CN103483115A - Preparation method of emulsifier for preparing emulsion explosive - Google Patents
Preparation method of emulsifier for preparing emulsion explosive Download PDFInfo
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- CN103483115A CN103483115A CN201310473181.5A CN201310473181A CN103483115A CN 103483115 A CN103483115 A CN 103483115A CN 201310473181 A CN201310473181 A CN 201310473181A CN 103483115 A CN103483115 A CN 103483115A
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Abstract
The invention discloses a preparation method of an emulsifier for preparing an emulsion explosive. The preparation method is characterized in that the preparation method comprises the following steps: 1, copolymer preparation: mixing polyolefin, vinyl acetate and excess maleic anhydride, adding a solvent xylene, uniformly mixing, adding an initiator, carrying out a stirring reaction, distilling for removing xylene, removing superfluous maleic anhydride, and cooling to obtain a copolymer; and 2, emulsifier synthesis: carrying out stirring mixing of the copolymer and mineral oil to obtain a mixture, heating the mixture under the protection of nitrogen, adding alcohol amine, carrying out a stirring reaction, adding diatomite, uniformly mixing, and carrying out pumping filtration to obtain a reddish-brown clear oily final product-emulsifier. The emulsion explosive prepared by using the emulsifier prepared through the preparation method has a high storage stability, and the reaction temperatures in the preparation process of the emulsifier are not greater than 100DEG C, so the production cost is reduced, and the product safety is improved.
Description
Technical field
The invention belongs to the explosive technical field, specifically, relate to a kind of preparation method of the emulsifying agent for the preparation of emulsion explosive.
Background technology
Emulsion explosive uses extensively, and it forms is oversaturated water-in-oil emulsion in oil phase material at room temperature in essence.Effect by emulsifying agent makes the oil phase material of 10wt% that the inorganic oxide salt brine solution emulsification of 90wt% is formed to water-in-oil matrix.In this case, the inorganic salt solution of dissolving is metastable, trends towards crystallization.If ammonium nitrate crystal is separated out, will produce detrimentally affect to emulsion (solidify, can't pumping) and detonator sensitivity, as poor as Storage Stability of Emulsion Explosive, and miss-fire.In order to keep the stability of emulsion explosive, therefore, emulsifying agent requires to be adapted to stably prepare water in oil emulsion, and the requirement of emulsifying agent is become to higher.
Emulsifier is various, is divided into low molecule emulsifying agent and macromolecule emulsifier two classes.Low molecule emulsifying agent Span-80 is representative, but the emulsifying film intensity of its formation is very poor, and matrix stability is very low.As United States Patent (USP) 3,447,978 disclose a kind of water in oil emulsifying agent, sorbitol ester wherein, and fatty acid glycerine fat or phosphatide are used in emulsifying agent, but this emulsifying agent does not have permanent stability.Macromolecule emulsifier is the emulsifying agent for the preparation of emulsion explosive that developed recently gets up, and is mainly to take polyisobutene as main, carries out modifying and decorating and obtains, and can effectively improve the stability in storage of matrix.But the shortcoming on this emulsifying agent ubiquity is synthetic, due to potential ethylene linkage reaction, require it lower synthetic in very high temperature (180-230 ℃), and long reaction time, causes its high energy consumption and expensive.As patent CN101152993B, CN1158833A etc. prepare macromolecule emulsifier under 200 ℃ of left and right.
The prior art shortcoming: the emulsifying base poor storage stability that emulsifying agent emulsification obtains, the temperature of reaction in the emulsifying agent building-up process requires high, and production cost is high and dangerous.
Summary of the invention
For solving above technical problem, the object of the present invention is to provide a kind of emulsifying agent stability in storage good, production cost is low, and the preparation method of the emulsifying agent for the preparation of emulsion explosive of safety.
Usually the emulsifier in emulsion explosives of preparation is a kind of amphiphile, amphiphilic molecule structure, and an end is hydrophilic group, and an end is oleophilic group.Because the polyolefine segment is longer, the maleic anhydride segment is shorter, so its wetting ability is bad, cause the more difficult emulsification of emulsifying agent, by in the polyisobutene copolymerization, introducing vinyl acetate, the ester bond of vinyl carboxylates can increase the wetting ability of molecule, can make emulsifying agent emulsification be more prone to, and make the temperature of reaction in itself and maleic anhydride, polyolefine copolyreaction, also reduced follow-up reaction synthesis temperature simultaneously.
The object of the present invention is achieved like this: a kind of preparation method of the emulsifying agent for the preparation of emulsion explosive, and its key is to be comprised of following preparation process:
(1) prepare multipolymer: first polyolefine 800-950 part, vinyl carboxylates 9.9-39.6 part and excessive maleic anhydride are mixed by weight, and add excessive solvent xylene, at 70 ℃ of-80 ℃ of temperature, mix, add again the initiator of 9-9.9 part under the condition that vacuumizes and compensate nitrogen, stirring reaction 10h-30h at 70 ℃ of-80 ℃ of temperature, then remove removal xylene by distillation, then under maximum 200 ℃/20mbar, remove excessive maleic anhydride, the cooling multipolymer that obtains;
(2) synthetic emulsifier: by multipolymer and mineral oil, by ratio of weight and the number of copies for the ratio of 2:1 is uniformly mixed, mixture is heated to 90 ℃-100 ℃ under nitrogen protection; Add 29.3 parts of hydramine, then mixture stirring reaction 5h-8h at 90 ℃ of-100 ℃ of temperature; Add diatomite to mix, obtain being the final product-emulsifying agent of the limpid oily of reddish-brown at 100 ℃ of lower suction filtrations.
Above-mentioned initiator is dibenzoyl peroxide or the benzoyl peroxide tert-butyl ester.
Above-mentioned hydramine is diethylin ethanol.
The structural formula of above-mentioned vinyl carboxylates is
r wherein
2for C
8-C
12alkyl.
Above-mentioned vinyl carboxylates is vinyl neodecanoate.
Stating the polyolefine carbon content is C
40– C
500; And described polyolefinic end alkene content>85%.
Said polyolefins is polyisobutene.
One, conventional emulsifier and emulsifying agent Performance Ratio of the present invention are:
1, the water-soluble value of emulsifying base and viscosity is more as shown in table 1:
The detection of the water-soluble value of table 1 emulsifying base and viscosity
Wherein the hydramine reagent of emulsifying agent A is trolamine, and does not add vinyl carboxylates;
Emulsifying agent B is gained emulsifying agent of the present invention.
Comparative result: relatively find that by table 1 the water-soluble value of emulsifying base and viscosity that emulsifying agent B obtains all are less than emulsifying agent B, and the stability of the lower emulsifying base of water-soluble value is higher.
2, Storage Stability of Emulsion Explosive detects as shown in table 2:
Detection after the high cold cycle of table 2 emulsion explosive
Wherein the hydramine reagent of emulsifying agent A is trolamine, and does not add vinyl carboxylates;
Emulsifying agent B is gained emulsifying agent of the present invention.
Comparative result: by table 2, relatively find to pass through the stability in storage of emulsion explosive B higher than emulsion explosive A.
Two, in sum: by relatively finding, the stability in storage of the emulsion explosive that emulsifying agent of the present invention prepares is higher.
Beneficial effect:
The preparation method of a kind of emulsifying agent for the preparation of emulsion explosive of the present invention, the stability in storage of the emulsion explosive that emulsifying agent prepares is high, and in the emulsifying agent preparation process, temperature of reaction all is less than or equal to 100 ℃, and production cost is reduced, the security of production is improved.
Embodiment
Below in conjunction with embodiment, the invention will be further described:
Embodiment 1:
(1) prepare multipolymer: in the four-hole boiling flask stirred at the band of 2L, first will hold the polyisobutene 800g of alkene content>85%, vinyl neodecanoate 39.6g and excessive maleic anhydride mix, and add excessive solvent xylene, at 80 ℃ of temperature, mix, system vacuumizes 3 times to 100mbar and each inflated with nitrogen compensation, at 80 ℃ of temperature, the dibenzoyl peroxide that adds 9.9g, stirring reaction 20h at 80 ℃ of temperature, then remove removal xylene by distillation, again under maximum 200 ℃/20mbar, remove excessive maleic anhydride, the cooling 952g multipolymer that obtains,
(2) synthetic emulsifier: 207g multipolymer and 103.5g mineral oil are uniformly mixed, and mixture is heated to 90 ℃ under nitrogen protection; Add 29.3g diethylin ethanol, then mixture stirring reaction 5h at 100 ℃ of temperature; Add diatomite to mix, at 100 ℃ of lower suction filtrations, obtain final product-emulsifying agent that 271g is the limpid oily of reddish-brown; This emulsifying agent acid number is 28.0mg KOH/g; Nitrogen content is 0.91%.
Embodiment 2:
(1) prepare multipolymer: in the four-hole boiling flask stirred at the band of 2L, first will hold the polyisobutene 810g of alkene content>85%, vinyl neodecanoate 17.8g and excessive maleic anhydride mix, and add excessive solvent xylene, at 70 ℃ of temperature, mix, system vacuumizes 3 times to 100mbar and each inflated with nitrogen compensation, at 75 ℃ of temperature, the benzoyl peroxide tert-butyl ester that adds 9.6g, stirring reaction 20h at 70 ℃ of temperature, then remove removal xylene by distillation, again under maximum 200 ℃/20mbar, remove excessive maleic anhydride, the cooling 928g multipolymer that obtains,
(2) synthetic emulsifier: 227g multipolymer and 113.5g mineral oil are uniformly mixed, and mixture is heated to 100 ℃ under nitrogen protection; Add 29.3g diethylin ethanol, then mixture stirring reaction 8h at 90 ℃ of temperature; Add diatomite to mix, at 100 ℃ of lower suction filtrations, obtain final product-emulsifying agent that 299g is the limpid oily of reddish-brown; This emulsifying agent acid number is 25.5mg KOH/g; Nitrogen content is 0.86%.
Embodiment 3:
(1)) prepare multipolymer: in the four-hole boiling flask stirred at the band of 2L, first will hold the polyisobutene 950g of alkene content>85%, vinyl neodecanoate 9.9g and excessive maleic anhydride mix, and add excessive solvent xylene, at 75 ℃ of temperature, mix, system vacuumizes 3 times to 100mbar and each inflated with nitrogen compensation, at 70 ℃ of temperature, the benzoyl peroxide tert-butyl ester that adds 9.0g, stirring reaction 20h at 75 ℃ of temperature, then remove removal xylene by distillation, again under maximum 200 ℃/20mbar, remove excessive maleic anhydride, the cooling 1077g multipolymer that obtains,
(2) synthetic emulsifier: 206g multipolymer and 103g mineral oil are uniformly mixed, and mixture is heated to 95 ℃ under nitrogen protection; Add 29.3g diethylin ethanol, then mixture stirring reaction 7h at 95 ℃ of temperature; Add diatomite to mix, at 100 ℃ of lower suction filtrations, obtain final product-emulsifying agent that 320g is the limpid oily of reddish-brown; This emulsifying agent acid number is 22.3mg KOH/g; Nitrogen content is 0.97%.
Claims (7)
1. the preparation method for the preparation of the emulsifying agent of emulsion explosive is characterized in that being comprised of following preparation process:
(1) prepare multipolymer: first polyolefine 800-950 part, vinyl carboxylates 9.9-39.6 part and excessive maleic anhydride are mixed by weight, and add excessive solvent xylene, at 70 ℃ of-80 ℃ of temperature, mix, add again the initiator of 9-9.9 part under the condition that vacuumizes and compensate nitrogen, stirring reaction 10h-30h at 70 ℃ of-80 ℃ of temperature, then remove removal xylene by distillation, then under maximum 200 ℃/20mbar, remove excessive maleic anhydride, the cooling multipolymer that obtains;
(2) synthetic emulsifier: by multipolymer and mineral oil, by ratio of weight and the number of copies for the ratio of 2:1 is uniformly mixed, mixture is heated to 90 ℃-100 ℃ under nitrogen protection; Add 29.3 parts of hydramine, then mixture stirring reaction 5h-8h at 90 ℃ of-100 ℃ of temperature; Add diatomite to mix, obtain being the final product-emulsifying agent of the limpid oily of reddish-brown at 100 ℃ of lower suction filtrations.
2. according to claim 1 for the preparation of the preparation method of the emulsifying agent of emulsion explosive, it is characterized in that: described initiator is dibenzoyl peroxide or the benzoyl peroxide tert-butyl ester.
3. according to claim 1 for the preparation of the preparation method of the emulsifying agent of emulsion explosive, it is characterized in that: described hydramine is diethylin ethanol.
4. according to claim 1 for the preparation of the preparation method of the emulsifying agent of emulsion explosive, it is characterized in that: the structural formula of described vinyl carboxylates is
r wherein
2for C
8-C
12alkyl.
5. according to claim 4 for the preparation of the preparation method of the emulsifying agent of emulsion explosive, it is characterized in that: described vinyl carboxylates is vinyl neodecanoate.
6. according to claim 1 for the preparation of the preparation method of the emulsifying agent of emulsion explosive, it is characterized in that: described polyolefine carbon content is C
40– C
500; And described polyolefinic end alkene content>85%.
7. according to claim 6 for the preparation of the preparation method of the emulsifying agent of emulsion explosive, it is characterized in that: described polyolefine is polyisobutene.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103755503A (en) * | 2014-01-23 | 2014-04-30 | 葛洲坝易普力股份有限公司 | Polymer emulsifier for mixed emulsified explosive and preparation method of polymer emulsifier |
| CN107473913A (en) * | 2017-09-13 | 2017-12-15 | 南通意特化工有限公司 | A kind of novel emulsion explosive compound emulsifying agent |
| CN107935797A (en) * | 2017-11-29 | 2018-04-20 | 淄博汇通油脂精细化工有限公司 | Extemporaneous preparation mining explosive emulsifying agent and preparation method thereof |
| CN115433050A (en) * | 2022-08-31 | 2022-12-06 | 河南久联神威民爆器材有限公司 | Improved emulsion explosive and preparation method and application thereof |
| CN118459298A (en) * | 2024-05-13 | 2024-08-09 | 浙江顺源化工有限公司 | Preparation method of emulsifier and emulsion explosive containing emulsifier |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103755503A (en) * | 2014-01-23 | 2014-04-30 | 葛洲坝易普力股份有限公司 | Polymer emulsifier for mixed emulsified explosive and preparation method of polymer emulsifier |
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| CN107473913A (en) * | 2017-09-13 | 2017-12-15 | 南通意特化工有限公司 | A kind of novel emulsion explosive compound emulsifying agent |
| CN107935797A (en) * | 2017-11-29 | 2018-04-20 | 淄博汇通油脂精细化工有限公司 | Extemporaneous preparation mining explosive emulsifying agent and preparation method thereof |
| CN115433050A (en) * | 2022-08-31 | 2022-12-06 | 河南久联神威民爆器材有限公司 | Improved emulsion explosive and preparation method and application thereof |
| CN118459298A (en) * | 2024-05-13 | 2024-08-09 | 浙江顺源化工有限公司 | Preparation method of emulsifier and emulsion explosive containing emulsifier |
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