CN108865264B - Preparation method of quaternary ammonium salt modified chlorinated paraffin - Google Patents
Preparation method of quaternary ammonium salt modified chlorinated paraffin Download PDFInfo
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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 quaternary ammonium salt modified chlorinated paraffin, which adopts a 2-step method to prepare chlorinated paraffin 70, promotes pretreated chlorinated paraffin to further react into chlorinated paraffin 70 under the action of an initiator, introduces heat-resistant ester amine in the reaction process, and realizes the modification of the chlorinated paraffin 70 through the quaternization reaction of the ester amine and dimethyl carbonate.
Description
Technical Field
The invention belongs to the field of chlorinated paraffin, and particularly relates to a preparation method of quaternary ammonium salt modified chlorinated paraffin.
Background
Chlorinated paraffin has the characteristics of no odor, no toxicity, flame retardance, low volatility, good compatibility with PVC resin and the like, is often 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, and contains a small amount or trace of unstable chlorine atoms on tertiary carbon atoms, so that when the chlorinated paraffin is heated or irradiated by sunlight, the unstable chlorine atoms and adjacent hydrogen atoms can be separated from a carbon chain at the same time to release HCl, and the HCl can further promote the decomposition of the chlorinated paraffin; therefore, the chlorinated paraffin product is stored for too long or the color of the chlorinated paraffin product is gradually deepened when the chlorinated paraffin product is heated, so that the use of the chlorinated paraffin product is influenced, the purity of raw materials used by the domestic chlorinated paraffin, and chlorination reaction processes and equipment are different from those in foreign countries, so that the chlorinated paraffin has poor thermal stability, the addition amount of a thermal stabilizer is large, and the share of the cost of the stabilizer in the chlorinated paraffin is high, therefore, one of the purposes of the invention is to improve the thermal stability of the chlorinated paraffin without adopting a mode of blending and storing the chlorinated paraffin and a heat-resistant stabilizer;
chlorinated paraffin is used as an extreme pressure additive, and can react with the surface of metal at a higher temperature to generate a chloride extreme pressure film with a layered crystal structure, so that the increase of substances retained on a blade is prevented, the generation of built-up edges is slowed down, the abrasion of a cutter is reduced, and the surface roughness of a workpiece is reduced.
Disclosure of Invention
The invention aims to provide a preparation method of quaternary ammonium salt modified chlorinated paraffin 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 quaternary ammonium salt modified chlorinated paraffin comprises the following steps:
(1) adding 1.8-2 parts by weight of octyl isothiazolinone into dimethyl carbonate with the weight being 10-17 times of that of the octyl isothiazolinone, and uniformly stirring to obtain a bacteriostatic solution;
(2) adding 90-100 parts by weight of refined wax into the antibacterial solution, uniformly stirring, feeding into a reaction kettle, introducing chlorine, adjusting the temperature of the reaction kettle to be 40-50 ℃, stirring for reaction until the specific gravity of the liquid reaches 1.37-1.50, discharging and cooling to obtain a pretreated paraffin solution;
(3) adding 0.8-1 part by weight of zinc stearate soap into 10-13 times of anhydrous ethanol, stirring for dissolving, adding 10-12 parts by weight of triethanolamine, slowly raising the temperature to 50-55 ℃, keeping the temperature and stirring for 20-40 minutes, and distilling to remove ethanol to obtain heat-resistant modified triethanolamine;
(4) mixing the heat-resistant modified triethanolamine with 13-20 parts by weight of stearic acid, uniformly stirring, feeding into a reaction kettle, adding p-toluenesulfonic acid accounting for 2-3% of the weight of the mixture, introducing nitrogen, adjusting the temperature of the reaction kettle to 150-;
(5) adding 0.8-1.5 parts by weight of surfactant into deionized water with the weight being 10-17 times of that of the surfactant, and uniformly stirring to obtain water dispersion;
(6) adding the heat-resistant ester amine into the pretreated paraffin solution, uniformly stirring, feeding into a reaction kettle, introducing nitrogen, adjusting the temperature of the reaction kettle to 55-60 ℃, reacting for 30-40 hours, adding the aqueous dispersion, uniformly stirring, introducing chlorine, adjusting the pressure of the reaction kettle to 0.2-0.3Mpa, adding 0.1-0.2 part by weight of an initiator, adjusting the temperature of the reaction kettle to 90-110 ℃, reacting for 4-6 hours, discharging, carrying out rotary evaporation at 93-95 ℃ for 1-2 hours, carrying out suction filtration, washing a filter cake with alkali liquor, and drying at normal temperature to obtain the heat-resistant ester amine.
The surfactant is one of dodecyl dimethyl ammonium bromide and dodecyl benzene sulfonic acid sodium.
The initiator is ammonium persulfate.
The alkali liquor is sodium hydroxide solution with the concentration of 0.1-0.2 mol/L.
The invention has the advantages that:
the invention takes refined wax as raw material, dimethyl carbonate solution of octyl isothiazolinone as reaction solution, the pretreated chlorinated paraffin is obtained through chlorine reaction, then zinc stearate soap is adopted to treat triethanolamine, the triethanolamine is mixed with stearic acid for reaction, heat-resistant modified ester amine is obtained, then the pretreated chlorinated paraffin is promoted to further react under the action of an initiator to form chlorinated paraffin 70, the heat-resistant ester amine is introduced in the reaction process, the modification of the chlorinated paraffin 70 is realized through the quaternization reaction of the ester amine and the dimethyl carbonate, the invention adopts a water phase method to prepare the chlorinated paraffin 70, various modification treatments are adopted in the preparation process, the bacteriostasis, the heat-resistant stability and the like of the finished chlorinated paraffin material are improved, the finished material obtained through the modification treatment has good storage stability, and the quaternary ammonium salt can be dispersed into water during use, the modified chlorinated paraffin 70 has good dispersibility, improves the characteristic that the traditional chlorinated paraffin 70 is insoluble in water, mostly only serves as a flame retardant, enriches the efficacy, enlarges the application range, can be dispersed in water for use, has good environmental protection, can be widely used for stamping, stretching, drawing and cutting of various metals such as stainless steel and the like, has good lubricating effect, can be cleaned by directly washing with water after use, does not need a large amount of organic solvent, saves resources, and is convenient and environment-friendly.
Detailed Description
Example 1
A preparation method of quaternary ammonium salt modified chlorinated paraffin comprises the following steps:
(1) adding 1.8 parts by weight of octyl isothiazolinone into dimethyl carbonate with the weight being 10 times of that of the octyl isothiazolinone, and uniformly stirring to obtain a bacteriostatic solution;
(2) adding 90 parts by weight of refined wax into the antibacterial solution, uniformly stirring, feeding into a reaction kettle, introducing chlorine, adjusting the temperature of the reaction kettle to 40 ℃, stirring for reaction until the specific gravity of the liquid reaches 1.37, discharging and cooling to obtain a pretreated paraffin solution;
(3) adding 0.8 weight part of zinc stearate soap into 10 times of absolute ethyl alcohol, stirring for dissolving, adding 10 weight parts of triethanolamine, slowly raising the temperature to 50 ℃, keeping the temperature and stirring for 20-40 minutes, and distilling to remove the ethanol to obtain heat-resistant modified triethanolamine;
(4) mixing the heat-resistant modified triethanolamine with 13 parts by weight of stearic acid, uniformly stirring, feeding into a reaction kettle, adding p-toluenesulfonic acid accounting for 2% of the weight of the mixture, introducing nitrogen, adjusting the temperature of the reaction kettle to 170 ℃, stirring for reacting for 6 hours, cooling to normal temperature, discharging and cooling to obtain heat-resistant esteramine;
(5) adding 0.8 weight part of dodecyl dimethyl ammonium bromide into deionized water with the weight of 10 parts of dodecyl dimethyl ammonium bromide, and uniformly stirring to obtain a water dispersion;
(6) adding the heat-resistant ester amine into the pretreated paraffin solution, uniformly stirring, feeding into a reaction kettle, introducing nitrogen, adjusting the temperature of the reaction kettle to 55 ℃, reacting for 30 hours, adding the aqueous dispersion, uniformly stirring, introducing chlorine, adjusting the pressure of the reaction kettle to 0.2Mpa, adding 0.1 part by weight of ammonium persulfate, adjusting the temperature of the reaction kettle to 90 ℃, reacting for 4 hours, discharging, carrying out rotary evaporation at 93 ℃ for 1 hour, carrying out suction filtration, washing a filter cake with alkali liquor, and drying at normal temperature to obtain the heat-resistant ester amine.
The alkali liquor is a sodium hydroxide solution with the concentration of 0.1 mol/L.
Example 2
A preparation method of quaternary ammonium salt modified chlorinated paraffin comprises the following steps:
(1) adding 2 parts by weight of octyl isothiazolinone into 17 times of dimethyl carbonate, and uniformly stirring to obtain a bacteriostatic solution;
(2) adding 100 parts by weight of refined wax into the antibacterial solution, uniformly stirring, feeding into a reaction kettle, introducing chlorine, adjusting the temperature of the reaction kettle to 50 ℃, stirring for reaction until the specific gravity of the liquid reaches 1.48, discharging and cooling to obtain a pretreated paraffin solution;
(3) adding 1 weight part of zinc stearate soap into anhydrous ethanol 13 times the weight of the zinc stearate soap, stirring for dissolving, adding 12 weight parts of triethanolamine, slowly raising the temperature to 55 ℃, keeping the temperature and stirring for 20-40 minutes, and distilling to remove ethanol to obtain heat-resistant modified triethanolamine;
(4) mixing the heat-resistant modified triethanolamine with 20 parts by weight of stearic acid, uniformly stirring, feeding into a reaction kettle, adding p-toluenesulfonic acid accounting for 3% of the weight of the mixture, introducing nitrogen, adjusting the temperature of the reaction kettle to 180 ℃, stirring for reacting for 6 hours, cooling to normal temperature, discharging and cooling to obtain heat-resistant esteramine;
(5) adding 1 part by weight of sodium dodecyl benzene sulfonate into deionized water 17 times of the weight of the sodium dodecyl benzene sulfonate, and uniformly stirring to obtain a water dispersion;
(6) adding the heat-resistant ester amine into the pretreated paraffin solution, uniformly stirring, feeding into a reaction kettle, introducing nitrogen, adjusting the temperature of the reaction kettle to 60 ℃, reacting for 40 hours, adding the aqueous dispersion, uniformly stirring, introducing chlorine, adjusting the pressure of the reaction kettle to 0.3Mpa, adding 0.2 part by weight of ammonium persulfate, adjusting the temperature of the reaction kettle to 110 ℃, reacting for 6 hours, discharging, carrying out rotary evaporation at 95 ℃ for 2 hours, carrying out suction filtration, washing a filter cake with alkali liquor, and drying at normal temperature to obtain the heat-resistant ester amine.
The alkali liquor is a sodium hydroxide solution with the concentration of 0.2 mol/L.
Example 3
A preparation method of quaternary ammonium salt modified chlorinated paraffin comprises the following steps:
(1) adding 1.9 parts by weight of octyl isothiazolinone into dimethyl carbonate with the weight being 12 times of that of the octyl isothiazolinone, and uniformly stirring to obtain a bacteriostatic solution;
(2) adding 95 parts by weight of refined wax into the antibacterial solution, uniformly stirring, feeding into a reaction kettle, introducing chlorine, adjusting the temperature of the reaction kettle to 43 ℃, stirring for reaction until the specific gravity of the liquid reaches 1.44, discharging and cooling to obtain a pretreated paraffin solution;
(3) adding 0.9 weight part of zinc stearate soap into 12 times of absolute ethanol, stirring for dissolving, adding 11 weight parts of triethanolamine, slowly raising the temperature to 52 ℃, keeping the temperature and stirring for 23 minutes, and distilling to remove ethanol to obtain heat-resistant modified triethanolamine;
(4) mixing the heat-resistant modified triethanolamine with 17 parts by weight of stearic acid, uniformly stirring, feeding into a reaction kettle, adding p-toluenesulfonic acid accounting for 2% of the weight of the mixture, introducing nitrogen, adjusting the temperature of the reaction kettle to 173 ℃, stirring for reacting for 6 hours, cooling to normal temperature, discharging and cooling to obtain heat-resistant esteramine;
(5) adding 0.9 weight part of surfactant into deionized water with the weight being 12 times of that of the surfactant, and uniformly stirring to obtain water dispersion;
(6) adding the heat-resistant ester amine into the pretreated paraffin solution, uniformly stirring, feeding into a reaction kettle, introducing nitrogen, adjusting the temperature of the reaction kettle to 58 ℃, reacting for 32 hours, adding the aqueous dispersion, uniformly stirring, introducing chlorine, adjusting the pressure of the reaction kettle to 0.23Mpa, adding 0.13 weight part of initiator, adjusting the temperature of the reaction kettle to 95 ℃, reacting for 5 hours, discharging, carrying out rotary evaporation at 93 ℃ for 1 hour, carrying out suction filtration, washing a filter cake with alkali liquor, and drying at normal temperature to obtain the heat-resistant ester amine.
The surfactant is dodecyl dimethyl ammonium bromide.
The initiator is ammonium persulfate.
The alkali liquor is a sodium hydroxide solution with the concentration of 0.14 mol/L.
And (3) performance testing:
comparative test data of the quaternary ammonium salt-modified chlorinated paraffin according to examples 1, 2 and 3 of the present invention and the commercially available chlorinated paraffin 70 (comparative example) are shown in the following table:
the experimental process for testing the thermal decomposition resistance temperature adopted by the invention comprises the following steps:
1. instrument and test paper
(1) Test tube: the inner diameter is 12 +/-1 mm, the outer diameter is 14 +/-1 mm, and the length is 95 +/-1 mm.
(2) Heat-resistant glass: the internal diameter is 140 +/-5 mm, the external diameter is 150 +/-5 mm, the height is 110 +/-5 mm, the upper part is attached with an asbestos cover with the thickness of 5 mm, 4-6 symmetrical test tube holes are covered on the asbestos cover, and a hole for a thermometer and a hole for a stirrer are respectively inserted in the proper positions in the middle.
(3) A thermometer: the graduation is 0-200 ℃, and the division value is 1 ℃.
(4) An electric stirrer and an attached speed regulating device.
(5) A flat electric furnace: 1000-.
(6) And (3) glycerol.
(7) Congo red test paper.
2. Measurement procedure
The test tube was filled with 1 + -0.1 g of sample, a congo red test paper (flush) was inserted into the upper edge of the tube, the congo red test paper was held at about 7 mm in the space of the test tube, the mouth of the test tube was plugged with a rubber stopper, the test tube was placed in a glycerol bath so that the upper part of the test tube was 14 mm from the lid (exposed part) of the bath and the level of glycerol was about 50 mm from the upper edge of the test tube. And simultaneously, inserting a thermometer into a proper position close to the center of the oil bath, enabling the center of the mercury ball and the sample to be on the same level, heating the oil bath, continuously stirring, enabling the temperature rise speed to be not more than 4 ℃ per minute, raising the temperature at 2 ℃ per minute when the temperature is close to 30 ℃ before the thermal decomposition temperature, and recording the temperature when the lower side of the Congo red test paper is blue, namely the thermal decomposition temperature of the sample.
3. Precision degree
The number of differences between the results of the parallel measurements is not more than 2 ℃ and the arithmetic mean of the results of the parallel measurements is taken as the thermal decomposition temperature of the sample.
Claims (4)
1. The preparation method of the quaternary ammonium salt modified chlorinated paraffin is characterized by comprising the following steps:
(1) adding 1.8-2 parts by weight of octyl isothiazolinone into dimethyl carbonate with the weight being 10-17 times of that of the octyl isothiazolinone, and uniformly stirring to obtain a bacteriostatic solution;
(2) adding 90-100 parts by weight of refined wax into the antibacterial solution, uniformly stirring, feeding into a reaction kettle, introducing chlorine, adjusting the temperature of the reaction kettle to be 40-50 ℃, stirring for reaction until the specific gravity of the liquid reaches 1.37-1.50, discharging and cooling to obtain a pretreated paraffin solution;
(3) adding 0.8-1 part by weight of zinc stearate soap into 10-13 times of anhydrous ethanol, stirring for dissolving, adding 10-12 parts by weight of triethanolamine, slowly raising the temperature to 50-55 ℃, keeping the temperature and stirring for 20-40 minutes, and distilling to remove ethanol to obtain heat-resistant modified triethanolamine;
(4) mixing the heat-resistant modified triethanolamine with 13-20 parts by weight of stearic acid, uniformly stirring, feeding into a reaction kettle, adding p-toluenesulfonic acid accounting for 2-3% of the weight of the mixture, introducing nitrogen, adjusting the temperature of the reaction kettle to 150-;
(5) adding 0.8-1.5 parts by weight of surfactant into deionized water with the weight being 10-17 times of that of the surfactant, and uniformly stirring to obtain water dispersion;
(6) adding the heat-resistant ester amine into the pretreated paraffin solution, uniformly stirring, feeding into a reaction kettle, introducing nitrogen, adjusting the temperature of the reaction kettle to 55-60 ℃, reacting for 30-40 hours, adding the aqueous dispersion, uniformly stirring, introducing chlorine, adjusting the pressure of the reaction kettle to 0.2-0.3Mpa, adding 0.1-0.2 part by weight of an initiator, adjusting the temperature of the reaction kettle to 90-110 ℃, reacting for 4-6 hours, discharging, carrying out rotary evaporation at 93-95 ℃ for 1-2 hours, carrying out suction filtration, washing a filter cake with alkali liquor, and drying at normal temperature to obtain the heat-resistant ester amine.
2. The method for preparing quaternary ammonium salt modified chlorinated paraffin according to claim 1, wherein the surfactant is one of dodecyl dimethyl ammonium bromide and dodecyl benzene sulfonic acid sodium.
3. The method for preparing quaternary ammonium salt modified chlorinated paraffin according to claim 1, wherein the initiator is ammonium persulfate.
4. The method for preparing quaternary ammonium salt modified chlorinated paraffin according to claim 1, wherein the alkali solution is sodium hydroxide solution with concentration of 0.1-0.2 mol/L.
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| CN110511576A (en) * | 2019-07-23 | 2019-11-29 | 肥东县云武研发有限公司 | A kind of glass lost-wax process casting paraffin and preparation method thereof |
| CN112647286A (en) * | 2019-11-03 | 2021-04-13 | 苏州新而特纺织有限公司 | Textile dye |
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| CN102533404A (en) * | 2011-07-11 | 2012-07-04 | 布兰诺工业包装材料(上海)有限公司 | Efficient lubrication type anti-rust oil and preparation method thereof |
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