CN112300398A - Low-nitrogen high-molecular emulsifier and preparation method thereof - Google Patents
Low-nitrogen high-molecular emulsifier and preparation method thereof Download PDFInfo
- Publication number
- CN112300398A CN112300398A CN202011297699.4A CN202011297699A CN112300398A CN 112300398 A CN112300398 A CN 112300398A CN 202011297699 A CN202011297699 A CN 202011297699A CN 112300398 A CN112300398 A CN 112300398A
- Authority
- CN
- China
- Prior art keywords
- emulsifier
- nitrogen
- low
- reacting
- emulsion explosive
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
- C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C08G81/021—Block or graft polymers containing only sequences of polymers of C08C or C08F
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B23/00—Compositions characterised by non-explosive or non-thermic constituents
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a low-nitrogen polymer emulsifier and a preparation method thereof, and relates to the technical field of emulsifier preparation. The low-nitrogen polymer emulsifier and the preparation method thereof comprise the following steps: s1, putting polyolefin anhydride into a reaction kettle, heating to 60-140 ℃, and reacting under the protection of nitrogen according to the molar ratio of the polyolefin anhydride to the polyhydroxyhydramine of 1: 1.6 to 2.0, adding polyhydroxyhydramine, and reacting at the temperature of 120-190 ℃ for 2 to 8 hours to obtain a product A. The low-nitrogen high-molecular emulsifier has a multi-hanging structure, has a strong steric hindrance effect, increases the strength of a microemulsion oil film of the emulsion explosive, improves the storage period of the emulsion explosive, increases the plasticity of the emulsifier, can replace a T155 emulsifier to be used in the powdery emulsion explosive, has better dispersing capacity while maintaining the strength of the oil film, reduces mechanical shearing, forms a better microemulsion structure, is beneficial to oil film repair in the vacuum dehydration process of the powdery emulsion explosive, improves the power and the storage period of the emulsion explosive, and reduces the manufacturing cost.
Description
Technical Field
The invention relates to the technical field of emulsifier preparation, in particular to a low-nitrogen polymer emulsifier and a preparation method thereof.
Background
The powdered explosive is prepared with oxidant solution with relatively low water content or molten oxidant fine liquid as dispersed phase and oil phase solution of specific carbonaceous fuel and emulsifier as continuous phase, and through powerful shearing under certain technological conditions to form water-in-oil emulsion matrix, spray milling, rotary flash evaporation or cooling solidification and crushing. In order to facilitate emulsification, the oil phase material forms fluid with excellent fluidity when heated to a certain temperature, so as to ensure that the oxidant phase can be stirred and sheared under the action of the emulsifier to form high-quality latex. The emulsion matrix should solidify rapidly and completely encapsulate the oxidant phase crystallites upon proper cooling, so that the solidified oil film should have a tensile strength, i.e., plasticity or toughness, to prevent the oxidant phase crystallites from breaking through the oil film barrier and connecting into sheets.
The emulsifier for the powdered emulsion explosive is essential for forming an excellent emulsion matrix. Compared with the conventional emulsion explosive, the melting point temperature of the oil phase of the powdery emulsion explosive and the melting point temperature of the oxidant are high, so that the emulsifier has high temperature resistance correspondingly.
The T155 polymer emulsifier commonly used in the prior art is a low-nitrogen polymer succinimide emulsifier, is widely applied to the production of powdery emulsion explosives, has a macromolecular framework structure, increases the strength of an oil film, and simultaneously has the five-membered ring structure of succinimide to play a role in enhancing the toughness of the oil film. However, due to the low nitrogen content, the T155 emulsifier has poor hydrophilicity, so that a larger shearing force is needed in the emulsification process, and in the production process of the existing emulsion explosive, the production line has strict limitation on the equipment pressure due to safety considerations, so that the T155 emulsifier has relatively poor emulsification performance and is difficult to emulsify, and in addition, the production raw material of the emulsifier is polyamine, so that the price is relatively high.
Disclosure of Invention
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides a low-nitrogen high-molecular emulsifier and a preparation method thereof, which solve the problem that the common T155 high-molecular emulsifier in the prior art is a low-nitrogen high-molecular succinimide emulsifier, is widely applied to the production of powdery emulsion explosives, has a high-molecular framework structure, increases the strength of an oil film, and simultaneously has the effect of enhancing the toughness of the oil film due to the five-membered ring structure of succinimide. However, due to the low nitrogen content, the T155 emulsifier has poor hydrophilicity, which causes the requirement of larger shearing force in the emulsification process, and in the production process of the existing emulsion explosive, the production line has strict limitation on the equipment pressure due to safety considerations, so the T155 emulsifier has relatively poor emulsification performance and is difficult to emulsify, and in addition, the production raw material of the emulsifier is polyamine, which causes the problem of relatively high price.
(II) technical scheme
In order to achieve the purpose, the invention is realized by the following technical scheme: a low-nitrogen high-molecular emulsifier and its preparing process includes the following steps:
s1, putting polyolefin anhydride into a reaction kettle, heating to 60-140 ℃, and reacting under the protection of nitrogen according to the molar ratio of the polyolefin anhydride to the polyhydroxyhydramine of 1: 1.6 to 2.0, adding polyhydroxyhydramine, and reacting at the temperature of 120-;
s2, adding polyolefin anhydride into a reaction kettle, heating to 60-140 ℃, and mixing according to the molar mass ratio of the polyolefin anhydride of 1: 0.5-1: 1 adding an acid catalyst according to a molar ratio of polyolefin acid anhydride to water of 1: adding water into the mixture for 0.5 to 1 hour, and reacting for 0.5 to 3 hours; heating to 90-150 ℃, and adding the acidic catalyst according to a molar mass ratio of 1: 0.5-1: 2.0, adding an alkaline catalyst, and reacting for 1-4h to obtain a product B;
s3, mixing the product A of the step S1 and the product B of the step S2 according to the molar ratio of 1: 1.0 to 4.0, reacting with nitrogen at 190 ℃ for 2 to 8 hours to obtain the low-nitrogen polymer emulsifier.
Preferably, in step S3, diluent oil is added to facilitate reaction and thorough mixing, and the diluent oil is mechanical oil or paraffin-based base oil, wherein the mass ratio of the polyolefin maleic anhydride to the diluent oil is 1: 0.2-1: 3.0.
(III) advantageous effects
The invention provides a low-nitrogen polymer emulsifier and a preparation method thereof. The method has the following beneficial effects:
the low-nitrogen polymer emulsifier and the preparation method thereof have a multi-hanging structure, have stronger steric hindrance effect, increase the strength of a microemulsion oil film of the emulsion explosive, improve the storage period of the emulsion explosive, have a lactone ring structure, the structure is similar to succinimide, is a five-membered or six-membered lactone ring, increases the plasticity of the emulsifier, the plasticizing effect of the powder is the same as that of succinimide, and can replace T155 emulsifier to be used in powdery emulsion explosive, the emulsion explosive has better dispersion capability while keeping the strength of an oil film by introducing more hydrophilic groups, reduces mechanical shearing to form a better micro emulsion structure, ensures that an emulsifier has plasticizing capability by virtue of a lactone ring structure, is beneficial to oil film repair in the vacuum dehydration process of the powdery emulsion explosive, improves the power and the storage period of the emulsion explosive, takes alcohol amine as a raw material, is cheaper than polyamine, and reduces the manufacturing cost.
Drawings
FIG. 1 is a chemical structural formula of product A of the present invention;
FIG. 2 is a chemical structural formula of the product B of the present invention (five-membered ring on the left and six-membered ring on the right);
FIG. 3 is a chemical structural formula of the low-nitrogen polymeric emulsifier of the present invention;
FIG. 4 is an infrared spectrum of the low-nitrogen polymeric emulsifier of the present invention;
FIG. 5 is a table of IR spectra of low-nitrogen polymeric emulsifiers;
FIG. 6 is a schematic diagram showing the ratio of polymeric emulsifier in the powdered emulsion explosive (spray pulverization) in example 3;
FIG. 7 is a schematic diagram showing the storage properties of the emulsion explosive in the form of a high molecular weight emulsifier powder (spray powder) in example 3.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Referring to fig. 1-7, the present invention provides a technical solution: a low-nitrogen high-molecular emulsifier and its preparing process includes the following steps:
s1, putting polyolefin anhydride into a reaction kettle, heating to 60-140 ℃, and reacting under the protection of nitrogen according to the molar ratio of the polyolefin anhydride to the polyhydroxyhydramine of 1: 1.6 to 2.0, adding polyhydroxyhydramine, and reacting at the temperature of 120-;
s2, adding polyolefin anhydride into a reaction kettle, heating to 60-140 ℃, and mixing according to the molar mass ratio of the polyolefin anhydride of 1: 0.5-1: 1 adding an acid catalyst according to a molar ratio of polyolefin acid anhydride to water of 1: adding water into the mixture for 0.5 to 1 hour, and reacting for 0.5 to 3 hours; heating to 90-150 ℃, and adding the acidic catalyst according to a molar mass ratio of 1: 0.5-1: 2.0, adding an alkaline catalyst, and reacting for 1-4h to obtain a product B;
s3, mixing the product A of the step S1 and the product B of the step S2 according to the molar ratio of 1: 1.0-4.0, reacting at 190 ℃ for 2-8h under the protection of nitrogen to obtain a low-nitrogen polymer emulsifier, adding diluent oil to facilitate the reaction and the thorough mixing, wherein the diluent oil is mechanical oil or paraffin-based base oil, and the mass ratio of the polyolefin maleic anhydride to the diluent oil is 1: 0.2-1: 3.0.
example 1: preparation of low-nitrogen high-molecular emulsifier
The method comprises the following steps:
firstly, putting polyisobutylene maleic anhydride into a reaction kettle, heating to 120 ℃, and reacting with nitrogen under the condition that the molar ratio of the polyisobutylene maleic anhydride to the methyl diethanolamine is 1.0: 1.8 adding methyldiethanolamine, and reacting at 120 ℃ for 4h to obtain a product A;
and secondly, putting the polyisobutene maleic anhydride into a reaction kettle, heating to 80 ℃, and mixing according to a molar mass ratio of the polyisobutene maleic anhydride to hydrochloric acid (37%): 1 hydrochloric acid (37%) was added in a molar ratio of polyisobutylene maleic anhydride and water of 1: 0.8, adding water, and reacting for 1 h; heating to 120 ℃, and mixing the hydrochloric acid and the sodium carbonate according to a molar mass ratio of 1: 0.5, adding sodium carbonate, and reacting for 3 hours to obtain a product B;
and step three, mixing the first-step product A and the second-step product B according to a molar ratio of 1: 2, adding the mixture into a reaction kettle, and reacting the mixture with nitrogen for 4 hours at 160 ℃ to obtain the polymer emulsifier with a multi-hanging structure.
Example 2: preparation of low-nitrogen high-molecular emulsifier
The method comprises the following steps:
firstly, putting polyisobutylene maleic anhydride into a reaction kettle, heating to 120 ℃, and reacting with nitrogen under the condition that the molar ratio of the polyisobutylene maleic anhydride to the ethyl diethanol amine is 1.0: 2.0, adding ethyl diethanol amine, and reacting for 4 hours at 120 ℃ to obtain a product A;
and secondly, putting the polyisobutene maleic anhydride into a reaction kettle, heating to 80 ℃, and mixing according to a molar mass ratio of the polyisobutene maleic anhydride to sulfuric acid (98%): 0.8 addition of sulfuric acid (98%), in a molar ratio of polyisobutene maleic anhydride to water of 1: 0.8, adding water, and reacting for 1 h; heating to 120 ℃, and mixing the raw materials according to the molar mass ratio of sulfuric acid to sodium carbonate of 1: 1, adding sodium carbonate, and reacting for 3 hours to obtain a product B;
and step three, mixing the first-step product A and the second-step product B according to a molar ratio of 1: 2, adding the mixture into a reaction kettle, and reacting the mixture for 6 hours at 180 ℃ under the protection of nitrogen to obtain the polymer emulsifier with a multi-hanging structure.
Example 3: preparation of low-nitrogen high-molecular emulsifier
The method comprises the following steps:
firstly, putting polyisobutylene maleic anhydride into a reaction kettle, heating to 120 ℃, and reacting under the protection of nitrogen according to the molar ratio of polyisobutylene maleic anhydride to triethanolamine of 1.0: 1.8 adding triethanolamine, and reacting at 120 ℃ for 4h to obtain a product A;
and secondly, putting the polyisobutylene maleic anhydride into a reaction kettle, heating to 80 ℃, and mixing the polyisobutylene maleic anhydride and the phosphoric acid (with the mass concentration of 52%) according to a molar mass ratio of 1: 1 adding phosphoric acid (mass concentration is 52%), and mixing according to a molar ratio of polyisobutylene maleic anhydride to water of 1: 0.8, adding water, and reacting for 1 h; heating to 120 ℃, and mixing the raw materials according to the molar mass ratio of sulfuric acid to sodium carbonate of 1: 1.5, adding sodium carbonate, and reacting for 3 hours to obtain a product B;
and step three, mixing the first-step product A and the second-step product B according to a molar ratio of 1: 2, adding the mixture into a reaction kettle, and reacting the mixture with nitrogen for 4 hours at 140 ℃ to obtain the polymer emulsifier with a multi-hanging structure.
In conclusion, the low-nitrogen polymer emulsifier and the preparation method thereof have a multi-hanging structure, have stronger steric hindrance effect, increase the strength of the microemulsion oil film of the emulsion explosive, improve the storage period of the emulsion explosive, have a lactone ring structure, the structure is similar to succinimide, is a five-membered or six-membered lactone ring, increases the plasticity of the emulsifier, the plasticizing effect of the powder is the same as that of succinimide, and can replace T155 emulsifier to be used in powdery emulsion explosive, the emulsion explosive has better dispersion capability while keeping the strength of an oil film by introducing more hydrophilic groups, reduces mechanical shearing to form a better micro emulsion structure, ensures that an emulsifier has plasticizing capability by virtue of a lactone ring structure, is beneficial to oil film repair in the vacuum dehydration process of the powdery emulsion explosive, improves the power and the storage period of the emulsion explosive, takes alcohol amine as a raw material, is cheaper than polyamine, and reduces the manufacturing cost.
It is noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (2)
1. A low-nitrogen high-molecular emulsifier and a preparation method thereof are characterized in that: the method comprises the following steps:
s1, putting polyolefin anhydride into a reaction kettle, heating to 60-140 ℃, and reacting under the protection of nitrogen according to the molar ratio of the polyolefin anhydride to the polyhydroxyhydramine of 1: 1.6 to 2.0, adding polyhydroxyhydramine, and reacting at the temperature of 120-;
s2, adding polyolefin anhydride into a reaction kettle, heating to 60-140 ℃, and mixing according to the molar mass ratio of the polyolefin anhydride of 1: 0.5-1: 1 adding an acid catalyst according to a molar ratio of polyolefin acid anhydride to water of 1: adding water into the mixture for 0.5 to 1 hour, and reacting for 0.5 to 3 hours; heating to 90-150 ℃, and adding the acidic catalyst according to a molar mass ratio of 1: 0.5-1: 2.0, adding an alkaline catalyst, and reacting for 1-4h to obtain a product B;
s3, mixing the product A of the step S1 and the product B of the step S2 according to the molar ratio of 1: 1.0 to 4.0, reacting with nitrogen at 190 ℃ for 2 to 8 hours to obtain the low-nitrogen polymer emulsifier.
2. The low-nitrogen polymeric emulsifier and the preparation method thereof according to claim 1, wherein the low-nitrogen polymeric emulsifier comprises: in step S3, diluent oil is added to facilitate the reaction and the thorough mixing, wherein the diluent oil is mechanical oil or paraffin-based base oil, and the mass ratio of the polyolefin maleic anhydride to the diluent oil is 1: 0.2-1: 3.0.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011297699.4A CN112300398A (en) | 2020-11-19 | 2020-11-19 | Low-nitrogen high-molecular emulsifier and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011297699.4A CN112300398A (en) | 2020-11-19 | 2020-11-19 | Low-nitrogen high-molecular emulsifier and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112300398A true CN112300398A (en) | 2021-02-02 |
Family
ID=74334905
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011297699.4A Pending CN112300398A (en) | 2020-11-19 | 2020-11-19 | Low-nitrogen high-molecular emulsifier and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112300398A (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN103012023A (en) * | 2012-12-14 | 2013-04-03 | 倪欧琪 | Emulsifying agent for industrial explosive and preparation method of emulsifying agent |
| CN111732676A (en) * | 2020-07-02 | 2020-10-02 | 安徽金奥博化工科技有限公司 | Polymer emulsifier with multi-hanging structure and preparation method thereof |
-
2020
- 2020-11-19 CN CN202011297699.4A patent/CN112300398A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN103012023A (en) * | 2012-12-14 | 2013-04-03 | 倪欧琪 | Emulsifying agent for industrial explosive and preparation method of emulsifying agent |
| CN111732676A (en) * | 2020-07-02 | 2020-10-02 | 安徽金奥博化工科技有限公司 | Polymer emulsifier with multi-hanging structure and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| DE3000610C2 (en) | Process for the production of aromatic polyesters | |
| DE69007344T2 (en) | Block copolymer composition. | |
| CN104559234B (en) | Asphalt viscosity reducer and asphalt composition | |
| CN105315471A (en) | Emulsified SBS modified asphalt and reparation method thereof, waterproof coating and reparation method thereof | |
| CN100378138C (en) | Process for improving friability and cold-flow of carbon dioxide epoxy propylane copolymer | |
| DE1256418B (en) | Process for the production of nitrogen-containing, optionally foamed synthetic resins from derivatives of aromatic carboxylic acids and polyisocyanates | |
| CN113025071B (en) | High-doping-amount SBS (styrene butadiene styrene) modified emulsified asphalt for cold-mix plant recycling and preparation method thereof | |
| EP1529767B1 (en) | Explosives containing modified copolymers made from polyisobutylene and maleic anhydride as emulsifier | |
| CN102898941A (en) | Modified nylon powder coating and preparation method thereof | |
| CN106626665A (en) | Nano insulating sealing strip and preparation method thereof | |
| CN104710310B (en) | O-maleoyl lactate ester compound and preparation method thereof and the application in polycarboxylate water-reducer synthesizes | |
| Gaw et al. | Preparation of polyimide-epoxy composites | |
| CN112300398A (en) | Low-nitrogen high-molecular emulsifier and preparation method thereof | |
| CN101198564A (en) | Modified sulphur and product comprising modified sulphur as binder | |
| JP2930511B2 (en) | Aqueous polyolefin composition and method for producing the same | |
| CN113461930A (en) | Anhydride and epoxy macromolecule chain-extending tackifier and preparation method and application thereof | |
| CN100564445C (en) | Petroleum resin emulsion and preparation thereof and the application aspect exterior coating | |
| CN107151371A (en) | Ceramic polymer material with self-supporting performance and preparation method thereof | |
| CN1609079A (en) | Emulsifier for powdered emulsified explosive and its prepn process | |
| WO2008132051A1 (en) | Thermoreactive composition and method for the production thereof | |
| JP2000515564A (en) | Aqueous polyamide dispersion | |
| DE2247824A1 (en) | COMPOSITIONS | |
| CN111732676A (en) | Polymer emulsifier with multi-hanging structure and preparation method thereof | |
| KR101493648B1 (en) | Asphalt Modifier Block Copolymer and Asphalt Composition Comprising the Same | |
| CN104829898A (en) | Rubber homogenizing agent and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210202 |