CN106590189A - Fluororesin-modified high-chlorinated polyethylene anti-corrosion composite coating and preparation method of same - Google Patents
Fluororesin-modified high-chlorinated polyethylene anti-corrosion composite coating and preparation method of same Download PDFInfo
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- CN106590189A CN106590189A CN201611008013.9A CN201611008013A CN106590189A CN 106590189 A CN106590189 A CN 106590189A CN 201611008013 A CN201611008013 A CN 201611008013A CN 106590189 A CN106590189 A CN 106590189A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D123/00—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers
- C09D123/26—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers modified by chemical after-treatment
- C09D123/28—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers modified by chemical after-treatment by reaction with halogens or compounds containing halogen
- C09D123/286—Chlorinated polyethylene
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- C—CHEMISTRY; METALLURGY
- 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
- C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
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- C—CHEMISTRY; METALLURGY
- 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
- C08F285/00—Macromolecular compounds obtained by polymerising monomers on to preformed graft polymers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- 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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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
- C09D5/1662—Synthetic film-forming substance
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- Wood Science & Technology (AREA)
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- Polymers & Plastics (AREA)
- General Chemical & Material Sciences (AREA)
- Graft Or Block Polymers (AREA)
Abstract
The invention discloses a fluororesin-modified high-chlorinated polyethylene anti-corrosion composite coating, which is composed of, by weight, 60-80 parts of high-chlorinated polyethylene, 24-35 parts of chitosan, 0.6-2 parts of dibenzoyl peroxide, 7-14 parts of beta-hydroxyethyl methylacrylate, a proper amount of ethyl acetate, a proper amount of deionized water, 0.8-2 parts of tert-butyl hydroperoxide, 12-20 parts of hexafluorobutyl methylacrylate, a proper amount of anhydrous ethanol, 2-4 parts of chlorinated paraffin, 2-6 parts of titanium dioxide, 1-2 parts of a defoamer, a proper amount of dimethylbenzene, 3-8 parts of fluorocarbon resin, 7-15 parts of polyvinylidene fluoride resin, and 16-22 parts of dimethyl acetamide. In the invention, the beta-hydroxyethyl methylacrylate is used for grafting the high-chlorinated polyethylene; copolymerization with the hexafluorobutyl methylacrylate monomer is carried out so as to introduce a fluorine-containing group; and then the material is grafted and compounded with the chitosan to prepare the chitosan-grafted fluorine-containing acrylate/high-chlorinated polyethylene terpolymer. The anti-corrosion composite coating is high in antifouling property and anti-corrosion property and has excellent adhesion force.
Description
Technical field
The invention belongs to corrosion resistant coating field, and in particular to a kind of fluororesin modified highly-chlorinated polyethylene anti-corrosion composite coating
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.As double bond is not contained in molecular structure, chlorine atom is random again, 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 propertiess 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 which《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 property, 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
The lone pair electrons or pi-electron of coordination are formed after lotus with the outer layer unoccupied orbital with ferrum, adsorption layer is increased with metal surface active force
By force, adsorb membrane stability to improve.
Therefore the present invention is using methacrylic acid-beta-hydroxy ethyl ester grafting highly-chlorinated polyethylene, poly- using aqueous-phase suspending afterwards
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 fluororesin modified highly-chlorinated polyethylene anti-corrosion composite coating
And preparation method thereof, there is provided the antiseptic property of coating, pollution resistance and adhesive force.
A kind of fluororesin modified highly-chlorinated polyethylene anti-corrosion composite coating, is made up of the raw material of following weight portion：High chlorine
Change polyethylene 60-80 parts, shitosan 24-35 parts, dibenzoyl peroxide 0.6-2 parts, methacrylic acid-beta-hydroxy ethyl ester 7-14
Part, appropriate ethyl acetate, appropriate deionized water, tert-butyl hydroperoxide 0.8-2 part, Hexafluorobutyl mathacrylate 12-20 parts,
Appropriate dehydrated alcohol, chlorinated paraffin 2-4 parts, titanium dioxide 2-6 parts, defoamer 1-2 parts, appropriate dimethylbenzene, fluorocarbon resin 3-8 parts,
Polyvinylidene fluoride resin 7-15 parts, dimethyl acetylamide 16-22 parts.
Comprise the following steps that：
（1）The preparation of highly-chlorinated polyethylene grafted methacrylic acid-beta-hydroxy ethyl ester：
Successively 1/5 part of highly-chlorinated polyethylene, dibenzoyl peroxide, methacrylic acid-beta-hydroxy ethyl ester are added to containing two
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 which is uniformly dispersed and stablizes, nitrogen is passed through to 85-95 DEG C of reaction 2-4 hour, uses hot water wash afterwards
Wash, constant temperature is dried under vacuum in 55-65 DEG C, obtain final product graft product；
（2）Chitosan graft fluorinated acrylate/highly-chlorinated polyethylene terpolymer：
During shitosan after dried is placed in equipped with reflux condensing tube, agitator, the there-necked flask of thermometer, plus deionization
Water, immersion are swelling to be overnight placed in thermostat water bath, 55-65 DEG C of stirring 5-10 minute, Deca tert-butyl hydroperoxide, stirring
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）The preparation of Kynoar glue：
Dimethyl acetylamide is placed in the jacket reactor with stirring, during by oil bath heating to 105-115 DEG C, under agitation
Polyvinylidene fluoride resin is slowly added to, continues stirring 40-60 minutes, Kynoar is made after material is in colorless and transparent
Glue；
（4）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, adds step（2）The terpolymer of preparation, step（3）It is poly-
Vinylidene liquid cement agitation mix homogeneously, is warmed up to 45-52 DEG C, adds fluorocarbon resin, titanium dioxide, chlorinated paraffin and froth breaking
Agent, high speed 1500-3000r/min stirring 3-5 hours, with 20 mesh filter screen coarse filtration；
（5）The material of above-mentioned coarse filtration being ground into sand mill, fineness being ground to for≤40 m, the control of sand mill outlet temperature exists
≤ 60 DEG C, reuse dimethylbenzene and viscosity is adjusted in 160-220（S）- 4 glasss are applied, filtered, packed with 120 mesh vibrosieves.
Wherein, described step（1）In dimethylbenzene and ethyl acetate mixtures be by body by dimethylbenzene with 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 complex is obtained,
As fluorine electronegativity is big, C-F bond energys are high, and ultraviolet does not have any impact, shows that the coating has super-weathering resistance, by changing on which
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；Anti-corrosion of the present invention is applied in addition
, when protecting metal to use, when having iron ion or other digestion of metallic ion, the polar group on shitosan also can be by which for material
Complexation is lived, and is formed fine and close " passivating film ", is prevented the carrying out further corroded.
（3）Polyvinylidene fluoride resin has the characteristic of fluororesin and resins for universal use concurrently, except with good chemical resistance,
Heat-resisting quantity, oxidative resistance, weatherability, resistance to x radiation x performance, are added in anticorrosive paint with fluorocarbon resin compounding, give and producing
The excellent combination property of product.
Specific embodiment
A kind of fluororesin modified highly-chlorinated polyethylene anti-corrosion composite coating, is made up of the raw material of following weight portion：High chlorine
Change polyethylene 74, shitosan 30, dibenzoyl peroxide 1.5, methacrylic acid-beta-hydroxy ethyl ester 12, appropriate ethyl acetate, go from
Sub- appropriate amount of water, tert-butyl hydroperoxide 1, Hexafluorobutyl mathacrylate 18, appropriate dehydrated alcohol, chlorinated paraffin 3, titanium dioxide 4,
Defoamer 1, appropriate dimethylbenzene, fluorocarbon resin 6, polyvinylidene fluoride resin 13, dimethyl acetylamide 20.
Comprise the following steps that：
（1）The preparation of highly-chlorinated polyethylene grafted methacrylic acid-beta-hydroxy ethyl ester：
Successively 1/5 part of highly-chlorinated polyethylene, dibenzoyl peroxide, methacrylic acid-beta-hydroxy ethyl ester are added to containing two
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 which 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 is placed in equipped with reflux condensing tube, agitator, the there-necked flask of thermometer, plus deionization
Water, immersion are swelling to be overnight placed in thermostat water bath, and 60 DEG C are stirred 8 minutes, and Deca tert-butyl hydroperoxide 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）The preparation of Kynoar glue：
Dimethyl acetylamide is placed in the jacket reactor with stirring, during by oil bath heating to 110 DEG C, under agitation slowly
Polyvinylidene fluoride resin is added, continues stirring 50 minutes, Kynoar glue is made after material is in colorless and transparent；
（4）Remaining HCPE is dissolved in xylene solvent, while stirring, while put into, mixing speed control exist
70r/min, until being completely dissolved into clear viscous liquids, adds step（2）The terpolymer of preparation, step（3）It is poly- partially
Fluorothene liquid cement agitation mix homogeneously, is warmed up to 50 DEG C, adds fluorocarbon resin, titanium dioxide, chlorinated paraffin and defoamer, at a high speed
2500r/min is stirred 4 hours, with 20 mesh filter screen coarse filtration；
（5）The material of coarse filtration is ground into sand mill, is ground to fineness for≤40 m, and the control of sand mill outlet temperature is ≤60
DEG C, reuse dimethylbenzene viscosity is adjusted in 160-220（S）- 4 glasss are applied, filtered, packed with 120 mesh vibrosieves.
Wherein, described step（1）In dimethylbenzene and ethyl acetate mixtures be by body by dimethylbenzene with 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 room temperature：
10%HCl aqueous solutions >=360h, coating is non-foaming, do not fall off；
20%H2SO4Aqueous solution >=360h, coating are non-foaming, do not fall off；
20%NaOH aqueous solutions >=360h, coating are non-foaming, do 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 fluororesin modified highly-chlorinated polyethylene anti-corrosion composite coating, it is characterised in that by the raw material of following weight portion
Composition：Highly-chlorinated polyethylene 60-80 parts, shitosan 24-35 parts, dibenzoyl peroxide 0.6-2 parts, methacrylic acid-β-hydroxyl
Ethyl ester 7-14 parts, appropriate ethyl acetate, appropriate deionized water, tert-butyl hydroperoxide 0.8-2 part, Hexafluorobutyl mathacrylate
12-20 parts, appropriate dehydrated alcohol, chlorinated paraffin 2-4 parts, titanium dioxide 2-6 parts, defoamer 1-2 parts, appropriate dimethylbenzene, fluorine carbon tree
Fat 3-8 parts, polyvinylidene fluoride resin 7-15 parts, dimethyl acetylamide 16-22 parts.
2. the preparation side of a kind of fluororesin modified highly-chlorinated polyethylene anti-corrosion composite coating 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：
Successively 1/5 part of highly-chlorinated polyethylene, dibenzoyl peroxide, methacrylic acid-beta-hydroxy ethyl ester are added to containing two
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 which is uniformly dispersed and stablizes, nitrogen is passed through to 85-95 DEG C of reaction 2-4 hour, uses hot water wash afterwards
Wash, constant temperature is dried under vacuum in 55-65 DEG C, obtain final product graft product；
（2）Chitosan graft fluorinated acrylate/highly-chlorinated polyethylene terpolymer：
During shitosan after dried is placed in equipped with reflux condensing tube, agitator, the there-necked flask of thermometer, plus deionization
Water, immersion are swelling to be overnight placed in thermostat water bath, 55-65 DEG C of stirring 5-10 minute, Deca tert-butyl hydroperoxide, stirring
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）The preparation of Kynoar glue：
Dimethyl acetylamide is placed in the jacket reactor with stirring, during by oil bath heating to 105-115 DEG C, under agitation
Polyvinylidene fluoride resin is slowly added to, continues stirring 40-60 minutes, Kynoar is made after material is in colorless and transparent
Glue；
（4）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, adds step（2）The terpolymer of preparation, step（3）It is poly-
Vinylidene liquid cement agitation mix homogeneously, is warmed up to 45-52 DEG C, adds fluorocarbon resin, titanium dioxide, chlorinated paraffin and froth breaking
Agent, high speed 1500-3000r/min stirring 3-5 hours, with 20 mesh filter screen coarse filtration；
（5）The material of above-mentioned coarse filtration being ground into sand mill, fineness being ground to for≤40 m, the control of sand mill outlet temperature exists
≤ 60 DEG C, reuse dimethylbenzene and viscosity is adjusted in 160-220（S）- 4 glasss are applied, filtered, packed with 120 mesh vibrosieves.
3. the preparation side of a kind of fluororesin modified highly-chlorinated polyethylene anti-corrosion composite coating according to claims 2
Method, it is characterised in that described step（1）In dimethylbenzene and ethyl acetate mixtures be by body by dimethylbenzene with ethyl acetate
Product is than being 3：1 mixes.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611008013.9A CN106590189A (en) | 2016-11-16 | 2016-11-16 | Fluororesin-modified high-chlorinated polyethylene anti-corrosion composite coating and preparation method of same |
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| CN201611008013.9A CN106590189A (en) | 2016-11-16 | 2016-11-16 | Fluororesin-modified high-chlorinated polyethylene anti-corrosion composite coating and preparation method of same |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108661191A (en) * | 2018-05-21 | 2018-10-16 | 安徽朗凯奇防水科技股份有限公司 | A kind of composite of water-proof coiled material and its preparation process |
| CN114606561A (en) * | 2022-03-24 | 2022-06-10 | 瑞晟通金属(广东)有限公司 | Anti-aging aluminum alloy and preparation method thereof |
Citations (1)
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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 |
-
2016
- 2016-11-16 CN CN201611008013.9A patent/CN106590189A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
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| 熊琼: "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》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108661191A (en) * | 2018-05-21 | 2018-10-16 | 安徽朗凯奇防水科技股份有限公司 | A kind of composite of water-proof coiled material and its preparation process |
| CN114606561A (en) * | 2022-03-24 | 2022-06-10 | 瑞晟通金属(广东)有限公司 | Anti-aging aluminum alloy and preparation method thereof |
| CN114606561B (en) * | 2022-03-24 | 2024-02-20 | 瑞晟通金属(广东)有限公司 | Anti-aging aluminum alloy and preparation method thereof |
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Application publication date: 20170426 |