CN102718613A - Half-esterification high polymer emulsifying agent for industrial explosives - Google Patents
Half-esterification high polymer emulsifying agent for industrial explosives Download PDFInfo
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- CN102718613A CN102718613A CN2012102252205A CN201210225220A CN102718613A CN 102718613 A CN102718613 A CN 102718613A CN 2012102252205 A CN2012102252205 A CN 2012102252205A CN 201210225220 A CN201210225220 A CN 201210225220A CN 102718613 A CN102718613 A CN 102718613A
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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
Technical field
The present invention relates to organic chemical industry's synthesis technical field, specifically a kind of half ester macromolecule emulsifier that is used for industrial explosive.
Background technology
Emulsion [explosive is made up of with interior (water) mutually foreign minister's (oil phase).Emulsifying agent is foreign minister's a main ingredient, and its function is with a large amount of interior uniform and stable matrix that are emulsified into mutually.Because internal-phase ratio example very high (interior 17 times of being about foreign minister's weight mutually), and contain a large amount of unstable crystalline structure particles, so formed emulsifying base breakdown of emulsion very easily.The main path of head it off be exploitation with in the high-quality emulsifying agent that is complementary, so the synthesized high-performance emulsifying agent has become the core technology of preparation emulsion [explosive.The molecule of emulsifying agent generally is made up of lipophilic group and hydrophilic radical.When two kinds of groups can not directly link to each other, have between them one with these two kinds of groups that group can both be connected, be called the bridge formation group.In fact a lot of emulsifying agents all are to be made up 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 oil phase and water respectively, are arranged in interfacial film, prevent the particle accumulation that emulsification is good, impel emulsion stability.
Domestic first-generation emulsifying agent multiselect is used the small molecules tensio-active agent, as being the ester emulsifying agent of feedstock production with oleic acid, sorbyl alcohol etc., like Span-80 emulsifying agent (also comprising LM201 emulsifying agent and compound emulsifying agent thereof).Because the Span-80 emulsifying agent is formed distribute different (is the mixture of dibasic acid esters, three esters and the polyester of main body with the monoesters), causes the emulsifying power difference of product in emulsion [explosive, thereby has influenced emulsifying effectiveness and explosive package stability.S-generation emulsifying agent multiselect is used to improve the stability in storage and the water repelling property of emulsion [explosive, like succimide series macromolecular emulsifying agent with the higher non-ester-type tensio-active agent of molecular weight.Compare with first-generation emulsifying agent,, have stronger stability and higher blast performance, particularly shelf lives and can improve 2-3 doubly with the emulsion [explosive of succimide series products as emulsifying agent.But succimide series macromolecular emulsifying agent exists nitrogen content low, and molecular polarity is weak, wetting ability is poor, also has problems such as emulsifying power is low, emulsion strength height.And as the polyethylene polyamine of one of succimide series macromolecular emulsifying agent raw materials for production, because environmental requirement, its output and kind be atrophy gradually, and follows source of goods shortage, and the price of polyethylene polyamine is also progressively improving.
Summary of the invention
It is low that technical assignment of the present invention provides a kind of production cost, and emulsifying property is good, and oil film is firmer, and turndown ratio is used for the half ester macromolecule emulsifier of industrial explosive greatly.
Technical assignment of the present invention realizes that by following mode this emulsifying agent is made by the component of following composition by weight proportion relation:
Lipophilic ingredient: 500～1500 parts, the bridge formation component: 98～232 parts, one 31～200 parts of hydrophilic components, 2 61～375 parts of hydrophilic components;
Described lipophilic ingredient is Vestolen PP 7052, 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 terepthaloyl moietie, USP Kosher, Diethylene Glycol or tetramethylolmethane;
Described hydrophilic component two is one or more the mixture in Monoethanolamine MEA BASF, diethylolamine, the trolamine;
Procedure of processing is following:
Lipophilic ingredient put into have in the heating and the reaction kettle of whipping appts, heat temperature raising to 100～190 ℃ are dropped into the bridge formation component again in reaction kettle; Holding temperature, and stirred 0.5～1 hour, be warming up to 200～240 ℃; Reacted 2～5 hours; When reactant acid number and free acid anhydrides touch the mark when requiring, finish reaction, filter crude product; Add hydrophilic component one then, warming while stirring to 160～180 ℃, in 2～4 hours reaction times, after esterification was accomplished, cooling added the dilution of neutral oil component; Add hydrophilic component two then, warming while stirring to 120～140 ℃, 2～4 hours reaction times; After amination reaction is accomplished; Temperature control carries out vacuum hydro-extraction for 130～140 ℃, and reaction finished when moisture not had was deviate from, and filtered and promptly got the half ester macromolecule emulsifier.
Described reactant acid number is 75～240mgKOH/g, free acid anhydrides 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 Witcizer 300 or diethyl phthalate.
A kind of half ester macromolecule emulsifier that is used for industrial explosive of the present invention is compared with prior art has following characteristics:
The present invention adopts polyolefine and polyvalent alcohol of different molecular weight etc. for feedstock production goes out the half ester macromolecule emulsifier, and this emulsifying agent had both had the fast advantage of SP-80 class emulsifying agent emulsifying rate, had characteristics such as the succimide stability in storage is good again; And further improved the process of dynamite substrate performance, and be that the emulsion [explosive that emulsifying agent prepares has the little water-in-oil-type particle that is evenly distributed with product of the present invention, emulsifying property is good; Oil film is firmer; Turndown ratio is big, and process of dynamite substrate is stable, and good blast performance is arranged; Therefore, half ester macromolecule emulsifier of the present invention is the requisite starting material of the hgh-performance emulsified explosive of preparation; Simultaneously; Because the alcohols wide material sources of one of raw material that emulsifying agent is produced and cheap; Both alleviate the deficiency of the succimide class explosive emulsifying agent raw material polyethylene polyamine source of goods, with the low cost of product, filled up the industrial blank of domestic polyol ester family macromolecule emulsifying agent again.
Embodiment
Embodiment 1:
Get the 500kg Vestolen PP 7052 and put into and have in the heating and the reaction kettle of whipping appts, heat temperature raising to 100～190 ℃ are dropped into the 98kg maleic acid again in reaction kettle; Holding temperature, and stirred 0.5～1 hour, be warming up to 200～240 ℃; Reacted 2～5 hours, when the reactant acid number is 75～240mgKOH/g, free acid anhydrides accounts for 0.8% of resultant of reaction weight; Finish reaction, filter crude product; Add 31kg terepthaloyl moietie then, warming while stirring to 160～180 ℃, in 2～4 hours reaction times, after esterification was accomplished, cooling added the Witcizer 300 dilution; Add the 61kg Monoethanolamine MEA BASF then; Warming while stirring to 120～140 ℃, 2～4 hours reaction times is after amination reaction is accomplished; Temperature control carries out vacuum hydro-extraction for 130～140 ℃; Vacuum tightness is-0.1 ± 0.01mpa, and reaction finished when moisture not had was deviate from, and filtered and promptly got the half ester macromolecule emulsifier.
This half ester macromolecule emulsifier outward appearance is a brown viscous liquid; The acid number scope is 5～20mgKOH/g; The saponification value scope is 50～70mgKOH/g; Viscosity 250～500mm in the time of 100 ℃
2/ s; Water-content＜0.1%.
Embodiment 2:
Get the 1500kg polyisobutene and put into and have in the heating and the reaction kettle of whipping appts, heat temperature raising to 100～190 ℃ are dropped into the 232kg FUMARIC ACID TECH GRADE again in reaction kettle; Holding temperature, and stirred 0.5～1 hour, be warming up to 200～240 ℃; Reacted 2～5 hours, when the reactant acid number is 75～240mgKOH/g, free acid anhydrides accounts for 0.3% of resultant of reaction weight; Finish reaction, filter crude product; Add the 200kg USP Kosher then, warming while stirring to 160～180 ℃, in 2～4 hours reaction times, after esterification was accomplished, cooling added the diethyl phthalate dilution; The mixture that adds 375kg diethylolamine and trolamine then; Warming while stirring to 120～140 ℃, 2～4 hours reaction times is after amination reaction is accomplished; Temperature control carries out vacuum hydro-extraction for 130～140 ℃; Vacuum tightness is-0.1 ± 0.01mpa, and reaction finished when moisture not had was deviate from, and filtered and promptly got the half ester macromolecule emulsifier.
This half ester macromolecule emulsifier outward appearance is a brown viscous liquid; The acid number scope is 5～20mgKOH/g; The saponification value scope is 50～70mgKOH/g; Viscosity 250～500mm in the time of 100 ℃
2/ s; Water-content＜0.1%.
Embodiment 3:
Get the 1000kg poly-n-butene and put into and have in the heating and the reaction kettle of whipping appts, heat temperature raising to 100～190 ℃ are dropped into the 150kg MALEIC ANHYDRIDE again in reaction kettle; Holding temperature, and stirred 0.5～1 hour, be warming up to 200～240 ℃; Reacted 2～5 hours, when the reactant acid number is 75～240mgKOH/g, when not having free acid anhydrides; Finish reaction, filter crude product; Add the 100kg Diethylene Glycol then, warming while stirring to 160～180 ℃, in 2～4 hours reaction times, after esterification was accomplished, cooling added the Witcizer 300 dilution; Add the 150kg trolamine then; Warming while stirring to 120～140 ℃, 2～4 hours reaction times is after amination reaction is accomplished; Temperature control carries out vacuum hydro-extraction for 130～140 ℃; Vacuum tightness is-0.1 ± 0.01mpa, and reaction finished when moisture not had was deviate from, and filtered and promptly got the half ester macromolecule emulsifier.
This half ester macromolecule emulsifier outward appearance is a brown viscous liquid; The acid number scope is 5～20mgKOH/g; The saponification value scope is 50～70mgKOH/g; Viscosity 250～500mm in the time of 100 ℃
2/ s; Water-content＜0.1%.
Embodiment 4:
Get the 1200kg polypenthylene and put into and have in the heating and the reaction kettle of whipping appts, heat temperature raising to 100～190 ℃ are dropped into the 200kg MALEIC ANHYDRIDE again in reaction kettle; Holding temperature, and stirred 0.5～1 hour, be warming up to 200～240 ℃; Reacted 2～5 hours, when the reactant acid number is 75～240mgKOH/g, free acid anhydrides accounts for 0.1% of resultant of reaction weight; Finish reaction, filter crude product; Add the 150kg tetramethylolmethane then, warming while stirring to 160～180 ℃, in 2～4 hours reaction times, after esterification was accomplished, cooling added the Witcizer 300 dilution; The mixture that adds 200kg Monoethanolamine MEA BASF, diethylolamine and trolamine then; Warming while stirring to 120～140 ℃, 2～4 hours reaction times is after amination reaction is accomplished; Temperature control carries out vacuum hydro-extraction for 130～140 ℃; Vacuum tightness is-0.1 ± 0.01mpa, and reaction finished when moisture not had was deviate from, and filtered and promptly got the half ester macromolecule emulsifier.
This half ester macromolecule emulsifier outward appearance is a brown viscous liquid; The acid number scope is 5～20mgKOH/g; The saponification value scope is 50～70mgKOH/g; Viscosity 250～500mm in the time of 100 ℃
2/ s; Water-content＜0.1%.
Claims (4)
1. half ester macromolecule emulsifier that is used for industrial explosive is characterized in that this emulsifying agent is made by the component of following composition by weight proportion relation:
Lipophilic ingredient: 500～1500 parts, the bridge formation component: 98～232 parts, one 31～200 parts of hydrophilic components, 2 61～375 parts of hydrophilic components;
Described lipophilic ingredient is Vestolen PP 7052, 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 terepthaloyl moietie, USP Kosher, Diethylene Glycol or tetramethylolmethane;
Described hydrophilic component two is one or more the mixture in Monoethanolamine MEA BASF, diethylolamine, the trolamine;
Procedure of processing is following:
Lipophilic ingredient put into have in the heating and the reaction kettle of whipping appts, heat temperature raising to 100～190 ℃ are dropped into the bridge formation component again in reaction kettle; Holding temperature, and stirred 0.5～1 hour, be warming up to 200～240 ℃; Reacted 2～5 hours; When reactant acid number and free acid anhydrides touch the mark when requiring, finish reaction, filter crude product; Add hydrophilic component one then, warming while stirring to 160～180 ℃, in 2～4 hours reaction times, after esterification was accomplished, cooling added the dilution of neutral oil component; Add hydrophilic component two then, warming while stirring to 120～140 ℃, 2～4 hours reaction times; After amination reaction is accomplished; Temperature control carries out vacuum hydro-extraction for 130～140 ℃, and reaction finished when moisture not had was deviate from, and filtered and promptly got the half ester macromolecule emulsifier.
2. the half ester macromolecule emulsifier that is used for industrial explosive according to claim 1 is characterized in that described reactant acid number is 75～240mgKOH/g, free acid anhydrides account for resultant of reaction weight 1% in.
3. the half ester macromolecule emulsifier that is used for industrial explosive according to claim 1 is characterized in that the vacuum tightness of described vacuum hydro-extraction is-0.1 ± 0.01mpa.
4. the half ester macromolecule emulsifier that is used for industrial explosive according to claim 1 is characterized in that described neutral oil component is Witcizer 300 or diethyl phthalate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201210225220.5A CN102718613B (en) | 2012-07-03 | 2012-07-03 | Half-esterification high polymer emulsifying agent for industrial explosives |
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| CN201210225220.5A CN102718613B (en) | 2012-07-03 | 2012-07-03 | Half-esterification high polymer emulsifying agent for industrial explosives |
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| CN102718613B CN102718613B (en) | 2014-09-03 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102976877A (en) * | 2012-12-24 | 2013-03-20 | 江南大学 | Novel emulsifier for emulsion explosive and preparation method of novel emulsifier |
| CN102992922A (en) * | 2012-12-24 | 2013-03-27 | 江南大学 | Novel polymer emulsifier and preparation method thereof |
| CN105237500A (en) * | 2015-11-03 | 2016-01-13 | 葛洲坝易普力股份有限公司 | Macromolecular emulsifying agent suitable for up-hole blasting charge and preparation method thereof |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2048881C1 (en) * | 1992-10-27 | 1995-11-27 | Виктор Сергеевич Илюхин | Emulsifying composition |
| CN1067039C (en) * | 1996-01-17 | 2001-06-13 | 中国石油化工总公司 | Emulsifier for emulsified explosive and its preparation process |
| US6368367B1 (en) * | 1999-07-07 | 2002-04-09 | The Lubrizol Corporation | Process and apparatus for making aqueous hydrocarbon fuel compositions, and aqueous hydrocarbon fuel composition |
| CN1415588A (en) * | 2001-10-30 | 2003-05-07 | 中国石油化工股份有限公司 | Emulsifier utilized for emulsion explosive and its preparation method |
| CN1152123C (en) * | 2000-07-20 | 2004-06-02 | 中国石油化工集团公司 | Fuel oil emulsifier and its producing process |
| US6780209B1 (en) * | 2000-01-24 | 2004-08-24 | The Lubrizol Corporation | Partially dehydrated reaction product process for making same, and emulsion containing same |
| CN1609079A (en) * | 2003-10-24 | 2005-04-27 | 中国石油化工股份有限公司 | Emulsifier for powdered emulsified explosive and its prepn process |
| US20050120619A1 (en) * | 2001-06-29 | 2005-06-09 | Frederick W Koch | Emulsified fuel compositions prepared employing emulsifier derived from high polydispersity olefin polymers |
| US20060223945A1 (en) * | 2003-01-21 | 2006-10-05 | Hollingshurst Claire L | Low color polyisobutylene succinic anhydride-derived emulsifiers |
| CN101602634A (en) * | 2009-05-26 | 2009-12-16 | 锦州康泰润滑油添加剂有限公司 | Ester emulsifier for industrial emulsion explosive and preparation method thereof |
| CN101679691A (en) * | 2007-05-31 | 2010-03-24 | 赢创罗麦斯添加剂有限责任公司 | improved polymer dispersions |
-
2012
- 2012-07-03 CN CN201210225220.5A patent/CN102718613B/en not_active Expired - Fee Related
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2048881C1 (en) * | 1992-10-27 | 1995-11-27 | Виктор Сергеевич Илюхин | Emulsifying composition |
| CN1067039C (en) * | 1996-01-17 | 2001-06-13 | 中国石油化工总公司 | Emulsifier for emulsified explosive and its preparation process |
| US6368367B1 (en) * | 1999-07-07 | 2002-04-09 | The Lubrizol Corporation | Process and apparatus for making aqueous hydrocarbon fuel compositions, and aqueous hydrocarbon fuel composition |
| US6780209B1 (en) * | 2000-01-24 | 2004-08-24 | The Lubrizol Corporation | Partially dehydrated reaction product process for making same, and emulsion containing same |
| CN1152123C (en) * | 2000-07-20 | 2004-06-02 | 中国石油化工集团公司 | Fuel oil emulsifier and its producing process |
| US20050120619A1 (en) * | 2001-06-29 | 2005-06-09 | Frederick W Koch | Emulsified fuel compositions prepared employing emulsifier derived from high polydispersity olefin polymers |
| CN1415588A (en) * | 2001-10-30 | 2003-05-07 | 中国石油化工股份有限公司 | Emulsifier utilized for emulsion explosive and its preparation method |
| US20060223945A1 (en) * | 2003-01-21 | 2006-10-05 | Hollingshurst Claire L | Low color polyisobutylene succinic anhydride-derived emulsifiers |
| CN1609079A (en) * | 2003-10-24 | 2005-04-27 | 中国石油化工股份有限公司 | Emulsifier for powdered emulsified explosive and its prepn process |
| CN101679691A (en) * | 2007-05-31 | 2010-03-24 | 赢创罗麦斯添加剂有限责任公司 | improved polymer dispersions |
| CN101602634A (en) * | 2009-05-26 | 2009-12-16 | 锦州康泰润滑油添加剂有限公司 | Ester emulsifier for industrial emulsion explosive and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| 崔安娜，等: "聚异丁烯丁二酰亚胺乳化剂的研究与应用", 《矿冶》 * |
| 曾锡瑞，等: "TX-10对邻苯二甲酸二丁酯在水中增溶体系的研究", 《化学世界》 * |
| 谢丽: "聚异丁烯丁二酸醇胺乳化剂的合成、性能及应用研究", 《南京理工大学硕士论文》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102976877A (en) * | 2012-12-24 | 2013-03-20 | 江南大学 | Novel emulsifier for emulsion explosive and preparation method of novel emulsifier |
| CN102992922A (en) * | 2012-12-24 | 2013-03-27 | 江南大学 | Novel polymer emulsifier and preparation method thereof |
| 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 |
| CN105237500A (en) * | 2015-11-03 | 2016-01-13 | 葛洲坝易普力股份有限公司 | Macromolecular emulsifying agent suitable for up-hole blasting charge 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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| CN102718613B (en) | 2014-09-03 |
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