阅读说明：本技术 可整体剥除或加热清除的免清洗防锈材料及制备与应用 (Cleaning-free antirust material capable of being stripped or cleaned by heating as well as preparation and application thereof ) 是由 林建明 陈海康 易德成 曹晓梅 于 2021-10-10 设计创作，主要内容包括：本发明属于新型涂层材料技术领域,公开了一种可整体剥除或加热清除的免清洗防锈材料及制备与应用。所述制备方法包括：将蜡性物质与一部分烷烃溶剂混合均质,得到乳状液A；将弹性树脂加入到另一部分烷烃溶剂中,搅拌条件下加入防锈剂、界面处理剂,搅拌至完全溶解,得到树脂溶液B；将乳状液A与树脂溶液B混合均质,然后加入表面活性剂、消泡剂均质搅拌,过滤,得到可整体剥除或加热清除的免清洗防锈材料。本发明的免清洗防锈材料通过特定的弹性树脂与蜡性物质复配,在使用后的成膜状态为半透明软膜,相比现有油膜或脆性漆膜,可以通过整张撕下或加热融化/挥发清除,无需化学溶剂或清洗剂清除,显著降低VOC排放及化学溶剂危害。(The invention belongs to the technical field of novel coating materials, and discloses a cleaning-free antirust material capable of being stripped or cleaned by heating as well as preparation and application thereof. The preparation method comprises the following steps: mixing and homogenizing a waxy substance and a part of alkane solvent to obtain an emulsion A; adding the elastic resin into the other part of alkane solvent, adding the antirust agent and the interface treating agent under the stirring condition, and stirring until the antirust agent and the interface treating agent are completely dissolved to obtain a resin solution B; and mixing and homogenizing the emulsion A and the resin solution B, then adding a surfactant and a defoaming agent, homogenizing and stirring, and filtering to obtain the cleaning-free antirust material which can be stripped or removed by heating integrally. The cleaning-free antirust material is prepared by compounding the specific elastic resin and the waxy substance, and the film-forming state after the cleaning-free antirust material is a semitransparent soft film.)

1. The preparation method of the cleaning-free antirust material capable of being stripped or removed by heating integrally is characterized by comprising the following preparation steps:

(1) mixing and homogenizing a waxy substance and a part of alkane solvent to obtain an emulsion A;

(2) adding the elastic resin into the other part of alkane solvent, adding the antirust agent and the interface treating agent under the stirring condition, and stirring until the antirust agent and the interface treating agent are completely dissolved to obtain a resin solution B;

(3) and mixing and homogenizing the emulsion A and the resin solution B, then adding a surfactant and a defoaming agent, homogenizing and stirring, and filtering to obtain the cleaning-free antirust material which can be stripped or removed by heating integrally.

2. The method for preparing a cleaning-free antirust material capable of being stripped off or removed by heating as claimed in claim 1, wherein said waxy substance in step (1) is at least one selected from polyethylene wax, microcrystalline paraffin, silicon wax and tree wax.

3. The method for preparing a cleaning-free and rust-proof material capable of being stripped off or removed by heating as claimed in claim 1, wherein the waxy substance in step (1) is selected from oil-soluble silicon wax.

4. The method for preparing a cleaning-free antirust material capable of being stripped off or removed by heating integrally according to claim 1, wherein the waxy substance in the step (1) is selected from silicone wax containing a cyclic polysiloxane structure, and is prepared by the following method:

adding alpha-olefin and 1,3,5, 7-tetramethylcyclotetrasiloxane into a solvent, stirring, dissolving, uniformly mixing, adding a chloroplatinic acid catalyst, heating to 60-130 ℃ to perform hydrosilylation, and evaporating the solvent and unreacted raw materials after the reaction is finished to obtain the silicon wax containing the cyclic polysiloxane structure.

5. The method for preparing a non-cleaning antirust material capable of being stripped or removed by heating as claimed in claim 4, wherein the molar ratio of the added alpha-olefin to 1,3,5, 7-tetramethylcyclotetrasiloxane is 1-5: 1.

6. The method for preparing a cleaning-free antirust material capable of being stripped off or removed by heating as claimed in claim 1, wherein in the step (2), the elastic resin is at least one selected from acrylic resin, shellac resin, modified rosin resin and polyurethane resin.

7. The method for preparing a no-clean antirust material capable of being stripped off or removed by heating as claimed in claim 1, wherein said antirust agent in step (2) is at least one selected from barium petroleum sulfonate, sodium petroleum sulfonate, dodecenyl succinic acid, barium dinonylnaphthalene sulfonate, calcium petroleum sulfonate and calcium dinonylnaphthalene sulfonate; the interface treating agent is selected from at least one of low molecular methyl siloxane, ethyl siloxane, aminosiloxane and cyclosiloxane with the molecular weight of 200-5000; in the step (3), the surfactant is selected from at least one of sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester and fatty alcohol-polyoxyethylene ether; the defoaming agent is at least one of a silicon defoaming agent or a polyether defoaming agent.

8. The method for preparing the non-cleaning antirust material capable of being stripped or removed by heating as claimed in any one of claims 1 to 7, wherein the raw materials comprise the following components in percentage by mass: 5 to 10 percent of elastic resin, 1 to 12 percent of waxy substance, 65 to 85 percent of alkane solvent, 3 to 10 percent of antirust agent, 0.5 to 2.0 percent of surfactant, 0.1 to 0.5 percent of defoaming agent and 0.2 to 1.0 percent of interface treating agent.

9. A non-cleaning antirust material capable of being stripped or removed by heating in its entirety, which is prepared by the method according to any one of claims 1 to 8.

10. The use of the non-cleaning antirust material of claim 9 in the antirust treatment of metal products is characterized in that the application process comprises the following steps: soaking, brushing or spraying the cleaning-free antirust material on the surface of a metal product, drying and curing to obtain an antirust coating; when the metal product is used in the next working procedure, the antirust coating is removed by tearing or heating the whole sheet.

Technical Field

The invention belongs to the technical field of novel coating materials, and particularly relates to a cleaning-free antirust material capable of being stripped or cleaned by heating as well as preparation and application thereof.

Background

The metal corrosion problem is distributed in various industries of national economy, and the metal corrosion can greatly damage the performance and the commodity value of metal products and even cause major faults to scrap equipment. To avoid corrosion, various techniques and methods have been used to prevent corrosion of metals. Among them, the protection of metal products with rust preventive oil is one of the most common protection methods at present.

The wax film antirust oil is one kind of antirust oil, and the wax film antirust oil is solvent diluted antirust oil comprising film forming agent, efficient corrosion inhibitor and base oil. Compared with other types of anti-rust oil, the wax film oil has the characteristics of thin oil film, good anti-rust property, beautiful coating and the like. The antirust protective film containing wax can be obtained by adding some oil-soluble wax into solvent-diluted antirust oil or ultrathin layer antirust oil, and the salt mist resistance and atmospheric resistance of the oil film can be obviously improved. However, the wax is solid or semi-solid at normal temperature, is very easy to precipitate in the oil product, affects the appearance and quality of the oil product, and even is difficult to obtain an ideal antirust effect, so that the key for obtaining the wax-containing antirust oil with good stability and uniform film formation is to find the wax with good oil solubility and capable of obviously improving the antirust property. In addition, the existing wax film antirust oil is generally required to be removed by a chemical solvent after being used, so that VOC (volatile organic compounds) emission and chemical solvent damage are increased.

Patent CN102876095A discloses a wax film antirust oil, which comprises the following components in percentage by mass: film forming material sixteen, octadecenyl succinic acid amide 10-21%, oil soluble corrosion inhibitor 10-20%, diluting solvent 60-79%. The wax film antirust oil is easy to clean in the next working procedure by adopting hexadecenyl and octadecenyl succinic acid amide as a main film forming material, and the material is easy to emulsify, so that the wax film antirust oil can be cleaned cleanly by using high-pressure warm water. In addition, the hexadecyl-octadecenyl succinic acid amide has certain antirust performance, and an oil-soluble corrosion inhibitor with proper mass percentage is added, so that the comprehensive performance is exerted, and the antirust period is prolonged. However, the antirust oil can be cleaned by using high-pressure warm water, and the humidity and heat resistance of the antirust oil is insufficient, so that the antirust oil cannot be used under the humidity and heat conditions.

Patent CN 104312699A discloses an environment-friendly thixotropic antirust oil, which is composed of the following raw materials in parts by weight: 57-65 parts of paraffin-based base oil, 9-16 parts of naphthenic base oil, 6-11 parts of alkyl high-boiling-point substance base oil, 5-10 parts of barium-free antirust agent, 1-4 parts of thixotropic agent, 0.2-0.5 part of phenolic antioxidant, 0.1-0.5 part of anilino antioxidant, 0.2-1 part of olefine acid antioxidant and 2-3 parts of film-forming additive. The anti-rust oil has excellent high temperature resistance, damp and heat resistance, high salinity salt mist corrosion resistance and excellent anti-rust performance; the coating has better voltage resistance and is convenient for electrostatic spraying; has good cleaning performance, and the antirust oil film can be easily removed by using a neutral or alkaline water-based cleaning agent. But the durability of the rust preventive oil is to be further improved.

Patent CN105296080A discloses a wax film antirust agent, which selects wax substances as film forming substances, can effectively improve the thickness of an oil film, has good adhesiveness and is not easy to sag during construction, and an antirust wax film not only has hydrophobicity, but also has good compactness and toughness, thereby prolonging the antirust time of the antirust wax film; the petroleum solvent is used as carrier, and the antirust additive and mechanical oil are added to enhance the antirust performance. The rust-proof wax film layer formed by the rust inhibitor product can be easily removed by using a hydrocarbon solvent. But still increases VOC emissions and chemical solvent hazards.

Patent CN 105778702 a discloses a high-strength wear-resistant anti-rust paint, which comprises rosin phenol formaldehyde resin, modified polyurethane, styrene-acrylic emulsion, polyvinyl chloride resin, epoxy resin, rosin resin, epoxy resin, alkyd resin, butyl acetate, aluminum hydroxide, bentonite, barite powder, mica powder, zeolite powder, chlorinated paraffin, calcium ferrite, hexamethyl cellulose, citric acid and curing agent. The paint has high strength, good wear resistance and strong corrosion resistance. However, the paint is mainly used for long-term protection, is formed into a film which is brittle and is difficult to clean, needs to be cleaned, and is completely different from the application mode and the performance requirement of the traditional wax film antirust oil.

Disclosure of Invention

Aiming at the defects and shortcomings of the prior art, the invention aims to provide a preparation method of a cleaning-free antirust material which can be stripped or removed by heating. The cleaning-free antirust material is prepared by compounding the specific elastic resin and the waxy substance, and the film-forming state after the cleaning-free antirust material is a semitransparent soft film.

The invention also aims to provide the cleaning-free antirust material prepared by the method.

Still another object of the present invention is to provide the use of the above-mentioned cleaning-free antirust material in antirust treatment of metal products.

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

a preparation method of a cleaning-free antirust material capable of being stripped or removed by heating integrally comprises the following preparation steps:

(1) mixing and homogenizing a waxy substance and a part of alkane solvent to obtain an emulsion A;

(2) adding the elastic resin into the other part of alkane solvent, adding the antirust agent and the interface treating agent under the stirring condition, and stirring until the antirust agent and the interface treating agent are completely dissolved to obtain a resin solution B;

(3) and mixing and homogenizing the emulsion A and the resin solution B, then adding a surfactant and a defoaming agent, homogenizing and stirring, and filtering to obtain the cleaning-free antirust material which can be stripped or removed by heating integrally.

Further, the waxy substance in the step (1) is selected from at least one of polyethylene wax, microcrystalline paraffin, silicon wax and tree wax.

Further preferably, the waxy material in step (1) is selected from oil-soluble silicone waxes. The oil-soluble silicone wax is a long-carbon paraffin modified organic silicon polymer, and has high stability of a polysiloxane structure and good compatibility with grease. According to the difference of molecular weight, the appearance of the product can be light yellow transparent liquid or white solid, and the melting point is about-44-30 ℃. Compared with other wax substances, the oil-soluble silicon wax adopted by the invention has better salt spray corrosion resistance and damp and heat resistance.

Still more preferably, the waxy material in step (1) is selected from silicone waxes containing a cyclic polysiloxane structure, which are prepared by the following method:

adding alpha-olefin and 1,3,5, 7-tetramethylcyclotetrasiloxane (D4H) into a solvent, stirring, dissolving, uniformly mixing, adding a chloroplatinic acid catalyst, heating to 60-130 ℃ to perform hydrosilylation, and evaporating the solvent and unreacted raw materials after the reaction is finished to obtain the silicon wax containing the cyclic polysiloxane structure.

Further, the molar ratio of the alpha-olefin to the D4H is 1-5: 1.

Compared with the common chain polysiloxane structure silicone wax, the cleaning-free antirust material has the advantages that the storage stability of the cleaning-free antirust material and the heating removal efficiency after use can be obviously enhanced.

Further, the alkane solvent in the step (1) and the step (2) is at least one of straight-chain alkane and isoparaffin.

Further, the elastic resin in the step (2) is at least one selected from acrylic resin, shellac resin, modified rosin resin and polyurethane resin.

Further, in the step (2), the rust inhibitor is at least one selected from barium petroleum sulfonate (T701), sodium petroleum sulfonate (T702), dodecenylsuccinic acid (T746), barium dinonylnaphthalene sulfonate (T705), calcium petroleum sulfonate (T101, T102, T103) and calcium dinonylnaphthalene sulfonate (T705C).

Further, the interface treating agent in the step (2) is at least one selected from low molecular methyl siloxane, ethyl siloxane, amino siloxane and cyclosiloxane with the molecular weight of 200-5000.

Further, in the step (3), the surfactant is selected from at least one of sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester and fatty alcohol-polyoxyethylene ether.

Further, the defoaming agent in the step (3) is at least one of a silicon defoaming agent or a polyether defoaming agent.

Further, in the preparation method, the raw materials comprise the following components in percentage by mass: 5 to 10 percent of elastic resin, 1 to 12 percent of waxy substance, 65 to 85 percent of alkane solvent, 3 to 10 percent of antirust agent, 0.5 to 2.0 percent of surfactant, 0.1 to 0.5 percent of defoaming agent and 0.2 to 1.0 percent of interface treating agent.

Further, in the above preparation method, an oily dye may be optionally added to distinguish the film formation.

The cleaning-free antirust material capable of being stripped or removed by heating is prepared by the method.

The application of the cleaning-free antirust material in the antirust treatment of the metal product comprises the following application processes: soaking, brushing or spraying the cleaning-free antirust material on the surface of a metal product, drying and curing to obtain an antirust coating; when the metal product is used in the next working procedure, the antirust coating is removed by tearing or heating the whole sheet.

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

(1) the cleaning-free antirust material is prepared by compounding the specific elastic resin and the waxy substance, and the film-forming state after the cleaning-free antirust material is a semitransparent soft film.

(2) Compared with other wax substances, the oil-soluble silicon wax further has better salt mist corrosion resistance and damp and heat resistance.

(3) The invention further adopts the silicon wax containing the cyclic polysiloxane structure, so that the storage stability of the cleaning-free antirust material and the heating removal efficiency after use can be obviously enhanced.

Detailed Description

The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.

Example 1

The cleaning-free antirust material capable of being stripped or removed by heating integrally comprises the following components in percentage by mass: 5% of acrylic resin, 5% of polyethylene wax, 85% of isopentane solvent, T7023% of antirust agent, 1% of fatty alcohol-polyoxyethylene ether, 0.5% of GP-type glycerol polyether defoaming agent and 0.5% of low-viscosity methyl silicone oil (molecular weight is about 600). The cleaning-free antirust material is prepared by the following method:

(1) and mixing and homogenizing the polyethylene wax and a part of isopentane solvent to obtain emulsion A.

(2) Adding acrylic resin into the other part of isopentane solvent, adding antirust agent T702 and low-viscosity methyl silicone oil as an interface treatment agent under the stirring condition, and stirring until the mixture is completely dissolved to obtain resin solution B.

(3) And mixing and homogenizing the emulsion A and the resin solution B, then adding the surfactant fatty alcohol-polyoxyethylene ether and the GP-type glyceryl polyether defoaming agent, homogenizing and stirring, and filtering to obtain the cleaning-free antirust material which can be stripped or removed by heating integrally.

The appearance of the cleaning-free antirust material obtained in the embodiment is milk white liquid, and the film forming state is white semitransparent soft film (the cleaning-free antirust material is sprayed on the surface of a 45# steel product test sample, dried and cured to obtain an antirust film layer). The resulting flexible film was removed by tearing the whole sheet with a salt spray time of >24 hours.

Example 2

The cleaning-free antirust material capable of being stripped or removed by heating integrally comprises the following components in percentage by mass: 10% of shellac resin, 12% of oil-soluble silicone wax (commercially available, alkyl dimethyl polysiloxane), 70% of n-hexane solvent, 1015% of antirust agent T, 1.5% of sorbitan fatty acid ester, 0.5% of GP type glycerol polyether defoamer and 1% of low-viscosity amino silicone oil (molecular weight of about 800). The cleaning-free antirust material is prepared by the following method:

(1) and mixing and homogenizing the oil-soluble silicon wax and a part of n-hexane solvent to obtain an emulsion A.

(2) And adding the shellac resin into the other part of the n-hexane solvent, adding the antirust agent T101 and the low-viscosity amino silicone oil serving as the interface treating agent under the stirring condition, and stirring until the shellac resin and the low-viscosity amino silicone oil are completely dissolved to obtain a resin solution B.

(3) And mixing and homogenizing the emulsion A and the resin solution B, then adding a surfactant sorbitan fatty acid ester and a GP type glycerol polyether defoaming agent, homogenizing and stirring, and filtering to obtain the cleaning-free antirust material which can be stripped or removed by heating integrally.

The appearance of the cleaning-free antirust material obtained in the embodiment is milky white liquid, the film-forming state is a beige semitransparent soft film, the film-forming state can be removed by tearing the whole sheet, and the salt spray time is more than 24 hours (45# steel).

Example 3

The cleaning-free antirust material capable of being stripped or removed by heating integrally comprises the following components in percentage by mass: 6% of shellac resin, 5% of oil-soluble silicone wax (commercially available, alkyl dimethyl polysiloxane), 70% of n-hexane, 10% of C10-C12 isoparaffin, 705C 6% of antirust agent, 1.5% of polyoxyethylene sorbitan fatty acid ester, 0.5% of polyether organic silicon defoamer and 1% of cyclopenta dimethyl siloxane. The cleaning-free antirust material is prepared by the following method:

(1) and mixing and homogenizing the oil-soluble silicon wax and a part of mixed solvent of normal hexane and isoparaffin to obtain emulsion A.

(2) Adding the shellac resin into the other part of the mixed solvent of n-hexane and isoparaffin, adding the antirust agent T705C and the interfacial treatment agent cyclopenta dimethyl siloxane under stirring, and stirring until the materials are completely dissolved to obtain a resin solution B.

(3) And mixing and homogenizing the emulsion A and the resin solution B, then adding a surfactant polyoxyethylene sorbitan fatty acid ester and a polyether organic silicon defoaming agent, homogenizing and stirring, and filtering to obtain the cleaning-free antirust material which can be removed integrally or removed by heating.

The appearance of the cleaning-free antirust material obtained in the embodiment is milk white liquid, and the film-forming state is a beige semitransparent soft film which can be removed by tearing the whole sheet.

Example 4

The cleaning-free antirust material capable of being stripped or removed by heating integrally comprises the following components in percentage by mass: 6% of shellac resin, 5% of silicone wax (self-made) containing a cyclic polysiloxane structure, 70% of normal hexane, 10% of C10-C12 isoparaffin, 705C 6% of antirust agent, 1.5% of polyoxyethylene sorbitan fatty acid ester, 0.5% of polyether organic silicon defoamer and 1% of cyclopenta dimethyl siloxane. The cleaning-free antirust material is prepared by the following method:

(1) adding 1-decene and 1,3,5, 7-tetramethylcyclotetrasiloxane (D4H) into an isopropanol solvent according to the molar ratio of 4:1, stirring, dissolving and uniformly mixing, then adding an isopropanol solution catalyst of chloroplatinic acid, heating and refluxing to perform hydrosilylation, and evaporating the isopropanol solvent and unreacted raw materials after the reaction is finished to obtain the silicon wax containing a cyclic polysiloxane structure.

(2) And mixing and homogenizing silicon wax containing a cyclic polysiloxane structure and a part of mixed solvent of n-hexane and isoparaffin to obtain emulsion A.

(3) Adding the shellac resin into the other part of the mixed solvent of n-hexane and isoparaffin, adding the antirust agent T705C and the interfacial treatment agent cyclopenta dimethyl siloxane under stirring, and stirring until the materials are completely dissolved to obtain a resin solution B.

(4) And mixing and homogenizing the emulsion A and the resin solution B, then adding a surfactant polyoxyethylene sorbitan fatty acid ester and a polyether organic silicon defoaming agent, homogenizing and stirring, and filtering to obtain the cleaning-free antirust material which can be removed integrally or removed by heating.

The appearance of the cleaning-free antirust material obtained in the embodiment is milk white liquid, and the film-forming state is a beige semitransparent soft film which can be removed by tearing the whole sheet.

Example 5

The cleaning-free antirust material capable of being stripped or removed by heating integrally comprises the following components in percentage by mass: 6% of shellac resin, 5% of microcrystalline paraffin, 70% of n-hexane, 10% of C10-C12 isoparaffin, 705C 6% of antirust agent, 1.5% of polyoxyethylene sorbitan fatty acid ester, 0.5% of polyether organic silicon defoamer and 1% of cyclopenta dimethyl siloxane. The cleaning-free antirust material is prepared by the following method:

(1) and mixing and homogenizing the microcrystalline paraffin and a part of mixed solvent of n-hexane and isoparaffin to obtain the emulsion A.

(2) Adding the shellac resin into the other part of the mixed solvent of n-hexane and isoparaffin, adding the antirust agent T705C and the interfacial treatment agent cyclopenta dimethyl siloxane under stirring, and stirring until the materials are completely dissolved to obtain a resin solution B.

(3) And mixing and homogenizing the emulsion A and the resin solution B, then adding a surfactant polyoxyethylene sorbitan fatty acid ester and a polyether organic silicon defoaming agent, homogenizing and stirring, and filtering to obtain the cleaning-free antirust material which can be removed integrally or removed by heating.

The appearance of the cleaning-free antirust material obtained in the embodiment is milk white liquid, and the film-forming state is a beige semitransparent soft film which can be removed by tearing the whole sheet.

The storage stability (standing in an incubator at 40 ℃ for 6 months and observing whether precipitation or delamination occurs) and the salt spray corrosion resistance (GB/T10125-:

TABLE 1

	Example 3	Example 4	Example 5
				Stability of	Slight precipitation	Without precipitation or delamination	Without precipitation or delamination
Resistance to salt spray corrosion	76h	72h	50h
				Moisture and heat resistance	380h	366h	215h
Efficiency of cleaning	19min	6min	12min

As can be seen from the results in Table 1, the cleaning-free antirust materials obtained by the invention all have good antirust effect. Compared with other wax substances, the oil-soluble silicon wax has better salt mist corrosion resistance and damp and heat resistance, but the stability and the heating and removing efficiency are reduced to a certain extent. The silicon wax containing the cyclic polysiloxane structure can overcome the defects of common oil-soluble silicon wax, and can remarkably enhance the storage stability and heating removal efficiency of the antirust material while keeping a good antirust effect.

The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.