阅读说明：本技术 一种助磨剂的制备方法 (Preparation method of grinding aid ) 是由 张义 牟忠江 张磊 范士敏 于 2019-11-25 设计创作，主要内容包括：本发明公开了一种助磨剂的制备方法,包括多胺类单体和磷酸基聚醚单体,按照一定摩尔比例,在适当条件下聚合而成。本发明提供了一种制备方法简单、结构可调性强、助磨效果好、存储稳定性高的助磨剂。(The invention discloses a preparation method of a grinding aid, which comprises the step of polymerizing a polyamine monomer and a phosphate polyether monomer under proper conditions according to a certain molar ratio. The grinding aid provided by the invention has the advantages of simple preparation method, strong structure adjustability, good grinding aid effect and high storage stability.)

1. A preparation method of a grinding aid is characterized by comprising the following steps:

(1) the preparation method comprises a polyamine monomer and a phosphate polyether monomer, wherein the polyamine monomer is subjected to synthesis reaction, the dosage of alkylene oxide is 1.0-1.2 times of the molar weight of amino hydrogen (N-H) on organic amine, the organic amine is used for priming, the alkylene oxide is gradually dripped under the stirring condition, the reaction temperature is 80-120 ℃, the reaction pressure is the pressure generated by a reaction system, the pressure in a reaction kettle is controlled to be less than or equal to 0.4MPa by adjusting the charging rate of alkylene oxide, and after the charging of the alkylene oxide is finished, the heat preservation reaction is continuously carried out for 0.5-1.0H;

(2) reacting polyamine monomer and phosphate polyether monomer, wherein the molar ratio of the polyamine monomer to the phosphate polyether monomer is 1: (1.0-1.5), the amount of the catalyst is 3% -5% of the total mass of the polyamine monomer and the phosphate polyether monomer, the reaction temperature is 110-150 ℃, the reaction pressure is full vacuum, and the reaction pressure can be-0.08-0.1 MPa and the reaction time is 5-10 h in consideration of the operation process of a vacuum water pump and a vacuum oil pump and possible gas leakage points at the pipeline connection part;

(3) and after the reaction is finished, adding water to dilute to 40% -50%, cooling to room temperature, and then neutralizing by using 30% liquid alkali until the pH value is 7-14 to obtain a grinding aid finished product.

2. The method of preparing a grinding aid according to claim 1, wherein the grinding aid comprises: one structural formula of the grinding aid in the step (1) is shown as the following formula (1),

wherein R is¹Is one of methyl, ethyl, isopropyl, butyl, cyclohexyl, phenyl and other groups, R²Is one of hydrogen, methyl, hydroxymethyl, chloromethyl, isopropyl, butyl, phenoxy and the like, m represents the number of ethylene oxide structural units and is an integer between 4 and 50, n represents the number of propylene oxide structural units, and accounts for 0 to 30 percent of the number of the ethylene oxide structural units and is an integer more than or equal to 0.

3. The method of preparing a grinding aid according to claim 1, wherein the grinding aid comprises: the polyamine monomer is synthesized by ring-opening polymerization of organic amine and alkylene oxide, one structural formula of the polyamine monomer is shown as the following formula (2),

wherein R is²Is one or more of hydrogen, methyl, hydroxymethyl, chloromethyl, isopropyl, butyl, phenoxy, etc.

4. The method of preparing a grinding aid according to claim 1, wherein the grinding aid comprises: the organic amine comprises one of commercialized amine monomers such as ethylenediamine, propylenediamine, butylenediamine, hexamethylenediamine, cyclohexylamine, 1, 2-cyclohexanediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, and polyethylenepolyamine.

5. The method of preparing a grinding aid according to claim 1, wherein the grinding aid comprises: alkylene oxide including one or more of ethylene oxide, propylene oxide, glycidol, epichlorohydrin, isopropyl ethylene oxide, butyl ethylene oxide, glycidyl phenyl ether, styrene oxide, etc.

6. The method of preparing a grinding aid according to claim 1, wherein the grinding aid comprises: one of the structural formulas of the phosphate polyether monomer is shown as the following formula (3), and the phosphate polyether monomer is a common commercial phosphate polyether monomer, wherein an ethylene oxide structural unit and a propylene oxide structural unit in the structural formula can be subjected to random copolymerization or block copolymerization,

wherein R is¹Is one of methyl, ethyl, isopropyl, butyl, cyclohexyl, phenyl and other groups, m represents the number of ethylene oxide structural units and is an integer between 4 and 50, and n represents the number of propylene oxide structural units, accounts for 0 to 30 percent of the number of the ethylene oxide structural units and is an integer more than or equal to 0.

7. The method of preparing a grinding aid according to claim 1, wherein the grinding aid comprises: the catalyst is a strong acid catalyst, comprises one of concentrated sulfuric acid, trifluoromethanesulfonic acid, trifluoroethane sulfonic acid, strong acid cation resin NKC-9 and the like, and has a certain grinding-aid effect on slag due to sulfate.

8. The method of preparing a grinding aid according to claim 1, wherein the grinding aid comprises: and (4) the pH value of the finished grinding aid in the step (3) is 11-14.

Technical Field

The invention relates to a preparation method and application of a grinding aid, and belongs to the technical field of production of slag micropowder.

Background

Granulated blast furnace slag is called slag for short, is waste slag discharged when iron and steel enterprises smelt pig iron, produces 1 ton of pig iron, and can produce 0.5-1 ton of slag. As the biggest steel producing country in the world, the slag yield in China is considerable every year, and a large amount of accumulated slag not only occupies the land, but also has the potential problem of environmental pollution. From the chemical composition, the slag belongs to a silicate material with low calcium and high silicon, the slag powder is ground into slag micro powder, cement is replaced by the slag micro powder according to a certain proportion, the workability of concrete can be improved, the strength of the concrete is improved, the hydration heat of large-volume concrete is reduced, the alkali-aggregate reaction in the concrete is inhibited, the durability of the concrete is improved, and the economic and ecological benefits are good.

The slag micro powder has better activity (the specific surface area is more than or equal to 400m2/Kg) under the condition of certain fineness, because the slag has more vitreous body content and poorer grindability, and the energy consumption of slag grinding is 2-3 times of that of cement grinding [ Yangling and the like, the influence of an organic grinding aid on slag grinding, Chinese powder technology, 2010,16(5),72-74 ]. In the actual grinding process, the energy consumption of the slag grinding process is reduced by adding a grinding aid.

The grinding aid reported in documents and patents is mainly used for cement grinding, the research on the synthesis and application of slag grinding aid is less, the difference of slag and cement in physicochemical properties is not considered, and the grinding aid for cement is directly applied to the slag grinding process, so that the effect of the grinding aid is not obvious. The grinding aid effect of triethanolamine, triisopropanolamine, molasses, ethylene glycol, tributyl phosphate, calcium lignosulfonate and the like on slag by single use is showy compared, and researches show that the triethanolamine has the best effect, and the efficiency of a slag mill is obviously improved when the components are compounded for use [ test research on special grinding aid for slag [ D ], Wuhan: wuhan university of engineering, 2012 ]. Zhang Yougua and the like carry out compounding and laboratory small grinding tests on a plurality of commonly used grinding aid components, and researches show that the polyalcohol, the amine monomer and the naphthalene sulfonate have relatively obvious grinding aid effect on slag, the early strength of the mortar prepared from the slag using the polyalcohol as the grinding aid is higher, and the 28d strength of the mortar prepared from the slag using the amine monomer as the grinding aid is higher [ experimental research on the slag grinding aid [ J ], cement, 2003, (4),9-12 ].

The application of the polyol grinding aid in slag grinding is studied in detail by Zhangwei and the like [ comparative experimental study of the polyol grinding aid in blast furnace slag grinding [ J ], Chinese cement, 2014, (6),90-92], and the study finds that the grinding aid effect of the polyglycerol on slag is good. Similar results are found in researches of Liquan and the like, and the grinding aid compounded by replacing part of alcohol amine monomers with polymeric polyol has better grinding aid effect on slag [ application of polymeric polyol in slag grinding aid [ J ], cement, 2019, (5),27-28 ].

The research work shows that the grinding aid effect of the mineral slag grinding process with the amine monomer and the polyhydric alcohol as the grinding aids is good, and particularly after the amine monomer and the polyhydric alcohol are compounded, the grinding aid effect and the strength improving effect of each component on the mineral slag can be fully exerted. However, the grinding aid components used in the slag grinding process do not deviate from the cement grinding aid system at present, and research work is focused on several commonly used cement grinding aid components, including mono-nitrogen atom amines such as triethanolamine, triisopropanolamine, diethanol monoisopropanolamine, monoethanoldiisopropanolamine and the like, and polyhydric alcohols such as ethylene glycol, glycerol, polymeric polyol and the like. The amine and polyol structures often only contain alcohol amine groups or hydroxyl groups, the work of improving the grinding aid only stops simply compounding the amine and polyol monomers, and because the functional groups contained in the components are single, the dosage of each component has a good effect only when reaching a certain value, the dosage of the grinding aid is higher or the grinding effect is worse than expected.

Disclosure of Invention

The invention provides a preparation method of a grinding aid, which is simple in preparation method, strong in structure adjustability and good in grinding aid effect.

In order to achieve the purpose, the grinding aid is synthesized by taking polyamine monomers and phosphate polyether monomers as raw materials and reacting under the action of a catalyst and under certain temperature and pressure conditions.

Preferably, one of the grinding aids has a structural formula shown as the following formula (1),

wherein, R1 is one of methyl, ethyl, isopropyl, butyl, cyclohexyl, phenyl and the like, and R2 is one of hydrogen, methyl, hydroxymethyl, chloromethyl, isopropyl, butyl, phenoxy and the like. m represents the number of ethylene oxide structural units and is an integer between 4 and 50, and n represents the number of propylene oxide structural units, accounts for 0 to 30 percent of the number of the ethylene oxide structural units and is an integer greater than or equal to 0.

Preferably, the polyamine monomer is synthesized by ring-opening polymerization of organic amine and alkylene oxide, one structural formula of the polyamine monomer is shown as the following formula (2),

wherein, R2 is one or more of hydrogen, methyl, hydroxymethyl, chloromethyl, isopropyl, butyl, phenoxy, etc.

Preferably, the organic amine includes one of commercialized amine monomers such as ethylenediamine, propylenediamine, butylenediamine, hexylenediamine, cyclohexylamine, 1, 2-cyclohexanediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, and polyethylenepolyamine.

Preferably, the alkylene oxide comprises one or a mixture of several of ethylene oxide, propylene oxide, glycidol, epichlorohydrin, isopropyl ethylene oxide, butyl ethylene oxide, glycidyl phenyl ether, styrene oxide and the like.

Preferably, in the synthesis reaction of the polyamine monomer, the dosage of the alkylene oxide is 1.0-1.2 times of the molar weight of amino hydrogen (N-H) on the organic amine, the organic amine is used for priming, the alkylene oxide is gradually dripped under the stirring condition, the reaction temperature is 80-120 ℃, the reaction pressure is the pressure generated by the reaction system, the pressure in the reaction kettle is controlled to be less than or equal to 0.4MPa by adjusting the charging rate of the alkylene oxide, and the heat preservation reaction is continuously carried out for 0.5-1.0H after the charging of the alkylene oxide is finished.

Preferably, one of the structural formulas of the phosphate polyether monomer is shown as the following formula (3), and is a common commercial phosphate polyether monomer, wherein an ethylene oxide structural unit and a propylene oxide structural unit in the structural formula can be randomly copolymerized or block copolymerized,

wherein R1 is one of methyl, ethyl, isopropyl, butyl, cyclohexyl, phenyl and other groups, m represents the number of ethylene oxide structural units and is an integer between 4 and 50, n represents the number of propylene oxide structural units, and accounts for 0 to 30 percent of the number of the ethylene oxide structural units and is an integer greater than or equal to 0.

Preferably, the catalyst is a strong acid catalyst, and comprises one of concentrated sulfuric acid, trifluoromethanesulfonic acid, trifluoroethanesulfonic acid, strong acid cation resin NKC-9 and the like, and sulfate also has a certain grinding aid effect on slag.

Preferably, the catalyst in the present invention is concentrated sulfuric acid.

Preferably, the polyamine monomer and the phosphate polyether monomer are reacted, and the molar ratio of the polyamine monomer to the phosphate polyether monomer is 1: (1.0-1.5), and the amount of the catalyst is 3-5% of the total mass of the polyamine monomer and the phosphate polyether monomer.

Preferably, the reaction temperature of the reaction between the polyamine monomer and the phosphate polyether monomer is 110-150 ℃, the reaction pressure is full vacuum, and the reaction pressure can be-0.08-0.1 MPa and the reaction time is 5-10 h in consideration of the operation process of the vacuum water pump and the vacuum oil pump and the possible air leakage points at the pipeline connection.

Preferably, after the reaction of the polyamine monomer and the phosphate polyether monomer is finished, adding water to dilute to 40% -50%, cooling to room temperature, and then neutralizing with 30% liquid alkali until the pH value is 7-14 to obtain a grinding aid finished product. The phosphate group formed after the reaction is finished is relatively stable under alkaline conditions and at room temperature, and the alkali excitation is favorable for the slag grinding process and the performance of slag micropowder.

Preferably, the pH value of the finished grinding aid is 11-14.

Preferably, the dosage of the grinding aid in the slag grinding process is 0.01-0.05%, so that a good grinding aid effect can be achieved, and the dosage of the grinding aid is obviously lower than that of a commercially available grinding aid by 0.05-0.2%. .

Advantageous effects

The invention provides a preparation method of a grinding aid, which is simple in preparation method, strong in structure adjustability and good in grinding aid effect, and particularly the slag grinding aid reported by the invention has the following advantages:

(1) the grinding aid provided by the invention is used for improving the slag grinding process in a targeted manner, and organically combining the polyether polyol and the polyamine monomer which have a good grinding aid effect in the slag grinding process by an organic chemical synthesis means, so that the synergistic grinding aid effect of functional groups in the polyether polyol and the polyamine monomer is fully exerted, and the dosage of the slag grinding aid can be obviously reduced;

(2) the polyamine monomer has strong structure adjustability, and can fully optimize the structure-activity relationship of the polyamine monomer and adjust the improvement effect of the polyamine monomer on the strength of each age by adjusting the structure of the alkylene oxide participating in the reaction;

(3) the grinding aid is synthesized by using concentrated sulfuric acid as a catalyst, and sodium sulfate generated by neutralization after the reaction has a good grinding aid effect. In addition, phosphate bridging groups in the grinding aid are stable under alkaline conditions, the pH value of the grinding aid is adjusted to be alkaline, and the effect of alkali excitation on the slag grinding process can be fully exerted.

Detailed Description

The present invention is described in detail below by way of examples, which are intended to be illustrative only and not to be construed as limiting the scope of the invention, and one skilled in the art will be able to make variations within the scope of the invention based on the disclosure herein, in reagents, catalysts and reaction process conditions. All equivalent changes or modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.

All chemical reagents in the invention are commercial industrial grade purity products, the pH value in the embodiment of the invention is detected by using a pH meter, and the solid content is detected by using a rapid moisture meter. In the embodiment, the parts are referred to as mass parts, and the addition amount of other materials is converted into mass parts. The description of the commercial phospho polyether monomers and code numbers used in the examples of the present invention are shown in table 1.

TABLE 1 phosphoric acid polyether monomer and its code table