CN104193892B - A kind of preparation method of the polyquaternary ammonium salt with oil product antistatic property - Google Patents
A kind of preparation method of the polyquaternary ammonium salt with oil product antistatic property Download PDFInfo
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- CN104193892B CN104193892B CN201410373603.6A CN201410373603A CN104193892B CN 104193892 B CN104193892 B CN 104193892B CN 201410373603 A CN201410373603 A CN 201410373603A CN 104193892 B CN104193892 B CN 104193892B
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Abstract
The preparation method that the invention discloses a kind of polyquaternary ammonium salt with oil product antistatic property, step is as follows: initiator ammonium persulfate is completely dissolved in MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride and dimethyl diallyl ammonium chloride by (1), forms mixed liquor; (2) kerosene and dehydrated alcohol are added in container, then stir, logical nitrogen, it is warming up to 55-65 DEG C, then drips the mixed liquor that step (1) is prepared; (3) after dropwising, it is warming up to 75-85 DEG C, is incubated 4-6 hour; (4) pouring out reactant liquor, be cooled to room temperature, lower floor's white precipitate is polymerization product; (5) adding in acetone by gained crude product in step (4), sedimentation purifies, and filters, and dries, namely obtains the polyquaternary ammonium salt of the present invention. The present invention selects the aerial kerosene after petroleum ether and distillation to be test oil, and measurement result shows that prepared polyquaternary ammonium salt has excellent antistatic property, can be used as oil antistatic agent.
Description
Technical field
The present invention relates to technical field of chemistry and chemical engineering, the preparation method particularly relating to a kind of polyquaternary ammonium salt with oil product antistatic property.
Background technology
In the storage of oil product and transportation, have substantial amounts of charge collection inside oil product and be not easy to distribute, will blast when reaching capacity or run into the situation of naked light etc. accident, therefore certain diffusion velocity that can make electrostatic charge in oil product need to be added and increase, thus weakening charge collection, increase the material of the electric conductivity of liquid, be oil antistatic agent.
Oil antistatic agent conventional at present is divided into ion-type (including cationic and anionic), non-ionic and amphoteric antistatic additive. Wherein, cationic oil antistatic agent is mainly the quaternary ammonium alkyl of a little long-chain, phosphorus or salt, makes equilibrium ion with chloride. Polyquaternary ammonium salt refers to the high molecular polymer in molecule containing multiple quaternary ammonium cations, also can be used as flocculant, antibacterial, emulsifying agent, softening agent etc., so being widely used in the industries such as oil, chemical industry, printing and dyeing, article of everyday use. The polyquaternary ammonium salt of general bibliographical information is the homopolymerization by dimethyl diallyl ammonium chloride mostly or the copolyreaction with monomers such as acrylamides prepares, but about the not disclosed report of copolymerization of MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride Yu dimethyl diallyl ammonium chloride, so the present invention selects MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride (DMC) and dimethyl diallyl ammonium chloride (DMDAAC) to prepare polyquaternary ammonium salt for monomer.
The preparation method of conventional polyquaternary ammonium salt mainly has aqueous solution and via Inverse-Phase Suspension Polymerization. Water solution polymerization process system viscosity is very big, be not easy heat radiation, product is aqueous solution state, and aftertreatment technology is complicated; Inverse suspension method is polymerized discharged heat and can quickly diffuse in disperse medium, and heat radiation is very fast, and when reaction end is cooled to room temperature, polymerizate directly falls to bottom system, and aftertreatment technology is simple, and product is solid. Thus the present invention selects inverse suspension method to prepare polyquaternary ammonium salt.
Summary of the invention
The preparation method that the invention provides a kind of polyquaternary ammonium salt with oil product antistatic property.
Specifically comprising the following steps that of the preparation method of the polyquaternary ammonium salt with oil product antistatic property of the present invention
(1) initiator ammonium persulfate is completely dissolved in MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride and dimethyl diallyl ammonium chloride, forms mixed liquor (hereinafter referred to as monomer solution). The weight ratio of Ammonium persulfate., MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride and dimethyl diallyl ammonium chloride is 0.05-0.15:34-102:8-26;
(2) kerosene and dehydrated alcohol being added in container, the weight ratio of kerosene, dehydrated alcohol and monomer solution is 60-180:70-210:50-150, then stirs, logical nitrogen, it is warming up to 55-65 DEG C, after 40 minutes, then drips the monomer solution that step (1) is prepared;
(3) after dropwising, it is warming up to 75-85 DEG C, is incubated 4-6 hour;
(4) pouring out reactant liquor, be cooled to room temperature, lower floor's white precipitate is polymerization product;
(5) adding in acetone by gained crude product in step (4), sedimentation purifies, and filters, and dries, namely obtains the polyquaternary ammonium salt of the present invention.
In step (1), Ammonium persulfate., the weight ratio of MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride and dimethyl diallyl ammonium chloride is preferably 0.1:68:17.
In step (2), the weight ratio of kerosene, dehydrated alcohol and monomer solution is 120:140:100.
In step (3), it is preferable that be warming up to 60 DEG C.
In step (4), it is preferable that be warming up to 80 DEG C, it is incubated 5 hours.
The positive effect of the present invention is as follows:
The present invention selects MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride (DMC) and dimethyl diallyl ammonium chloride (DMDAAC) to prepare polyquaternary ammonium salt for monomer, and use the polyquaternary ammonium salt that the present invention is prepared by the mixed solvent of methanol and dehydrated alcohol fully to dissolve, selecting the aerial kerosene after petroleum ether and distillation is test oil, measurement result shows that prepared polyquaternary ammonium salt has excellent antistatic property, can be used as oil antistatic agent.
The polymerization generally used in polyquaternary ammonium salt preparation is water solution polymerization process, slowly makes temperature wayward owing to dispelling the heat, and gained polymerizate is all dissolved among system in preparation process, and reactant liquor is uniform state, it is difficult to separating-purifying. But the mixed liquor using kerosene and dehydrated alcohol in inverse suspension method of the present invention is disperse medium, it is possible to farthest reduce polymerizate dissolubility in system, so that it falls to voluntarily bottom system after reaction terminates.
Detailed description of the invention
The following examples are describing in further detail the present invention.
Embodiment 1
(1) initiator ammonium persulfate is completely dissolved in MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride and dimethyl diallyl ammonium chloride, forms mixed liquor. The weight ratio of Ammonium persulfate., MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride and dimethyl diallyl ammonium chloride is 0.1:34:8;
(2) kerosene and dehydrated alcohol being added in container, the weight ratio of kerosene, dehydrated alcohol and monomer solution is 120:140:100, then stirs, logical nitrogen, is warming up to 55 DEG C, after 40 minutes, then drips the mixed liquor that step (1) is prepared;
(3) after dropwising, it is warming up to 75 DEG C, is incubated 5 hours;
(4) pouring out reactant liquor, be cooled to room temperature, lower floor's white precipitate is polymerization product;
(5) adding in acetone by gained crude product in step (4), sedimentation purifies, and filters, and dries, namely obtains the polyquaternary ammonium salt of the present invention.
Embodiment 2
(1) initiator ammonium persulfate is completely dissolved in MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride and dimethyl diallyl ammonium chloride, forming mixed liquor, the weight ratio of Ammonium persulfate., MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride and dimethyl diallyl ammonium chloride is 0.15:102:26;
(2) kerosene and dehydrated alcohol being added in container, the weight ratio of kerosene, dehydrated alcohol and monomer solution is 180:210:150, then stirs, logical nitrogen, is warming up to 65 DEG C, after 40 minutes, then drips the mixed liquor that step (1) is prepared;
(3) after dropwising, it is warming up to 85 DEG C, is incubated 6 hours;
(4) pouring out reactant liquor, be cooled to room temperature, lower floor's white precipitate is polymerization product;
(5) adding in acetone by gained crude product in step (4), sedimentation purifies, and filters, and dries, namely obtains the polyquaternary ammonium salt of the present invention.
Embodiment 3
First 54.0g MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride and 13.5g dimethyl diallyl ammonium chloride being formed mixed liquor and add 250 ml beakers, stir, add 0.08g Ammonium persulfate., stirring is to fully dissolving, stand-by;
In being equipped with stirring, thermometer, the there-necked flask of 500 milliliters of Dropping funnel, add 100.0g kerosene and 82.5g dehydrated alcohol, stirring, logical nitrogen, be warming up to 60 DEG C, the monomer initiator mixed liquor that dropping has been dissolved;
After dropwising, it is warming up to 80 DEG C, is incubated 5 hours;
Pour out reactant liquor, be cooled to room temperature, take off a layer white precipitate, add stirring in acetone, obtain white powder precipitation, filtering drying, namely obtain the polyquaternary ammonium salt of the present invention.
National Standard of the People's Republic of China GB6950-2001 specifies that the antistatic property of oil product is to be evaluated by the value of static electrical conductivity, and ou Safe Rest Conductivity of Light Fuel Oil value should be greater than 50pS/m. The polyquaternary ammonium salt preparation technology evaluated in the present invention is DMC60.0g, DMDAAC7.5g, Ammonium persulfate. 0.08g, kerosene 82.5g, dehydrated alcohol 100.0g, dropping temperature 60 DEG C, holding temperature 80 DEG C, temperature retention time 6h.
The static electrical conductivity of aerial kerosene after measuring petroleum ether according to National Standard of the People's Republic of China's GB/T12580-90 method for measuring and distill. Take methanol 3 milliliters, dehydrated alcohol 12 milliliters, add in 50 ml beakers, fully dissolve each other, quantitative polyquaternary ammonium salt product is dissolved in configured mixed solvent again, and stirring is to fully dissolving, after being separately added into 120 milliliters of petroleum ether and distilling in aerial kerosene, measure the electrical conductivity of the two, carry out blank assay simultaneously. Mensuration can obtain the relation between polymerizate addition and test oil product electrical conductivity, shown in result table 1-1:
The impact on electrical conductivity of the table 1-1 addition
By table 1-1 it can be seen that prepared polyquaternary ammonium salt has excellent antistatic property, can be used as oil antistatic agent.
Although an embodiment of the present invention has been shown and described, for the ordinary skill in the art, being appreciated that and these embodiments can be carried out multiple change, amendment, replacement and modification without departing from the principles and spirit of the present invention, the scope of the present invention be defined by the appended.
Claims (4)
1. the preparation method of a polyquaternary ammonium salt with oil product antistatic property, it is characterised in that: specifically comprising the following steps that of described method
(1) initiator ammonium persulfate is completely dissolved in MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride and dimethyl diallyl ammonium chloride, forming monomer solution, the weight ratio of Ammonium persulfate., MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride and dimethyl diallyl ammonium chloride is 0.05-0.15:34-102:8-26;
(2) kerosene and dehydrated alcohol being added in container, the weight ratio of kerosene, dehydrated alcohol and monomer solution is 120:140:100, then stirs, logical nitrogen, it is warming up to 55-65 DEG C, after 40 minutes, then drips the monomer solution that step (1) is prepared;
(3) after dropwising, it is warming up to 75-85 DEG C, is incubated 4-6 hour;
(4) pouring out reactant liquor, be cooled to room temperature, lower floor's white precipitate is polymerization product;
(5) adding in acetone by gained crude product in step (4), sedimentation purifies, and filters, and dries, namely obtains polyquaternary ammonium salt.
2. preparation method as claimed in claim 1, it is characterised in that: in step (1), the weight ratio of Ammonium persulfate., MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride and dimethyl diallyl ammonium chloride is 0.1:68:17.
3. preparation method as claimed in claim 1, it is characterised in that: in step (2), it is warming up to 60 DEG C.
4. preparation method as claimed in claim 1, it is characterised in that: in step (3), it is warming up to 80 DEG C, is incubated 5 hours.
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| CN104479067B (en) * | 2014-12-12 | 2017-01-11 | 华东理工大学 | Amphoteric ionic antistatic agent for acrylonitrile butadiene styrene (ABS) and preparation method of antistatic agent |
| CN106190369B (en) * | 2016-07-14 | 2018-03-02 | 西北大学 | A kind of hydrophobic type polyquaternium oil antistatic agent and preparation method thereof |
| CN106319681A (en) * | 2016-08-29 | 2017-01-11 | 董晓 | Preparation method of easy-to-color anti-static spandex fibers |
| CN107325213B (en) * | 2017-08-09 | 2019-09-10 | 江苏富淼科技股份有限公司 | A kind of MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride method for producing polymer of adjustable molecular weight section |
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| CN101628953A (en) * | 2009-08-11 | 2010-01-20 | 华南师范大学 | High molecular weight cationic polyacrylamide preparation method |
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| CN103242473A (en) * | 2013-04-15 | 2013-08-14 | 北京恒聚化工集团有限责任公司 | Beaded polydimethyldiallyl ammonium chloride and preparation method thereof |
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| CN101029109A (en) * | 2007-02-01 | 2007-09-05 | 江南大学 | Production of cationic microsphere with crosslinked swelling function |
| CN101628953A (en) * | 2009-08-11 | 2010-01-20 | 华南师范大学 | High molecular weight cationic polyacrylamide preparation method |
| CN102796496A (en) * | 2012-08-09 | 2012-11-28 | 中国海洋石油总公司 | Cation coating agent for water-base drilling fluid and preparation method thereof |
| CN103242473A (en) * | 2013-04-15 | 2013-08-14 | 北京恒聚化工集团有限责任公司 | Beaded polydimethyldiallyl ammonium chloride and preparation method thereof |
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