阅读说明：本技术 一种乳胶基质远程配送用乳化剂及其制备方法与应用 (Emulsifier for remote delivery of latex matrix and preparation method and application thereof ) 是由 赵华平 董云 李俊杰 于 2021-08-04 设计创作，主要内容包括：本发明公开了一种乳胶基质远程配送用乳化剂及其制备方法与应用,其乳化剂包括聚烯烃羧酸酐、醇或聚氧乙烯烷基醚、二酰肼、稀释油,所述聚烯烃羧酸酐、醇或聚氧乙烯烷基醚、二酰肼的摩尔比为1.0：0.5～1.2：0.5～1.2,所述稀释油的质量为聚烯烃羧酸酐质量的0.3～1倍；其制备方法包括以下步骤：S1、在反应釜中加入聚烯烃羧酸酐；S2、在反应釜中通入保护气体；S3、在反应釜中加入醇或聚氧乙烯烷基醚,加入稀释油,加热至100℃-120℃,保温2-3h；S4、在保护气体下加入二酰肼,升温至160-180℃,保温搅拌4h-6h；S5、趁热过滤,所得滤液即为乳化剂成品；制备得到的该乳化剂制备的乳胶基质流动性好、储存稳定、抗颠簸性能和耐泵送性能优越,适于乳胶基质远程配送。(The invention discloses an emulsifier for latex matrix remote distribution and a preparation method and application thereof, wherein the emulsifier comprises polyolefin carboxylic anhydride, alcohol or polyoxyethylene alkyl ether, dihydrazide and diluent oil, and the molar ratio of the polyolefin carboxylic anhydride, the alcohol or polyoxyethylene alkyl ether and the dihydrazide is 1.0: 0.5-1.2: 0.5 to 1.2, wherein the mass of the diluent oil is 0.3 to 1 time of that of the polyolefin carboxylic anhydride; the preparation method comprises the following steps: s1, adding polyolefin carboxylic anhydride into a reaction kettle; s2, introducing protective gas into the reaction kettle; s3, adding alcohol or polyoxyethylene alkyl ether into a reaction kettle, adding diluent oil, heating to 100-120 ℃, and preserving heat for 2-3 hours; s4, adding dihydrazide under protective gas, heating to 160-180 ℃, and stirring for 4-6 h under heat preservation; s5, filtering while the mixture is hot, wherein the obtained filtrate is the finished product of the emulsifier; the latex matrix prepared by the emulsifier has good fluidity, stable storage, excellent anti-bumping performance and pumping resistance, and is suitable for the remote delivery of the latex matrix.)

1. An emulsifier for remote delivery of a latex matrix, comprising: the emulsifier comprises polyolefin carboxylic anhydride, alcohol or polyoxyethylene alkyl ether, dihydrazide and diluent oil, wherein the molar ratio of the polyolefin carboxylic anhydride, the alcohol or the polyoxyethylene alkyl ether to the dihydrazide is 1.0: 0.5-1.2: 0.5 to 1.2, and the mass of the diluent oil is 0.3 to 1 time of that of the polyolefin carboxylic anhydride.

2. The emulsion of claim 1, wherein: the polyolefin carboxylic acid anhydride is any one of polyethylene succinic anhydride, polypropylene succinic anhydride, polybutylene succinic anhydride, polyisobutylene succinic anhydride and polypentene succinic anhydride; the polyolefin chain in the polyolefin carboxylic anhydride has a molecular weight of 500-2000.

3. The emulsion of claim 1, wherein: the alcohol is C3-C10 polyhydric alcohol or polyglycerol, and the polymerization degree n of the polyglycerol is 3-6.

4. The emulsion of claim 1, wherein: the polyoxyethylene alkyl ether has an oxyethylene group number of 3 to 8 and an alkyl group carbon number of 11 to 15.

5. The latex matrix according to claim 1The emulsifier for process distribution is characterized in that: the structural formula of the dihydrazide isWherein R is a carbon chain of C5-C12.

6. A method of preparing an emulsifier for remote delivery of a latex matrix according to any of claims 1 to 5, comprising the steps of: s1, adding polyolefin carboxylic anhydride into a reaction kettle; s2, introducing protective gas into the reaction kettle; s3, adding alcohol or polyoxyethylene alkyl ether into a reaction kettle, adding diluent oil, heating to 100-120 ℃, and preserving heat for 2-3 hours; s4, adding dihydrazide under protective gas, heating to 160-180 ℃, and stirring for 4-6 h under heat preservation; s5, filtering while the mixture is hot, wherein the obtained filtrate is the finished product of the emulsifier.

7. The method of claim 6, wherein the emulsifier is selected from the group consisting of: the protective gas is inert gas.

8. Use of an emulsifier for remote delivery of an emulsion matrix, wherein the emulsifier produced by the method of claim 6 or claim 7 is used in an explosive.

Technical Field

The invention relates to the technical field of industrial explosive production, in particular to an emulsifier for remote delivery of an emulsion matrix and a preparation method and application thereof.

Background

The emulsifier is used as a key component in the emulsion explosive, and the type, performance index and content of the emulsifier have obvious influence on the quality, the size, the stability and the detonation performance of an emulsion system.

The low-molecular emulsifier represented by Span-80 has high emulsifying efficiency and low cost, and can meet the production of conventional emulsion explosive, but emulsion particles form micelles, and an interface forms a film which is not tightly packed, and the formed film is very thin (the thickness is about the thickness)) And an elastic frame structure is not provided, so that the interfacial film has insufficient elasticity, is easy to age and crack, has poor stability and short product storage period.

The emulsion particles in the emulsion system formed by the macromolecular emulsifier represented by the polyisobutylene succinic anhydride derivative form micelles, the interface forms a macromolecular framework and a well-accumulated monomolecular interfacial film, and the emulsion system has good elasticity, strong elasticity and large thickness (reaching the thickness of the macromolecular emulsifier)). Because the particles form a three-dimensional barrier film and are charged with the same kind of charges, electrostatic repulsion is generated among the particles, the anti-agglomeration structure is favorable for improving the stability, and the product has a long storage period.

Patents US20060223945a1, CN1158833A and the like disclose polyisobutylene succinate emulsifiers using glycerol as an esterification reagent, CN1186078, US4225589, US6770605, US4119553 and the like disclose polyisobutylene succinate emulsifiers using pentaerythritol as an esterification reagent, and US3381022 discloses polyisobutylene succinate emulsifiers using ethylene glycol as an esterification reagent.

The latex matrix prepared by the high-molecular emulsifying agent has good storage stability, but has poor bumping resistance and pumping resistance, high dynamic viscosity at normal temperature, large yield stress, poor fluidity and difficult pumping, and the long-distance distribution of the latex matrix is difficult to realize due to the defects.

Disclosure of Invention

The invention aims to provide an emulsifier for remote delivery of latex matrix, and a preparation method and application thereof.

In order to achieve the above purpose, the invention provides the following technical scheme:

an emulsifier for remote dispensing of latex matrix, which comprises polyolefin carboxylic anhydride, alcohol or polyoxyethylene alkyl ether, dihydrazide and diluent oil, wherein the molar ratio of the polyolefin carboxylic anhydride, the alcohol or polyoxyethylene alkyl ether and the dihydrazide is 1.0: 0.5-1.2: 0.5 to 1.2, and the mass of the diluent oil is 0.3 to 1 time of that of the polyolefin carboxylic anhydride.

According to the technical scheme, alcohol or polyoxyethylene alkyl ether is adopted for directional ring opening and mono-esterification, then the di-hydrazide reaction is carried out on the di-esterified fatty alcohol or polyoxyethylene alkyl ether, enough hydrophilic groups are introduced, and the hydrophilic-lipophilic balance is achieved between the di-esterified fatty alcohol and the hydrophilic groups, so that the obtained emulsifier has good emulsifying property and emulsifying stability, and the prepared latex matrix has good storage stability, anti-bumping and pumping-resistant properties.

Further, the polyolefin carboxylic acid anhydride is any one of polyethylene succinic anhydride, polypropylene succinic anhydride, polybutylene succinic anhydride, polyisobutylene succinic anhydride and polypentene succinic anhydride; the polyolefin chain in the polyolefin carboxylic anhydride has a molecular weight of 500-2000.

Further, the alcohol is C3-C10 polyhydric alcohol or polyglycerol, and the polymerization degree n of the polyglycerol is 3-6.

Further, the polyoxyethylene alkyl ether has an oxyethylene group number of 3 to 8 and an alkyl group number of carbon atoms of 11 to 15.

Further, the structural formula of the dihydrazide is shown in the specificationWherein R is a carbon chain of C5-C12.

Through the technical scheme, due to the existence of C5-C12 carbon chains in the dihydrazide structure, the rigidity of the molecular structure is obviously reduced, the dynamic viscosity and the yield stress of the prepared latex matrix are obviously reduced, the excellent flowability and the excellent pumping performance are shown, and the method is very suitable for the development of a centralized preparation and remote distribution mode of the latex matrix.

A method of preparing an emulsifier for remote delivery of a latex matrix, comprising the steps of: s1, adding polyolefin carboxylic anhydride into a reaction kettle; s2, introducing protective gas into the reaction kettle; s3, adding alcohol or polyoxyethylene alkyl ether into a reaction kettle, adding diluent oil, heating to 100-120 ℃, and preserving heat for 2-3 hours; s4, adding dihydrazide under protective gas, heating to 160-180 ℃, and stirring for 4-6 h under heat preservation; s5, filtering while the mixture is hot, wherein the obtained filtrate is the finished product of the emulsifier.

By adopting the technical scheme, the carbonization can be effectively prevented by adding the protective gas, and the generation of impurities is reduced; the heating temperature is 100-120 ℃, and the heat preservation is carried out for 2-3h, so that only the mono-esterification but not the multi-esterification can be controlled; after the dihydrazide is added, the yield of the dihydrazide product can be more than 90 percent by stirring for 4 to 6 hours at the temperature of 180 ℃.

Further, the protective gas is an inert gas.

The emulsifier for remote delivery of the emulsion matrix prepared by the preparation method is applied to explosives.

Compared with the prior art, the invention has the beneficial effects that:

an emulsifier for remote delivery of latex matrix, which comprises polyolefin carboxylic anhydride, alcohol or polyoxyethylene alkyl ether, dihydrazide and diluent oil, wherein the mole ratio of the polyolefin carboxylic anhydride, the alcohol or polyoxyethylene alkyl ether and the dihydrazide is 1.0: 0.5-1.2: 0.5 to 1.2, the mass of the diluent oil is 0.3 to 1.2 times of the mass of the polyolefin carboxylic anhydride; alcohol or polyoxyethylene alkyl ether is adopted for directional ring opening and mono-esterification, then the di-hydrazide is subjected to a dihydrazide reaction, enough hydrophilic groups are introduced, and hydrophilic-lipophilic balance is achieved with lipophilic groups, so that the obtained emulsifier has good emulsifying property and emulsifying stability, and the prepared latex matrix has good storage stability and bump and pumping resistance;

the structural formula of the dihydrazide isWherein R is a carbon chain of C5-C12; due to the existence of C5-C12 carbon chains in the dihydrazide structure, the rigidity of the molecular structure is obviously reduced, the dynamic viscosity and the yield stress of the prepared latex matrix are obviously reduced, the excellent fluidity and the pumping performance are shown, and the method is very suitable for the development of centralized preparation and remote distribution modes of the latex matrix.

Detailed Description

The present invention will be described in further detail with reference to test examples and specific embodiments. It should be understood that the scope of the above-described subject matter is not limited to the following examples, and any techniques implemented based on the disclosure of the present invention are within the scope of the present invention.

The raw material sources are all commercially available.

Further, the polyolefin carboxylic acid anhydride is any one of polyethylene succinic anhydride, polypropylene succinic anhydride, polybutylene succinic anhydride, polyisobutylene succinic anhydride and polypentene succinic anhydride; the polyolefin chain of the polyolefin carboxylic anhydride has a molecular weight of 500 to 2000.

Further, the alcohol is C3-C10 polyhydric alcohol or polyglycerol, and the polymerization degree n of the polyglycerol is 3-6.

Further, the polyoxyethylene alkyl ether has an oxyethylene group number of 3 to 8 and an alkyl group having 11 to 15 carbon atoms.

Further, the structural formula of the dihydrazide is shown in the specificationWherein R is a carbon chain of C5-C12.

Examples

Example 1

The emulsifier of the embodiment is prepared from the following raw materials: the polyolefin carboxylic acid anhydride is polypropylene succinic anhydride, the alcohol is neopentyl glycol, the dihydrazide is adipic dihydrazide, and the diluent oil is 60SN base oil.

A method of preparing an emulsifier for remote delivery of a latex matrix, comprising the steps of:

s1, adding 1mol of polypropylene succinic anhydride into the reaction kettle;

s2, introducing ammonia gas into the reaction kettle;

s3, adding 1.1mol of neopentyl glycol into a reaction kettle, weighing the 60SN base oil to enable the mass of the 60SN base oil to be 0.8 time of that of 1mol of polypropylene succinic anhydride, then adding the 60SN base oil, heating to 120 ℃, and preserving heat for 2 hours;

s4, heating to 170 ℃, adding 0.8mol of adipic dihydrazide under ammonia gas, and stirring for 4 hours under heat preservation;

s5, filtering while the solution is hot to obtain a finished product.

Example 2

The emulsifier of the embodiment is prepared from the following raw materials: the polyolefin carboxylic acid anhydride is polyisobutylene succinic anhydride, the alcohol is 1, 6-hexanediol, the dihydrazide is glutaryl hydrazine, and the diluent oil is 220SN base oil.

A method of preparing an emulsifier for remote delivery of a latex matrix, comprising the steps of:

s1, adding 1mol of polyisobutylene succinic anhydride into the reaction kettle;

s2, introducing ammonia gas into the reaction kettle;

s3, adding 1.2mol of 1, 6-hexanediol into a reaction kettle, weighing the 220SN base oil to ensure that the mass of the 220SN base oil is the same as that of 1mol of polyisobutylene succinic anhydride, then adding the 220SN base oil, heating to 110 ℃, and preserving heat for 3 hours;

s4, heating to 160 ℃, adding 0.7mol of glutaryl hydrazine under ammonia gas, and stirring for 6 hours under heat preservation;

s5, filtering while the solution is hot to obtain a finished product.

Example 3

The emulsifier of the embodiment is prepared from the following raw materials: the polyolefin carboxylic acid anhydride is selected from the group consisting of poly (pentylene succinic anhydride), the alcohol is selected from the group consisting of trimethylolpropane, the dihydrazide is selected from the group consisting of pimeloyl dihydrazide, and the diluent oil is selected from the group consisting of 150SN base oil.

A method of preparing an emulsifier for remote delivery of a latex matrix, comprising the steps of:

s1, adding 1mol of poly (glutaric anhydride) into the reaction kettle;

s2, introducing ammonia gas into the reaction kettle;

s3, adding 1mol of trimethylolpropane into a reaction kettle, weighing 150SN base oil to enable the weight of the 150SN base oil to be 0.5 times that of 1mol of polyglutamene succinic anhydride, then adding 150SN base oil, heating to 120 ℃, and preserving heat for 3 hours;

s4, heating to 180 ℃, adding 1mol of pimeloyl dihydrazide under ammonia gas, and stirring for 4 hours under heat preservation;

s5, filtering while the solution is hot to obtain a finished product.

Example 4

The emulsifier of the embodiment is prepared from the following raw materials: the polyolefin carboxylic acid anhydride is polybutylene succinic anhydride, the polyoxyethylene alkyl ether is polyoxyethylene pentadecyl (4) ether, the dihydrazide is adipic dihydrazide, and the diluent oil is 150SN base oil.

A method of preparing an emulsifier for remote delivery of a latex matrix, comprising the steps of:

s1, adding 1mol of polybutylene succinic anhydride into the reaction kettle;

s2, introducing ammonia gas into the reaction kettle;

s3, adding 0.8mol of polyoxyethylene pentadecyl (4) ether into a reaction kettle, weighing 150SN base oil to enable the weight of the 150SN base oil to be 0.5 time that of 1mol of polyglutamene succinic anhydride, then adding 150SN base oil, heating to 120 ℃, and preserving heat for 2 hours;

s4, heating to 170 ℃, adding 1mol of adipic dihydrazide under ammonia gas, keeping the temperature and stirring for 4 h;

s5, filtering while the solution is hot to obtain a finished product.

Example 5

The emulsifier of the embodiment is prepared from the following raw materials: the polyolefin carboxylic acid anhydride is polyisobutylene succinic anhydride, polyoxyethylene alkyl ether is polyoxyethylene dodecyl (7) ether, dihydrazide is glutaryl hydrazine, and the diluent oil is 60SN base oil.

A method of preparing an emulsifier for remote delivery of a latex matrix, comprising the steps of:

s1, adding 1mol of polyisobutylene succinic anhydride into the reaction kettle;

s2, introducing ammonia gas into the reaction kettle;

s3, adding 1mol of polyoxyethylene dodecyl (7) ether into a reaction kettle, wherein the weight of 60SN base oil is 0.7 times that of 1mol of polyisobutylene succinic anhydride, adding 60SN base oil, heating to 110 ℃, and preserving heat for 3 hours;

s4, heating to 160 ℃, adding 0.7mol of glutaryl hydrazine under ammonia gas, and stirring for 6 hours under heat preservation;

s5, filtering while the solution is hot to obtain a finished product.

Example 6

The emulsifier of the embodiment is prepared from the following raw materials: the polyolefin carboxylic acid anhydride is selected from the group consisting of polypentaolefin succinic anhydride, polyoxyethylene alkyl ether is selected from the group consisting of polyoxyethylene tridecyl (5) ether, dihydrazide is selected from the group consisting of pimeloyl dihydrazide, and the diluent oil is selected from the group consisting of 150SN base oil.

A method of preparing an emulsifier for remote delivery of a latex matrix, comprising the steps of:

s1, adding 1mol of poly (glutaric anhydride) into the reaction kettle;

s2, introducing ammonia gas into the reaction kettle;

s3, adding 1.2mol of polyoxyethylene tridecyl (5) ether into a reaction kettle, weighing 150SN base oil to enable the mass of the 150SN base oil to be the same as that of 1mol of poly (pentylene succinic anhydride), then adding 150SN base oil, heating to 120 ℃, and preserving heat for 3 hours;

s4, heating to 180 ℃, adding 1mol of pimeloyl dihydrazide under ammonia gas, and stirring for 4 hours under heat preservation;

s5, filtering while the solution is hot to obtain a finished product.

Example 7

The emulsifier of the embodiment is prepared from the following raw materials: the polyolefin carboxylic acid anhydride is polypropylene succinic anhydride, the alcohol is triglycerol, the dihydrazide is adipamide, and the diluent oil is 60SN base oil.

A method of preparing an emulsifier for remote delivery of a latex matrix, comprising the steps of:

s1, adding 1mol of polypropylene succinic anhydride into the reaction kettle;

s2, introducing ammonia gas into the reaction kettle;

s3, adding 0.5mol of triglycerin into the reaction kettle, weighing the 60SN base oil to enable the mass of the 60SN base oil to be 0.8 times of that of 1mol of polypropylene succinic anhydride, then adding the 60SN base oil, heating to 100 ℃, and preserving heat for 2.5 hours;

s4, heating to 160 ℃, adding 0.8mol of adipic dihydrazide under ammonia gas, and stirring for 4 hours under heat preservation;

s5, filtering while the solution is hot to obtain a finished product.

Example 8

The emulsifier of the embodiment is prepared from the following raw materials: the polyolefin carboxylic acid anhydride is polyisobutylene succinic anhydride, the alcohol is tetrapolyglycerol, the dihydrazide is glutaryl hydrazine, and the diluent oil is 150SN base oil.

A method of preparing an emulsifier for remote delivery of a latex matrix, comprising the steps of:

s1, adding 1mol of polyisobutylene succinic anhydride into the reaction kettle;

s2, introducing ammonia gas into the reaction kettle;

s3, adding 0.7mol of tetraglycerol into a reaction kettle, weighing 220SN base oil to enable the mass of 150SN base oil to be 0.5 times of that of 1mol of polyisobutylene succinic anhydride, then adding 150SN base oil, heating to 110 ℃, and preserving heat for 3 hours;

s4, heating to 170 ℃, adding 1mol of glutaryl hydrazine in ammonia gas, and stirring for 6h under heat preservation;

s5, filtering while the solution is hot to obtain a finished product.

Example 9

The emulsifier of the embodiment is prepared from the following raw materials: the polyolefin carboxylic acid anhydride is selected from the group consisting of polypentaolefin succinic anhydride, alcohol is selected from the group consisting of hexaglycerol, dihydrazide is selected from the group consisting of pimeloyl dihydrazide, and the diluent oil is selected from the group consisting of 220SN base oil.

A method of preparing an emulsifier for remote delivery of a latex matrix, comprising the steps of:

s1, adding 1mol of poly (glutaric anhydride) into the reaction kettle;

s2, introducing ammonia gas into the reaction kettle;

s3, adding 1mol of hexaglycerol into a reaction kettle, weighing the 220SN base oil to enable the mass of the 220SN base oil to be 0.3 times that of 1mol of poly (pentylene succinic anhydride), then adding the 220SN base oil, heating to 120 ℃, and preserving heat for 3 hours;

s4, heating to 180 ℃, adding 1.2mol of pimeloyl dihydrazide under ammonia gas, and stirring for 6 hours under heat preservation;

s5, filtering while the solution is hot to obtain a finished product.

Comparative example

A commercially available T154 emulsifier is selected.

Application example

The emulsion matrices prepared from the emulsifiers of examples 1 to 9 and comparative example were tested to prepare formed explosives.

Performance test

The performance of the emulsion matrix and the performance of the mixed emulsion explosive are tested, and the test results are shown in the following table 1:

TABLE 1 emulsion matrix Properties and Mixed emulsion explosive Properties Table made with emulsifier

Compared with the comparative examples, the emulsifying agent disclosed by the invention has good emulsifying property and emulsifying stability, the prepared emulsion matrix has low normal-temperature dynamic viscosity, small yield stress, good fluidity, easiness in pumping, stability in storage, excellent bumping resistance and pumping resistance, the field charging and blasting after remote distribution, the blasting speed in a hole is more than 5800m/s, the overall performance is excellent, and the emulsifying agent is very suitable for the centralized preparation and remote distribution modes of the emulsion matrix.

The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.