A spot-resistant rust preventive oil complex composition and a method for preparing the same

Abstract

The application discloses an anti-spotting and anti-rust oil composite agent composition and a preparation method thereof, wherein components and contents of the anti-spotting and anti-rust oil composite agent composition are as follows in percentage by mass: composite calcium anti-rust agent 5-40%; barium sulfonate anti-rust agent 20-70%; organic carboxylic acid anti-rust agent 5-20%; film forming agent 5-20%; non-ferrous metal corrosion inhibitor 0.1-3%; antioxidant 0.3-1.0%; cosolvent 5-15%; base oil 5-15%. The anti-spotting and anti-rust oil composite agent composition provided by the application has excellent anti-spotting performance while keeping the salt spray resistance and the damp heat resistance from being reduced.

Description

Technical Field

[0001] This invention relates to an anti-stain and anti-rust oil composite composition and its preparation method. Background Technology

[0002] Barium sulfonate, as a representative of sulfonate rust inhibitors, is the earliest and most widely used rust inhibitor in China. It exhibits excellent rust prevention properties, superior water displacement, salt spray resistance, and damp heat resistance, providing excellent rust prevention for various metals. Its effectiveness is even more pronounced when combined with other types of rust inhibitors. Technicians have developed various rust-preventive oil composite compositions using barium sulfonate as the main component.

[0003] Patent CN103305317A discloses a metal rust-inhibiting composite agent containing oil-soluble polyaniline and its application. This patent combines barium petroleum sulfonate with oil-soluble polyaniline and dodecenylsuccinic acid to prepare a rust-inhibiting oil composite composition. This composite agent exhibits good solubility, no phase separation, and a uniform and stable solution system. It can be formulated into lubricating oil-type rust-inhibiting oil, solvent-diluted rust-inhibiting oil without film-forming agents, or hard-film rust-inhibiting oil. The resulting rust-inhibiting oil has a low total dosage, low viscosity, and good rust-inhibiting effect, especially outstanding salt spray resistance. When the total dosage of the rust-inhibiting composite agent is less than 9%, the salt spray rust prevention period of the formulated lubricating oil-type rust-inhibiting oil, solvent-diluted rust-inhibiting oil without film-forming agents, and hard-film rust-inhibiting oil are greater than 6 days, greater than 11 days, and greater than 31 days, respectively, and the wet heat rust prevention period is greater than 60 days for all three.

[0004] Patent CN103965994 discloses a no-clean rust-preventive oil composite additive and its preparation method. The invention comprises 5-20% benzotriazole, 10-45% heptadecanyl imidazoline succinic acid ammonium salt, 10-45% barium petroleum sulfonate, 15-55% low-alkalinity calcium petroleum sulfonate, 15-55% zinc didecyl thiamethoxam sulfonate, and 5-15% diluent oil. Adding the above composition to the corresponding base oil in a certain proportion yields a film-film rust-preventive oil, which can satisfy both the purpose of sealing and preventing rust and the purpose of preventing rust between machining processes. Because this rust-preventive composite additive has good compatibility and is a film-film rust preventive, it can achieve no-clean assembly.

[0005] Patent CN110343561 uses alkyl sulfonates, alkenyl succinic acid, sorbitan oleate, methyl benzotriazole or benzotriazole, polymeric film-forming agents, base oils, and antioxidant BHT as raw materials. It utilizes the positive synergistic effect between the raw materials to fully leverage the functional potential of each raw material and formulate a rust-preventive oil composite additive that simultaneously possesses excellent salt spray resistance and humid heat resistance.

[0006] Patent CN112500913 discloses a high-efficiency rust-preventive oil composite composition and its preparation method. The high-efficiency rust-preventive oil composite composition comprises the following components in parts by weight: 30-35 parts barium petroleum sulfonate, 30-35 parts dinonylnaphthalene sulfonate, 18-23 parts dodecenylsuccinic acid, 1-5 parts benzotriazole, 0.5-1 part antioxidant, and 10-15 parts film-forming agent. Through the technical solution of this invention, the raw materials for the prepared high-efficiency rust-preventive oil composite composition are relatively common, and after being formulated into a rust-preventive oil, it can give the workpiece excellent resistance to salt spray and damp heat.

[0007] Barium sulfonate has excellent rust-preventive properties, but it is prone to staining in some situations, especially when workpieces are stacked, the stains are more obvious. Summary of the Invention

[0008] To improve the problem of stains on workpieces, this invention provides an anti-stain and rust-preventive oil composite composition and its preparation method, as follows:

[0009] In a first aspect, the present invention provides an anti-stain and rust-preventive oil composite composition, wherein the components and contents of the anti-stain and rust-preventive oil composite composition are as follows, by mass percentage:

[0010] Compound calcium acid rust inhibitor 5-40%;

[0011] Barium sulfonate rust inhibitor 20-70%;

[0012] Organic carboxylic acid rust inhibitors: 5-20%;

[0013] Film-forming agent 5-20%;

[0014] Non-ferrous metal corrosion inhibitor 0.1-3%;

[0015] Antioxidant 0.3-1.0%;

[0016] 5-15% co-solvent;

[0017] Base oil 5-15%.

[0018] In one or more preferred embodiments, the components and contents of the anti-stain and anti-rust oil composite composition, by mass percentage, are as follows:

[0019] Compound calcium acid rust inhibitor 7-35%;

[0020] Barium sulfonate rust inhibitor 25-65%;

[0021] Organic carboxylic acid rust inhibitors: 7-15%;

[0022] Film-forming agent 7-15%;

[0023] Non-ferrous metal corrosion inhibitor 0.3-2.5%;

[0024] Antioxidant 0.5-0.8%;

[0025] Cosolvent 7-12%;

[0026] Base oil content: 7-12%.

[0027] In one or more optional embodiments, the composite calcium acid rust inhibitor has the structural formula [(DNNSA)]. x (FA) y (PIBSA) z ]2·Ca, where DNNSA is dinonylnaphthalenesulfonic acid, FA is a monobasic fatty acid, PIBSA is polyisobutylene succinic anhydride, x+y+z=1, x=0.5~0.9, y=0~0.5, z=0~0.5.

[0028] In one or more optional embodiments, the FA is one or more of caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid or oleic acid in any proportion.

[0029] In one or more alternative embodiments, the PIBSA is an additive intermediate prepared by reacting highly reactive polyisobutylene with a molecular weight of 1000 or 1300 with maleic anhydride.

[0030] In one or more optional embodiments, the barium sulfonate rust inhibitor is at least one of petroleum barium sulfonate, neutral dinonylnaphthalene sulfonate, and basic dinonylnaphthalene sulfonate.

[0031] In one or more optional embodiments, the organic carboxylic acid rust inhibitor is at least one of dodecenyl succinic acid, dodecenyl succinic acid half ester, and N-oleoyl sarcosine.

[0032] In one or more optional embodiments, the film-forming agent is at least one of petrolatum, paraffin wax, oxidized paraffin wax, oil-soluble asphalt, ethylene-propylene copolymer, methacrylate copolymer, polyisobutylene, hydrogenated styrene diene copolymer, lanolin, and lanolin soap.

[0033] In one or more optional embodiments, the non-ferrous metal corrosion inhibitor is at least one of benzotriazole, methylbenzotriazole, sodium benzotriazole, and sodium methylbenzotriazole.

[0034] In one or more optional embodiments, the antioxidant is at least one of phenolic antioxidants and amine antioxidants.

[0035] In one or more alternative embodiments, the co-solvent is Span 80 or diethylene glycol monobutyl ether.

[0036] In one or more alternative embodiments, the base oil is at least one of industrial white oil, mineral oil, synthetic oil, and recycled oil.

[0037] Secondly, the present invention also provides a method for preparing the aforementioned anti-stain and anti-rust oil composite composition, the method comprising:

[0038] Heat and stir the base oil at 60-70°C, add film-forming agent and antioxidant, stir at high speed for 0.5-2 hours, then add barium sulfonate rust inhibitor, compound calcium acid rust inhibitor, organic carboxylic acid rust inhibitor, non-ferrous metal corrosion inhibitor and co-solvent in sequence, and stir at high speed at 50-60°C for 1-3 hours.

[0039] The anti-stain and anti-rust oil composite composition provided by the present invention has the characteristics of good oil solubility and strong adaptability. While maintaining the anti-salt spray performance and anti-damp heat performance, it has excellent anti-stain performance. Detailed Implementation

[0040] The following provides a detailed description of the embodiments of the present invention: These embodiments are implemented based on the technical solution of the present invention, and provide detailed implementation methods and processes. However, the scope of protection of the present invention is not limited to the following embodiments. Process parameters not specified in the following embodiments are generally performed under conventional conditions.

[0041] The endpoints and any values ​​of the ranges disclosed in this invention are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed in this invention.

[0042] The following provides a detailed description of various specific embodiments of the anti-stain and anti-rust oil composite composition and its preparation method provided in the embodiments of the present invention.

[0043] Example 1

[0044] Preparation of composite calcium acid rust inhibitor:

[0045] Step (1) Add 91.6g of n-heptane and 4.2g of deionized water to a 500ml three-necked flask equipped with a reflux condenser, and then add 78.2g of dinonylnaphthalenesulfonic acid (DNNSA), 3.5g of n-decanoic acid (hereinafter referred to as FA) and 10.0g of polyisobutylene succinic anhydride (PIBSA) in sequence to obtain an acidic mixture;

[0046] Step (2) Turn on the magnetic stirrer, heat the acidic mixture to 70±5℃, and then slowly add 7.4g of calcium hydroxide to neutralize the mixture. Pay attention to the addition rate of calcium hydroxide, so that the foam formed does not overflow into the reflux tube.

[0047] Step (3) React under reflux for about 3 hours, add 91.6g of Dalian 150SN base oil, slowly heat to 150±5℃ to remove solvent, and after no solvent flows out, reduce pressure to 1-3kPa and continue distillation. After the solution stops boiling and no solvent flows out, the composite calcium acid rust inhibitor [(DNNSA)] is obtained. 0.85 (FA) 0.05 (PIBSA) 0.1 ]2·Ca, with a yield of 99.2%, this composite calcium acid rust inhibitor is a brown viscous liquid.

[0048] Preparation of rust-preventive oil composite composition:

[0049] Liaohe No. 10 base oil was heated and stirred at 60-70℃, and petrolatum and 4,4-methylene (2,6-di-tert-butylphenol) were added. The mixture was stirred at high speed for 0.5-2 hours. Then, barium petroleum sulfonate, compound calcium acid rust inhibitor, dodecenyl succinic acid, benzotriazole and diethylene glycol monobutyl ether were added in sequence. The mixture was stirred at high speed at 50-60℃ for 1-3 hours to obtain the rust-inhibiting oil composite composition. The components and contents (by mass percentage) of the rust-inhibiting oil composite composition are shown in Table 1.

[0050] Table 1. Components and content of the anti-staining and anti-rust oil composite composition in Example 1

[0051] Components content(%) Barium petroleum sulfonate 70 Compound calcium acid rust inhibitor 5 Dodecenyl succinic acid 5 Vaseline 5 benzotriazole 0.3 4,4-Methylene(2,6-di-tert-butylphenol) 0.3 Diethylene glycol monobutyl ether 5 Liaohe No. 10 9.4

[0052] Comparative Example 1

[0053] Similar to Example 1, except that the composite calcium acid rust inhibitor in Example 1 is replaced with barium petroleum sulfonate.

[0054] Example 2

[0055] Preparation of composite calcium acid rust inhibitor: same as in Example 1.

[0056] Preparation of rust-preventive oil composite composition:

[0057] HVI150 was heated and stirred at 60-70℃, and then oxidized paraffin and 2,6-di-tert-butyl-p-cresol were added. The mixture was stirred at high speed for 0.5-2 hours. Then, neutral dinonylnaphthalenesulfonate barium, compound calcium acid rust inhibitor, dodecenyl succinate half ester, benzotriazole and Span 80 were added in sequence. The mixture was stirred at high speed at 50-60℃ for 1-3 hours to obtain the rust-preventive oil composite composition. The components and contents (by mass percentage) of the rust-preventive oil composite composition are shown in Table 2.

[0058] Table 2. Components and content of the anti-staining and anti-rust oil composite composition in Example 2

[0059] Components Quality fraction (%) Neutral dinonylnaphthalenesulfonate barium 20 Compound calcium acid rust inhibitor 40 Dodecenyl succinate half-ester 10 Oxidized paraffin 8.9 benzotriazole 0.1 2,6-Di-tert-butyl-p-cresol 1 Sipan 80 5 HVI150 15

[0060] Comparative Example 2

[0061] Similar to Example 2, except that the composite calcium acid rust inhibitor in Example 2 is replaced with neutral dinonylnaphthalene sulfonate barium.

[0062] Example 3

[0063] Preparation of composite calcium acid rust inhibitor: same as in Example 1.

[0064] Preparation of rust-preventive oil composite composition:

[0065] The No. 20 transformer oil was heated and stirred at 60-70℃, lanolin and N-phenyl-α-naphthylamine were added, and the mixture was stirred at high speed for 0.5-2 hours. Then, alkaline dinonylnaphthalenesulfonate barium, compound calcium acid rust inhibitor, N-oleoylsarcosine, benzotriazole sodium salt and Span 80 were added in sequence. The mixture was stirred at high speed at 50-60℃ for 1-3 hours to obtain the rust-inhibiting oil composite composition. The components and contents (by mass percentage) of the rust-inhibiting oil composite composition are shown in Table 3.

[0066] Table 3. Components and content of the anti-staining and anti-rust oil composite composition in Example 3

[0067]

[0068]

[0069] Comparative Example 3

[0070] Similar to Example 3, except that the composite calcium acid rust inhibitor in Example 3 is replaced with alkaline dinonylnaphthalene sulfonate barium.

[0071] Example 4

[0072] Preparation of composite calcium acid rust inhibitor: same as in Example 1.

[0073] Preparation of rust-preventive oil composite composition:

[0074] Trimethylolpropane ester was heated and stirred at 60-70°C, lanolin soap and dialkyldiphenylamine were added, and the mixture was stirred at high speed for 0.5-2 hours. Then, barium petroleum sulfonate, compound calcium acid rust inhibitor, dodecenyl succinic acid, sodium methylbenzotriazole and Span 80 were added in sequence. The mixture was stirred at high speed at 50-60°C for 1-3 hours to obtain the rust-inhibiting oil composite composition. The components and contents (by mass percentage) of the rust-inhibiting oil composite composition are shown in Table 4.

[0075] Table 4. Components and content of the anti-stain and anti-rust oil composite composition in Example 4

[0076] Components Quality fraction (%) Barium petroleum sulfonate 45 Compound calcium acid rust inhibitor 10 Dodecenyl succinic acid 15 Lanolin soap 12 Sodium methylbenzotriazole 2.5 Dialkyldiphenylamine 0.5 Sipan 80 5 Trimethylolpropane 10

[0077] Comparative Example 4

[0078] Similar to Example 4, except that the composite calcium acid rust inhibitor in Example 4 is replaced with barium petroleum sulfonate.

[0079] Example 5

[0080] Preparation of composite calcium acid rust inhibitor: same as in Example 1.

[0081] Preparation of rust-preventive oil composite composition:

[0082] The 350SN recycled base oil was heated and stirred at 60-70°C, and polyisobutylene and 2,6-di-tert-butyl-p-cresol were added. The mixture was stirred at high speed for 0.5-2 hours. Then, alkaline dinonylnaphthalenesulfonate barium, compound calcium acid rust inhibitor, dodecenyl succinic acid, methylbenzotriazole and diethylene glycol monobutyl ether were added in sequence. The mixture was stirred at high speed at 50-60°C for 1-3 hours to obtain the rust-preventive oil composite composition. The components and contents (by mass percentage) of the rust-preventive oil composite composition are shown in Table 5.

[0083] Table 5. Components and content of the anti-staining and anti-rust oil composite composition in Example 5

[0084] Components Quality fraction (%) Basic barium dinonylnaphthalenesulfonate 55 Compound calcium acid rust inhibitor 10 Dodecenyl succinic acid 7 Polyisobutylene 7 Methylbenzotriazole 0.5 2,6-Di-tert-butyl-p-cresol 0.5 Diethylene glycol monobutyl ether 10 350SN Regenerated Base Oil 10

[0085] Comparative Example 5

[0086] Similar to Example 5, except that the composite calcium acid rust inhibitor in Example 5 is replaced with alkaline dinonylnaphthalene sulfonate barium.

[0087] Example 6

[0088] The rust-preventive oil composite compositions prepared in Examples 1-5 and Comparative Examples 1-5 were dissolved in Liaohe No. 10 base oil at a ratio of 10:90, and their rust-preventive performance was tested.

[0089] Overlap test: Add 12 drops of deionized water to the test piece coated with rust-preventive oil, stack them in pairs, place a 1000g weight on top of the stacked pieces, and place them in an 82℃ oven for 24 hours. Observe the contamination of the metal surface by the rust-preventive oil. The experimental result is whether there is overlap or no overlap.

[0090] The damp heat test shall be conducted according to the GB / T 2361 method;

[0091] The salt spray test shall be conducted according to the SH / T 0081 method;

[0092] Water displacement test: Add 2g of deionized water to the strip of steel wool, place it in a 100ml concentration bottle, then add the sample, start timing, and observe the volume of water displaced at 3 minutes and 10 minutes respectively.

[0093] The test results are shown in Table 6 below.

[0094] Table 6. Performance of Rust Inhibiting Oil Composite Compositions

[0095]

[0096] As can be seen from the analysis in Table 6, the rust-preventive oil composite composition with added compound calcium acid rust inhibitor provided by the present invention has good oil solubility. While having excellent resistance to damp heat, salt spray and water displacement, it also has anti-staining properties. It can be used for indoor rust prevention of steel in high humidity, high heat and high salt environment, with a rust prevention period of not less than 2 years.

[0097] Although specific embodiments of the invention have been described in detail, those skilled in the art will understand that various modifications and substitutions can be made to those details based on all the teachings disclosed, and all such changes are within the scope of protection of this invention. The full scope of this invention is given by the appended claims and any equivalents thereof.

Claims

1. A stain-resistant and rust-preventive oil composite composition, characterized in that, The components and contents of the anti-stain and anti-rust oil composite composition, by mass percentage, are as follows: Compound calcium acid rust inhibitor 5~40%; Barium sulfonate rust inhibitor 20-70%; Organic carboxylic acid rust inhibitors: 5-20%; Film-forming agent 5~20%; Non-ferrous metal corrosion inhibitor 0.1~3%; Antioxidant 0.3~1.0%; 5-15% co-solvent; Base oil 5~15%; The structural formula of the composite calcium acid rust inhibitor is [(DNNSA)]. x (FA) y (PIBSA) z ]2·Ca, where DNNSA is dinonylnaphthalenesulfonic acid, FA is a monobasic fatty acid, PIBSA is polyisobutylene succinic anhydride, x+y+z=1, x=0.5~0.9, y=0~0.5, z=0~0.5; The FA is one or more of the following in any proportion: caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, and oleic acid. The PIBSA is an additive intermediate prepared by reacting highly active polyisobutylene with a molecular weight of 1000 or 1300 with maleic anhydride. The barium sulfonate rust inhibitor is at least one of petroleum barium sulfonate, neutral dinonylnaphthalene sulfonate, and basic dinonylnaphthalene sulfonate. The organic carboxylic acid rust inhibitor is at least one of dodecenyl succinic acid, dodecenyl succinic acid half ester, and N-oleoyl sarcosine.

2. The anti-stain and anti-rust oil composite composition as described in claim 1, characterized in that, The components and contents of the anti-stain and anti-rust oil composite composition, by mass percentage, are as follows: Compound calcium acid rust inhibitor 7~35%; Barium sulfonate rust inhibitor 25~65%; Organic carboxylic acid rust inhibitors: 7-15%; Film-forming agent 7~15%; Non-ferrous metal corrosion inhibitor 0.3~2.5%; Antioxidant 0.5-0.8%; Cosolvent 7~12%; Base oil 7~12%; The sum of the mass percentages of the above components is 100%.

3. The anti-stain and anti-rust oil composite composition as described in claim 1, characterized in that, The film-forming agent is at least one of petrolatum, paraffin wax, oxidized paraffin wax, oil-soluble asphalt, ethylene-propylene copolymer, methacrylate copolymer, polyisobutylene, hydrogenated styrene diene copolymer, lanolin, and lanolin soap.

4. The anti-stain and anti-rust oil composite composition as described in claim 1, characterized in that, The non-ferrous metal corrosion inhibitor is at least one of benzotriazole, methylbenzotriazole, sodium benzotriazole, and sodium methylbenzotriazole.

5. The anti-stain and anti-rust oil composite composition as described in claim 1, characterized in that, The antioxidant is at least one of phenolic antioxidants and amine antioxidants.

6. The anti-stain and anti-rust oil composite composition as described in claim 1, characterized in that, The cosolvent is Span 80 or diethylene glycol monobutyl ether.

7. The anti-stain and anti-rust oil composite composition as described in claim 1, characterized in that, The base oil is at least one of mineral oil, synthetic oil, and recycled oil.

8. The anti-stain and anti-rust oil composite composition as described in claim 1, characterized in that, The base oil is at least one of industrial white oil, synthetic oil, and recycled oil.

9. A method for preparing the anti-staining and anti-rust oil composite composition according to claim 1, characterized in that, The method includes: Heat and stir the base oil at 60-70°C, add the film-forming agent and antioxidant, stir at high speed for 0.5-2 hours, then add barium sulfonate rust inhibitor, compound calcium acid rust inhibitor, organic carboxylic acid rust inhibitor, non-ferrous metal corrosion inhibitor and cosolvent in sequence, and stir at high speed at 50-60°C for 1-3 hours.

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