CN105348416A - Novel emulsion explosive polymer emulsifier and preparation method thereof - Google Patents
Novel emulsion explosive polymer emulsifier and preparation method thereof Download PDFInfo
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- CN105348416A CN105348416A CN201510736905.XA CN201510736905A CN105348416A CN 105348416 A CN105348416 A CN 105348416A CN 201510736905 A CN201510736905 A CN 201510736905A CN 105348416 A CN105348416 A CN 105348416A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/14—Esterification
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- 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
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/06—Polyethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/12—Polypropene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/14—Copolymers of propene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
- C08J2323/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
Abstract
The invention discloses a novel emulsion explosive polymer emulsifier. The novel emulsion explosive polymer emulsifier is prepared from polyolefin, dicarboxylic acid or acid anhydride, polyol, hydrazine and diluent oil, wherein a mole ratio of polyolefin, dicarboxylic acid or acid anhydride, polyol to hydrazine is 1.0: 1.0-2.0: 1.0-1.5: 0.4-0.6 and the mass of the diluent oil is 0.5-1.5 times that of polyolefin. The preparation method comprises 1, adding polyolefin into a reactor, heating the polyolefin to a temperature of 70-80 DEG C, adding dicarboxylic acid or acid anhydride into the polyolefin, carrying out stirring, heating and reaction processes, and filtering the reaction product, 2, returning the compound synthesized by the step 1 into the reactor, adding diluent oil and polyol into the synthesized compound, and carrying out stirring heating for a heat reaction to obtain an esterification product, and 3, cooling the esterification product, adding hydrazine into the product and carrying out a reaction process. The polymer emulsifier is especially suitable for low shear emulsification or mixing emulsification technology-based preparation of a latex matrix.
Description
Technical field
The present invention relates to technical field of chemical synthesis, be specifically related to a kind of novel emulsion explosive macromolecule emulsifier and preparation method thereof.
Background technology
The performance of emulsifying agent has material impact to the quality of emulsion explosive, the performance such as blast performance and storge quality.Therefore, the performance of emulsifying agent, is more and more subject to the attention of emulsion explosive industry.
Emulsion explosive polyolefins emulsifying agent originates from the polyisobutene succinimide class ashless dispersant in lubricating oil additive, and the various polyolefins emulsifying agents of follow-up research and development are mostly based on this.And the advantage of polyisobutene succinimide class emulsifying agent to be emulsion explosive prepared therefrom comparatively stable, the storage time is relatively long; But its emulsifying property is relatively poor, more difficult emulsifying effect, its raw materials for production price is relatively high in addition.
Domestic a lot of macromolecule emulsifiers used all rely on from external import, expensive; Domestic rarely have several Production in Chemical Plant macromolecule emulsifiers, and owing to not quite understanding explosive, cause the demand of the macromolecule emulsifier of domestic Production in Chemical Plant and explosive enterprise not to be mate very much, therefore develop macromolecule emulsifier for particularly important Min Bao enterprise.
Disclosing a kind of in US20060223945A1, CN1158833A take glycerine as the polyisobutylene succinic acid ester emulsifying agent of esterifying reagent.Disclosing a kind of in US6527885, US4919179, CN1415588A take alcohol amine compound as the polyisobutylene butanedioic anhydride class emulsifying agent of derivatization reagent.Along with the development of emulsion matrix low sheraing emulsifying process, the requirement of emulsifier for emulsion explosive is more and more stricter, and current emulsifying agent low sheraing plays newborn ability and stability in storage can meet the demands.
Summary of the invention
The object of this invention is to provide a kind of low sheraing play newborn ability and storge quality superior, emulsion explosive macromolecule emulsifier being suitable for low sheraing emulsification or mixing and emulsifying technique and preparation method thereof.
Technical scheme of the present invention is as follows:
A kind of novel emulsion explosive macromolecule emulsifier, is obtained by polyolefine, dicarboxylic acid or acid anhydrides, polyvalent alcohol, hydrazine and thinning oil; The mol ratio of described polyolefine, dicarboxylic acid or acid anhydrides, polyvalent alcohol, hydrazine is 1.0:1.0 ~ 2.0:1.0 ~ 1.5:0.4 ~ 0.6:0.5 ~ 1.5, and the quality of described thinning oil is 0.5 ~ 1.5 times of polyolefine quality.
As preferably, described polyolefine is selected from the one in polyethylene, polypropylene, polybutene, polyisobutene, polypenthylene, polystyrene, ethylene-propylene copolymer or propylene-isobutylene copolymers.
As preferably, described polyolefin molecular weight is 500 ~ 3000, and end alkene content is greater than 85%.
As preferably, described dicarboxylic acid or acid anhydrides are selected from one or more mixtures in maleic acid, FUMARIC ACID TECH GRADE, propene dicarboxylic acid, maleic anhydride.
As preferably, described polyvalent alcohol is selected from one or more mixtures in 1,2-PD, BDO, 1,6-hexylene glycol, neopentyl glycol, dipropylene glycol, TriMethylolPropane(TMP), trimethylolethane, glycerine, Xylitol, sorbyl alcohol.
As preferably, described thinning oil is 60N base oil, 150N base oil, 220N base oil, 32# base oil or toluene.
A preparation method for aforementioned novel emulsion explosive macromolecule emulsifier, for polyolefine first carries out alkylation reaction with dicarboxylic acid or acid anhydrides, then carries out esterification with polyvalent alcohol, carries out crosslinking reaction obtain finally by hydrazine; Concrete preparation process comprises the steps:
(1) drop in reactor by polyolefine, be heated to 70 ~ 80 DEG C, add dicarboxylic acid or acid anhydrides under nitrogen protection condition, insulated and stirred 1 ~ 2h, be warming up to 180 ~ 240 DEG C, reaction 3 ~ 7h, filters and obtains polyolefin carboxylic acid or polyolefin carboxylic acid's acid anhydride;
(2) polyolefin carboxylic acid step (1) synthesized or polyolefin carboxylic acid's acid anhydride is counter throws back in reactor, under nitrogen protection condition, add thinning oil and polyvalent alcohol, heat while stirring, be warming up to 110 ~ 160 DEG C, reaction 4 ~ 6h, obtains esterification products;
(3) esterification products that step (2) is synthesized is cooled to 65 ~ 90 DEG C, under nitrogen protection condition, adds hydrazine, insulated and stirred 1 ~ 6h, obtain macromolecule emulsifier of the present invention.
The invention has the beneficial effects as follows: this macromolecule emulsifier is due to the crosslinked action of hydrazine, there is good emulsifying performance and stable emulsifying performance, show the low sheraing more superior than other emulsifying agents and play newborn ability, be more suitable for low sheraing emulsification or mixing and emulsifying technique prepares emulsion matrix.Present invention process is simple, environmental protection, raw material sources are wide, production cost is low.
Embodiment
Below in conjunction with embodiment, the invention will be further described, but not thereby limiting the invention.
Experimental technique in following embodiment, if no special instructions, is ordinary method.
Embodiment 1 prepares novel emulsion explosive macromolecule emulsifier
Operate in accordance with the following steps:
(1) propylene-isobutylene copolymers is dropped in reactor, be heated to 70 DEG C, under nitrogen protection condition, add the catalyzer Benzoyl Peroxide tert-butyl ester of propene dicarboxylic acid and catalytic amount, insulated and stirred 2h, be warming up to 180 DEG C, reaction 7h, filters and obtains polyolefine propene dicarboxylic acid;
(2) polyolefine propene dicarboxylic acid step (1) synthesized is counter to be thrown back in reactor, adds 60N base oil and glycerine, heats while stirring, be warming up to 110 DEG C under nitrogen protection condition, and reaction 6h, obtains esterification products;
(3) esterification products that step (2) is synthesized is cooled to 65 DEG C, under nitrogen protection condition, adds hydrazine (i.e. hydrazine), insulated and stirred 6h; obtain macromolecule emulsifier of the present invention; density is 0.931g/mL, and acid number is 12.7mgKOH/g, and viscosity is 193.57mm
2/ s, productive rate is 95%.
In above step, the proportioning of each chemicals is: 0.5 times of the mol ratio of propylene-isobutylene copolymers, propene dicarboxylic acid, glycerine, hydrazine to be the quality of 1.0:1.0:1.0:0.4,60N base oil be propylene-isobutylene copolymers amount.
Embodiment 2 prepares novel emulsion explosive macromolecule emulsifier
Operate in accordance with the following steps:
(1) drop in reactor by polypropylene, be heated to 80 DEG C, add maleic acid, insulated and stirred 1h under nitrogen protection condition, be warming up to 240 DEG C, reaction 3h, filters and obtains polyacrylonitrile-butadiene diacid;
(2) polyacrylonitrile-butadiene diacid step (1) synthesized is counter to be thrown back in reactor, adds 150N base oil and trimethylolethane, heats while stirring, be warming up to 160 DEG C under nitrogen protection condition, and reaction 4h, obtains esterification products;
(3) esterification products that step (2) is synthesized is cooled to 90 DEG C, under nitrogen protection condition, adds hydrazine (i.e. hydrazine), insulated and stirred 1h; obtain macromolecule emulsifier of the present invention; density is 0.883g/mL, and acid number is 8.2mgKOH/g, and viscosity is 141.39mm
2/ s, productive rate is 96%.
The quality that in above step, the proportioning of each chemicals is polypropylene, the mol ratio of maleic acid, trimethylolethane, hydrazine is 1.0:2.0:1.5:0.6,150N base oil is 1.5 times of polypropylene quality.
Embodiment 3 prepares novel emulsion explosive macromolecule emulsifier
Operate in accordance with the following steps:
(1) drop in reactor by polyisobutene, be heated to 75 DEG C, add maleic anhydride, insulated and stirred 1.5h under nitrogen protection condition, be warming up to 220 DEG C, reaction 5h, filters and obtains polyisobutylene butanedioic anhydride;
(2) polyisobutylene butanedioic anhydride step (1) synthesized is counter to be thrown back in reactor, under nitrogen protection condition, add 220N base oil and dipropylene glycol and TriMethylolPropane(TMP), heat while stirring, be warming up to 150 DEG C, reaction 5h, obtains esterification products;
(3) esterification products that step (2) is synthesized is cooled to 75 DEG C, under nitrogen protection condition, adds hydrazine (i.e. hydrazine), insulated and stirred 5h; obtain macromolecule emulsifier of the present invention; density is 0.917g/mL, and acid number is 10.3mgKOH/g, and viscosity is 176.29mm
2/ s, productive rate is 96%.
In above step, the proportioning of each chemicals is polyisobutene, the mol ratio of maleic anhydride, dipropylene glycol, TriMethylolPropane(TMP), hydrazine is the quality of 1.0:1.5:0.7:0.7:0.5,220N base oil and the identical in quality of polyisobutene.
Embodiment 4 prepares novel emulsion explosive macromolecule emulsifier
Operate in accordance with the following steps:
(1) drop in reactor by polyethylene, be heated to 75 DEG C, add FUMARIC ACID TECH GRADE, insulated and stirred 1.5h under nitrogen protection condition, be warming up to 200 DEG C, reaction 4h, filters and obtains polyethylene succinic acid;
(2) polyethylene succinic acid step (1) synthesized is counter to be thrown back in reactor, adds 32# base oil and 1,2-PD, heats while stirring, be warming up to 140 DEG C under nitrogen protection condition, and reaction 4h, obtains esterification products;
(3) esterification products that step (2) is synthesized is cooled to 80 DEG C, under nitrogen protection condition, adds hydrazine (i.e. hydrazine), insulated and stirred 4h; obtain macromolecule emulsifier of the present invention; density is 0.905g/mL, and acid number is 11.3mgKOH/g, and viscosity is 181.35mm
2/ s, productive rate is 96%.
The quality that in above step, the proportioning of each chemicals is polyethylene, the mol ratio of FUMARIC ACID TECH GRADE, 1,2-PD, hydrazine is 1.0:1.4:1.3:0.5,32# base oil is 1.1 times of polyethylene quality.
Embodiment 5 prepares novel emulsion explosive macromolecule emulsifier
Operate in accordance with the following steps:
(1) drop in reactor by polypenthylene, be heated to 75 DEG C, add maleic acid and FUMARIC ACID TECH GRADE, insulated and stirred 1.5h under nitrogen protection condition, be warming up to 210 DEG C, reaction 3h, filters and obtains polypenthylene succinic acid;
(2) polypenthylene succinic acid step (1) synthesized is counter to be thrown back in reactor, adds 32# base oil and BDO, heats while stirring, be warming up to 150 DEG C under nitrogen protection condition, and reaction 5h, obtains esterification products;
(3) esterification products that step (2) is synthesized is cooled to 70 DEG C, under nitrogen protection condition, adds hydrazine (i.e. hydrazine), insulated and stirred 3h; obtain macromolecule emulsifier of the present invention; density is 0.899g/mL, and acid number is 10.4mgKOH/g, and viscosity is 172.33mm
2/ s, productive rate is 97%.
In above step, the proportioning of each chemicals is polypenthylene, the mol ratio of maleic acid, FUMARIC ACID TECH GRADE, BDO, hydrazine is the quality of 1.0:0.6:0.7:1.2:0.5,32# base oil and the identical in quality of polypenthylene.
In the embodiment above, described polyolefine can also be the one in polybutene, polystyrene or ethylene-propylene copolymer, described dicarboxylic acid or acid anhydrides also can be the multiple mixture of maleic acid, FUMARIC ACID TECH GRADE, propene dicarboxylic acid, maleic anhydride, described polyvalent alcohol also can be 1,2-propylene glycol, 1, one or more mixtures in 4-butyleneglycol, 1,6-hexylene glycol, neopentyl glycol, dipropylene glycol, TriMethylolPropane(TMP), trimethylolethane, glycerine, Xylitol, sorbyl alcohol; Embodiment does not limit the scope of the invention.
The performance measurement of embodiment 6 emulsifying agent
One, emulsification experiment
Macromolecule emulsifier I ~ V (rotating speed 500r/min) under low sheraing emulsification condition obtained for embodiment 1 to 5 is carried out emulsification experiment, and tested breast time, the water-soluble value of emulsion matrix and viscosity, observe emulsion matrix state, experimental result is as shown in table 1.
Table 1 emulsifying agent low sheraing emulsification experiment result
Macromolecule emulsifier I ~ V that embodiment 1 to 5 is obtained carries out emulsification experiment under mixing and emulsifying condition, and test newborn time, the water-soluble value of emulsion matrix and viscosity, and observation emulsion matrix state, experimental result is as shown in table 2.
Table 2 emulsifying agent mixing and emulsifying experimental result
As can be seen from Table 1 and Table 2, the emulsifying property that the emulsifying agent that the inventive method obtains shows under low sheraing or mixing and emulsifying condition, plays breast fast, and matrix is stablized, and is suitable for low sheraing emulsification or mixing and emulsifying technique prepares emulsion matrix.
Two, stability in storage experiment
Macromolecule emulsifier I ~ the V obtained by embodiment 1 to 5 prepares emulsion matrix, and carry out room temperature storage experiment and high/low temperature circulation experiment (45 DEG C store 8 hours ,-30 DEG C storages 16 hours is a circulation), experimental result is as shown in table 3.
Table 3 emulsion matrix stability in storage experimental result
As can be seen from Table 3, the stability in storage that emulsion matrix prepared by the emulsifying agent that the inventive method obtains shows.
Three, long-range experiment of jolting
Macromolecule emulsifier I ~ the V obtained by embodiment 1 to 5 prepares emulsion matrix, and carry out long-range experiment of jolting, experimental result is as shown in table 4.
Table 4 emulsion matrix jolts experimental result
As can be seen from Table 4, the anti-ability of jolting that emulsion matrix prepared by the emulsifying agent that the inventive method obtains shows, is suitable for the long-range dispensing of emulsion matrix.
Four, pumping experiment
Macromolecule emulsifier I ~ the V obtained by embodiment 1 to 5 prepares emulsion matrix, and carry out pumping experiment, experimental result is as shown in table 5.
Table 5 emulsion matrix pumping experimental result
As can be seen from Table 5, the pump-conveying property repeatedly that the emulsion matrix that prepared by emulsifying agent of the present invention does very well.
Five, explosion velocity experiment
Macromolecule emulsifier I ~ the V obtained by embodiment 1 to 5 prepares the mixed loading emulsion explosive, carries out on-the-spot explosion, explosion velocity 5700 ~ 5900m/s in hole, and quick-fried heap surface lumpiness is even, and bulk is few, meets onsite application requirement.
Claims (7)
1. a novel emulsion explosive macromolecule emulsifier, is characterized in that: obtained by polyolefine, dicarboxylic acid or acid anhydrides, polyvalent alcohol, hydrazine and thinning oil; The mol ratio of described polyolefine, dicarboxylic acid or acid anhydrides, polyvalent alcohol, hydrazine is 1.0:1.0 ~ 2.0:1.0 ~ 1.5:0.4 ~ 0.6, and the quality of described thinning oil is 0.5 ~ 1.5 times of polyolefine quality.
2. novel emulsion explosive macromolecule emulsifier as claimed in claim 1, is characterized in that: described polyolefine is selected from the one in polyethylene, polypropylene, polybutene, polyisobutene, polypenthylene, polystyrene, ethylene-propylene copolymer or propylene-isobutylene copolymers.
3. novel emulsion explosive macromolecule emulsifier as claimed in claim 1, is characterized in that: described polyolefin molecular weight is 500 ~ 3000, and end alkene content is greater than 85%.
4. novel emulsion explosive macromolecule emulsifier as claimed in claim 1, is characterized in that: described dicarboxylic acid or acid anhydrides are selected from one or more mixtures in maleic acid, FUMARIC ACID TECH GRADE, propene dicarboxylic acid, maleic anhydride.
5. novel emulsion explosive macromolecule emulsifier as claimed in claim 1, it is characterized in that: described polyvalent alcohol is selected from 1,2-propylene glycol, 1, one or more mixtures in 4-butyleneglycol, 1,6-hexylene glycol, neopentyl glycol, dipropylene glycol, TriMethylolPropane(TMP), trimethylolethane, glycerine, Xylitol, sorbyl alcohol.
6. novel emulsion explosive macromolecule emulsifier as claimed in claim 1, is characterized in that: described thinning oil is 60N base oil, 150N base oil, 220N base oil, 32# base oil or toluene.
7. a preparation method for the novel emulsion explosive macromolecule emulsifier of claim 1, is characterized in that: polyolefine first carries out alkylation reaction with dicarboxylic acid or acid anhydrides, then carries out esterification with polyvalent alcohol, carries out crosslinking reaction obtain finally by hydrazine; Concrete preparation process comprises the steps:
(1) drop in reactor by polyolefine, be heated to 70 ~ 80 DEG C, add dicarboxylic acid or acid anhydrides under nitrogen protection condition, insulated and stirred 1 ~ 2h, be warming up to 180 ~ 240 DEG C, reaction 3 ~ 7h, filters and obtains polyolefin carboxylic acid or polyolefin carboxylic acid's acid anhydride;
(2) polyolefin carboxylic acid step (1) synthesized or polyolefin carboxylic acid's acid anhydride is counter throws back in reactor, under nitrogen protection condition, add thinning oil and polyvalent alcohol, heat while stirring, be warming up to 110 ~ 160 DEG C, reaction 4 ~ 6h, obtains esterification products;
(3) esterification products that step (2) is synthesized is cooled to 65 ~ 90 DEG C, under nitrogen protection condition, adds hydrazine, insulated and stirred 1 ~ 6h, obtain macromolecule emulsifier of the present invention.
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| CN105968236A (en) * | 2016-06-14 | 2016-09-28 | 中国葛洲坝集团易普力股份有限公司 | Novel emulgator for emulsified explosive and preparation method of novel emulgator |
| CN106084096A (en) * | 2016-06-14 | 2016-11-09 | 中国葛洲坝集团易普力股份有限公司 | emulsifier for emulsion explosive and preparation method thereof |
| CN110862471A (en) * | 2019-11-07 | 2020-03-06 | 葛洲坝易普力湖北昌泰民爆有限公司 | Method for synthesizing polyisobutylene succinic acid alcohol ester high-molecular emulsifier for emulsion explosive |
| 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 |
| CN115558044A (en) * | 2022-09-30 | 2023-01-03 | 北矿亿博(沧州)科技有限责任公司 | Crosslinkable polymer emulsifier and preparation method thereof, latex matrix and emulsion explosive |
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