阅读说明：本技术 一种混凝土韧性增强型链状醇胺类铁盐组合物及其制备方法 (Concrete toughness-enhanced chain alkanolamine ferric salt composition and preparation method thereof ) 是由 江波 霍佳腾 王淑嫱 柯凯 储劲松 于 2021-07-22 设计创作，主要内容包括：本发明公开了一种混凝土韧性增强型链状醇胺类铁盐组合物及其制备方法,首先在惰性气氛保护的反应器中加入460-480份链状醇胺、0.15-0.45份催化剂、0.10-0.35份抗氧化剂和1.2-2.5份螯合剂,并搅拌,然后再在搅拌的条件下加入6-7份铁盐、1-2份金属盐进行反应,反应时间为2-3小时,反应体系的温度保持在0-30℃,加入完毕后,再回流2-3小时并保持加热；之后过滤除去滤渣,对滤液进行升温减压精馏,得到产品液体,所得产品液体再升温减压蒸馏得到产品醇胺类铁盐。本发明使用直接反应法制备成一种混凝土韧性增强型链状醇胺类铁盐组合物,这种金属醇胺盐所使用的醇胺可以起到很好的吸附作用,提高混凝土的韧性和抗弯性能。(The invention discloses a concrete toughness enhanced chain alcohol amine ferric salt composition and a preparation method thereof, wherein 460-480 parts of chain alcohol amine, 0.15-0.45 part of catalyst, 0.10-0.35 part of antioxidant and 1.2-2.5 parts of chelating agent are added into a reactor protected by inert atmosphere and stirred, then 6-7 parts of ferric salt and 1-2 parts of metal salt are added under the stirring condition for reaction, the reaction time is 2-3 hours, the temperature of a reaction system is kept at 0-30 ℃, and after the addition is finished, the reflux is carried out for 2-3 hours and the heating is kept; and then filtering to remove filter residues, heating and carrying out reduced pressure rectification on the filtrate to obtain product liquid, and heating and carrying out reduced pressure distillation on the obtained product liquid to obtain the product of the alcamine ferric salt. The invention prepares the chain alkanolamine ferric salt composition with the enhanced concrete toughness by using a direct reaction method, and the alcohol amine used by the metal alkanolamine salt can play a good role in adsorption, thereby improving the toughness and the bending resistance of the concrete.)

1. A preparation method of a concrete toughness-enhanced chain alkanolamine ferric salt composition is characterized by comprising the following operation steps:

the method comprises the following steps: adding 480 parts of 460-480 parts of chain alcohol amine, 0.15-0.45 part of catalyst, 0.10-0.35 part of antioxidant and 1.2-2.5 parts of chelating agent into a reactor protected by inert atmosphere by mass fraction, stirring, adding 6-7 parts of iron salt and 1-2 parts of metal salt under the condition of stirring for reaction for 2-3 hours, keeping the temperature of a reaction system at 0-30 ℃, and refluxing for 2-3 hours and keeping heating after the addition is finished;

step two: filtering to remove filter residue, heating the filtrate, carrying out reduced pressure rectification, evaporating the solvent to obtain a product liquid, and heating the product liquid, and carrying out reduced pressure distillation to obtain the product of the alcamine ferric salt.

2. The preparation method of the concrete toughness-enhanced chain alkanolamine iron salt composition as claimed in claim 1, wherein: the chain alcohol amine is tetrahydroxyethyl ethylene diamine and/or hydroxyethyl ethylene diamine.

3. The preparation method of the concrete toughness-enhanced chain alkanolamine iron salt composition as claimed in claim 1, wherein: the iron salt is ferrous sulfate.

4. The preparation method of the concrete toughness-enhanced chain alkanolamine iron salt composition as claimed in claim 1, wherein: the metal salt is zinc sulfate and/or magnesium sulfate.

5. The preparation method of the concrete toughness-enhanced chain alkanolamine iron salt composition as claimed in claim 1, wherein: the catalyst is one or more of anhydrous aluminum chloride, mercuric chloride and iodine solution.

6. The preparation method of the concrete toughness-enhanced chain alkanolamine iron salt composition as claimed in claim 1, wherein: the chelating agent is any one or more of acetic acid, imino disuccinic acid tetrasodium and glutamic acid N, N-diacetic acid.

7. The preparation method of the concrete toughness-enhanced chain alkanolamine iron salt composition as claimed in claim 1, wherein: the antioxidant is any one or more of tea polyphenol, vitamin E and tert-butyl hydroquinone.

8. A concrete toughness-enhanced chain alkanolamine ferric salt composition is polymerized from the following components:

6-7 parts of iron salt;

1-2 parts of metal salt;

chain alcohol amine 460 and 480 parts;

1.2-2.5 parts of a chelating agent;

0.10-0.35 part of antioxidant;

0.15-0.45 part of catalyst.

Technical Field

The invention belongs to the technical field of concrete, and particularly relates to a concrete toughness-enhanced chain alkanolamine ferric salt composition and a preparation method thereof.

Background

Alkali metal alkoxides are very important fine chemicals and are widely used in the fields of medicine, biology, materials and the like. The metal alkoxide can be used for preparing nano materials by a hydrolysis method, and can also be used as a catalyst and an initiator in chemical reactions. Metal alkoxides are part of a broad class of metal organic compounds that are intermediate between inorganic and organic compounds. With the rapid development of alkoxide Sol-Gel method (Sol-Gel), the research on metal alkoxide chemistry is greatly promoted, and a foundation is laid for developing new applications of alkoxide and preparing new materials. At present, the research on alkoxide synthesis, performance and application has become one of the hot spots of research. Has great theoretical significance and important practical value.

The patent CN102898279A discloses a preparation method of a solid metal alkoxide, relates to a preparation method of a solid metal alkoxide, and belongs to the technical field of metal alkoxide preparation. Mixing metal fuel and inorganic salt to obtain a mixture; grinding and compounding the obtained mixture in a ball mill to obtain a high-activity alcohol reaction metal material; adding an alcohol solvent into the obtained high-activity alcohol reaction metal material, reacting the high-activity alcohol reaction metal material with the alcohol solvent at normal temperature or under a heating condition, and after the reaction is finished, distilling and drying in vacuum to obtain the solid metal alkoxide. The invention adopts a high-energy ball milling method to prepare a high-activity alcohol reaction metal material, and the active material can rapidly react with alcohol to generate metal alkoxide; the method has high efficiency and simple process, and the obtained metal alkoxide has high purity.

The invention discloses a preparation method of an M-O-R metal alkoxide carbon fiber interface, and particularly discloses a preparation method of an M-O-R metal alkoxide carbon fiber interface, which belongs to the field of carbon fiber reinforcement interface modification, aims to make up for the defects of the prior art, and provides a preparation method of a metal fiber interface integrating oxidation resistance thermophysical properties and structural functions by utilizing the strong reaction activity of metal alkoxide, carrying out chemical reaction with a plurality of reagents, having the characteristics of volatility and solubility of an organic solvent of a covalent compound and adopting an alkoxide sol-gel method and a vacuum impregnation method. The method has the advantages of improving the product quality and prolonging the service life.

The patent CN107900372A discloses a method for preparing a homogeneous phase iron-aluminum bimetallic powder material by using bimetallic alkoxide as a precursor, and the invention discloses a method for preparing a homogeneous phase iron-aluminum bimetallic powder material by using bimetallic alkoxide as a precursor. The method is characterized in that iron-aluminum bimetallic alkoxide is used as a precursor for preparing the reaction, and reactants such as alkoxide and the like are controlled to be uniformly mixed in the reaction, so that the finally prepared material achieves the characteristic of homogeneous distribution. The material overcomes the defects that zero-valent iron is easy to oxidize and agglomerate and the material cost is high; the bimetal system can provide more reactive active sites, has good adsorption capacity on Cr (VI), has no secondary pollution to the environment, is an environment-friendly green material, and promotes the wide application and popularization of the iron-aluminum bimetal powder material in environmental remediation.

Different from the patents, the invention aims to prepare the chain alkanolamine ferric salt composition with the enhanced concrete toughness. The invention uses metal iron and chain hydramine to react to prepare chain hydramine iron salt, and the chain hydramine iron salt is used in concrete to improve the performance of an interface transition zone of the concrete. In the preparation process, the chelating agent and the antioxidant are added to protect ferrous ions and prevent the ferrous ions from being oxidized. Ferrous ions can participate in C in concrete₄The hydration of AF assists to form gelatinous ferrite, reduces the crystal-to-gel ratio of concrete hydration products and improves the toughness of concrete.

Disclosure of Invention

Aiming at the defects in the prior art, the invention aims to provide a preparation method and an application method of a concrete toughness enhanced chain alkanolamine iron salt composition. The preparation method has the advantages of simple preparation process, excellent product performance, good stability and wide adaptability.

The invention takes ferric salt and long-chain alcohol ether as synthetic raw materials to prepare long-chain alcohol amine ferric salt which is used for modifying concrete. The long-chain alcohol amine iron salt has good effectThe adsorption and the coating performance can be combined with concrete particles, and ferrous ions are introduced to participate in the hydration process of the concrete, so that the C content in the concrete is improved₄The content of AF.

The technical scheme of the invention is as follows:

a preparation method of a concrete toughness-enhanced chain alkanolamine ferric salt composition is characterized by comprising the following operation steps:

the method comprises the following steps: adding 480 parts of 460-480 parts of chain alcohol amine, 0.15-0.45 part of catalyst, 0.10-0.35 part of antioxidant and 1.2-2.5 parts of chelating agent into a reactor protected by inert atmosphere by mass fraction, stirring, adding 6-7 parts of iron salt and 1-2 parts of metal salt under the condition of stirring for reaction for 2-3 hours, keeping the temperature of a reaction system at 0-30 ℃, and refluxing for 2-3 hours and keeping heating after the addition is finished;

step two: filtering to remove filter residue, heating the filtrate, carrying out reduced pressure rectification, evaporating the solvent to obtain a product liquid, and heating the product liquid, and carrying out reduced pressure distillation to obtain the product of the alcamine ferric salt.

The chain alcohol amine is tetrahydroxyethyl ethylenediamine and hydroxyethyl ethylenediamine, and is preferably a composition of the tetrahydroxyethyl ethylenediamine and the hydroxyethyl ethylenediamine in a mass ratio of 4: 1.

The iron salt is ferrous sulfate.

The metal salt is any one or more of zinc sulfate and magnesium sulfate, and is preferably a zinc sulfate and magnesium sulfate composition with the mass ratio of 1: 1.

The catalyst is one or more of anhydrous aluminum chloride, mercuric chloride and iodine solution, and is preferably an anhydrous aluminum chloride and mercuric chloride composition with the mass ratio of 2: 3.

The chelating agent is composed of one or more of acetic acid, tetrasodium iminodisuccinate and glutamic acid N, N-diacetic acid, and is preferably a composition of tetrasodium iminodisuccinate and glutamic acid N, N-diacetic acid in a mass ratio of 1: 2.

The antioxidant is any one or more of tea polyphenol, vitamin E and tert-butyl hydroquinone, and is preferably a composition of the tea polyphenol and the tert-butyl hydroquinone in a mass ratio of 1: 1.

A concrete toughness-enhanced chain alkanolamine ferric salt composition is polymerized from the following components:

6-7 parts of iron salt;

1-2 parts of metal salt;

chain alcohol amine 460 and 480 parts;

1.2-2.5 parts of a chelating agent;

0.10-0.35 part of antioxidant;

0.15-0.45 part of catalyst.

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

1. the alcohol amine ferric salt prepared by the invention is used for toughening, reinforcing and modifying concrete, wherein C in the concrete₄The hydration of AF consumes easily dissociated CH, so that the enrichment of CH in concrete on an interface is reduced, the dissociation of CH can cause cracks on the concrete interface, and C₄The hydration of AF can reduce the generation of cracks at the concrete interface and improve the toughness and the strength of the concrete.

2. According to the invention, the antioxidant and the chelating agent are added in the preparation of the alcohol amine ferric salt, the antioxidant and the chelating agent can play a role in protecting ferrous ions, the chelating agent can complex the ferrous ions to prevent the ferrous ions from being oxidized into ferric ions, the antioxidant can reduce the possibility of oxidation of uncomplexed ferrous ions, and the antioxidant and the chelating agent can play a good role in protecting after being compounded and added.

3. The invention also introduces magnesium, zinc and other ions into the metal alkoxide, the magnesium ions have certain expansibility, and can play a role in inhibiting the volume shrinkage of the concrete so as to prevent the concrete from cracking. In addition, the zinc ions in the concrete can also properly improve the mechanical property, the durability and the volume stability of the concrete, and improve the strength and the toughness of the concrete.

Detailed Description

The applicant will make further detailed descriptions of technical solutions and advantages of the present invention with reference to specific examples, but it should be understood that the following examples should not be construed as limiting the scope of the claims of the present application in any way.

Example 1

A concrete toughness-enhanced chain alkanolamine ferric salt composition is polymerized from the following components:

iron salt: 6 parts of ferrous sulfate;

metal salt: 1 part of a zinc sulfate and magnesium sulfate composition with the mass ratio of 1: 1;

chain alcohol amine: 460 parts of a composition of tetrahydroxyethyl ethylenediamine and hydroxyethyl ethylenediamine in a mass ratio of 4: 1;

chelating agent: 1.7 parts of composition of imino disuccinic acid tetrasodium and glutamic acid N, N-diacetic acid with the mass ratio of 1: 2;

antioxidant: 0.29 part of composition of tea polyphenol and tert-butyl hydroquinone with the mass ratio of 1: 1;

catalyst: 0.33 part of anhydrous aluminum chloride and mercuric chloride composition with the mass ratio of 2: 3;

a preparation method of a concrete toughness enhanced chain alkanolamine ferric salt composition sequentially comprises the following operation steps:

the method comprises the following steps: adding 460 parts of tetrahydroxyethyl ethylenediamine and hydroxyethylethylene diamine composition in a mass ratio of 4:1, 0.33 part of anhydrous aluminum chloride and mercuric chloride composition in a mass ratio of 2:3, 0.29 part of tea polyphenol and tert-butyl hydroquinone composition in a mass ratio of 1:1 and 1.7 parts of tetrasodium iminodisuccinate and glutamic acid N, N-diacetic acid composition in a mass ratio of 1:2 into a reactor protected by inert atmosphere, stirring, adding 6 parts of ferrous sulfate, 1 part of zinc sulfate and magnesium sulfate composition in a mass ratio of 1:1 under the stirring condition, reacting for 2.5 hours, keeping the temperature of a reaction system at 20 ℃, refluxing for 3 hours and keeping heating after the addition is finished;

step two: filtering to remove filter residues, heating and carrying out reduced pressure rectification on the filtrate, evaporating the solvent to obtain a product liquid, and heating and carrying out reduced pressure distillation on the obtained product liquid to obtain a product of alcamine ferric salt, namely the concrete toughness enhanced chain alcamine ferric salt composition.

Examples 2-6 were prepared in the same manner as in example 1, with the compositional differences specified in Table 1 and the process parameter differences specified in Table 2.

Table 1 shows the differences between the compositions of examples 2 to 6 of the present invention and example 1

Table 2 shows the difference between the processes of examples 2 to 6 of the present invention and example 1 in terms of parameters

And (3) detecting data:

the embodiment of the invention and the Wuhan quadrupole concrete SJ-D type concrete synergist are prepared into a C50 concrete sample, and the following table is obtained through concrete performance detection. (maximum crack width of crack resistance of flat plate method crack test was measured according to the dynamic crack resistance standard of JG/T157-2004 industry standard).

Table 3 shows the properties of modified concrete of examples 1 to 7 of the present invention and comparative examples

As can be seen from Table 3, the advantages of the present invention over the prior art in terms of neat paste flow, crack resistance, flexural strength and compressive strength are significant.

The above embodiments are merely illustrative of the present invention and are not to be construed as limiting the invention. Although the present invention has been described in detail with reference to the embodiments, it should be understood by those skilled in the art that various combinations, modifications or equivalents may be made to the technical solution of the present invention without departing from the spirit and scope of the technical solution of the present invention, and the technical solution of the present invention is covered by the claims of the present invention.