阅读说明：本技术 一种改性聚偏二氟乙烯氟碳涂料及其制备方法 (A kind of modified polyvinylidene fluoride fluorocarbon coating and preparation method thereof ) 是由 叶秀芳 陈东初 卢俊麒 李剑斌 万星雨 于 2019-08-26 设计创作，主要内容包括：本发明公开了一种改性聚偏二氟乙烯氟碳涂料,其包括改性聚偏二氟乙烯树脂分散液,其按原料重量份计包括聚偏二氟乙烯树脂30～45份、改性剂5～15份、引发剂0.5～1.5份、溶剂35～60份,所述改性剂由聚乙二醇单马来酸酯和聚乙二醇甲基丙烯酸酯按重量份比例为1:0.5～1.5组成。本发明创新地从分子设计的角度出发,选用聚乙二醇单马来酸酯和聚乙二醇甲基丙烯酸酯为改性剂,使聚偏二氟乙烯树脂具有亲水性的侧键,将树脂基体由纯PVDF树脂的强疏水性改性为具有两亲性的改性氟碳树脂,并以改性聚偏二氟乙烯树脂分散液作为主要成膜物,获得综合性能媲美现有溶剂型氟碳涂料的水性化改性聚偏二氟乙烯氟碳涂料。(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.)

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.

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.