CN109021648B - Preparation method of special super-hydrophobic anti-corrosion chlorinated paraffin for coating - Google Patents
Preparation method of special super-hydrophobic anti-corrosion chlorinated paraffin for coating Download PDFInfo
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- CN109021648B CN109021648B CN201810793159.1A CN201810793159A CN109021648B CN 109021648 B CN109021648 B CN 109021648B CN 201810793159 A CN201810793159 A CN 201810793159A CN 109021648 B CN109021648 B CN 109021648B
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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
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G73/00—Recovery or refining of mineral waxes, e.g. montan wax
- C10G73/38—Chemical modification of petroleum
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Abstract
The invention discloses a preparation method of super-hydrophobic anticorrosion chlorinated paraffin special for paint, which comprises the steps of treating a paraffin raw material by polymethylhydrosiloxane, then preparing chlorinated paraffin, promoting hydrophobic modification of the polymethylhydrosiloxane by the obtained chlorinated paraffin under the catalysis of a platinum catalyst, then carrying out surface treatment by oleic acid, preparing paraffin modified imidazoline through high-temperature cyclization, and finally blending and esterifying the paraffin and adipoyl chloride to obtain a finished product.
Description
Technical Field
The invention belongs to the field of chlorinated paraffin, and particularly relates to a preparation method of super-hydrophobic anti-corrosion chlorinated paraffin special for a coating.
Background
The chlorinated paraffin has the characteristics of no odor, no toxicity, flame retardance, low volatility, good compatibility with PVC resin and the like, is usually used as a plasticizer of polyvinyl chloride, an additive of rubber, paint and ink, an additive of machining lubricating oil, an anticoagulant, a flame retardant of plastic and rubber and the like, is mostly used as a flame retardant and a plasticizer when being used as the additive of the paint, has weak functionality although the application range is wide, and therefore the invention aims to research the modified chlorinated paraffin specially used for the anticorrosive paint, so that the modified chlorinated paraffin also has certain hydrophobicity and corrosion resistance, and the surface permeability resistance and corrosion resistance effect of a coating are enhanced.
Disclosure of Invention
The invention aims to provide a preparation method of special super-hydrophobic anti-corrosion chlorinated paraffin for a coating, aiming at the defects and shortcomings of the prior art.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of special super-hydrophobic anti-corrosion chlorinated paraffin for coating comprises the following steps:
(1) adding 14-20 parts by weight of polymethylhydrosiloxane into absolute ethyl alcohol with the weight 10-13 times of that of polymethylhydrosiloxane, uniformly stirring, raising the temperature to 90-95 ℃, adding 90-100 parts by weight of solid paraffin, keeping the temperature and stirring for 20-30 minutes, distilling, and removing ethanol to obtain organic silicon modified paraffin;
(2) adding 1-2 parts by weight of stearate into dimethyl carbonate with the weight being 10-20 times of that of the stearate, and uniformly stirring to obtain a dimethyl carbonate solution;
(3) feeding the organic silicon modified paraffin into a reaction kettle, introducing chlorine, adjusting the temperature of the reaction kettle to be 50-60 ℃, reacting until the specific gravity of liquid is 1.65-1.75, and discharging to obtain organic silicon modified chlorinated paraffin;
(4) adding the organic silicon modified chlorinated paraffin into the dimethyl carbonate solution, uniformly stirring, feeding into an ice water bath, adding 0.04-0.1 part by weight of platinum catalyst, stirring for reaction for 3-5 hours, discharging, adding 20-36 parts by weight of oleic acid, raising the temperature to 65-70 ℃, keeping the temperature and stirring for 1-2 hours, and cooling to obtain a hydrophobic modified chlorinated paraffin solution;
(5) taking 10-13 parts by weight of diethylenetriamine, adding the diethylenetriamine into the hydrophobic modified chlorinated paraffin solution, adding 0.3-0.6 part by weight of metal oxide, introducing nitrogen, raising the temperature to 146 ℃, keeping the temperature and stirring for 3-5 hours, continuing raising the temperature to 200-210 ℃, reacting for 110 minutes, and carrying out reduced pressure distillation to obtain paraffin modified imidazoline;
(6) adding the paraffin modified imidazoline into dimethyl carbonate with the weight 1.7-2 times of that of the paraffin modified imidazoline, uniformly stirring, adding 0.1-0.2 part by weight of an acid-binding agent, sending into an ice-water bath, adding 5-7 parts by weight of adipoyl chloride, stirring for reacting for 3-4 hours, performing rotary evaporation, removing the dimethyl carbonate, drying for 1-2 hours at the temperature of 60-70 ℃ in vacuum, discharging and cooling to obtain the special super-hydrophobic anticorrosive chlorinated paraffin for the coating.
The stearate is one of zinc stearate, calcium stearate and barium stearate.
The metal oxide is one of aluminum oxide and ferric oxide.
The acid-binding agent is pyridine.
The invention has the advantages that:
according to the invention, firstly, the paraffin raw material is treated by polymethylhydrosiloxane, then chlorinated paraffin is prepared, the obtained chlorinated paraffin promotes hydrophobic modification of the polymethylhydrosiloxane under the catalysis of a platinum catalyst, then surface treatment is carried out by oleic acid, paraffin modified imidazoline is prepared by high-temperature cyclization, and finally blending esterification is carried out with adipoyl chloride, so that the obtained esterified material has good compatibility with the chlorinated paraffin, and thus stable improved composite chlorinated paraffin can be obtained; the chlorinated paraffin disclosed by the invention has good surface hydrophobic property and good corrosion resistance, is particularly suitable to be used as an additive of an anticorrosive coating, and can play a good corrosion inhibition effect.
Detailed Description
Example 1
A preparation method of special super-hydrophobic anti-corrosion chlorinated paraffin for coating comprises the following steps:
(1) adding 20 parts by weight of polymethylhydrosiloxane into anhydrous ethanol 13 times of the polymethylhydrosiloxane, uniformly stirring, raising the temperature to 95 ℃, adding 100 parts by weight of solid paraffin, keeping the temperature and stirring for 30 minutes, distilling, and removing ethanol to obtain organic silicon modified paraffin;
(2) adding 2 parts by weight of stearate into dimethyl carbonate with the weight being 20 times of that of the stearate, and uniformly stirring to obtain a dimethyl carbonate solution;
(3) feeding the organic silicon modified paraffin into a reaction kettle, introducing chlorine, adjusting the temperature of the reaction kettle to 60 ℃, reacting until the specific gravity of liquid is 1.75, and discharging to obtain organic silicon modified chlorinated paraffin;
(4) adding the organosilicone modified chlorinated paraffin into the dimethyl carbonate solution, uniformly stirring, feeding into an ice water bath, adding 0.04 weight part of platinum catalyst, stirring for reaction for 3 hours, discharging, adding 20 weight parts of oleic acid, raising the temperature to 65 ℃, keeping the temperature, stirring for 1 hour, and cooling to obtain a hydrophobic modified chlorinated paraffin solution;
(5) adding 13 parts by weight of diethylenetriamine into the hydrophobic modified chlorinated paraffin solution, adding 0.6 part by weight of metal oxide, introducing nitrogen, raising the temperature to 146 ℃, keeping the temperature and stirring for 5 hours, continuing raising the temperature to 210 ℃, reacting for 110 minutes, and carrying out reduced pressure distillation to obtain paraffin modified imidazoline;
(6) adding the paraffin modified imidazoline into dimethyl carbonate with the weight 2 times that of the paraffin modified imidazoline, uniformly stirring, adding 0.2 part by weight of an acid binding agent, sending into an ice water bath, adding 7 parts by weight of adipoyl chloride, stirring for reacting for 4 hours, performing rotary evaporation, removing the dimethyl carbonate, drying for 2 hours at 70 ℃ in vacuum, discharging and cooling to obtain the special super-hydrophobic anticorrosive chlorinated paraffin for the coating.
The stearate is barium stearate.
The metal oxide is ferric oxide.
The acid-binding agent is pyridine.
Example 2
A preparation method of special super-hydrophobic anti-corrosion chlorinated paraffin for coating comprises the following steps:
(1) adding 14 parts by weight of polymethylhydrosiloxane into absolute ethyl alcohol which is 10 times of the polymethylhydrosiloxane, uniformly stirring, raising the temperature to 90 ℃, adding 90 parts by weight of solid paraffin, keeping the temperature and stirring for 20 minutes, distilling, and removing the ethyl alcohol to obtain organic silicon modified paraffin;
(2) adding 1 part by weight of stearate into dimethyl carbonate with the weight being 10 times of that of the stearate, and uniformly stirring to obtain a dimethyl carbonate solution;
(3) feeding the organic silicon modified paraffin into a reaction kettle, introducing chlorine, adjusting the temperature of the reaction kettle to 50 ℃, reacting until the specific gravity of liquid is 1.65, and discharging to obtain organic silicon modified chlorinated paraffin;
(4) adding the organosilicone modified chlorinated paraffin into the dimethyl carbonate solution, uniformly stirring, feeding into an ice water bath, adding 0.1 part by weight of platinum catalyst, stirring for reaction for 5 hours, discharging, adding 36 parts by weight of oleic acid, raising the temperature to 70 ℃, keeping the temperature, stirring for 2 hours, and cooling to obtain a hydrophobic modified chlorinated paraffin solution;
(5) adding 10 parts by weight of diethylenetriamine into the hydrophobic modified chlorinated paraffin solution, adding 0.3 part by weight of metal oxide, introducing nitrogen, raising the temperature to 140 ℃, keeping the temperature and stirring for 3 hours, continuing raising the temperature to 200 ℃, reacting for 100 minutes, and carrying out reduced pressure distillation to obtain paraffin modified imidazoline;
(6) adding the paraffin modified imidazoline into dimethyl carbonate with the weight 1.7 times of that of the paraffin modified imidazoline, uniformly stirring, adding 0.1 part by weight of an acid binding agent, sending into an ice water bath, adding 5 parts by weight of adipoyl chloride, stirring for reacting for 3 hours, performing rotary evaporation, removing the dimethyl carbonate, drying for 1 hour at the temperature of 60 ℃ in vacuum, discharging and cooling to obtain the special super-hydrophobic anti-corrosion chlorinated paraffin for the coating.
The stearate is zinc stearate.
The metal oxide is aluminum oxide.
The acid-binding agent is pyridine.
And (3) performance testing:
taking a commercially available solvent-free epoxy resin anticorrosive paint:
the product standard is as follows:
01 (test tube method), brownish red, no mechanical impurity;
the viscosity of 02 (coating a No. 4 cup) is 30-80S;
the gelling time is 6-10 min;
04 drying the thick layer, wherein the surface is uniform at 150 ℃ for 2 h;
05 flexural strength 59.2 mpa;
(1) and (3) corrosion inhibition performance testing:
selecting A3 steel with size of 60mm × 20mm × 3mm, treating with commercially available solvent-free epoxy resin anticorrosive paint, curing, placing in 6% hydrochloric acid solution, standing at normal temperature for 24 hours, and measuring corrosion rate (g (m) by weight loss2·h)－1) The result is a;
the super-hydrophobic anti-corrosion chlorinated paraffin special for the coating in the embodiment 1 of the invention is adopted to blend the A3 steel which is the same with the commercially available solvent-free epoxy resin anticorrosive coating in different addition amounts, and the addition amounts of the super-hydrophobic anti-corrosion chlorinated paraffin special for the coating are 5%, 10% and 13% of the commercially available solvent-free epoxy resin anticorrosive coating; the corrosion rate (g. (m.) was measured by the above-mentioned test method2·h)－1) The results are respectively expressed as b, c and d;
the super-hydrophobic anti-corrosion chlorinated paraffin special for the coating in embodiment 2 of the invention is adopted to blend the A3 steel which is the same with the commercially available solvent-free epoxy resin anticorrosive coating in different addition amounts, and the addition amounts of the super-hydrophobic anti-corrosion chlorinated paraffin special for the coating are 5%, 10% and 13% of the commercially available solvent-free epoxy resin anticorrosive coating; the corrosion rate (g. (m.) was measured by the above-mentioned test method2·h)－1) The results are respectively counted as e, f and g;
as a result: a is 2.95, b is 1.13, c is 0.87, d is 1.27, e is 1.05, f is 0.70, g is 1.09;
as can be seen, the paint added with the special super-hydrophobic anti-corrosion chlorinated paraffin for the paint has better anti-corrosion effect than the commercially available anti-corrosion paint; the addition amount of the special super-hydrophobic anti-corrosion chlorinated paraffin for the coating is optimally 10%.
(2) And (3) hydrophobic property test:
measured according to GB/T26490-2011:
the water rolling angle of the super-hydrophobic anti-corrosion chlorinated paraffin special for the coating is less than or equal to 5 degrees;
static water contact angle: > 150 deg.
Claims (4)
1. The preparation method of the special super-hydrophobic anti-corrosion chlorinated paraffin for the coating is characterized by comprising the following steps of:
(1) adding 14-20 parts by weight of polymethylhydrosiloxane into absolute ethyl alcohol with the weight 10-13 times of that of polymethylhydrosiloxane, uniformly stirring, raising the temperature to 90-95 ℃, adding 90-100 parts by weight of solid paraffin, keeping the temperature and stirring for 20-30 minutes, distilling, and removing ethanol to obtain organic silicon modified paraffin;
(2) adding 1-2 parts by weight of stearate into dimethyl carbonate with the weight being 10-20 times of that of the stearate, and uniformly stirring to obtain a dimethyl carbonate solution;
(3) feeding the organic silicon modified paraffin into a reaction kettle, introducing chlorine, adjusting the temperature of the reaction kettle to be 50-60 ℃, reacting until the specific gravity of liquid is 1.65-1.75, and discharging to obtain organic silicon modified chlorinated paraffin;
(4) adding the organic silicon modified chlorinated paraffin into the dimethyl carbonate solution, uniformly stirring, feeding into an ice water bath, adding 0.04-0.1 part by weight of platinum catalyst, stirring for reaction for 3-5 hours, discharging, adding 20-36 parts by weight of oleic acid, raising the temperature to 65-70 ℃, keeping the temperature and stirring for 1-2 hours, and cooling to obtain a hydrophobic modified chlorinated paraffin solution;
(5) taking 10-13 parts by weight of diethylenetriamine, adding the diethylenetriamine into the hydrophobic modified chlorinated paraffin solution, adding 0.3-0.6 part by weight of metal oxide, introducing nitrogen, raising the temperature to 146 ℃, keeping the temperature and stirring for 3-5 hours, continuing raising the temperature to 200-210 ℃, reacting for 110 minutes, and carrying out reduced pressure distillation to obtain paraffin modified imidazoline;
(6) adding the paraffin modified imidazoline into dimethyl carbonate with the weight 1.7-2 times of that of the paraffin modified imidazoline, uniformly stirring, adding 0.1-0.2 part by weight of an acid-binding agent, sending into an ice-water bath, adding 5-7 parts by weight of adipoyl chloride, stirring for reacting for 3-4 hours, performing rotary evaporation, removing the dimethyl carbonate, drying for 1-2 hours at the temperature of 60-70 ℃ in vacuum, discharging and cooling to obtain the special super-hydrophobic anticorrosive chlorinated paraffin for the coating.
2. The preparation method of the special superhydrophobic anticorrosive chlorinated paraffin for paint according to claim 1, wherein the stearate is one of zinc stearate, calcium stearate and barium stearate.
3. The preparation method of the special superhydrophobic anticorrosive chlorinated paraffin for coatings according to claim 1, wherein the metal oxide is one of aluminum oxide and ferric oxide.
4. The preparation method of the special superhydrophobic anticorrosive chlorinated paraffin for coatings according to claim 1, wherein the acid-binding agent is pyridine.
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| CN111205767B (en) * | 2020-02-26 | 2022-02-01 | 科顺防水科技股份有限公司 | Super-hydrophobic coating for corrosion prevention and freeze-thaw resistance of concrete and preparation method thereof |
| CN112047640A (en) * | 2020-09-16 | 2020-12-08 | 中山庞玻新型装饰玻璃有限公司 | Degerming and sterilizing functional glass |
| CN115261069B (en) * | 2022-06-29 | 2024-02-20 | 海南汉地阳光石油化工有限公司 | Preparation method of novel coastal anti-corrosion coating blending agent |
| CN118389193B (en) * | 2024-03-14 | 2024-10-01 | 安徽星鑫材料科技股份有限公司 | Chlorinated paraffin/graphene composite material and preparation method and application thereof |
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| JP2001070795A (en) * | 1999-09-03 | 2001-03-21 | Japan Energy Corp | Solid acid catalyst, preparation thereof and method for isomerizing hydrocarbon using the catalyst |
| WO2010124823A1 (en) * | 2009-04-28 | 2010-11-04 | Clariant International Ltd | Laundry detergent compositions |
| CN103540361A (en) * | 2012-07-12 | 2014-01-29 | 中国科学院大连化学物理研究所 | Preparation method of chlorinated paraffin |
| CN104593071A (en) * | 2013-10-30 | 2015-05-06 | 青岛旺裕橡胶制品有限公司 | Preparation method of chlorinated paraffin |
| CN107557071B (en) * | 2017-09-19 | 2019-03-15 | 安徽星鑫化工科技有限公司 | A kind of organic-silicon-modified chlorinated paraffin and preparation method thereof |
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Address after: 237451 Huhu Town, Huoqiu County, Lu'an City, Anhui Province Patentee after: Anhui Xingxin Material Technology Co.,Ltd. Address before: 237451 Huhu Town, Huoqiu County, Lu'an City, Anhui Province Patentee before: ANHUI XINGXIN CHEMICAL TECHNOLOGY Co.,Ltd. |
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