阅读说明：本技术 一种改性高保坍萘系减水剂及其制备方法 (Modified high slump loss resistant naphthalene water reducer and preparation method thereof ) 是由 马丽涛 董翠平 欧大康 彭城 宋宝 杨道顺 尤健健 王超 史明珠 于 2020-06-15 设计创作，主要内容包括：本发明涉及到建筑材料技术领域,具体涉及到一种改性高保坍萘系减水剂及其制备方法。一种改性高保坍萘系减水剂,其原料包括酚类化合物、改性剂、萘油、磺化剂、醛类化合物、pH调节剂、水,其中改性剂为C8～C12烷基硅烷偶联剂、氨基硅烷偶联剂、巯基硅烷偶联剂的特定比例复配物。本发明通过改性剂对减水剂原料中的其他成分进行改性处理,并调控各组分在体系中的相对含量,有效提高了减水剂的减水率,用于混凝土中可有效延缓水泥水化的时间,提高了其坍落度,且改善了坍落度的保持时间。(The invention relates to the technical field of building materials, in particular to a modified high slump loss resistant naphthalene water reducer and a preparation method thereof. A modified high slump loss resistant naphthalene water reducer comprises raw materials of a phenolic compound, a modifier, naphthalene oil, a sulfonating agent, an aldehyde compound, a pH regulator and water, wherein the modifier is a compound of C8-C12 alkyl silane coupling agent, amino silane coupling agent and mercapto silane coupling agent in a specific ratio. According to the invention, other components in the raw material of the water reducing agent are modified by the modifier, and the relative content of each component in the system is regulated, so that the water reducing rate of the water reducing agent is effectively improved, the cement hydration time can be effectively delayed when the water reducing agent is used in concrete, the slump is improved, and the slump retention time is improved.)

1. The modified high slump loss resistant naphthalene water reducer is characterized in that raw materials of the modified high slump loss resistant naphthalene water reducer comprise a phenolic compound, a modifier, naphthalene oil, a sulfonating agent, an aldehyde compound, a pH regulator and water.

2. The modified high slump loss resistant naphthalene series water reducing agent as claimed in claim 1, wherein the modifier comprises an alkyl silane coupling agent, and the alkyl silane coupling agent is a C8-C12 alkyl silane coupling agent.

3. The modified high slump loss resistant naphthalene series water reducing agent according to claim 2, characterized in that the modifying agent further comprises an aminosilane coupling agent, and the mass ratio of the aminosilane coupling agent to the alkylsilane coupling agent is (0.3-0.5): 1.

4. the modified high slump loss resistant naphthalene series water reducing agent according to claim 3, wherein the modifying agent further comprises a mercaptosilane coupling agent, and the mass ratio of the mercaptosilane coupling agent to the alkyl silane coupling agent is (0.05-0.15): 1.

5. the modified high slump loss resistant naphthalene series water reducing agent according to claim 1, wherein the mass ratio of the phenolic compound to the modifier is 1: (0.05-0.3).

6. The modified high slump loss resistant naphthalene series water reducer as claimed in claim 1, wherein the phenolic compound accounts for 5-10% of the total mass of the water reducer.

7. The modified high slump loss resistant naphthalene water reducer as claimed in claim 1, wherein naphthalene oil accounts for 12-20% of the total mass of the water reducer.

8. The modified high slump loss resistant naphthalene series water reducing agent according to claim 7, wherein the mass ratio of the sulfonating agent to naphthalene oil is (1-1.6): 1.

9. the preparation method of the modified high slump loss resistant naphthalene water reducer according to any one of claims 1 to 8, characterized by comprising the following steps: putting the phenolic compound into a reaction device for heating, then adding the modifier, and stirring; then adding naphthalene oil, and heating; then, dripping a sulfonating agent, and preserving heat; then cooling, adding water and preserving heat; then dripping aldehyde compounds, and preserving heat; and then cooling, and adding a pH regulator for neutralization treatment to obtain the modified high slump loss resistant naphthalene water reducer.

10. The preparation method of the modified high slump loss resistant naphthalene series water reducer as claimed in claim 9, wherein the preparation method comprises the following steps: putting the phenolic compound into a reaction device, heating to 80-100 ℃, adding a modifier, and stirring for 20-50 min; then adding naphthalene oil, and heating to 140-160 ℃; then, dropwise adding a sulfonating agent, keeping the temperature for 2-3.5 hours after dropwise adding within 25-35 min; then cooling to 110-125 ℃, adding water, and keeping the temperature for 0.3-0.6 h; then, dripping an aldehyde compound, keeping the temperature for 2-4 hours after dripping within 1.5-3.5 hours; and then cooling to below 80 ℃, and adding a pH regulator for neutralization treatment to obtain the modified high slump loss resistant naphthalene water reducer.

Technical Field

The invention relates to the technical field of building materials, in particular to a modified high slump loss resistant naphthalene water reducer and a preparation method thereof.

Background

The naphthalene water reducer is a representative of the second-generation water reducer, has the characteristics of high water reducing rate, good cement adaptability, stable performance, moderate price and the like, and is one of the water reducers with the largest production and the widest use in China at present. However, the water reducing agent sold in the market at present is difficult to meet the requirements of the building material field on various aspects such as high water reducing performance, cement hydration delaying performance, slump constant and slump constant retaining performance of the water reducing agent.

The naphthalene oil is coal tar distillate with distillation range of 210-230 ℃ in the process of preparing industrial naphthalene or refined naphthalene, wherein the naphthalene content is 40-95%, and the naphthalene oil also contains a small amount of phenols, indole and other compounds with complex components. Because the boiling points are close, the components are complex and difficult to separate and purify, and secondary pollution is caused to the environment.

Disclosure of Invention

In order to solve the technical problems, the invention provides a modified high slump loss resistant naphthalene water reducer, which comprises the raw materials of a phenolic compound, a modifier, naphthalene oil, a sulfonating agent, an aldehyde compound, a pH regulator and water.

As a preferable technical scheme of the invention, the modifier comprises an alkyl silane coupling agent, and the alkyl silane coupling agent is a C8-C12 alkyl silane coupling agent.

As a preferable technical scheme, the modifier further comprises an aminosilane coupling agent, and the mass ratio of the aminosilane coupling agent to the alkylsilane coupling agent is (0.3-0.5): 1.

as a preferable technical scheme, the modifier further comprises a mercaptosilane coupling agent, and the mass ratio of the mercaptosilane coupling agent to the alkyl silane coupling agent is (0.05-0.15): 1.

as a preferred technical solution of the present invention, the mass ratio of the phenolic compound to the modifier is 1: (0.05-0.3).

As a preferable technical scheme, the phenolic compound accounts for 5-10% of the total mass of the water reducing agent.

As a preferable technical scheme, the naphthalene oil accounts for 12-20% of the total mass of the water reducing agent.

As a preferable technical scheme, the mass ratio of the sulfonating agent to the naphthalene oil is (1-1.6): 1.

the second aspect of the present invention provides a preparation method of the modified high slump loss resistant naphthalene water reducer, wherein the preparation method comprises the following steps: putting the phenolic compound into a reaction device for heating, then adding the modifier, and stirring; then adding naphthalene oil, and heating; then, dripping a sulfonating agent, and preserving heat; then cooling, adding water and preserving heat; then dripping aldehyde compounds, and preserving heat; and then cooling, and adding a pH regulator for neutralization treatment to obtain the modified high slump loss resistant naphthalene water reducer.

As a preferable technical scheme of the invention, the preparation method comprises the following steps: putting the phenolic compound into a reaction device, heating to 80-100 ℃, adding a modifier, and stirring for 20-50 min; then adding naphthalene oil, and heating to 140-160 ℃; then, dropwise adding a sulfonating agent, keeping the temperature for 2-3.5 hours after dropwise adding within 25-35 min; then cooling to 110-125 ℃, adding water, and keeping the temperature for 0.3-0.6 h; then, dripping an aldehyde compound, keeping the temperature for 2-4 hours after dripping within 1.5-3.5 hours; and then cooling to below 80 ℃, and adding a pH regulator for neutralization treatment to obtain the modified high slump loss resistant naphthalene water reducer.

Has the advantages that: the invention provides a modified high slump loss resistant naphthalene water reducer, which is characterized in that other components in the water reducer are modified by using a C8-C12 alkyl silane coupling agent, an aminosilane coupling agent and a mercaptosilane coupling agent in a specific proportion as modifiers, and the relative content of the components in a system effectively improves the water reducing rate of the water reducer, can effectively delay the cement hydration time when used in concrete, improves the slump loss of the concrete and improves the slump loss retaining performance.

Detailed Description

The disclosure may be understood more readily by reference to the following detailed description of preferred embodiments of the invention and the examples included therein. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification, including definitions, will control.

The terms "comprises," "comprising," "includes," "including," "has," "having," "contains," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.

When an amount, concentration, or other value or parameter is expressed as a range, preferred range, or as a range of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when a range of "1 to 5" is disclosed, the described range should be interpreted to include the ranges "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a range of values is described herein, unless otherwise stated, the range is intended to include the endpoints thereof and all integers and fractions within the range.

In addition, the indefinite articles "a" and "an" preceding an element or component of the invention are not intended to limit the number requirement (i.e., the number of occurrences) of the element or component. Thus, "a" or "an" should be read to include one or at least one, and the singular form of an element or component also includes the plural unless the stated number clearly indicates that the singular form is intended.

In order to solve the technical problems, the invention provides a modified high slump loss resistant naphthalene water reducer, which comprises the raw materials of a phenolic compound, a modifier, naphthalene oil, a sulfonating agent, an aldehyde compound, a pH regulator and water.

Modifying agent

In some embodiments, the modifying agent comprises an alkylsilane coupling agent that is a C8 to C12 alkylsilane coupling agent.

In a preferred embodiment, the modifier further comprises an aminosilane coupling agent, and the mass ratio of the aminosilane coupling agent to the alkylsilane coupling agent is (0.3-0.5): 1; preferably, the mass ratio of the aminosilane coupling agent to the alkylsilane coupling agent is 0.4: 1.

in a more preferred embodiment, the modifier further comprises a mercaptosilane coupling agent, and the mass ratio of the mercaptosilane coupling agent to the alkylsilane coupling agent is (0.05 to 0.15): 1; preferably, the mass ratio of the mercaptosilane coupling agent to the alkylsilane coupling agent is 0.07: 1.

in some embodiments, the mass ratio of phenolic compound to modifier is 1: (0.05 to 0.3); preferably, the mass ratio of the phenolic compound to the modifier is 1: 0.12.

examples of alkylsilane coupling agents include, but are not limited to: dodecyl triethoxysilane (CAS number: 18536-91-9), dodecyl trimethoxysilane (CAS number: 3069-21-4), octyl triethoxysilane (CAS number: 2943-75-1).

Examples of aminosilane coupling agents include, but are not limited to: gamma-aminopropyltrimethoxysilane (CAS number: 13822-56-5), gamma-aminopropyltriethoxysilane (CAS number: 919-30-2), N- (. beta. -aminoethyl) -gamma-aminopropylmethyldimethoxysilane (CAS number: 3069-29-2), N- (. beta. -aminoethyl) -gamma-aminopropylmethyltrimethoxysilane (CAS number: 1760-24-3), N-N-butyl-3-aminopropyltrimethoxysilane (CAS number: 31024-56-3).

Examples of mercaptosilane coupling agents include, but are not limited to: 3-mercaptopropyltriethoxysilane (CAS No.: 14814-09-6), mercaptopropyltrimethoxysilane (CAS No.: 4420-74-0).

In the invention, alkyl silane coupling agent is added as modifier, and long chain alkyl extends into the flocculation structure to react with the free water in the flocculation structure to change the free water into free water, thereby improving the fluidity of the mixture and obviously reducing the water consumption of the concrete. In order to prevent the water reducing agent from being viscous and stirring immovably in the preparation process and ensure high water reducing rate, the silane coupling agent is a C8-C12 alkyl silane coupling agent.

In addition, the applicant unexpectedly finds that the water consumption required by mixing the concrete with water can be further reduced by simultaneously adding a small amount of aminosilane coupling agent into the modifier, the hydration of the cement can be effectively delayed, and the slump of the concrete is improved. Presumably, the amino silane coupling agent modifies components such as phenolic compounds and naphthalene oil in raw materials to graft organic groups containing amino groups on the surfaces of the components, so that on one hand, flocculation structures among cement particles cannot be formed, further, the water consumption of concrete is reduced, on the other hand, the adsorption capacity of water reducing agent molecules on the surfaces of the cement particles is enhanced, a compact adsorption film layer is formed on the surfaces of the cement particles, and Ca (OH) is inhibited₂The formation of the crystal effectively delays the hydration reaction of the cement. In addition, the applicant finds that the modifier is added with a very small amount of mercaptosilane coupling agent, so that the surface of the effective component in the water reducing agent is grafted with mercapto groups, and the concrete can keep better slump for a long time.

Phenolic compounds

The phenolic compound refers to a compound in which a hydroxyl group is directly bonded to a carbon atom on a benzene ring in a molecular structure, and the phenolic compound is not particularly limited in the present invention, and examples of the phenolic compound include, but are not limited to: phenol (CAS number: 108-95-2), hydroquinone (CAS number: 123-31-9), catechol (CAS number: 120-80-9), cresol (CAS number: 1319-77-3), naphthol (CAS number: 1321-67-1), 2-methyl-1-naphthol (CAS number: 7469-77-4), bi-2-naphthol (CAS number: 602-09-5), 1-naphthol-2 naphthol condensate (CAS number: 611-49-4).

In some embodiments, the phenolic compound accounts for 5-10% of the total mass of the water reducing agent; preferably, the phenolic compound accounts for 8% of the total mass of the water reducing agent.

In some embodiments, the naphthalene oil accounts for 12-20% of the total mass of the water reducer; preferably, the naphthalene oil accounts for 13% of the total mass of the water reducing agent. The naphthalene oil can be selected from the raw materials on the market.

In some embodiments, the mass ratio of the sulfonating agent to the naphthalene oil is (1-1.6): 1; preferably, the mass ratio of the sulfonating agent to the naphthalene oil is 1.4: 1. in the present invention, the sulfonating agent is not particularly limited, and concentrated sulfuric acid having a concentration of 98 wt% may be used.

The pH adjuster is not particularly limited in the present invention, and includes, but is not limited to: sodium hydroxide, sodium carbonate, sodium bicarbonate, potassium hydroxide, potassium carbonate; preferably, the pH regulator in the present invention is sodium hydroxide solution with a concentration of 32 wt%.

The aldehyde compound is not particularly limited in the present invention, and includes, but is not limited to: formaldehyde, acetaldehyde, propionaldehyde; preferably, formaldehyde is used as the aldehyde compound in the present invention.

In order to ensure the feasibility of the preparation process of the water reducing agent and the performance of the water reducing agent, the relative contents of phenolic compounds and naphthalene oil in the raw material components in the system need to be regulated and controlled. In addition, the color of the naphthalene oil used in the invention is too dark, and the color change is not easy to observe in the sulfonation process of the water reducing agent preparation, so the dosage of the sulfonating agent needs to be controlled to control the sulfonation degree.

The invention also provides a preparation method of the modified high slump loss resistant naphthalene water reducer, which comprises the following steps: putting the phenolic compound into a reaction device for heating, then adding the modifier, and stirring; then adding naphthalene oil, and heating; then, dripping a sulfonating agent, and preserving heat; then cooling, adding water and preserving heat; then dripping aldehyde compounds, and preserving heat; and then cooling, and adding a pH regulator for neutralization treatment to obtain the modified high slump loss resistant naphthalene water reducer.

In a preferred embodiment, the preparation method comprises the following steps: putting the phenolic compound into a reaction device, heating to 80-100 ℃, adding a modifier, and stirring for 20-50 min; then adding naphthalene oil, and heating to 140-160 ℃; then, dropwise adding a sulfonating agent, keeping the temperature for 2-3.5 hours after dropwise adding within 25-35 min; then cooling to 110-125 ℃, adding water, and keeping the temperature for 0.3-0.6 h; then, dripping an aldehyde compound, keeping the temperature for 2-4 hours after dripping within 1.5-3.5 hours; and then cooling to below 80 ℃, and adding a pH regulator for neutralization treatment to obtain the modified high slump loss resistant naphthalene water reducer.

In a more preferred embodiment, the preparation method comprises the steps of: putting the phenolic compound into a reaction device, heating to 100 ℃, then adding the modifier, and stirring for 30 min; then adding naphthalene oil, and heating to 150 ℃; then, dripping a sulfonating agent, keeping the temperature for 3 hours after dripping within 30 min; then cooling to 120 ℃, adding water, and keeping the temperature for 0.5 h; then, dripping an aldehyde compound, keeping the temperature for 2 hours after dripping for 2 hours; and then cooling to below 80 ℃, adding a pH regulator to neutralize the system pH to 7-9, and thus obtaining the modified high slump loss resistant naphthalene water reducer.

Wherein, in the processes of adding aldehyde compound, heat preservation reaction and the like, if the material is particularly viscous, a small amount of water is added for many times. The naphthalene oil can be a product on the market, and the naphthalene component content of the naphthalene oil can be 45-95%.

The naphthalene oil (naphthalene content about 82%) in all the examples of the present application is derived from the residue of the 210-230 ℃ fraction in the naphthalene refining process of Ward chemical technology, Inc., Xiao county; the formaldehyde content is 35-37 wt%.