CN102718613B - Half-esterification high polymer emulsifying agent for industrial explosives - Google Patents

Half-esterification high polymer emulsifying agent for industrial explosives Download PDF

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Publication number
CN102718613B
CN102718613B CN201210225220.5A CN201210225220A CN102718613B CN 102718613 B CN102718613 B CN 102718613B CN 201210225220 A CN201210225220 A CN 201210225220A CN 102718613 B CN102718613 B CN 102718613B
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emulsifying agent
parts
components
component
reaction
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CN102718613A (en
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郭君岐
孙友梅
马晓燕
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POLY EXPLOSIVES (JINAN) CO Ltd
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POLY EXPLOSIVES (JINAN) CO Ltd
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Abstract

The invention discloses a half-esterification high polymer emulsifying agent for industrial explosives and belongs to the technical field of organic chemical synthesis. The emulsifying agent is prepared by the following components of, by weight, 500-1500 parts of oleophylic components, 98-232 parts of bridging components, 31-200 parts of first hydrophilic components, and 61-375 parts of second hydrophilic components, wherein the oleophylic components are polypropylene, polyisobutene or poly n-butene, or polypentylene; the bridging components are maleic acids, fumaric acids or maleic anhydride; the first hydrophilic components are ethylene glycol, glycerol, diethylene glycol or pentaerythritol; and the second hydrophilic components are one or more of a mixture of monoethanolamine, diethanol amine and triethanolamine. Compared with emulsifying agents in prior art, the half-esterification high polymer emulsifying agent has the advantages of being low in production cost, good in emulsifying performance, sturdy in oil film, and large in operation elasticity; and emulsified explosives prepared by the emulsifying agent are stable in matrix and good in exploding performance.

Description

A kind of half esterification macromolecule emulsifier for industrial explosive
Technical field
The present invention relates to organic chemical industry's synthesis technical field, specifically a kind of half esterification macromolecule emulsifier for industrial explosive.
Background technology
Emulsion explosive is comprised of foreign minister's (oil phase) and interior phase (water).Emulsifying agent is foreign minister's main ingredient, and its function is by a large amount of interior uniform and stable matrix that is emulsified into mutually.Due to interior phase ratio very high (be inside about mutually foreign minister's weight 17 times), and contain a large amount of unstable crystalline structure particles, therefore formed emulsifying base breakdown of emulsion very easily.The main path of head it off be exploitation with in the quality milk agent that matches, so synthesized high-performance emulsifying agent has become the core technology of preparing emulsion explosive.The molecule of emulsifying agent generally consists of lipophilic group and hydrophilic radical.When two kinds of groups can not directly be connected, between them, have one with these two kinds of groups that group can be connected, be called bridge formation group.In fact a lot of emulsifying agents are all to consist of above three kinds of groups.On oil phase and aqueous phase interface, the lipophilic group of emulsifying agent molecule and hydrophilic radical are adsorbed on respectively oil phase and water, are arranged in interfacial film, prevent the particle accumulation that emulsification is good, impel emulsion stability.
Domestic first-generation emulsifying agent multiselect small molecules tensio-active agent, the ester emulsifying agent that oleic acid, sorbyl alcohol etc. are prepared as raw material as take, as Span-80 emulsifying agent (also comprising LM201 emulsifying agent and compound emulsifying agent thereof).Because Span-80 emulsifying agent forms distribute different (mixture of the dibasic acid esters that the monoesters of take is main body, three esters and polyester), cause the emulsifying power difference of product in emulsion explosive, thereby affected emulsifying effectiveness and explosive package stability.The higher non-ester-type tensio-active agent of molecular weight for s-generation emulsifying agent multiselect, for improving stability in storage and the water repelling property of emulsion explosive, as succimide series macromolecular emulsifying agent.Compare with first-generation emulsifying agent, using succimide series products as the emulsion explosive of emulsifying agent, there is stronger stability and higher blast performance, particularly shelf lives and can improve 2-3 doubly.But succimide series macromolecular emulsifying agent exists nitrogen content low, molecular polarity is weak, wetting ability is poor, also has the problems such as emulsifying power is low, emulsion strength is high.And as the polyethylene polyamine of one of succimide series macromolecular emulsifying agent raw materials for production, due to environmental requirement, its output and kind be atrophy gradually, and follow source of goods shortage, the price of polyethylene polyamine is also progressively improving.
summary of the invention
It is low that technical assignment of the present invention is to provide a kind of production cost, and emulsifying property is good, and oil film is firmer, and turndown ratio is greatly for half esterification macromolecule emulsifier of industrial explosive.
Technical assignment of the present invention is realized in the following manner, and this emulsifying agent is made by the component of following composition by weight proportion relation:
Lipophilic ingredient: 500~1500 parts, bridge formation component: 98~232 parts, one 31~200 parts of hydrophilic components, 2 61~375 parts of hydrophilic components;
Described lipophilic ingredient is polypropylene, polyisobutene, poly-n-butene or polypenthylene;
Described bridge formation component is maleic acid, FUMARIC ACID TECH GRADE or MALEIC ANHYDRIDE;
Described hydrophilic component one is ethylene glycol, glycerol, Diethylene Glycol or tetramethylolmethane;
Described hydrophilic component two is one or more the mixture in Monoethanolamine MEA BASF, diethanolamine, trolamine;
Procedure of processing is as follows:
Lipophilic ingredient is put in the reactor with heating and whipping appts, be heated to 100~190 ℃, in reactor, drop into bridge formation component again, holding temperature, and stir 0.5~1 hour, be warming up to 200~240 ℃, react 2~5 hours, when reactant acid number and free acid value touch the mark while requiring, finish reaction, filter crude product; Then add hydrophilic component one, warming while stirring to 160~180 ℃, in 2~4 hours reaction times, after esterification completes, cooling adds the dilution of neutral oil component; Then add hydrophilic component two, warming while stirring to 120~140 ℃, 2~4 hours reaction times, after amination reaction completes, 130~140 ℃ of temperature controls carry out vacuum hydro-extraction, and when having moisture to deviate from, reaction finishes, and filters and obtain half esterification macromolecule emulsifier.
Described reactant acid number is 75~240mgKOH/g, free acid value account for resultant of reaction weight 1% in.
The vacuum tightness of described vacuum hydro-extraction is-0.1 ± 0.01mpa.
Described neutral oil component is dibutyl phthalate or diethyl phthalate.
Compared to the prior art a kind of half esterification macromolecule emulsifier for industrial explosive of the present invention has following characteristics:
The present invention adopts the polyolefine of different molecular weight and polyvalent alcohol etc. to prepare half esterification macromolecule emulsifier for raw material, this emulsifying agent had both had advantages of that SP-80 class emulsifying agent emulsifying rate was fast, there is again the features such as succimide stability in storage is good, and further improved process of dynamite substrate performance, the emulsion explosive that the product of the present invention of take is prepared as emulsifying agent has the little water-in-oil-type particle being evenly distributed, emulsifying property is good, oil film is firmer, turndown ratio is large, process of dynamite substrate is stable, there is good blast performance, therefore, half esterification macromolecule emulsifier of the present invention is the requisite starting material of the hgh-performance emulsified explosive of preparation, simultaneously, the alcohols wide material sources of one of raw material of producing due to emulsifying agent and cheap, both alleviate the deficiency of the succimide class explosive emulsifying agent raw material polyethylene polyamine source of goods, by the low cost of product, filled up the industrial blank of domestic polyol ester family macromolecule emulsifying agent again.
Embodiment
Embodiment 1:
Getting 500kg polypropylene puts in the reactor with heating and whipping appts, be heated to 100~190 ℃, in reactor, drop into 98kg maleic acid again, holding temperature, and stir 0.5~1 hour, be warming up to 200~240 ℃, react 2~5 hours, when reactant acid number is 75~240mgKOH/g, free acid value accounts for 0.8% of resultant of reaction weight, finish reaction, filter crude product; Then add 31kg ethylene glycol, warming while stirring to 160~180 ℃, in 2~4 hours reaction times, after esterification completes, cooling adds dibutyl phthalate dilution; Then add 61kg Monoethanolamine MEA BASF, warming while stirring to 120~140 ℃, 2~4 hours reaction times, after amination reaction completes, 130~140 ℃ of temperature controls carry out vacuum hydro-extraction, vacuum tightness is-0.1 ± 0.01mpa, and when having moisture to deviate from, reaction does not finish, and filters and obtain half esterification macromolecule emulsifier.
This half esterification macromolecule emulsifier outward appearance is brown viscous liquid; Acid number scope is 5~20mgKOH/g; Saponification value scope is 50~70mgKOH/g; Viscosity 250~500mm in the time of 100 ℃ 2/ s; Water-content < 0.1%.
Embodiment 2:
Getting 1500kg polyisobutene puts in the reactor with heating and whipping appts, be heated to 100~190 ℃, in reactor, drop into 232kg FUMARIC ACID TECH GRADE again, holding temperature, and stir 0.5~1 hour, be warming up to 200~240 ℃, react 2~5 hours, when reactant acid number is 75~240mgKOH/g, free acid value accounts for 0.3% of resultant of reaction weight, finish reaction, filter crude product; Then add 200kg glycerol, warming while stirring to 160~180 ℃, in 2~4 hours reaction times, after esterification completes, cooling adds diethyl phthalate dilution; Then the mixture that adds 375kg diethanolamine and trolamine, warming while stirring to 120~140 ℃, 2~4 hours reaction times, after amination reaction completes, 130~140 ℃ of temperature controls carry out vacuum hydro-extraction, vacuum tightness is-0.1 ± 0.01mpa, and when having moisture to deviate from, reaction does not finish, and filters and obtain half esterification macromolecule emulsifier.
This half esterification macromolecule emulsifier outward appearance is brown viscous liquid; Acid number scope is 5~20mgKOH/g; Saponification value scope is 50~70mgKOH/g; Viscosity 250~500mm in the time of 100 ℃ 2/ s; Water-content < 0.1%.
Embodiment 3:
Getting 1000kg poly-n-butene puts in the reactor with heating and whipping appts, be heated to 100~190 ℃, in reactor, drop into 150kg MALEIC ANHYDRIDE again, holding temperature, and stir 0.5~1 hour, be warming up to 200~240 ℃, react 2~5 hours, when reactant acid number is 75~240mgKOH/g, during without free acid value, finish reaction, filter crude product; Then add 100kg Diethylene Glycol, warming while stirring to 160~180 ℃, in 2~4 hours reaction times, after esterification completes, cooling adds dibutyl phthalate dilution; Then add 150kg trolamine, warming while stirring to 120~140 ℃, 2~4 hours reaction times, after amination reaction completes, 130~140 ℃ of temperature controls carry out vacuum hydro-extraction, vacuum tightness is-0.1 ± 0.01mpa, and when having moisture to deviate from, reaction does not finish, and filters and obtain half esterification macromolecule emulsifier.
This half esterification macromolecule emulsifier outward appearance is brown viscous liquid; Acid number scope is 5~20mgKOH/g; Saponification value scope is 50~70mgKOH/g; Viscosity 250~500mm in the time of 100 ℃ 2/ s; Water-content < 0.1%.
Embodiment 4:
Getting 1200kg polypenthylene puts in the reactor with heating and whipping appts, be heated to 100~190 ℃, in reactor, drop into 200kg MALEIC ANHYDRIDE again, holding temperature, and stir 0.5~1 hour, be warming up to 200~240 ℃, react 2~5 hours, when reactant acid number is 75~240mgKOH/g, free acid value accounts for 0.1% of resultant of reaction weight, finish reaction, filter crude product; Then add 150kg tetramethylolmethane, warming while stirring to 160~180 ℃, in 2~4 hours reaction times, after esterification completes, cooling adds dibutyl phthalate dilution; Then the mixture that adds 200kg Monoethanolamine MEA BASF, diethanolamine and trolamine, warming while stirring to 120~140 ℃, 2~4 hours reaction times, after amination reaction completes, 130~140 ℃ of temperature controls carry out vacuum hydro-extraction, vacuum tightness is-0.1 ± 0.01mpa, and when having moisture to deviate from, reaction does not finish, and filters and obtain half esterification macromolecule emulsifier.
This half esterification macromolecule emulsifier outward appearance is brown viscous liquid; Acid number scope is 5~20mgKOH/g; Saponification value scope is 50~70mgKOH/g; Viscosity 250~500mm in the time of 100 ℃ 2/ s; Water-content < 0.1%.

Claims (4)

1. for a half esterification macromolecule emulsifier of industrial explosive, it is characterized in that this emulsifying agent is made by the component of following composition by weight proportion relation:
Lipophilic ingredient: 500~1500 parts, bridge formation component: 98~232 parts, one 31~200 parts of hydrophilic components, 2 61~375 parts of hydrophilic components;
Described lipophilic ingredient is polypropylene, polyisobutene, poly-n-butene or polypenthylene;
Described bridge formation component is maleic acid, FUMARIC ACID TECH GRADE or MALEIC ANHYDRIDE;
Described hydrophilic component one is ethylene glycol, glycerol, Diethylene Glycol or tetramethylolmethane;
Described hydrophilic component two is one or more the mixture in Monoethanolamine MEA BASF, diethanolamine, trolamine;
Procedure of processing is as follows:
Lipophilic ingredient is put in the reactor with heating and whipping appts, be heated to 100~190 ℃, in reactor, drop into bridge formation component again, holding temperature, and stir 0.5~1 hour, be warming up to 200~240 ℃, react 2~5 hours, when reactant acid number is 75~240mgKOH/g, without free acid value or free acid value account for resultant of reaction weight 0.3%, 0.8% time, finish reaction, filter crude product; Then add hydrophilic component one, warming while stirring to 160~180 ℃, in 2~4 hours reaction times, after esterification completes, cooling adds the dilution of neutral oil component; Then add hydrophilic component two, warming while stirring to 120~140 ℃, 2~4 hours reaction times, after amination reaction completes, 130~140 ℃ of temperature controls carry out vacuum hydro-extraction, and when having moisture to deviate from, reaction finishes, and filters and obtain half esterification macromolecule emulsifier.
2. the half esterification macromolecule emulsifier for industrial explosive according to claim 1, is characterized in that described reactant acid number is 75~240mgKOH/g, free acid value account for resultant of reaction weight 1% in.
3. the half esterification macromolecule emulsifier for industrial explosive according to claim 1, the vacuum tightness that it is characterized in that described vacuum hydro-extraction is-0.1 ± 0.01mpa.
4. the half esterification macromolecule emulsifier for industrial explosive according to claim 1, is characterized in that described neutral oil component is dibutyl phthalate or diethyl phthalate.
CN201210225220.5A 2012-07-03 2012-07-03 Half-esterification high polymer emulsifying agent for industrial explosives Expired - Fee Related CN102718613B (en)

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CN102992922B (en) * 2012-12-24 2015-08-05 江南大学 A kind of macromolecule emulsifier and preparation method thereof
CN102976877B (en) * 2012-12-24 2015-08-05 江南大学 A kind of emulsifier for emulsion explosive and preparation method thereof
CN105237500B (en) * 2015-11-03 2018-03-16 葛洲坝易普力股份有限公司 It is suitable for macromolecule emulsifier of uphole shooting powder charge and preparation method thereof

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