阅读说明：本技术 一种混凝土抗腐蚀剂及其制备方法 (Concrete corrosion inhibitor and preparation method thereof ) 是由 鹿立云 王晓芳 盛思仲 黄雪 段周玉 于 2021-07-15 设计创作，主要内容包括：本发明涉及混凝土抗腐蚀领域,具体涉及一种混凝土抗腐蚀剂及其制备方法。所述抗腐蚀剂,按重量份数计,制备原料包括以下组分：三官能团度聚醚多元醇80-100份、均苯三酚三缩水甘油醚30-40份、三辛基胺乙基氢氧化铵30-40份和间二甲苯二胺10-20份。本发明将均苯三酚三缩水甘油醚和三辛基胺乙基氢氧化铵反应后的整体作为三官能团度聚醚多元醇的扩链剂使用,再经过固化得到本发明的抗腐蚀剂。本发明的抗腐蚀剂可以在完全固化前采用喷涂的方式涂覆在混能表面,固化后形成致密的疏水高分子膜,隔绝腐蚀环境,起到较好的保护混凝土的作用。(The invention relates to the field of concrete corrosion resistance, in particular to a concrete corrosion inhibitor and a preparation method thereof. The anticorrosive agent comprises the following raw materials in parts by weight: 80-100 parts of trifunctional polyether polyol, 30-40 parts of phloroglucinol triglycidyl ether, 30-40 parts of trioctylamine ethyl ammonium hydroxide and 10-20 parts of m-xylene diamine. The corrosion inhibitor is prepared by using the whole body of the reacted phloroglucinol triglycidyl ether and trioctylamine ethyl ammonium hydroxide as a chain extender of the trifunctional polyether polyol and curing the chain extender. The anticorrosive agent can be coated on the energy mixing surface by adopting a spraying mode before complete curing, and a compact hydrophobic polymer film is formed after curing, so that the anticorrosive agent can isolate the corrosive environment and play a better role in protecting concrete.)

1. The concrete anticorrosive agent comprises the following components in parts by weight:

trifunctional polyether polyol, phloroglucinol triglycidyl ether, trioctylamine ethyl ammonium hydroxide and m-xylene diamine.

2. The corrosion inhibitor of claim 1, wherein the preparation raw materials comprise the following components in parts by weight:

80-100 parts of trifunctional polyether polyol, 30-40 parts of phloroglucinol triglycidyl ether, 30-40 parts of trioctylamine ethyl ammonium hydroxide and 10-20 parts of m-xylene diamine.

3. The corrosion inhibitor of claim 1 wherein said trifunctional polyether polyol has a weight average molecular weight of 500-700.

4. The corrosion inhibitor of claim 1 wherein said trifunctional polyether polyol has a hydroxyl value of 200-400 mgKOH/g; viscosity of 200-600mPa^.s。

5. The corrosion inhibitor of claim 1 further comprising an antioxidant and an antifoaming agent; the antioxidant is selected from phosphite antioxidants, and the addition amount is 1-3 parts; the defoaming agent is selected from organosilicon defoaming agents, and the addition amount is 0.1-0.5 part.

6. The corrosion inhibitor of claim 1 wherein said phosphite based antioxidant is selected from the group consisting of chemnox 168, chemnox 626 and chemnoxTP 80.

7. A process for the preparation of an anticorrosive agent as claimed in any of claims 1 to 6, comprising the steps of:

s1: mixing phloroglucinol triglycidyl ether and trioctylamine ethyl ammonium hydroxide, and heating for reaction;

s2: after the reaction of S1, adding trifunctional polyether polyol, and continuing heating for polymerization;

s3: adding m-xylene diamine into the mixture obtained after the reaction of S2 to continue the reaction, and cooling to obtain the corrosion inhibitor;

such as addition of an antioxidant and/or an antioxidant, is added at S3.

8. The method according to claim 7, wherein the reaction temperature in S1 is 60-80 ℃, and the reaction time is 2-3 h.

9. The method according to claim 7, wherein the polymerization temperature in S2 is 90-110 ℃ and the reaction time is 4-6 h.

10. The method according to claim 7, wherein the reaction time is 1 to 2 hours and the reaction temperature is 20 to 30 ℃ in S3.

Technical Field

The invention relates to the field of concrete corrosion resistance, in particular to a concrete corrosion inhibitor and a preparation method thereof.

Background

The concrete has the advantages of simple and convenient manufacturing process, low price, stable physical and chemical properties and the like, and is widely applied to the civil engineering industry. Concrete requires resistance to various damaging elements under actual use conditions, ability to maintain strength and appearance integrity for long periods of time, and ability to maintain its safety, normal use and acceptable appearance without additional costly reinforcement over the specified service life and under various environmental conditions, which is known as the durability of concrete.

There are many causes for affecting the durability of concrete, among which the use environment acts for the longest duration in the whole life cycle of the concrete structure and the influence on the durability of concrete is the greatest, and the corrosion environment is also a main cause of causing the destruction of the concrete structure inevitably. The aggressive environment of concrete includes: carbonization environment, freeze thawing environment, chloride ion corrosion environment, sulfate corrosion environment, etc. Whereas sulfate and chloride attacks are the most complex and specific.

One is to improve the chemical stability of concrete, and adopts high-performance concrete to improve the internal composition of the concrete; another approach is to apply a protective coating to the surface of the concrete to improve the overall resistance of the concrete to various corrosive media. Improving the resistance of concrete itself to corrosion is the most important and fundamental protection principle, but the first method has certain limitations. Firstly, the important performance defects of high-performance concrete are high self-shrinkage and brittleness; secondly, the concrete is a porous material, the corrosion of the concrete structure caused by environmental factors such as seawater, freezing and the like is mostly started from the surface, and the concrete alone is not enough to realize durable protection. The protective coating is more convenient to operate and is easier to repair when damaged.

The concrete protective coating is based on organic polymers and mainly comprises the following components: the concrete surface anticorrosive coatings such as epoxy anticorrosive coatings, polyurethane anticorrosive coatings, chlorinated rubber anticorrosive coatings, highly chlorinated polyethylene anticorrosive coatings, acrylate anticorrosive coatings and the like are characterized in that a layer of concrete surface anticorrosive coatings is formed, which can effectively isolate permeation and diffusion of harmful substances such as chloride ions, acid gases and the like in concrete, is particularly suitable for concrete protection in a marine erosion environment characterized by salt mist water vapor, and is one of technologies for protecting the surface of a concrete structure constructed in the marine environment.

Chinese patent application CN102719173A discloses an epoxy anticorrosive paint for underwater concrete, which takes liquid epoxy resin DER351 as a base material; polysulfide rubber is taken as a toughening agent; pentanediol glycidyl ether 6286 is used as a diluent; zinc phosphate and iron oxide red are used as active anticorrosive pigments, and spherical silicon carbide, ceramic microspheres, mica iron oxide, sericite and precipitated barium sulfate are used as fillers; cashew nut shell oil modified phenolic aldehyde amine and modified fatty amine are used as curing agents; the solvent-free and bi-component epoxy anticorrosive paint for underwater concrete is prepared by using a silane coupling agent 1121 as an adhesion promoter through a conventional preparation process under the coordination of a functional auxiliary agent. The coating has good environmental protection property, can be directly coated or scraped on an underwater concrete wet interface, is quickly cured to form a film, has excellent adhesive force, abrasion resistance and strong corrosion resistance, and is widely applied to corrosion prevention of various underwater concrete facilities.

Chinese patent application CN102286137A discloses a preparation method of polyether modified epoxy resin for marine concrete coating, belonging to the field of organic chemical material synthesis. The preparation method comprises the steps of firstly carrying out ring-opening reaction on epoxy resin and acrylic acid to prepare epoxy acrylic resin, then carrying out addition reaction on diisocyanate and polyether to prepare isocyanate-terminated prepolymer, and finally carrying out crosslinking reaction on the isocyanate-terminated prepolymer and the epoxy acrylic resin to form an interpenetrating network polymer, namely the polyether modified epoxy resin. The modified epoxy resin has high flexibility, can form a compact coating with good toughness after being cured, and has good impact resistance, thereby improving the corrosion resistance.

Chinese patent application CN111117423A discloses an elastic epoxy resin coating and a preparation method thereof. The coating comprises epoxy resin, scales, modified resin, an additive, an auxiliary agent, a solvent and a curing agent, and is mainly used as a concrete anticorrosive coating. Compared with the common epoxy coating, the coating has excellent ductility and elongation at break, has good corrosion resistance, can be widely applied to the protection of concrete structures in various heavy corrosion environments such as acid, alkali, salt, ocean, soil, chemical industry atmosphere and the like, and has excellent protective performance.

Disclosure of Invention

The invention aims to provide a concrete corrosion inhibitor with a better protection effect.

The purpose of the invention is realized by the following technical scheme.

The concrete corrosion inhibitor comprises the following raw materials in parts by weight:

80-100 parts of trifunctional polyether polyol,

30-40 parts of phloroglucinol triglycidyl ether,

30-40 parts of trioctylamine ethyl ammonium hydroxide

And 10-20 parts of m-xylene diamine.

Further, the weight average molecular weight of the trifunctional polyether polyol is 500-700.

Further, the hydroxyl value of the trifunctional polyether polyol is 200-400 mgKOH/g.

Further, the viscosity of the trifunctional polyether polyol is 200-600 mPas.

Alternatively, the trifunctional polyether polyol is known to those skilled in the art and is prepared by addition polymerization of an initiator (active hydrogen group-containing compound) with Ethylene Oxide (EO), Propylene Oxide (PO), Butylene Oxide (BO), or the like in the presence of a catalyst. The polyol initiator can be selected from trihydric alcohols such as glycerol, glycerol trimethylolpropane and the like and polyols such as pentaerythritol, tetrol, xylitol, sorbitol, sucrose and the like; the amine initiator is triamine diethylenetriamine and the like. Such as products under the brand numbers Puranol G305, Puranol G306 or Puranol G307. The source of the trifunctional polyether polyol is not specially limited, and a commercial product with 3 functionality and the molecular weight of 500-700 is adopted.

Further, the corrosion inhibitor also comprises an antioxidant and an antifoaming agent.

Further, the antioxidant is selected from phosphite antioxidants, and the addition amount is 1-3 parts.

Further, the defoaming agent is selected from organosilicon defoaming agents, and the addition amount is 0.1-0.5 part.

The silicone defoaming agent used in the present invention is not particularly limited, and may be a commercially available silicone defoaming agent having a defoaming effect.

Further, the phosphite antioxidant is selected from chemnox 168, chemnox 626 or chemnox tp 80.

The invention also provides a preparation method of the corrosion inhibitor.

A preparation method of the corrosion inhibitor comprises the following steps:

s1: mixing phloroglucinol triglycidyl ether and trioctylamine ethyl ammonium hydroxide, and heating for reaction;

s2: after the reaction of S1, adding trifunctional polyether polyol, and continuing heating for polymerization;

s3: and adding m-xylene diamine into the mixture obtained after the reaction of S2 to continue the reaction, and cooling to obtain the anticorrosive agent.

Further, in S1, the reaction temperature is 60-80 ℃, and the reaction time is 2-3 h.

Further, in S2, the reaction temperature is 90-110 ℃ and the reaction time is 4-6 h.

Further, in S3, the reaction time is 1-2h, and the reaction temperature is 20-30 ℃.

The term phloroglucinol triglycidyl ether as used in the present invention has the structure of formula I below:

the term trioctylamine ethylammonium hydroxide according to the present invention is sufficient to have the following formula II:

the invention has the advantages that:

1. the corrosion inhibitor is prepared by using the whole body obtained by reacting the formula II and the formula I as a chain extender of the polyether polyol with three functionality degrees and curing. The anticorrosive agent can be coated on the energy mixing surface by adopting a spraying mode before complete curing, and a compact hydrophobic polymer film is formed after curing, so that the anticorrosive agent can isolate the corrosive environment and play a better role in protecting concrete.

2. According to the invention, the formula I is adopted to modify the trifunctional polyether polyol, the obtained high molecular chains are intertwined, the compactness is better, and the structure of the formula II is further introduced, so that the alkyl chain with a proper length is provided, and the finally cured polymer film has a compact structure and strong hydrophobicity.

3. The anticorrosive agent has better peel strength after being sprayed on the surface of concrete and cured.

Detailed Description

Example 1

A concrete corrosion inhibitor prepared by the steps of:

s1: mixing 40 parts of phloroglucinol triglycidyl ether and 40 parts of trioctylamine ethyl ammonium hydroxide, heating to 80 ℃, and reacting for 2 hours;

s2: after the reaction of S1 is finished, adding 100 parts of trifunctional polyether polyol (Puranol G305), heating to 100 ℃, and continuing the reaction for 4 hours;

s3: and adding 10 parts of m-xylene diamine into the mixture obtained after the reaction of S2, continuing the reaction for 1 hour, and cooling to 25 ℃ to obtain the anticorrosive agent.

Example 2

A concrete corrosion inhibitor prepared by the steps of:

s1: mixing 30 parts of phloroglucinol triglycidyl ether and 40 parts of trioctylamine ethyl ammonium hydroxide, heating to 60 ℃, and reacting for 3 hours;

s2: after the reaction of S1 is finished, adding 80 parts of trifunctional polyether polyol (Puranol G307), heating to 90 ℃, and continuing the reaction for 6 hours;

s3: and adding 20 parts of m-xylene diamine, 0.3 part of polydimethylsiloxane and 2 parts of chemnox 168 into the mixture obtained after the reaction of S2, continuing the reaction for 2 hours, and cooling to 25 ℃ to obtain the anticorrosive.

Example 3

A concrete corrosion inhibitor prepared by the steps of:

s1: mixing 40 parts of phloroglucinol triglycidyl ether and 30 parts of trioctylamine ethyl ammonium hydroxide, heating to 60 ℃, and reacting for 3 hours;

s2: after the reaction of S1 is finished, adding 80 parts of trifunctional polyether polyol (Puranol G306), heating to 110 ℃, and continuing the reaction for 4 hours;

s3: and adding 15 parts of m-xylene diamine into the mixture obtained after the reaction of S2, continuing the reaction for 1 hour, and cooling to 25 ℃ to obtain the anticorrosive agent.

Example 4

A concrete corrosion inhibitor prepared by the steps of:

s1: mixing 40 parts of phloroglucinol triglycidyl ether and 40 parts of trioctylamine ethyl ammonium hydroxide, heating to 80 ℃, and reacting for 2 hours;

s2: after the reaction of S1 is finished, adding 100 parts of trifunctional polyether polyol (Puranol G305), heating to 100 ℃, and continuing the reaction for 4 hours;

s3: and adding 10 parts of m-xylene diamine into the mixture obtained after the reaction of S2, continuing to react for 1 hour, adding 2 parts of chemnox 626 and 0.2 part of organosilicon defoaming agent, and cooling to 25 ℃ to obtain the corrosion inhibitor.

Comparative example 1

Replacement of formula I by formula Ia in comparison with example 1

Comparative example 2

Compared with example 1, formula II is replaced by formula IIa

Comparative example 3

Compared with example 1, formula II is replaced by formula IIb

The product of the invention forms a polymer film with the thickness of 300-500 mu m on the surface of a concrete product by a spraying mode. Its protective properties are derived from the hydrophobic and Cl-resistance properties of the product^-And sulfate corrosion capability.

The materials used were all those in accordance with the standard documents referred to below.

And the impermeability test is carried out by referring to the water absorption ratio (48h) in JC/T474 + 2008 mortar and concrete waterproofing agent, and after 28 days of curing, a polymer film with the thickness of 300 + 500 mu m is formed on the surface of a concrete product in a spraying mode for testing.

The water absorption ratio is equal to the water absorption of the concrete to be detected/the water absorption of the reference concrete 100%.

Water contact angle test: the measurement is carried out by using a contact angle measuring instrument, the measurement temperature is room temperature (20 ℃), the relative humidity is 60-70%, the size of the used water drop is 5 mu L, four points are selected for all samples to be measured, and the average value is taken as the size of the contact angle.

Peel Strength testing is described in GB/T2790-1995 Peel Strength test method Flexible vs. rigid materials.

The corrosion resistance test is carried out by referring to the compression strength ratio in JT/T1011-2006 concrete sulfate corrosion-resistant corrosion inhibitor, wherein the corrosion solution comprises the following components: NaCl 60g/L, MgSO₄ 4.8g/L，MgCl₂ 5.6g/L，CaSO₄2.4g/L，KHCO₃0.4g/L, after the sample is normally maintained for 28 days, a polymer film with the thickness of 300-500 mu m is formed on the surface of the concrete product in a spraying mode, the sample to be tested is moved into an erosion solution, the reference substance is soaked by clear water, and the compressive strength ratio of the 7 th day and the 28 th day of erosion is tested.

The compressive strength ratio is equal to the compressive strength of the concrete in the erosion liquid/the compressive strength of the standard concrete in the clear water is 100 percent

The test results are shown in Table 1.

TABLE 1 Experimental data for each sample

When the compressive strength ratio is less than 100%, which indicates that the concrete is affected by erosion, it can be seen that, as the erosion time increases in the products of comparative examples 1 to 3, the coating may be damaged, and the concrete is invaded by the erosion liquid, resulting in a decrease in the compressive strength ratio of the concrete, and the performance of the base cement without the coating is severely decreased, but the effect of the corrosion inhibitor provided by the present invention is not achieved.

Finally, it should be noted that the above-mentioned contents are only used for illustrating the technical solutions of the present invention, and not for limiting the protection scope of the present invention, and that the simple modifications or equivalent substitutions of the technical solutions of the present invention by those of ordinary skill in the art can be made without departing from the spirit and scope of the technical solutions of the present invention.