate-styrene polymer is added simultaneously
Mixing is uniformly dispersed；
2) initiator is added in nitrogen atmosphere, stirs 30min at room temperature and is uniformly dispersed；
3) 85 DEG C are heated to, 30h is stirred to react, removes nitrogen atmosphere, deionized water is added, obtains precipitating crude product；
4) crude product vacuum filter will be precipitated into filter cake, dissolved with nmp solution, the mixed solution of again with methanol and petroleum ether
Precipitating is filtered, 48h is filtered by vacuum, and modified polyvinylidene fluoride copolymer is obtained；
5) by modified polyvinylidene fluoride copolymer and by 1,1,3- 3-methyl cyclohexanol ketenes and N- methyl in ice-water bath
The solvent mixing that pyrrolidones mixes is uniformly dispersed, and obtains 2 modified polyvinylidene fluoride resin dispersion liquid of embodiment.
The preparation method of modified polyvinylidene fluoride fluorocarbon coating:
1) pigments and fillers, curing agent, auxiliary agent, cosolvent and deionized water are mixed by formula ratio, is stirred with the speed of 1500rpm
8min is mixed, then 10min is stirred with the speed of 3000rpm, obtains white mill base；
2) white mill base is mixed with the modified polyvinylidene fluoride resin dispersion liquid of formula ratio, under 2000rpm speed
25min is stirred, pH=8~9 are adjusted, it is ground, obtain 2 modified polyvinylidene fluoride fluorocarbon coating finished product of embodiment.
Embodiment 3
Modified polyvinylidene fluoride resin dispersion liquid raw material components are based on parts by weight of raw materials including gathering inclined two in the present embodiment
45 parts of fluoroethylene resin, 5 parts of modifying agent, 1.5 parts of initiator, 40 parts of solvent, wherein the modifying agent is by polyethyleneglycol Malaysia
Acid esters and polyethylene glycol methacrylate-styrene polymer ratio by weight mix for 1:1, and the initiator is by stannous chloride and N-
Nitroso di-iso-butylmanice mixes in mass ratio for 1:3, and the solvent presses volume by 1,1,3- 3-methyl cyclohexanol ketenes and NMP
Than being mixed for 1:1.
Modified polyvinylidene fluoride fluorocarbon coating raw material components are based on parts by weight of raw materials including modified polyvinilidene in the present embodiment
70 parts of fluoride resin dispersion liquid, 7 parts of curing agent, 17 parts of pigments and fillers, 15 parts of auxiliary agent, 15 parts of cosolvent, 25 parts of deionized water,
Wherein the curing agent is CIT, and the pigments and fillers are made of 12 parts of organic modification montmonrillonites and 5 parts of ultrafine mica powders, described to help
Agent is mould proof by 4 parts of BYK-163 wetting dispersing agents, 3 parts of decylene glycol ester coalescing agents, 4 parts of fluorin modified crylic acid levelling agents, 1 part of MIT
Preservative, 1 part of organic silicon defoamer and 2 parts of ethanol amine pH adjusting agent compositions, the cosolvent is by 5 parts of dipropylene glycol methyl ethers and 10
Part dipropylene composition.
The preparation method of modified polyvinylidene fluoride resin dispersion liquid:
1) polyvinylidene fluoride resin powder is sufficiently dissolved into 50 parts of nmp solution by formula ratio, stirs and heats
System is cooled to room temperature to 50 DEG C of sufficiently dissolutions, polyethyleneglycol maleate and polyethylene glycol methacrylate-styrene polymer is added simultaneously
Mixing is uniformly dispersed；
2) initiator is added in nitrogen atmosphere, stirs 30min at room temperature and is uniformly dispersed；
3) 95 DEG C are heated to, 15h is stirred to react, removes nitrogen atmosphere, deionized water is added, obtains precipitating crude product；
4) crude product vacuum filter will be precipitated into filter cake, dissolved with nmp solution, the mixed solution of again with methanol and petroleum ether
Precipitating is filtered, 48h is filtered by vacuum, and modified polyvinylidene fluoride copolymer is obtained；
5) by modified polyvinylidene fluoride copolymer and by 1,1,3- 3-methyl cyclohexanol ketenes and N- methyl in ice-water bath
The solvent mixing that pyrrolidones mixes is uniformly dispersed, and obtains 3 modified polyvinylidene fluoride resin dispersion liquid of embodiment.
The preparation method of modified polyvinylidene fluoride fluorocarbon coating:
1) pigments and fillers, curing agent, auxiliary agent, cosolvent and deionized water are mixed by formula ratio, is stirred with the speed of 2000rpm
15min is mixed, then 25min is stirred with the speed of 2000rpm, obtains white mill base；
2) white mill base is mixed with the modified polyvinylidene fluoride resin dispersion liquid of formula ratio, under 1500rpm speed
30min is stirred, pH=8~9 are adjusted, it is ground, obtain 3 modified polyvinylidene fluoride fluorocarbon coating finished product of embodiment.
Embodiment 4
Modified polyvinylidene fluoride resin dispersion liquid raw material components are based on parts by weight of raw materials including gathering inclined two in the present embodiment
40 parts of fluoroethylene resin, 15 parts of modifying agent, 0.5 part of initiator, 60 parts of solvent, wherein the modifying agent is by polyethyleneglycol Malaysia
Acid esters and polyethylene glycol methacrylate-styrene polymer ratio by weight mix for 1:1, and the initiator is by stannous chloride and N-
Nitroso di-iso-butylmanice mixes in mass ratio for 1:3, and the solvent presses volume by 1,1,3- 3-methyl cyclohexanol ketenes and NMP
Than being mixed for 1:1.
Modified polyvinylidene fluoride fluorocarbon coating raw material components are based on parts by weight of raw materials including modified polyvinilidene in the present embodiment
40 parts of fluoride resin dispersion liquid, 2 parts of curing agent, 12 parts of pigments and fillers, 6 parts of auxiliary agent, 5 parts of cosolvent, 10 parts of deionized water,
Described in curing agent be CIT, the pigments and fillers are made of 7 parts of organic modification montmonrillonites and 5 parts of ultrafine mica powders, the auxiliary agent by
1 part of BYK-163 wetting dispersing agent, 1 part of decylene glycol ester coalescing agent, 1 part of fluorin modified crylic acid levelling agent, 1 part of MIT fungus-proof antisepsis
Agent, 1 part of organic silicon defoamer and 1 part of ethanol amine pH adjusting agent composition, the cosolvent is by 2 parts of dipropylene glycol methyl ethers and 3 part two
Propandiol butyl ether composition.
The preparation method of modified polyvinylidene fluoride resin dispersion liquid:
1) polyvinylidene fluoride resin powder is sufficiently dissolved into 30 parts of nmp solution by formula ratio, stirs and heats
System is cooled to room temperature to 50 DEG C of sufficiently dissolutions, polyethyleneglycol maleate and polyethylene glycol methacrylate-styrene polymer is added simultaneously
Mixing is uniformly dispersed；
2) initiator is added in nitrogen atmosphere, stirs 30min at room temperature and is uniformly dispersed；
3) 85 DEG C are heated to, 20h is stirred to react, removes nitrogen atmosphere, deionized water is added, obtains precipitating crude product；
4) crude product vacuum filter will be precipitated into filter cake, dissolved with nmp solution, the mixed solution of again with methanol and petroleum ether
Precipitating is filtered, 48h is filtered by vacuum, and modified polyvinylidene fluoride copolymer is obtained；
5) by modified polyvinylidene fluoride copolymer and by 1,1,3- 3-methyl cyclohexanol ketenes and N- methyl in ice-water bath
The solvent mixing that pyrrolidones mixes is uniformly dispersed, and obtains 4 modified polyvinylidene fluoride resin dispersion liquid of embodiment.
The preparation method of modified polyvinylidene fluoride fluorocarbon coating:
1) pigments and fillers, curing agent, auxiliary agent, cosolvent and deionized water are mixed by formula ratio, is stirred with the speed of 2000rpm
15min is mixed, then 25min is stirred with the speed of 2000rpm, obtains white mill base；
2) white mill base is mixed with the modified polyvinylidene fluoride resin dispersion liquid of formula ratio, under 1500rpm speed
30min is stirred, pH=8~9 are adjusted, it is ground, obtain 4 modified polyvinylidene fluoride fluorocarbon coating finished product of embodiment.
Embodiment 5
Modified polyvinylidene fluoride resin dispersion liquid raw material components are based on parts by weight of raw materials including gathering inclined two in the present embodiment
45 parts of fluoroethylene resin, 5 parts of modifying agent, 1 part of initiator, 50 parts of solvent, wherein the modifying agent is by polyethyleneglycol maleic acid
Ester and polyethylene glycol methacrylate-styrene polymer ratio by weight mix for 1:1.2, and the initiator is by stannous chloride and N-
Nitroso di-iso-butylmanice mixes in mass ratio for 1:2.8, and the solvent presses body by 1,1,3- 3-methyl cyclohexanol ketenes and NMP
Product ratio mixes for 1:2.
Modified polyvinylidene fluoride fluorocarbon coating raw material components are based on parts by weight of raw materials including modified polyvinilidene in the present embodiment
50 parts of fluoride resin dispersion liquid, 5 parts of curing agent, 35 parts of pigments and fillers, 12 parts of auxiliary agent, 15 parts of cosolvent, 25 parts of deionized water,
Wherein the curing agent is HDI, and the pigments and fillers are by 10 parts of organic modification montmonrillonites, the titanium dioxide of 15 parts of rutile-types and 10 parts
Ultrafine mica powder composition, the auxiliary agent is by 3 parts of BYK-163 wetting dispersing agents, 3 parts of decylene glycol ester coalescing agents, 2 parts of fluorine richness third
Olefin(e) acid levelling agent, 2 parts of MIT fungusproof anti-corrosion agents, 1 part of organic silicon defoamer and 1 part of ethanol amine pH adjusting agent composition, the cosolvent
It is made of 7 parts of dipropylene glycol methyl ethers and 8 parts of dipropylenes.
The preparation method of modified polyvinylidene fluoride resin dispersion liquid:
1) polyvinylidene fluoride resin powder is sufficiently dissolved into 50 parts of nmp solution by formula ratio, stirs and heats
System is cooled to room temperature to 50 DEG C of sufficiently dissolutions, polyethyleneglycol maleate and polyethylene glycol methacrylate-styrene polymer is added simultaneously
Mixing is uniformly dispersed；
2) initiator is added in nitrogen atmosphere, stirs 30min at room temperature and is uniformly dispersed；
3) 90 DEG C are heated to, 30h is stirred to react, removes nitrogen atmosphere, deionized water is added, obtains precipitating crude product；
4) crude product vacuum filter will be precipitated into filter cake, dissolved with nmp solution, the mixed solution of again with methanol and petroleum ether
Precipitating is filtered, 48h is filtered by vacuum, and modified polyvinylidene fluoride copolymer is obtained；
5) by modified polyvinylidene fluoride copolymer and by 1,1,3- 3-methyl cyclohexanol ketenes and N- methyl in ice-water bath
The solvent mixing that pyrrolidones mixes is uniformly dispersed, and obtains 5 modified polyvinylidene fluoride resin dispersion liquid of embodiment.
The preparation method of modified polyvinylidene fluoride fluorocarbon coating:
1) pigments and fillers, curing agent, auxiliary agent, cosolvent and deionized water are mixed by formula ratio, is stirred with the speed of 1500rpm
10min is mixed, then 20min is stirred with the speed of 3000rpm, obtains white mill base；
2) white mill base is mixed with the modified polyvinylidene fluoride resin dispersion liquid of formula ratio, under 2000rpm speed
20min is stirred, pH=8~9 are adjusted, it is ground, obtain 5 modified polyvinylidene fluoride fluorocarbon coating finished product of embodiment.
Embodiment 6: performance detection data
The modified polyvinylidene fluoride fluorocarbon coating finished product that Examples 1 to 5 is prepared into is subjected to performance detection respectively, and is selected
With U.S.'s Su Wei PVDF solvent based coating fluorocarbon coating (product type 5000HG) its testing result such as the following table 1 as a comparison case
It is shown.
1 embodiment of table and comparative example properties testing result
Above-described embodiment is the preferred embodiment of the present invention, all with similar technique of the invention and made equivalence changes,
It should belong to protection category of the invention.
Claims (10)
1. a kind of modified polyvinylidene fluoride fluorocarbon coating, it is characterised in that: including modified polyvinylidene fluoride resin dispersion liquid,
Its based on parts by weight of raw materials including 30~45 parts of polyvinylidene fluoride resin, 5~15 parts of modifying agent, 0.5~1.5 part of initiator,
35~60 parts of solvent, the modifying agent is by polyethyleneglycol maleate and polyethylene glycol methacrylate-styrene polymer ratio by weight
For the composition of 1:0.5~1.5.
2. a kind of modified polyvinylidene fluoride fluorocarbon coating according to claim 1, it is characterised in that: the initiator by
Stannous chloride and N- nitroso di-iso-butylmanice are that 1:2.5~3.5 mix in mass ratio.
3. a kind of modified polyvinylidene fluoride fluorocarbon coating according to claim 1, it is characterised in that: the solvent by 1,
1,3- 3-methyl cyclohexanol ketenes and NMP are that 1:1~2 mix by volume.
4. a kind of modified polyvinylidene fluoride fluorocarbon coating according to claim 1, it is characterised in that: the modified polyvinilidene
The preparation method of fluoride resin dispersion liquid includes the following steps:
1) polyvinylidene fluoride resin powder is sufficiently dissolved into nmp solution, modifying agent is added and mixing is uniformly dispersed；
2) initiator is added in nitrogen atmosphere, is dispersed with stirring at room temperature uniformly；
3) 85~95 DEG C are heated to, 15~30h is stirred to react, removes nitrogen atmosphere, deionized water is added, obtains precipitating thick production
Object；
4) crude product vacuum filter will be precipitated into filter cake, dissolved with nmp solution, the mixed solution of again with methanol and petroleum ether is heavy
It forms sediment, filtering, vacuum filtration, obtains modified polyvinylidene fluoride copolymer；
5) modified polyvinylidene fluoride copolymer and solvent mixing are uniformly dispersed in ice-water bath, obtain modified polyvinilidene two
Fluoroethylene resin dispersion liquid.
5. a kind of modified polyvinylidene fluoride fluorocarbon coating according to claim 4, it is characterised in that: described in step 5)
The mass ratio of modified polyvinylidene fluoride copolymer and solvent is 1:0.5~1.5.
6. described in any item a kind of modified polyvinylidene fluoride fluorocarbon coatings according to claim 1~5, it is characterised in that by original
Material parts by weight meter include 40~70 parts of modified polyvinylidene fluoride resin dispersion liquid, 2~7 parts of curing agent, 10~35 parts of pigments and fillers,
5~15 parts of auxiliary agent, 5~20 parts of cosolvent, 5~25 parts of deionized water.
7. a kind of modified polyvinylidene fluoride fluorocarbon coating according to claim 6, it is characterised in that: the curing agent is
Cyanate compound.
8. a kind of modified polyvinylidene fluoride fluorocarbon coating according to claim 6, it is characterised in that: the pigments and fillers choosing
From at least one of organic modification montmonrillonite, rutile type titanium white, ultrafine mica powder.
9. a kind of preparation method of modified polyvinylidene fluoride fluorocarbon coating as described in any one of claims 1 to 8, feature
It is to comprise the technical steps that:
1) pigments and fillers, curing agent, auxiliary agent, cosolvent and deionized water are mixed, with the speed of 1500~2000rpm stirring 8~
15min, then 10~25min is stirred with the speed of 2500~3000rpm, obtain white mill base；
2) white mill base is mixed with modified polyvinylidene fluoride resin dispersion liquid, stirs 15 under 1500~2000rpm speed
~25min adjusts pH=8~9, ground, obtains modified polyvinylidene fluoride fluorocarbon coating finished product.
10. a kind of preparation method of modified polyvinylidene fluoride fluorocarbon coating according to claim 9, it is characterised in that:
The auxiliary agent includes wetting dispersing agent, coalescing agent, levelling agent, mildew and algae agent, defoaming agent and pH adjusting agent.
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| PCT/CN2020/107905 WO2021036754A1 (en) | 2019-08-26 | 2020-08-07 | Modified polyvinylidene fluoride fluorocarbon coating and preparation method therefor |
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| WO2021036754A1 (en) * | 2019-08-26 | 2021-03-04 | 佛山科学技术学院 | Modified polyvinylidene fluoride fluorocarbon coating and preparation method therefor |
| CN118374245A (en) * | 2024-06-20 | 2024-07-23 | 江苏一特新材料有限责任公司 | Flexible dispersion type binding material prepared by reactive extrusion, preparation method thereof and preparation method of thick-coating non-cracking positive plate |
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