CN106634583A - High chlorinated polyethylene composite coating with very good anti-corrosion property and preparation method of high chlorinated polyethylene composite coating - Google Patents
High chlorinated polyethylene composite coating with very good anti-corrosion property and preparation method of high chlorinated polyethylene composite coating Download PDFInfo
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- 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
- 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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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
- C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
- C08F255/023—On to modified polymers, e.g. chlorinated polymers
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F285/00—Macromolecular compounds obtained by polymerising monomers on to preformed graft polymers
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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
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
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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
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
- C09D5/1662—Synthetic film-forming substance
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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
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1687—Use of special additives
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
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Abstract
The invention discloses a high chlorinated polyethylene composite coating with a very good anti-corrosion property. The high chlorinated polyethylene composite coating consists of the following raw materials in parts by weight: 65-85 parts of high chlorinated polyethylene, 26-38 parts of chitosan, 0.8-2 parts of dibenzoyl peroxide, 10-17 parts of methacrylic acid-beta-hydroxyethyl acrylate, a proper amount of ethyl acetate, a proper amount of deionized water, 1-2 parts of tert-butyl hydroperoxide, 13-20 parts of methyl hexafluorobutyl acrylate, a proper amount of absolute ethyl alcohol, 2-4 parts of chlorinated paraffin, 3-5 parts of titanium dioxide, 1-2 parts of defoaming agent, a proper amount of xylene, 3-8 parts of methyltriacetoxysilane, 2-5 parts of tetraethyl orthosilicate and 1-3 parts of titanium trimethylsiloxide. As methacrylic acid-beta-hydroxyethyl acrylate is adopted to graft high chlorinated polyethylene, is subsequently copolymerized with a methyl hexafluorobutyl acrylate monomer to introduce fluorine-containing groups, and is further grafted and compounded with chitosan, a chitosan grafted fluorinated acrylate/high chlorinated polyethylene terpolymer is prepared, and the high chlorinated polyethylene composite coating is relatively good in pollution resistance, very good in corrosion resistance and excellent in adhesion property.
Description
Technical field
The invention belongs to corrosion resistant coating field, and in particular to a kind of highly-chlorinated polyethylene with extremely strong antiseptic property is compound to be applied
Material and preparation method thereof.
Background technology
Highly-chlorinated polyethylene chlorinty is high, also known as HCPE resins.White lightweight little particle, chlorinity>61%, thermal decomposition temperature
Degree>130 DEG C, 180 DEG C of heat-stable time>3min.Due to not containing double bond in molecular structure, chlorine atom is again random distribution, therefore
With good weatherability, ozone resistance, heat-resistant aging, flame resistance, chemical proofing and oil resistivity, but as single
The coating of film forming matter is very crisp, adhesive force is poor, therefore usually adds flexible resin in actual application to improve film
Performance, improves the weather resistance of film, while improving the physical and mechanical properties such as the adhesive force and gloss of film, such as adds alkyd tree
Fat, acrylic resin, chlorinated paraffin etc. are modified.
Zhou Geng's Bin, Yang Zhuoru et al. are at it《The preparation of fluoro-acrylate copolymer and its film coated surface hydro-oleophobicity
The research of energy》In one text, with monomers methyl methacrylate, butyl acrylate, acrylic acid, fluorine-containing(Methyl)Acrylate is original
Material, has synthesized a series of fluoro-acrylate copolymer.Introduce full-fluorine group to change acrylate polymer by side chain
Structure, so both maintained the original advantage of acrylate polymer, give again the distinctive hydrophobic, oleophobic of fluoropolymer,
Weatherability and self-cleaning performance so as to which integrated performance index is greatly improved.
There is shitosan certain bactericidal action to have inhibitory action to microbiologic(al) corrosion, play certain anti-pollution function, and
Itself is nontoxic, it may be said that be a kind of not only anti-corrosion but also antifouling green material.The structure of shitosan is much like with cellulose,
Equally there is good film forming, the hydroxyl and amino in structure makes molecule interchain there is stronger hydrogen bond, can bear certain
There is polar group as hydroxyl and amino in mechanical strength and tensile strength, and molecule, especially amino, become positively charged
There are the lone pair electrons or pi-electron that coordination is formed with the outer layer unoccupied orbital of iron after lotus, adsorption layer is increased with metal surface active force
By force, adsorb membrane stability to improve.
Therefore the present invention is poly- using aqueous-phase suspending afterwards using methacrylic acid-beta-hydroxy ethyl ester grafting highly-chlorinated polyethylene
It is legal that methacrylic acid-beta-hydroxy ethyl ester, Hexafluorobutyl mathacrylate monomer are successfully grafted in chitosan molecule, it is prepared for
Chitosan graft fluorinated acrylate/highly-chlorinated polyethylene terpolymer so that anticorrosive paint has higher pollution resistance, pole
Good anti-corrosive properties, excellent coating and excellent adhesive force.
The content of the invention
For the deficiencies in the prior art, the present invention provides a kind of highly-chlorinated polyethylene with extremely strong antiseptic property compound painting
Material and preparation method thereof, there is provided the antiseptic property of coating, pollution resistance and adhesive force.
A kind of highly-chlorinated polyethylene composite coating with extremely strong antiseptic property, is made up of the raw material of following weight portion:It is high
Haloflex 65-85 parts, shitosan 26-38 parts, dibenzoyl peroxide 0.8-2 parts, methacrylic acid-beta-hydroxy ethyl ester 10-
17 parts, appropriate ethyl acetate, appropriate deionized water, TBHP 1-2 parts, Hexafluorobutyl mathacrylate 13-20 parts,
Appropriate absolute ethyl alcohol, chlorinated paraffin 2-4 parts, titanium dioxide 3-5 parts, defoamer 1-2 parts, appropriate dimethylbenzene, trimethyl acetoxyl
Silane 3-8 parts, tetraethoxysilane 2-5 parts, trimethylsiloxy group titanium 1-3 parts.
Comprise the following steps that:
(1)The preparation of highly-chlorinated polyethylene grafted methacrylic acid-beta-hydroxy ethyl ester:
1/5 part of highly-chlorinated polyethylene, dibenzoyl peroxide, methacrylic acid-beta-hydroxy ethyl ester are added to containing two successively
In the there-necked flask of toluene and ethyl acetate mixtures, stirring makes highly-chlorinated polyethylene fully swelling, is then stirred vigorously and delays
It is slow to add deionized water, after it is uniformly dispersed and stablizes, nitrogen is passed through to 85-95 DEG C of reaction 2-4 hour, hot water wash is used afterwards
Wash, in 55-65 DEG C constant temperature is dried under vacuum to, obtain final product graft product;
(2)Chitosan graft fluorinated acrylate/highly-chlorinated polyethylene terpolymer:
During shitosan after dried process is placed in equipped with reflux condensing tube, agitator, the there-necked flask of thermometer, plus deionization
Water, immersion is swelling overnight in being placed in thermostat water bath, 55-65 DEG C of stirring 5-10 minute, TBHP to be added dropwise, and stirs
8-15 minutes, add step(1)Highly-chlorinated polyethylene grafted methacrylic acid-beta-hydroxy ethyl ester, Hexafluorobutyl mathacrylate, return
Under stream mode react 4-5 hours, be cooled to room temperature, filter, with absolute ethanol washing after, dry to constant weight, obtain chitosan graft
Fluorinated acrylate/highly-chlorinated polyethylene terpolymer;
(3)Prepare coating:
1., remaining HCPE is dissolved in xylene solvent, while stirring, while put into, mixing speed control exist
60-80r/min, until being completely dissolved into clear viscous liquids, then rises to 300-500r/min by mixing speed, adds trimethyl
Acetoxylsilane, tetraethoxysilane, stir 20-40 minutes;
2., step is added(2)The terpolymer of preparation is uniformly mixed, and is warmed up to 45-52 DEG C, sequentially adds trimethyl silicane
Epoxide titanium, titanium dioxide, chlorinated paraffin, defoamer, high speed 1500-3000r/min stirring 3-5 hours, with 20 mesh filter screen coarse filtration;
(4)The material of coarse filtration grinds into sand mill, and it is≤40 m to be ground to fineness, and sand mill outlet temperature is controlled≤60
DEG C, reuse dimethylbenzene and adjust viscosity in 160-220(S)- 4 glasss are applied, filtered, packed with 120 mesh vibratory sieves.
Wherein, described step(1)In dimethylbenzene and ethyl acetate mixtures be by body by dimethylbenzene and ethyl acetate
Product is than being 3:1 mixes.
Compared with prior art, the invention has the advantages that:
(1)The present invention is prepared for highly-chlorinated polyethylene grafted methacrylic acid-beta-hydroxy ethyl ester using suspension swelling Graft Method, afterwards
Fluoro-containing group is introduced with Hexafluorobutyl mathacrylate monomer copolymerization, fluorinated acrylate/highly-chlorinated polyethylene compound is obtained,
Because fluorine electronegativity is big, C-F bond energys are high, and ultraviolet does not have any impact on it, shows that the coating has super-weathering resistance, by changing
Property after fluorinated acrylate not only maintain acrylate primary characteristic, also effectively increase the weatherability of corrosion-inhibiting coating, anti-
Dirt, oil resistant resistance to water.
(2)The present invention is grafted to fluorinated acrylate in chitosan molecule using aqueous suspension polymerization, poly- using shell
The bactericidal action of sugar, improves the anti-soil antiseptic property of coating;Using polar group present in chitosan molecule, strengthen anti-corrosion
Coating and the active force of metal surface, improve absorption membrane stability, strengthen the adhesive force of anticorrosive paint;In addition anti-corrosion of the present invention is applied
, when protecting metal to use, when having iron ion or other digestion of metallic ion, the polar group on shitosan also can be by it for material
It is complexed, forms fine and close " passivating film ", prevents the carrying out of further corrosion.
(3)The present invention is had extremely strong using trimethylsiloxy group titanium with trimethylacetoxysilane, tetraethoxysilane
Antiseptic property, and liquid flow during ensure coating fastening be attached to painting charge level on, ensure that coating
Face and the directly contact in the external world, effectively completely cut off the corrosion of air.
Specific embodiment
A kind of highly-chlorinated polyethylene composite coating with extremely strong antiseptic property, is made up of the raw material of following weight portion:It is high
Haloflex 75, shitosan 33, dibenzoyl peroxide 1.5, methacrylic acid-beta-hydroxy ethyl ester 14, appropriate ethyl acetate goes
Ion appropriate amount of water, TBHP 1, Hexafluorobutyl mathacrylate 16, appropriate absolute ethyl alcohol, chlorinated paraffin 3, titanium dioxide
4, defoamer 1, appropriate dimethylbenzene, trimethylacetoxysilane 6, tetraethoxysilane 3, trimethylsiloxy group titanium 2.
Comprise the following steps that:
(1)The preparation of highly-chlorinated polyethylene grafted methacrylic acid-beta-hydroxy ethyl ester:
1/5 part of highly-chlorinated polyethylene, dibenzoyl peroxide, methacrylic acid-beta-hydroxy ethyl ester are added to containing two successively
In the there-necked flask of toluene and ethyl acetate mixtures, stirring makes highly-chlorinated polyethylene fully swelling, is then stirred vigorously and delays
It is slow to add deionized water, after it is uniformly dispersed and stablizes, it is passed through nitrogen and reacts 3 hours to 90 DEG C, afterwards with hot wash, in 60
DEG C constant temperature is dried under vacuum to, obtains final product graft product;
(2)Chitosan graft fluorinated acrylate/highly-chlorinated polyethylene terpolymer:
During shitosan after dried process is placed in equipped with reflux condensing tube, agitator, the there-necked flask of thermometer, plus deionization
Water, immersion, swelling overnight in being placed in thermostat water bath, 60 DEG C are stirred 8 minutes, and dropwise addition TBHP stirs 13 points
Clock, adds step(1)Highly-chlorinated polyethylene grafted methacrylic acid-beta-hydroxy ethyl ester, Hexafluorobutyl mathacrylate, reflux state
It is lower reaction 4.5 hours, be cooled to room temperature, filter, with absolute ethanol washing after, dry to constant weight, obtain chitosan graft fluorine-containing third
Olefin(e) acid ester/highly-chlorinated polyethylene terpolymer;
(3)Prepare coating:
1., remaining HCPE is dissolved in xylene solvent, while stirring, while put into, mixing speed control exist
80r/min, until being completely dissolved into clear viscous liquids, then rises to 500r/min by mixing speed, adds pivaloyl oxygen
Base silane, tetraethoxysilane, stir 30 minutes;
2., step is added(2)The terpolymer of preparation is uniformly mixed, and is warmed up to 50 DEG C, sequentially adds trimethyl silica
Base titanium, titanium dioxide, chlorinated paraffin, defoamer, high speed 2500r/min is stirred 4 hours, with 20 mesh filter screen coarse filtration;
(4)The material of coarse filtration grinds into sand mill, and it is≤40 m to be ground to fineness, and sand mill outlet temperature is controlled≤60
DEG C, reuse dimethylbenzene and adjust viscosity in 160-220(S)- 4 glasss are applied, filtered, packed with 120 mesh vibratory sieves.
Wherein, described step(1)In dimethylbenzene and ethyl acetate mixtures be by body by dimethylbenzene and ethyl acetate
Product is than being 3:1 mixes.
Coating property test result:
Resistance to impact:>=46kg/cm, pliability:≤ 2.2mm, adhesive force:1 grade;
Drying time(h):Surface drying≤0.5, does solid work≤4;
Decay resistance under normal temperature:
The 10%HCl aqueous solution >=360h, coating is non-foaming, do not fall off;
20%H2SO4The aqueous solution >=360h, coating is non-foaming, does not fall off;
The 20%NaOH aqueous solution >=360h, coating is non-foaming, does not fall off;
Resisting salt fog corrosion is tested >=50 times, and coating is non-foaming, without rotten, ruckbildung.
Claims (3)
1. a kind of highly-chlorinated polyethylene composite coating with extremely strong antiseptic property, it is characterised in that by the original of following weight portion
Material composition:Highly-chlorinated polyethylene 65-85 parts, shitosan 26-38 parts, dibenzoyl peroxide 0.8-2 parts, methacrylic acid-β-
Hydroxyl ethyl ester 10-17 part, appropriate ethyl acetate, appropriate deionized water, TBHP 1-2 parts, methacrylic acid hexafluoro fourth
Ester 13-20 parts, appropriate absolute ethyl alcohol, chlorinated paraffin 2-4 parts, titanium dioxide 3-5 parts, defoamer 1-2 parts, appropriate dimethylbenzene, front three
Base acetoxylsilane 3-8 parts, tetraethoxysilane 2-5 parts, trimethylsiloxy group titanium 1-3 parts.
2. the preparation side of a kind of highly-chlorinated polyethylene composite coating with extremely strong antiseptic property according to claims 1
Method, it is characterised in that comprise the following steps that:
(1)The preparation of highly-chlorinated polyethylene grafted methacrylic acid-beta-hydroxy ethyl ester:
1/5 part of highly-chlorinated polyethylene, dibenzoyl peroxide, methacrylic acid-beta-hydroxy ethyl ester are added to containing two successively
In the there-necked flask of toluene and ethyl acetate mixtures, stirring makes highly-chlorinated polyethylene fully swelling, is then stirred vigorously and delays
It is slow to add deionized water, after it is uniformly dispersed and stablizes, nitrogen is passed through to 85-95 DEG C of reaction 2-4 hour, hot water wash is used afterwards
Wash, in 55-65 DEG C constant temperature is dried under vacuum to, obtain final product graft product;
(2)Chitosan graft fluorinated acrylate/highly-chlorinated polyethylene terpolymer:
During shitosan after dried process is placed in equipped with reflux condensing tube, agitator, the there-necked flask of thermometer, plus deionization
Water, immersion is swelling overnight in being placed in thermostat water bath, 55-65 DEG C of stirring 5-10 minute, TBHP to be added dropwise, and stirs
8-15 minutes, add step(1)Highly-chlorinated polyethylene grafted methacrylic acid-beta-hydroxy ethyl ester, Hexafluorobutyl mathacrylate, return
Under stream mode react 4-5 hours, be cooled to room temperature, filter, with absolute ethanol washing after, dry to constant weight, obtain chitosan graft
Fluorinated acrylate/highly-chlorinated polyethylene terpolymer;
(3)Prepare coating:
1., remaining HCPE is dissolved in xylene solvent, while stirring, while put into, mixing speed control exist
60-80r/min, until being completely dissolved into clear viscous liquids, then rises to 300-500r/min by mixing speed, adds trimethyl
Acetoxylsilane, tetraethoxysilane, stir 20-40 minutes;
2., step is added(2)The terpolymer of preparation is uniformly mixed, and is warmed up to 45-52 DEG C, sequentially adds trimethyl silicane
Epoxide titanium, titanium dioxide, chlorinated paraffin, defoamer, high speed 1500-3000r/min stirring 3-5 hours, with 20 mesh filter screen coarse filtration;
(4)The material of coarse filtration grinds into sand mill, and it is≤40 m to be ground to fineness, and sand mill outlet temperature is controlled≤60
DEG C, reuse dimethylbenzene and adjust viscosity in 160-220(S)- 4 glasss are applied, filtered, packed with 120 mesh vibratory sieves.
3. the preparation side of a kind of highly-chlorinated polyethylene composite coating with extremely strong antiseptic property according to claims 2
Method, it is characterised in that described step(1)In dimethylbenzene and ethyl acetate mixtures be by body by dimethylbenzene and ethyl acetate
Product is than being 3:1 mixes.
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Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
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CN102863854A (en) * | 2012-10-18 | 2013-01-09 | 山东聊城齐鲁特种涂料有限责任公司 | High chlorinated potyethlene anti-corrosive paint and preparation method thereof |
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Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
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CN102863854A (en) * | 2012-10-18 | 2013-01-09 | 山东聊城齐鲁特种涂料有限责任公司 | High chlorinated potyethlene anti-corrosive paint and preparation method thereof |
Non-Patent Citations (1)
Title |
---|
熊琼等: "氯化聚乙烯溶胀悬浮接枝甲基丙烯酸-β-羟乙酯", 《高分子材料科学与工程》 * |
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