CN112626920A - Gas-phase antirust paper for galvanized sheet and preparation method thereof - Google Patents

Gas-phase antirust paper for galvanized sheet and preparation method thereof Download PDF

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Publication number
CN112626920A
CN112626920A CN202011466979.3A CN202011466979A CN112626920A CN 112626920 A CN112626920 A CN 112626920A CN 202011466979 A CN202011466979 A CN 202011466979A CN 112626920 A CN112626920 A CN 112626920A
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gas
phase
paper
fumed silica
reaction
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CN202011466979.3A
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Inventor
詹天荣
王磊
李文强
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Qingdao Xin Surplus Xin Packing Material Co ltd
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Qingdao Xin Surplus Xin Packing Material Co ltd
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    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H27/00Special paper not otherwise provided for, e.g. made by multi-step processes
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D295/00Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/16Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms
    • C07D295/20Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms by radicals derived from carbonic acid, or sulfur or nitrogen analogues thereof
    • C07D295/215Radicals derived from nitrogen analogues of carbonic acid
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00Coated paper; Coating material
    • D21H19/36Coatings with pigments
    • D21H19/38Coatings with pigments characterised by the pigments
    • D21H19/40Coatings with pigments characterised by the pigments siliceous, e.g. clays
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00Coated paper; Coating material
    • D21H19/36Coatings with pigments
    • D21H19/44Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
    • D21H19/46Non-macromolecular organic compounds
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/22Agents rendering paper porous, absorbent or bulky
    • D21H21/24Surfactants

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)

Abstract

An air phase antirust paper for galvanized plates and a preparation method thereof. The composite gas-phase slow-release layer comprises the following components in percentage by mass: 10-25% benzoic acid; 10-20% of sodium benzoate; 5-15% of monoethanolamine benzoate; 10-25% of benzotriazole; 10-30% of bipiperidinylmethyl urea; 5-30% of triethanolamine borate compound; 10-35% fumed silica. The compound vapor phase corrosion inhibitor is fully fused and interacted under the regulation of a nonionic surfactant triethanolamine borate; the fumed silica can be used as a support body of the vapor composite corrosion inhibitor, so that the specific surface area of the fumed silica is greatly improved, the fumed silica can be fully volatilized to the metal surface to form a protective film, and the vapor antirust performance can be better exerted through the synergistic effect.

Description

Gas-phase antirust paper for galvanized sheet and preparation method thereof
The technical field is as follows:
the invention relates to the field of nontoxic gas-phase antirust paper products suitable for galvanized sheet products, in particular to gas-phase antirust paper for galvanized sheet products and a preparation method thereof.
Background art:
the gas phase rust prevention technology is one of the important methods of non-contact rust prevention at present. It uses vapor phase Corrosion Inhibitor (VCI) to automatically volatilize gas at normal temperature to form a layer of protective film on the metal surface, thus inhibiting the generation of electrochemical reaction, and simultaneously blocking the Corrosion of some substances (such as water, oxygen and other acidic gases) which accelerate the Corrosion of the metal to the metal surface, thereby slowing down or preventing the Corrosion to the metal surface. Common packaging use forms are gas-phase rust preventive powder: placing a certain amount of vapor phase inhibitor in a packaging container or a sealed space; antirust paper: coating a vapor phase inhibitor on the base paper; gas-phase antirust film: the corrosion inhibitor is added to the plastic film. In the three using modes, the gas phase corrosion inhibitor continuously and slowly volatilizes through sublimation to form corrosion inhibitor gas, and the gas phase corrosion inhibitor gas diffuses to the surface of the metal and is communicated with the surface of the metal to form a molecular film through chemical bonds or adsorption, so that the corrosion on the surface of the metal is effectively inhibited.
The gas-phase antirust paper has a long history of being used for surface protection packaging of metal products, has the characteristics of non-contact antirust no dead angle, environmental friendliness, convenient use, cleanness and the like compared with the traditional antirust oil and water-soluble antirust liquid, and has been widely applied to the antirust corrosion of the production, transportation, storage and other links of metals and products thereof in recent years. In the effective chemical components used as the gas phase corrosion inhibitor at present, the nitroso-based corrosion inhibitor still occupies a great proportion, but researches have clearly shown that nitroso and secondary amine are easily converted into a strong carcinogen nitrosamine in organisms, and the waste gas phase antirust paper after being used can cause great pollution to the environment. On the other hand, part of the vapor phase corrosion inhibitor has a deliquescence phenomenon, can reduce the mechanical strength of the antirust packaging paper in the storage process, and is easily damaged by edges and corners of steel materials in the use process. Although researchers use a large amount of industrial modified zeolite to improve the performance of the anti-rust paper, the production of the industrial modified zeolite is harmful to the health of operators and pollutes the environment, and fire accidents easily occur, so that the safe production has potential risks. Furthermore, the use of industrially modified zeolites does not impose any particular requirements on their particle size, and they do not function as large as possible as a support for the dispersed vapor phase corrosion inhibitor. In addition, at present, the components in the formula of the gaseous corrosion inhibitor in most of the gaseous rust-proof paper are simply mixed physically or dissolved and mixed, and are connected with each other without proper surface active molecules, so that the components of the gaseous corrosion inhibitor cannot be completely fused with each other, and the gaseous rust-proof function of the gaseous corrosion inhibitor can be fully exerted. The gas phase antirust paper for some multi-metals cannot play a good role in a single metal product.
Therefore, the development and production of the gas phase antirust paper which has excellent antirust effect on galvanized sheet products, is environment-friendly and is simple and convenient to operate has important significance for solving the problem of corrosion in the process of storing and transporting metal products.
The nonionic surfactant can well link the components of the vapor phase corrosion inhibitor together, promote the mutual fusion of the components and fully exert the vapor phase corrosion inhibition performance of the components; meanwhile, the surface tension of the liquid can be greatly reduced, the wettability is enhanced, and the components of the vapor phase corrosion inhibitor are firmly and uniformly attached to the vapor phase anti-rust paper. The triethanolamine borate prepared by taking unsaturated acid, alcohol amine and boric acid which are abundant in natural resources as raw materials has a hydrophobic group and also contains a plurality of hydrophilic groups such as hydroxyl, amide and the like, so that the triethanolamine borate has high surface activity and strong wetting capability and has a dissolution promoting effect on organic gas phase molecules containing amino groups. More importantly, the amino and borate contained in the triethanolamine amine borate molecule can be used as an extreme pressure lubricant, a dispersion stabilizer, an adsorbent, an antirust agent and a wetting agent. However, their use as additives in gas-phase anti-rust paper technology has not been reported.
The invention content is as follows:
the invention aims to solve the defects in the prior art and provides gas-phase antirust paper for a galvanized plate and a preparation method thereof. Solves the problems of poor performance and environment generation of the gas phase antirust paper in use.
In order to solve the problems, the invention adopts the following technical scheme:
the gas-phase antirust paper for the galvanized plate is characterized by comprising a composite gas-phase slow-release layer and a raw paper layer, wherein the composite gas-phase slow-release layer comprises the following components in percentage by mass: 10-25% benzoic acid; 10-20% of sodium benzoate; 5-15% of monoethanolamine benzoate; 10-25% of benzotriazole; 10-30% of bipiperidinylmethyl urea; 5-30% of triethanolamine borate compound; 10-35% fumed silica;
the preparation method of the bipiperidine methyl urea compound comprises the following steps:
adding 10-30mL of formaldehyde solution with the concentration of 37% into a three-neck flask, slowly dripping 0.1-0.4mol of piperidine into a reaction bottle from a dropping funnel under the stirring condition of ice-water bath, and reacting for 0.5-1.0 hour under the same condition after finishing dripping; adding 0.05-0.2mol of urea into the reaction solution, changing the reaction into a reflux device, heating and refluxing for 5-30 minutes, naturally cooling after the reaction is finished, separating out crystals, performing suction filtration after the crystals are completely separated out, and recrystallizing a crude product by using ethanol to obtain the bipiperidine methylurea;
the preparation method of the gas-phase antirust paper for the galvanized plate comprises the following steps:
(a) adding a certain volume of deionized water into a reactor, heating to 40-60 ℃, sequentially adding benzoic acid, sodium benzoate, monoethanolamine benzoate, benzotriazole and bipiperidine methylurea which are components of the gas phase corrosion inhibitor according to mass percentage, and stirring and reacting after adding one component until the components are completely dissolved;
(b) adding the required amount of triethanolamine borate compound into the solution obtained in the step (a), stirring and reacting for half an hour at 40-60 ℃, and adjusting the pH to 8-9 by butyric acid or isobutanol amine;
(c) adding the required amount of fumed silica into the solution obtained in the step (b), stirring and reacting for 0.5-1 hour at 40-60 ℃ to fully and uniformly mix the reaction liquid, and naturally cooling to room temperature for later use;
(d) uniformly coating the dispersion liquid formed in the step (c) on fiber base paper, wherein the coating weight of the dispersion liquid on the fiber base paper is controlled to be 12 +/-2 g/cm2
The volume of deionized water in step (a) is such that the mass percentage of the gas phase slow release component in the dispersion formed in step (c) is between 15 and 40%.
Compared with the prior art, the invention has the outstanding characteristics and beneficial effects that:
the compound vapor phase corrosion inhibitor is dissolved in an aqueous medium step by step, various components are fully fused by utilizing multifunctional triethanolamine borate surfactant with extreme pressure lubrication, stable dispersion, adsorption, rust prevention, wetting and the like, and then the fumed silica is dispersed in the multifunctional triethanolamine borate surfactant to be used as a nano supporting substrate, so that the dispersibility and the vapor phase volatility of the vapor phase corrosion inhibitor in the anti-rust paper are improved, and a good vapor phase rust prevention effect is exerted. The invention does not relate to toxic or environment harmful substances, and belongs to an environment-friendly antirust product.
The specific implementation mode is as follows:
the present invention will be further understood in detail with reference to the following examples, but it should be understood that the scope of the present invention is limited only by the following examples. Various alterations and modifications made by those skilled in the art and conventional means without departing from the spirit of the invention are intended to be included within the scope of the invention.
Example 1:
the gas-phase antirust paper for the galvanized plate is characterized by comprising a composite gas-phase slow-release layer and a raw paper layer, wherein the composite gas-phase slow-release layer comprises the following components in percentage by mass: 15% benzoic acid; 13% sodium benzoate; 8% monoethanolamine benzoate; 20% of benzotriazole; 15% of bipiperidinylmethyl urea; 13% of a triethanolamine borate compound; 16% fumed silica;
the preparation method of the bipiperidine methyl urea compound comprises the following steps:
adding 18mL of formaldehyde solution with the concentration of 37% into a three-neck flask, slowly dripping 0.2mol of piperidine into a reaction bottle from a dropping funnel under the stirring condition of ice-water bath, and keeping the same condition for reacting for 0.5 hour after finishing dripping; adding 0.1mol of urea into the reaction solution, changing the reaction into a reflux device, heating and refluxing for 10 minutes, naturally cooling after the reaction is finished, separating out crystals, performing suction filtration after complete separation, and recrystallizing a crude product by using ethanol to obtain the bipiperidine methylurea;
the preparation method of the gas-phase antirust paper for the galvanized plate comprises the following steps:
(a) adding a certain volume of deionized water into a reactor, heating to 50 ℃, sequentially adding benzoic acid, sodium benzoate, monoethanolamine benzoate, benzotriazole and bipiperidine methylurea which are components of the gas phase corrosion inhibitor according to mass percentage, and stirring and reacting until the components are completely dissolved after each component is added;
(b) adding the required amount of triethanolamine borate compound into the solution obtained in the step (a), stirring and reacting for half an hour at 50 ℃, and adjusting the pH to be between 8 and 9 by using benzoic acid or monoethanolamine benzoate;
(c) adding the required amount of fumed silica into the solution obtained in the step (b), stirring and reacting for 0.5 hour at 50 ℃ to fully and uniformly mix the reaction liquid, and naturally cooling to room temperature for later use;
(d) uniformly coating the dispersion liquid formed in the step (c) on fiber base paper, wherein the coating weight of the dispersion liquid on the fiber base paper is controlled to be 10 +/-2 g/cm2
The volume of deionized water in step (a) is such that the mass percent of the gas phase extended release component in the dispersion formed in step (c) is 25%.
Example 2:
the gas-phase antirust paper for the galvanized plate is characterized by comprising a composite gas-phase slow-release layer and a raw paper layer, wherein the composite gas-phase slow-release layer comprises the following components in percentage by mass: 18% benzoic acid; 15% sodium benzoate; 10% monoethanolamine benzoate; 15% of benzotriazole; 12% bis-piperidine methylurea; 12% of a triethanolamine borate compound; 18% fumed silica;
the other steps are the same as in example 1.
Example 3:
the gas-phase antirust paper for the galvanized plate is characterized by comprising a composite gas-phase slow-release layer and a raw paper layer, wherein the composite gas-phase slow-release layer comprises the following components in percentage by mass: 13% benzoic acid; 12% sodium benzoate; 15% monoethanolamine benzoate; 16% benzotriazole; 15% of bipiperidinylmethyl urea; 16% of a triethanolamine borate compound; 13% fumed silica;
the other steps are the same as in example 1.
Example 4:
the gas-phase antirust paper for the galvanized plate is characterized by comprising a composite gas-phase slow-release layer and a raw paper layer, wherein the composite gas-phase slow-release layer comprises the following components in percentage by mass: 18% benzoic acid; 10% sodium benzoate; 10% monoethanolamine benzoate; 18% of benzotriazole; 18% of bipiperidinylmethyl urea; 15% of a triethanolamine borate compound; 11% fumed silica;
the other steps are the same as in example 1.
Comparative example 1:
the gas-phase antirust paper for the galvanized plate is characterized by comprising a composite gas-phase slow-release layer and a raw paper layer, wherein the composite gas-phase slow-release layer comprises the following components in percentage by mass: 13% benzoic acid; 12% sodium benzoate; 15% monoethanolamine benzoate; 16% benzotriazole; 15% of bipiperidinylmethyl urea; 13% fumed silica;
the other steps are the same as in example 1.
Comparative example 2:
the gas-phase antirust paper for the galvanized plate is characterized by comprising a composite gas-phase slow-release layer and a raw paper layer, wherein the composite gas-phase slow-release layer comprises the following components in percentage by mass: 13% benzoic acid; 12% sodium benzoate; 15% monoethanolamine benzoate; 16% benzotriazole; 15% of bipiperidinylmethyl urea; 16% of a triethanolamine borate compound;
the other steps are the same as in example 1.
Example 5 application effect test example
The gas phase rust preventive paper products obtained in examples 1, 2, 3 and 4 and comparative examples 1 and 2 were subjected to gas phase rust preventive treatment on galvanized sheets and their rust preventive properties were compared, and the test standards were referred to GB/T19532-:
Figure BDA0002834653170000041
the comparative test results in table 1 show that the rust inhibitive effect of the gas phase rust inhibitive paper of the present invention on various metals is better than that of comparative example 1 which does not contain triethanolamine borate additive and comparative example 2 which does not contain fumed silica nano support carrier, wherein the effect of example 1 is the best and is the preferred embodiment of the present invention. The gas-phase antirust paper has the selling price lower than one half of that of foreign similar products, has no toxic or side effect, does not pollute the environment, meets the requirements of national environmental protection standards, and can completely replace imported products. The analysis suggests that the gas phase corrosion inhibition mechanism of the compounds is as follows: on one hand, the compounded vapor phase corrosion inhibitor is fully fused and interacted under the regulation of a nonionic surfactant triethanolamine borate; on the other hand, the fumed silica is used as a support body of the fumed composite corrosion inhibitor, so that the specific surface area of the fumed silica is greatly improved, the fumed silica can be fully volatilized to the surface of metal, and the fumed rust-proof performance can be better exerted through the synergistic effect, wherein boric acid ester is contained in the molecules of the corrosion inhibitor; and N and O atoms in the molecule both contain lone-pair electrons, can form a coordination bond with a d electron empty orbit of Fe, and generate chemical adsorption; and the corrosion inhibition effect of organic salt in the compound corrosion inhibitor is added, so that the compound corrosion inhibitor forms a firm adsorption film on the metal surface to inhibit the contact of oxygen and water on the metal surface, and a good antirust effect is exerted.

Claims (1)

1. The gas-phase antirust paper for the galvanized plate is characterized by comprising a composite gas-phase slow-release layer and a raw paper layer, wherein the composite gas-phase slow-release layer comprises the following components in percentage by mass: 10-25% benzoic acid; 10-20% of sodium benzoate; 5-15% of monoethanolamine benzoate; 10-25% of benzotriazole; 10-30% of bipiperidinylmethyl urea; 5-30% of triethanolamine borate compound; 10-35% fumed silica;
the preparation method of the bipiperidine methyl urea compound comprises the following steps:
adding 10-30mL of formaldehyde solution with the concentration of 37% into a three-neck flask, slowly dripping 0.1-0.4mol of piperidine into a reaction bottle from a dropping funnel under the stirring condition of ice-water bath, and reacting for 0.5-1.0 hour under the same condition after finishing dripping; adding 0.05-0.2mol of urea into the reaction solution, changing the reaction into a reflux device, heating and refluxing for 5-30 minutes, naturally cooling after the reaction is finished, separating out crystals, performing suction filtration after the crystals are completely separated out, and recrystallizing a crude product by using ethanol to obtain the bipiperidine methylurea;
the preparation method of the gas-phase antirust paper for the galvanized plate comprises the following steps:
(a) adding a certain volume of deionized water into a reactor, heating to 40-60 ℃, sequentially adding benzoic acid, sodium benzoate, monoethanolamine benzoate, benzotriazole and bipiperidine methylurea which are components of the gas phase corrosion inhibitor according to mass percentage, and stirring and reacting after adding one component until the components are completely dissolved;
(b) adding the required amount of triethanolamine borate compound into the solution obtained in the step (a), stirring and reacting for half an hour at 40-60 ℃, and adjusting the pH to 8-9 by using benzoic acid or monoethanolamine benzoate;
(c) adding the required amount of fumed silica into the solution obtained in the step (b), stirring and reacting for 0.5-1 hour at 40-60 ℃ to fully and uniformly mix the reaction liquid, and naturally cooling to room temperature for later use;
(d) uniformly coating the dispersion liquid formed in the step (c) on fiber base paper, wherein the coating weight of the dispersion liquid on the fiber base paper is controlled to be 12 +/-2 g/cm2
The volume of deionized water in step (a) is such that the mass percentage of the gas phase slow release component in the dispersion formed in step (c) is between 15 and 40%.
CN202011466979.3A 2020-12-14 2020-12-14 Gas-phase antirust paper for galvanized sheet and preparation method thereof Withdrawn CN112626920A (en)

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CN115772822A (en) * 2022-12-12 2023-03-10 青岛科技大学 Gas-phase environment-friendly anti-rust paper for cast iron products and preparation method thereof

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CN104762623A (en) * 2014-12-30 2015-07-08 武汉江南铁依环保产业发展有限公司 Environment-friendly composite volatile corrosion inhibitor for galvanized steel sheet and preparation method thereof
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