CN116554738A - Chlorinated rubber steel anticorrosive paint modified by chlorine-containing polymer and preparation method thereof - Google Patents
Chlorinated rubber steel anticorrosive paint modified by chlorine-containing polymer and preparation method thereof Download PDFInfo
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- CN116554738A CN116554738A CN202310718319.7A CN202310718319A CN116554738A CN 116554738 A CN116554738 A CN 116554738A CN 202310718319 A CN202310718319 A CN 202310718319A CN 116554738 A CN116554738 A CN 116554738A
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- China
- Prior art keywords
- parts
- chlorinated rubber
- trichloroethylene
- anticorrosive paint
- chlorinated
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Links
- 229920001971 elastomer Polymers 0.000 title claims abstract description 84
- 239000005060 rubber Substances 0.000 title claims abstract description 84
- 239000003973 paint Substances 0.000 title claims abstract description 48
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 22
- 239000000460 chlorine Substances 0.000 title claims abstract description 22
- 239000010959 steel Substances 0.000 title claims abstract description 22
- 229910052801 chlorine Inorganic materials 0.000 title claims abstract description 21
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 229920000642 polymer Polymers 0.000 title claims abstract description 10
- 238000002360 preparation method Methods 0.000 title abstract description 7
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 claims abstract description 50
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000006227 byproduct Substances 0.000 claims abstract description 38
- 239000011347 resin Substances 0.000 claims abstract description 34
- 229920005989 resin Polymers 0.000 claims abstract description 34
- 239000002904 solvent Substances 0.000 claims abstract description 18
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 17
- 239000000945 filler Substances 0.000 claims abstract description 16
- 239000012767 functional filler Substances 0.000 claims abstract description 16
- 239000000049 pigment Substances 0.000 claims abstract description 14
- 239000012188 paraffin wax Substances 0.000 claims abstract description 13
- 239000002699 waste material Substances 0.000 claims abstract description 12
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 20
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 14
- -1 tetrachloroprene Chemical class 0.000 claims description 14
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 12
- 239000001993 wax Substances 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 239000004698 Polyethylene Substances 0.000 claims description 10
- 229920000573 polyethylene Polymers 0.000 claims description 10
- 239000000047 product Substances 0.000 claims description 10
- 239000003085 diluting agent Substances 0.000 claims description 9
- 239000002270 dispersing agent Substances 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- 239000002689 soil Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 8
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 7
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 7
- 238000004821 distillation Methods 0.000 claims description 7
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 7
- 239000010445 mica Substances 0.000 claims description 6
- 229910052618 mica group Inorganic materials 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 239000008096 xylene Substances 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 239000003921 oil Substances 0.000 claims description 5
- 238000010926 purge Methods 0.000 claims description 5
- 239000000758 substrate Substances 0.000 claims description 5
- 238000005292 vacuum distillation Methods 0.000 claims description 5
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 4
- IXQWNVPHFNLUGD-UHFFFAOYSA-N iron titanium Chemical compound [Ti].[Fe] IXQWNVPHFNLUGD-UHFFFAOYSA-N 0.000 claims description 4
- WVFBDVFCOCLEFM-UHFFFAOYSA-N 1,1,2,4,4-pentachlorobuta-1,3-diene Chemical compound ClC(Cl)=CC(Cl)=C(Cl)Cl WVFBDVFCOCLEFM-UHFFFAOYSA-N 0.000 claims description 3
- 229910001200 Ferrotitanium Inorganic materials 0.000 claims description 3
- 230000001680 brushing effect Effects 0.000 claims description 3
- 230000007062 hydrolysis Effects 0.000 claims description 3
- 238000006460 hydrolysis reaction Methods 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 238000005507 spraying Methods 0.000 claims description 3
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims description 2
- 238000000576 coating method Methods 0.000 abstract description 29
- 239000011248 coating agent Substances 0.000 abstract description 28
- 238000005260 corrosion Methods 0.000 abstract description 18
- 239000000463 material Substances 0.000 abstract description 16
- 230000007797 corrosion Effects 0.000 abstract description 12
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 150000003839 salts Chemical class 0.000 abstract description 6
- 239000002253 acid Substances 0.000 abstract description 5
- 239000003513 alkali Substances 0.000 abstract description 5
- 239000000853 adhesive Substances 0.000 abstract description 4
- 230000001070 adhesive effect Effects 0.000 abstract description 4
- 239000003607 modifier Substances 0.000 abstract description 2
- 239000004014 plasticizer Substances 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 5
- 238000010276 construction Methods 0.000 description 5
- 239000002585 base Substances 0.000 description 4
- 238000010073 coating (rubber) Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000004925 Acrylic resin Substances 0.000 description 3
- 229920000178 Acrylic resin Polymers 0.000 description 3
- 235000019198 oils Nutrition 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- KPZGRMZPZLOPBS-UHFFFAOYSA-N 1,3-dichloro-2,2-bis(chloromethyl)propane Chemical compound ClCC(CCl)(CCl)CCl KPZGRMZPZLOPBS-UHFFFAOYSA-N 0.000 description 1
- QMNWYGTWTXOQTP-UHFFFAOYSA-N 1h-triazin-6-one Chemical class O=C1C=CN=NN1 QMNWYGTWTXOQTP-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 241000895503 Metrosideros Species 0.000 description 1
- 206010051246 Photodermatosis Diseases 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical group ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical class C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 1
- 239000004842 bisphenol F epoxy resin Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000005536 corrosion prevention Methods 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 230000000382 dechlorinating effect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000010433 feldspar Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 239000000413 hydrolysate Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- MOUPNEIJQCETIW-UHFFFAOYSA-N lead chromate Chemical compound [Pb+2].[O-][Cr]([O-])(=O)=O MOUPNEIJQCETIW-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 230000001575 pathological effect Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000008845 photoaging Effects 0.000 description 1
- 238000006552 photochemical reaction Methods 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000009991 scouring Methods 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000001038 titanium pigment Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Classifications
-
- 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
- C09D115/00—Coating compositions based on rubber derivatives
- C09D115/02—Rubber derivatives containing halogen
-
- 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
-
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
-
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2265—Oxides; Hydroxides of metals of iron
Abstract
The invention discloses a chlorinated rubber steel anticorrosive paint modified by a chlorine-containing polymer and a preparation method thereof, wherein the paint comprises the following components in parts by weight: A. chlorinated rubber resin (CR) 20-30 parts; B. 15-20 parts of a solvent; C. 5-20 parts of trichloroethylene by-product; D. 5-20 parts of chlorinated paraffin; E. pigment and filler, 10-35 parts; F. 5-20 parts of functional filler; G. 0-5 parts of auxiliary agent. The paint and the preparation method thereof realize the full reuse of production waste. Compared with the prior art, the invention uses the trichloroethylene by-product to modify the chlorinated rubber anti-corrosion coating material, reduces the cost, improves the compactness and stability of a paint film, and is safe and reliable. By using trichloroethylene by-product and chlorinated paraffin plasticizer as modifier, the flexibility and compactness of the coating are enhanced, the adhesive force of the coating is improved, the thickness of the coating is increased, and the corrosion resistance of the coating to acid, alkali, salt and other mediums is improved. The modified chlorinated rubber anticorrosive paint obtained by the invention is particularly excellent in anticorrosive performance for steel.
Description
Technical Field
The invention belongs to the field of chemistry and chemical engineering, and particularly relates to a chlorinated rubber steel anticorrosive paint modified by a chlorine-containing polymer and a preparation method thereof.
Background
Steel is the most widely used metal in human life, but iron and steel products are corroded to different degrees in the environment, and economic loss caused by corrosion is extremely serious. It is counted that steel scrapped by corrosion annually worldwide accounts for about 30% of annual production, and about 10% of the annually produced steel is completely waste. The economic loss caused by corrosion of each industrial country is about 1% -4% of the total national production value. The steel products used in different environments should be coated with corresponding anti-corrosion coatings to prolong the service life of equipment, materials and buildings. The prior anticorrosive paint for steel mainly comprises chlorinated rubber, epoxy resin, polyurethane, polyester and the like, wherein the chlorinated rubber anticorrosive paint has excellent anticorrosive performance and simple construction, has the most coating anticorrosive application in various base materials and various environments, and is a base material of a heavy-duty anticorrosive paint which is more commonly used.
The Chlorinated Rubber (CR) is a product of natural rubber modified by chlorination, and is a mixture of trichlorides and tetrachloride with chlorine content of 40-65%, and has a structural general formula of [ C ] 10 H 11 Cl 7 ]N. The industrial chlorinated rubber is generally white or cream yellow powder, flake or fiber, the mass fraction of chlorine is 62-65%, and the industrial chlorinated rubber does not contain active groups such as double bonds, etc., so the industrial chlorinated rubber has stable chemical property and excellent corrosion resistance, and can resist acid and alkali, salt, chlorine and H 2 S、SO 2 And the like.
The chlorinated rubber anticorrosive paint has the following characteristics: (1) excellent corrosion resistance: the chlorinated rubber is a chemically inert film forming substance, so that the film has extremely low permeability to water vapor and oxygen, good sealing property and better resistance to atmosphere, moisture, salts, acid, alkali, oxidant, petroleum and the like. (2) flame retardant and mildew resistant properties: the polymer has high chlorine content, so that the polymer has the performance of inhibiting the growth of toxic bacteria. (3) The weather resistance is better, and the paint film is insensitive to photochemical reaction and oxidative degradation because of no double bond, can withstand the outdoor atmosphere, ultraviolet light, oxygen and cold and hot change effects, and has good stability. (4) better compatibility with other resins: various modified resins such as acrylic resin, aldehyde ketone resin, alkyd resin and the like can be added to improve the comprehensive performance of the coating film. (5) good construction performance: the paint is a single-component paint, can be applied to micro rust construction and is dried rapidly; the film can be formed at low temperature, and the construction is not limited by seasons and temperature; the recoating property is good; is suitable for any steel and cement surface.
CN 105315796A (CN 20140284787.9) discloses a chlorinated rubber coating for offshore environment and a preparation method thereof, wherein the modified chlorinated rubber resin, the modified hydrogenated bisphenol F epoxy resin, the epoxidized soybean oil and the mixed solvent of xylene and solvent oil are added, and then modified titanium dioxide, feldspar powder, talcum powder, silicon micropowder, mica powder, phthalocyanine green, chrome yellow, polyamide wax, chlorinated paraffin, hydroxytriazine derivative, epichlorohydrin and the like are mixed, stirred and ground to prepare the high-light weather-resistance chlorinated rubber coating for offshore environment, and the high-light weather-resistance chlorinated rubber coating is uniformly stirred and directly coated when in use: the paint can be used for construction at-20 ℃, has excellent storage stability, excellent ultraviolet aging resistance, adhesive force, acid resistance, alkali resistance, salt corrosion resistance and seawater scouring resistance, and can be used for corrosion prevention of marine structures such as ships, ocean platforms, wharfs and the like.
CN10289588A (CN 200710065584.0) provides an acrylic acid modified chlorinated rubber coating and a preparation method thereof, wherein the coating comprises 1 part by weight of chlorinated rubber, 0.05-0.4 part by weight of acrylic resin, 0.005-1.03 parts by weight of chlorinated paraffin, 0.008-0.5 part by weight of epoxy resin, 0.05-3.0 parts by weight of xylene, 0.01-1.5 parts by weight of heavy aromatic hydrocarbon solvent, 0.005-0.045 parts by weight of fluorocarbon modified acrylic resin, 0.006-0.5 parts by weight of titanium pigment, 0.01-0.8 parts by weight of talcum powder and 0.005-0.05 part by weight of organic clay, and has the characteristics of single-component packaging and normal-temperature drying film forming, and the coating has excellent physical properties, chemical resistance, salt spray resistance and photo-aging resistance, and can be used for protecting and coating the surface of steel structures in marine corrosion environments.
However, the chlorinated rubber anticorrosive paint in the prior art has excellent corrosion resistance, water resistance, weather resistance, flame retardance and quick-drying performance, but a paint film formed by the chlorinated rubber anticorrosive paint alone has poor flexibility and is easy to crack and peel. .
When producing trichloroethylene by using acetylene as a raw material, firstly, acetylene and chlorine are mixed in a ratio of 1: introducing the mixture into a chlorination reactor at a molar ratio of 2.05, reacting at a reaction temperature of 90-120 ℃ under vacuum with ferric chloride as a catalyst to generate tetrachloroethane, and then dechlorinating hydrogen chloride at a temperature of 180-280 ℃ under the action of the catalyst to generate trichloroethylene. Although the production process route is environment-friendly, about 1% of byproducts such as high-boiling substances, oligomers and the like are produced in the production process. At present, china has the production yield of hundreds of thousands tons of trichloroethylene, and various manufacturers expect to recycle the byproduct with high value, thereby realizing environmental and resource production, solving the environmental pollution caused by waste emission and generating better social and economic benefits.
Disclosure of Invention
Aiming at the defects of the prior art, the invention prepares the chlorinated rubber steel anticorrosive paint by using the by-product generated in the production of the trichloroethylene, and the trichloroethylene by-product can modify the chlorinated rubber resin base material and realize the high-value recycling of the trichloroethylene by-product. The chlorethylene byproduct modified chlorinated rubber can improve the compactness and toughness of a system, and overcomes the defects of poor flexibility and easy embrittlement and peeling of a paint film.
According to one aspect of the invention, an object of the invention is to provide a chlorinated rubber anticorrosive paint for steel modified by trichloroethylene to produce by-products, which is composed of the following components in parts by weight:
A. chlorinated rubber resin (CR), 20-30 parts,
B. solvent 15-20 parts
C. Trichloroethylene byproduct, 5-20 parts
D. 5-20 parts of chlorinated paraffin,
E. pigment and filler, 10-35 parts,
F. 5-20 parts of functional filler,
G. 0-5 parts of auxiliary agent.
Wherein the trichloroethylene byproduct refers to a residual waste liquid component generated in the process of producing trichloroethylene by taking acetylene as a raw material, and the main component is chlorine-containing polymer with the viscosity average molecular weight of 12 to 18 ten thousand, and is basically perchlorinated hydrocarbon such as: tetrachloroprene, pentachlorobutadiene, hexachloroprene, and the like, and also a small amount of hydrolysis products of ferric trichloride.
The trichloroethylene byproduct is obtained by the following method: firstly, carrying out low-temperature distillation on waste liquid for preparing trichloroethylene at 50-60 ℃, purging nitrogen to remove volatile matters, carrying out high-temperature distillation on obtained low-temperature distillate at 205-220 ℃, removing high-temperature fractions, and retaining residual components to obtain the trichloroethylene.
The chlorinated rubber resin (CR) is chlorinated rubber resin with chlorine content of 62-65% and average relative molecular weight of 15000-32000;
the solvent is selected from one or more of dimethylbenzene and 100# solvent oil;
the pigment filler is one or more selected from iron oxide red, mica iron oxide and talcum powder fillers;
the functional filler is a combination of ferrotitanium powder and barium sulfate;
the auxiliary agent is one or more selected from dispersing agent EFKA-4010, organic soil and polyethylene wax 201P.
Preferably, the chlorinated rubber anticorrosive paint for steel modified by a by-product generated by trichloroethylene according to the invention comprises the following raw materials in parts by weight:
A. chlorinated rubber resin (CR), 20-30 parts,
B. solvent 15-20 parts
C. 10-20 parts of trichloroethylene byproduct
D. 5-10 parts of chlorinated paraffin,
E. pigment and filler, 10-35 parts,
F. 5-20 parts of functional filler,
G. 0-3 parts of auxiliary agent.
Further preferably, the raw materials are as follows:
A. chlorinated rubber resin (CR), 20-30 parts,
B. solvent 15-20 parts
C. 10-20 parts of trichloroethylene byproduct
D. 5-10 parts of chlorinated paraffin,
E. 20-35 parts of pigment and filler,
F. 10-20 parts of functional filler,
G. 0-3 parts of auxiliary agent.
Further preferably, the functional filler is ferrotitanium powder and barium sulfate in a weight ratio of (1-2): a combination of (1-3); the auxiliary agent is dispersant EFKA-4010, organic soil and polyethylene wax with the weight ratio of (0.5-2): 1: 1.
According to another aspect of the present invention, another object of the present invention is to provide a method for preparing chlorinated rubber steel anticorrosive paint modified with trichloroethylene by-product, comprising the steps of:
mixing chlorinated rubber resin, trichloroethylene by-product, chlorinated paraffin, pigment filler, functional filler and auxiliary agent according to a certain proportion, grinding, high-speed dispersing and filtering so as to obtain the modified chlorinated rubber anticorrosive paint.
When the modified chlorinated rubber anticorrosive paint is used, a proper amount of diluent which is conventional in the art is required to be added, and the mixture is uniformly mixed, and the mixture is sprayed or brushed on the surface of a substrate to be coated within 8 hours.
The diluent is preferably xylene or 100# solvent oil. The diluent is generally used in an amount ofThe chlorinated rubber anticorrosive paint A kind of electronic device10-25wt%. Is known by the conventional technology in the art.
The invention has the beneficial effects that:
the trichloroethylene waste liquid is distilled at low temperature and high temperature to obtain about one third of residual components, and the high temperature fraction can be further recycled. The main component of the obtained residual component is chlorine-containing polymer with viscosity average molecular weight of 12 ten thousand or more, and in addition, hydrolysate of ferric trichloride, which is very favorable for improving the corrosion resistance of the corrosion-resistant coating material.
Compared with the prior art, the invention uses the trichloroethylene by-product to modify the chlorinated rubber anti-corrosion coating material, reduces the cost, improves the compactness and stability of a paint film, and is safe and reliable. By using trichloroethylene by-product and chlorinated paraffin plasticizer as modifier, the flexibility and compactness of the coating are enhanced, the adhesive force of the coating is improved, the thickness of the coating is increased, and the corrosion resistance of the coating to acid, alkali, salt and other mediums is improved. The modified chlorinated rubber anticorrosive paint obtained by the invention is particularly excellent in anticorrosive performance for steel.
Detailed Description
Hereinafter, the present invention will be described in detail. Before the description, it is to be understood that the terms used in this specification and the appended claims should not be construed as limited to general and dictionary meanings, but interpreted based on the meanings and concepts corresponding to technical aspects of the present invention on the basis of the principle that the inventor is allowed to define terms appropriately for the best explanation. Accordingly, the description set forth herein is merely a preferred example for the purpose of illustration and is not intended to limit the scope of the invention, so that it should be understood that other equivalents or modifications may be made thereto without departing from the spirit and scope of the invention.
All features or conditions defined herein in terms of numerical ranges or percentage ranges are for brevity and convenience only. Accordingly, the description of a numerical range or percentage range should be considered to cover and specifically disclose all possible sub-ranges and individual values within the range, particularly integer values. For example, a range description of "1 to 8" should be taken as having specifically disclosed all sub-ranges such as 1 to 7, 2 to 8, 2 to 6, 3 to 6, 4 to 8, 3 to 8, etc., particularly sub-ranges defined by all integer values, and should be taken as having specifically disclosed individual values such as 1, 2, 3, 4, 5, 6, 7, 8, etc. within the range. The foregoing explanation applies to all matters of the invention throughout its entirety unless indicated otherwise, whether or not the scope is broad.
If an amount or other numerical value or parameter is expressed as a range, preferred range, or a series of upper and lower limits, then it is understood that any range, whether or not separately disclosed, from any pair of the upper or preferred value for that range and the lower or preferred value for that range is specifically disclosed herein. Furthermore, where a range of numerical values is recited herein, unless otherwise stated, the range is intended to include the endpoints thereof, and all integers and fractions within the range.
In this context, numerical values should be understood to have the accuracy of the numerical significance of the numerical values provided that the objectives of the present invention are achieved. For example, the number 40.0 is understood to cover a range from 39.50 to 40.49.
In the chlorinated rubber steel anticorrosive paint modified by using trichloroethylene by-product, the trichloroethylene by-product refers to a residual component of waste liquid generated in the process of producing trichloroethylene by using acetylene as a raw material, and the main component is chlorine-containing polymer with viscosity average molecular weight of 12 ten thousand to 18 ten thousand, which is basically high-chlorine chlorinated hydrocarbon such as: tetrachloroprene, pentachlorobutadiene, hexachloroprene, and the like, and also a small amount of hydrolysis products of ferric trichloride.
The trichloroethylene byproduct is obtained by the following method: firstly, carrying out low-temperature distillation on waste liquid for preparing trichloroethylene at 50-60 ℃, purging nitrogen to remove volatile matters, carrying out high-temperature distillation on obtained low-temperature distillate at 205-220 ℃, removing high-temperature fractions, and retaining residual components to obtain the trichloroethylene. The temperature range of the high-temperature distillation has a great influence on the trichloroethylene byproduct, and if the temperature is lower than 205 ℃, the viscosity average molecular weight of the main component is lower, for example, lower than 12 ten thousand, so that the flexibility and compactness of the coating film are insufficient for the steel basal plane, the adhesive force of the coating film is improved, and the like; if the temperature is higher than 220 ℃, the viscosity average molecular weight of the main component is high, for example, higher than 18 ten thousand, so that the workability is seriously lowered and the coating film is not easy. Thus controlling the temperature of the high temperature distillation is critical to obtaining trichloroethylene by-product of the main component of suitable viscosity average molecular weight.
The chlorinated rubber resin (CR) is a chlorinated rubber resin with a chlorine content of 62-65% by mass, the average relative molecular weight of the chlorinated rubber resin is 15000-32000, the average relative molecular weight of the chlorinated rubber resin cannot be too low, the average relative molecular weight of the chlorinated rubber resin in the prior art is generally 5000-20000, but the chlorinated rubber resin in the range has poor compatibility with the trichloroethylene by-product of the present invention. The inventors have found that optimum film coating properties can be achieved by controlling the average relative molecular weight of the chlorinated rubber resin to 15000 to 32000.
In addition, the chlorine content of the chlorinated rubber resin cannot be too high, and the chlorinated rubber resin needs to be controlled to be 62-65%, and if the chlorine content is too high, for example, more than 65%, the chlorinated rubber resin is disadvantageous to the steel base surface.
The auxiliary agent is one or more selected from dispersing agent EFKA-4010, organic soil and polyethylene wax 201P, wherein the organic soil and the polyethylene wax are added to be used as anti-settling agents to avoid the pathological settlement of a paint film.
The following examples are merely illustrative of embodiments of the present invention and are not intended to limit the invention in any way, and those skilled in the art will appreciate that modifications may be made without departing from the spirit and scope of the invention. Unless otherwise specified, reagents and equipment used in the following examples are commercially available products.
The trichloroethylene by-product used in the examples was obtained as follows: firstly, carrying out low-temperature distillation on waste liquid produced by producing trichloroethylene by taking acetylene as a raw material at 55 ℃, purging nitrogen to remove volatile matters, carrying out high-temperature distillation on the obtained low-temperature distillate at 210 ℃, removing high-temperature fractions, and retaining residual components to obtain the product, wherein the viscosity average molecular weight of the main component is about 15.6 ten thousand.
The chlorinated rubber resin (CR) used in the examples was a chlorinated rubber resin having a chlorine content of 62 to 65% and an average relative molecular weight of 22000. The dispersing agent EFKA-4010 is sold by Kaijin chemical Co., ltd, and the polyethylene wax 201P is sold by Qingdao Xutai chemical Co., ltd.
Example 1
20 parts of chlorinated rubber resin (CR), 20 parts of solvent, 10 parts of trichloroethylene by-product, 9 parts of pigment filler iron oxide red, 9 parts of mica iron oxide, 9 parts of talcum powder, 10 parts of functional filler iron titanium powder, 10 parts of barium sulfate, 1 part of auxiliary agent dispersing agent EFKA-4010, 1 part of organic soil and 1 part of polyethylene wax 201P, and grinding, dispersing at high speed and filtering to obtain the modified chlorinated rubber anti-corrosion coating material.
When the modified chlorinated rubber anticorrosive coating material is applied, 15wt% of diluent xylene is added into the modified chlorinated rubber anticorrosive coating material to be uniformly mixed, and the mixture is sprayed or brushed on the surface of a substrate to be coated within 8 hours. According to the conventional technology in the field.
Example 2
25 parts of chlorinated rubber resin (CR), 15 parts of solvent, 13 parts of trichloroethylene by-product, 8 parts of pigment filler iron oxide red, 8 parts of mica iron oxide, 8 parts of talcum powder, 10 parts of functional filler iron titanium powder, 10 parts of barium sulfate, 1 part of auxiliary agent dispersing agent EFKA-4010, 1 part of organic soil and 1 part of polyethylene wax 201P, and carrying out grinding, high-speed dispersion and filtration to obtain the modified chlorinated rubber anti-corrosion coating material.
And adding 15wt% of diluent dimethylbenzene into the obtained modified chlorinated rubber anticorrosive coating material, uniformly mixing, and spraying or brushing the mixture onto the surface of a substrate to be coated within 8 hours. According to the conventional technology in the field.
Example 3
30 parts of chlorinated rubber resin (CR), 13 parts of solvent, 15 parts of trichloroethylene by-product, 8 parts of pigment filler iron oxide red, 8 parts of mica iron oxide, 8 parts of talcum powder, 10 parts of functional filler iron titanium powder, 10 parts of barium sulfate, 1 part of auxiliary agent dispersing agent EFKA-4010, 1 part of organic soil and 1 part of polyethylene wax 201P, and grinding, dispersing at high speed and filtering to obtain the modified chlorinated rubber anti-corrosion coating material.
And adding 15wt% of diluent dimethylbenzene into the obtained modified chlorinated rubber anticorrosive coating material, uniformly mixing, and spraying or brushing the mixture onto the surface of a substrate to be coated within 8 hours. According to the conventional technology in the field.
The product performance experiments of examples 1-3 above are listed in Table 1 below. Comparative example 1 is a lehua brand chlorinated rubber anticorrosive paint.
Comparative example 2
The trichloroethylene by-product used in this comparative example was obtained as follows: firstly, carrying out low-temperature distillation on waste liquid produced by producing trichloroethylene by taking acetylene as a raw material at 55 ℃, purging nitrogen to remove volatile matters, carrying out high-temperature distillation on the obtained low-temperature distillate at 180 ℃, removing high-temperature fractions, and retaining residual components to obtain the product, wherein the viscosity average molecular weight of the main component is about 9.8 ten thousand.
Modified chlorinated rubber anticorrosive coating materials were prepared and tested in the same manner as in example 1, and the test results are shown in table 1 below.
Comparative example 3
The chlorinated rubber resin (CR) used in this comparative example was a polyethylene resin having a chlorine content of 72% and an average relative molecular weight of 15000.
Modified chlorinated rubber anticorrosive coating materials were prepared and tested in the same manner as in example 1, and the test results are shown in table 1 below.
TABLE 1 comparison of chlorinated rubber anticorrosive paint Properties
The foregoing is merely illustrative of the present invention, and the present invention is not limited thereto, and any person skilled in the art will readily recognize that variations or substitutions are within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (9)
1. A chlorinated rubber anticorrosive paint modified by using trichloroethylene to generate byproducts for steel consists of the following components in parts by weight:
A. chlorinated rubber resin (CR), 20-30 parts,
B. solvent 15-20 parts
C. Trichloroethylene byproduct, 5-20 parts
D. 5-20 parts of chlorinated paraffin,
E. pigment and filler, 10-35 parts,
F. 5-20 parts of functional filler,
G. 0-5 parts of an auxiliary agent;
wherein the trichloroethylene byproduct refers to a residual waste liquid component generated in the process of producing trichloroethylene by taking acetylene as a raw material, and the main component is chlorine-containing polymer with the viscosity average molecular weight of 12 to 18 ten thousand, and is basically perchlorinated hydrocarbon such as: tetrachloroprene, pentachlorobutadiene, hexachloroprene, and the like, and also a small amount of hydrolysis products of ferric trichloride.
2. The chlorinated rubber anticorrosive paint according to claim 1, wherein the chlorinated rubber anticorrosive paint comprises the following components in parts by weight:
A. chlorinated rubber resin (CR), 20-30 parts,
B. solvent 15-20 parts
C. 10-20 parts of trichloroethylene byproduct
D. 5-10 parts of chlorinated paraffin,
E. pigment and filler, 10-35 parts,
F. 5-20 parts of functional filler,
G. 0-3 parts of auxiliary agent.
3. The chlorinated rubber anticorrosive paint according to claim 1, wherein the chlorinated rubber anticorrosive paint comprises the following components in parts by weight:
A. chlorinated rubber resin (CR), 20-30 parts,
B. solvent 15-20 parts
C. 10-20 parts of trichloroethylene byproduct
D. 5-10 parts of chlorinated paraffin,
E. 20-35 parts of pigment and filler,
F. 10-20 parts of functional filler,
G. 0-3 parts of auxiliary agent.
4. A chlorinated rubber anticorrosive paint according to any one of claims 1 to 3, wherein the trichloroethylene by-product is obtained by the following method: firstly, carrying out low-temperature distillation on waste liquid for preparing trichloroethylene at 50-60 ℃, purging nitrogen to remove volatile matters, carrying out high-temperature distillation on obtained low-temperature distillate at 205-220 ℃, removing high-temperature fractions, and retaining residual components to obtain the trichloroethylene.
5. A chlorinated rubber anticorrosive paint according to any one of claims 1 to 3, wherein the chlorinated rubber resin (CR) is a chlorinated rubber resin having a chlorine content of between 62% and 65% by mass, and an average relative molecular weight of 15000 to 32000;
preferably, the solvent is selected from one or more of xylene, 100# solvent oil;
preferably, the pigment filler is selected from one or more of iron oxide red, mica iron oxide and talcum powder filler;
preferably, the functional filler is a combination of ferrotitanium powder and barium sulfate;
preferably, the auxiliary agent is selected from one or more of dispersing agent EFKA-4010, organic soil and polyethylene wax 201P.
6. The chlorinated rubber anticorrosive paint according to claim 5, wherein the functional filler is a combination of iron-titanium powder and barium sulfate in a weight ratio of (1-2): (1-3); the auxiliary agent is a combination of dispersing agent EFKA-4010, organic soil and polyethylene wax in a weight ratio of (0.5-2) to 1:1.
7. A method for preparing the chlorinated rubber anticorrosive paint according to any one of claims 1 to 3, comprising the steps of:
mixing chlorinated rubber resin, trichloroethylene by-product, chlorinated paraffin, pigment filler, functional filler and auxiliary agent according to a certain proportion, grinding, high-speed dispersing and filtering so as to obtain the modified chlorinated rubber anticorrosive paint.
8. A chlorinated rubber anticorrosive paint according to any one of claims 1 to 3, wherein the chlorinated rubber anticorrosive paint is applied by adding a proper amount of diluent and mixing uniformly, and spraying or brushing the paint on the surface of a substrate to be coated within 8 hours.
9. The chlorinated rubber anticorrosive paint according to claim 8, wherein the diluent is xylene or 100# solvent oil, and the diluent is used in an amount of 10-25wt% of the chlorinated rubber anticorrosive paint.
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