High-stability composite anti-foaming agent, preparation method and application thereof, and marine lubricating oil

Abstract

The invention discloses a high-stability composite anti-foaming agent, a preparation method and application thereof, and marine lubricating oil, the composite anti-foaming agent composition comprises the following components by weight: 1-20 parts of a silicon type anti-foaming agent; 1 to 15 parts of a non-silicon type anti-foaming agent; 1-5 parts of a cosolvent; 65-95 parts of solvent oil, wherein the viscosity (25 DEG C) of the silicon type anti-foaming agent is 10-10000 mm < 2 > / s; the Brookfield viscosity (25 DEG C) of the non-silicon type anti-foaming agent is 100 to 150000 cps. The invention is suitable for marine oil which is seriously foamed or contains a large amount of detergent, and mainly solves the technical problems of unstable anti-foaming performance and poor storage stability of an anti-foaming agent in the marine oil in the prior art.

Description

Technical Field

[0001] The invention belongs to the technical field of lubricating oils, and in particular relates to a high-stability composite antifoaming agent, a preparation method and application thereof, and marine lubricating oil. Background Art

[0002] During the use of lubricating oil, it comes into contact with mixed air and generates bubbles through circulation. The generation of foam will bring many harms to the oil-using equipment and the lubricating oil itself, causing dry friction of mechanical parts, and may also cause air blockage to interrupt the oil supply of the oil pump, causing the wear of mechanical parts to increase and even damage. After the lubricating oil foams, the contact surface value with the air increases, which promotes the oxidation and deterioration of the lubricating oil and shortens the service life of the lubricating oil. Bubbles may even cause the lubricating oil to overflow and cause oil shortage accidents. In order to prevent the lubricating oil from generating a large number of bubbles and foams during the use of the equipment, anti-foaming agents are usually added to the oil to eliminate or inhibit foam. This method is simple and has the best effect, so it is widely used.

[0003] At present, the antifoaming agents used in the market are mainly divided into three categories: silicon-type, non-silicon-type and composite antifoaming agents. Silicon-type antifoaming agents are commonly used in polydimethylsiloxane, which has a good ability to inhibit foam at about 5-20ppm, but the solubility in lubricating oil and water is very low, and it is dispersed in the lubricating oil in the form of liquid droplets. With the extension of storage time, the organic silicon polymer antifoaming agent will be unstable and aggregate and settle, causing the performance of the antifoaming agent to fail. Non-silicon antifoaming agents are commonly used in acrylic acid ester non-silicon copolymers, which have better solubility in lubricating oil than silicon-type antifoaming agents, small dispersed particle size, less effect on air release, not easy to precipitate in oil products, and good antifoaming durability, but the amount added in lubricating oil is large, and it has good antifoaming performance only when the addition amount is 100-200ppm. When the addition amount is very low, the speed of eliminating foam is slow, and the time to eliminate the same volume of foam is even several times that of silicone oil.

[0004] Composite antifoaming agents balance the advantages and disadvantages of silicone oil and non-silicone antifoaming agents, and are composed of an appropriate proportion of the two. China Invention Patent Application Publication Specification CN105385484A proposes a method of compounding an organic fluorine-modified siloxane antifoaming agent with a copolymer of octyl acrylate and vinyl acetate; China Invention Patent Application Publication Specification CN104232246A proposes a method of compounding silicone oil, fluorine-containing silicone oil and acrylate polymer as an antifoaming agent. The antifoaming agent compositions disclosed in the above patent documents cannot meet the antifoaming performance indicators of marine medium-speed engine oils, and as the storage time increases, the antifoaming agent in the lubricating oil will gradually precipitate, and the antifoaming effect will be less durable. Therefore, it is urgently necessary to develop an antifoaming agent composition with good antifoaming effect and long-term storage, which is suitable for marine medium-speed engine oils with severe foaming effects. Summary of the invention

[0005] One of the technical problems to be solved by the present invention is that most of the existing composite antifoaming agents cannot meet the antifoaming index of marine lubricating oil, the antifoaming performance of the oil is unstable, and the amount of antifoaming agent added is large. Provided is a new composite antifoaming agent, which has good dispersibility in lubricating oil, excellent antifoaming performance of the oil, small addition amount, and stable storage. The second technical problem to be solved by the present invention is to provide a preparation method of the composite antifoaming agent corresponding to the first technical problem to be solved. The third technical problem to be solved by the present invention is to provide an application of the composite antifoaming agent.

[0006] In order to solve the above problems in the prior art, the present invention provides a high-stability composite antifoaming agent and a preparation method thereof.

[0007] In the first aspect, the present invention proposes a composite antifoaming agent, which comprises the following components by weight: 1 to 20 parts of a silicon-based antifoaming agent, 1 to 15 parts of a non-silicon-based antifoaming agent, 1 to 5 parts of a cosolvent, and 65 to 95 parts of solvent oil; the viscosity (25°C) of the silicon-based antifoaming agent is 10 to 10000 mm 2 For example, the viscosity of the silicon antifoaming agent (25°C) may be 15 mm 2 / s, 30mm 2 / s, 50mm 2 / s、100mm 2 / s, 150mm 2 / s、200mm 2 / s、300mm 2 / s、500mm 2 / s、800mm 2 / s、1000mm 2 / s、1500mm 2 / s、2000mm 2 / s、3000mm 2 / s、4000mm 2 / s、5000mm 2 / s、6000mm 2 / s、7000mm 2 / s、8000mm 2 / s、9000mm 2 / s、10000mm 2 / s or a range of its composition; the Brookfield viscosity (25°C) of the non-silicon antifoaming agent is 100 to 150,000 cps. For example, the viscosity (25°C) of the silicon antifoaming agent may be 100 cps, 150 cps, 200 cps, 300 cps, 500 cps, 600 cps, 800 cps, 1000 cps, 1500 cps, 2000 cps, 3000 cps, 4000 cps, 5000 cps, 6000 cps, 7000 cps, 8000 cps, 9000 cps, 1000 0cps, 20,000cps, 30,000cps, 40,000cps, 50,000cps, 60,000cps, 70,000cps, 80,000cps, 90,000cps, 100,000cps, 110,000cps, 120,000cps, 130,000cps, 136,000cps, 140,000cps, 150,000cps, or a range thereof.

[0008] As a specific embodiment of the present invention, the co-solvent is selected from at least one of Span 80, ethanol, ethylene glycol, cyclohexane, benzene, xylene, petroleum ether and acetone.

[0009] As a specific embodiment of the present invention, the solvent oil is preferably environmentally friendly and is selected from at least one of Class I base oil, Class II base oil, No. 20 solvent oil, aviation kerosene, D40, D60, D80, and D90.

[0010] In a second aspect, the present invention provides a method for preparing the composite antifoaming agent, comprising: mixing a silicon-based antifoaming agent, a non-silicon-based antifoaming agent and a cosolvent with solvent oil; preferably, adding the silicon-based antifoaming agent, the non-silicon-based antifoaming agent and the cosolvent into the solvent oil and mixing them evenly.

[0011] As a specific embodiment of the present invention, the preparation method comprises the following steps:

[0012] The silicon-based antifoaming agent and the non-silicon-based antifoaming agent are added to solvent oil and mixed evenly to obtain a mixture; a co-solvent is added to the obtained mixture, and the mixture is mixed evenly to obtain a composite antifoaming agent.

[0013] As a specific embodiment of the present invention, in the step S1, the mass ratio of the silicon-based antifoaming agent, the non-silicon-based antifoaming agent and the solvent oil is (1-20): (1-15): (65-95).

[0014] The mixing method is stirring; preferably, the stirring rate is 300-400 rpm, the stirring time is 0.25-1 h; and / or the mixing temperature is 30-45°C.

[0015] As a specific embodiment of the present invention, in the step S2, the mass ratio of the co-solvent to the mixture is (1-5): (67-130).

[0016] The mixing method is stirring; preferably, the stirring rate is 300-400 rpm, the stirring time is 0.25-1 h; and / or the mixing temperature is 30-45°C.

[0017] The above raw materials in the present invention can be prepared in-house or commercially available, and the present invention is not particularly limited thereto.

[0018] In a third aspect, the present invention provides application of the composite antifoaming agent in the field of marine lubricating oil.

[0019] In a fourth aspect, the present invention also provides a marine lubricating oil, wherein the marine lubricating oil contains any one of the above-mentioned composite antifoaming agents or contains a composite antifoaming agent prepared by any one of the above-mentioned preparation methods.

[0020] Preferably, in the marine lubricating oil, the mass fraction ratio of the composite antifoaming agent is 0.02% to 0.2%.

[0021] Compared with the prior art, the present invention has the following beneficial effects:

[0022] 1. The antifoaming agent of the present invention utilizes the characteristics of non-silicon antifoaming agents, such as good dispersion stability, not easy to precipitate in oil products, and good antifoaming persistence, and the characteristics of silicon antifoaming agents, such as low surface tension, strong antifoaming ability, low volatility and chemical inertness. By adding a co-solvent, on the basis of good antifoaming effect, the dispersion stability of the antifoaming agent is improved, so that the antifoaming agent can be stored for a long time without being easy to precipitate, thereby achieving good technical effects.

[0023] 2. The composite antifoaming agent of the present invention mainly solves the technical problem that the antifoaming agent in the prior art of marine oil antifoaming agent cannot be stored for a long time.

[0024] 3. The composite antifoaming agent of the present invention is suitable for marine oils with severe foaming or containing a large amount of detergent.

[0025] 4. The composite antifoaming agent of the present invention has good dispersibility in lubricating oil, excellent antifoaming performance of the oil, and a small amount of addition, and is not easy to precipitate during long-term storage. DETAILED DESCRIPTION

[0026] The present invention will be further described below in conjunction with specific embodiments, but they do not constitute any limitation to the present invention.

[0027] In each embodiment of the present invention, the specific information of the reagents used is as follows:

[0028] Silicone antifoaming agent: T901, viscosity (25°C) is 15-30mm 2 / s and 50~100mm 2 / s, Sinopec Lubricant Co., Ltd. Southwest Branch;

[0029] Non-silicon antifoaming agent: 9138, Brookfield viscosity (25°C) is 60,000-136,000 cps, Shanghai Qike Fluorosilicone New Materials Co., Ltd.; 9188, Brookfield viscosity (25°C) is 100-600 cps, Shanghai Qike Fluorosilicone New Materials Co., Ltd.;

[0030] Benzene, analytical grade, Sinopharm Group; acetone, analytical grade, Sinopharm Group; ethanol, analytical grade, Sinopharm Group; petroleum ether, analytical grade, Sinopharm Group; cyclohexane, analytical grade, Sinopharm Group; ethylene glycol, analytical grade, Sinopharm Group; xylene, analytical grade, Sinopharm Group; Span 80, Shanghai Tiantan Additive Co., Ltd.; No. 20 solvent oil, Changzhou Heshili Chemical Co., Ltd.; D40, Maoming Petrochemical; D60, Maoming Petrochemical; D80, Maoming Petrochemical; D90, Maoming Petrochemical; aviation kerosene, Gaoqiao Petrochemical; Class I base oil, Gaoqiao Petrochemical; Class II base oil, Gaoqiao Petrochemical.

[0031] Example 1 Composite antifoaming agent 1# and its preparation method

[0032] Components of composite antifoaming agent 1#, in parts by weight:

[0033] Silicone antifoaming agent: 10 parts viscosity (25°C) 50-100 mm 2 / s T901 silicon antifoaming agent;

[0034] Non-silicone anti-foaming agent: 5 parts of 9138 non-silicone anti-foaming agent with a Brookfield viscosity (25°C) of 60,000 to 136,000 cps;

[0035] Cosolvent: 1 part petroleum ether;

[0036] Environmentally friendly solvent oil: 84 parts of aviation kerosene.

[0037] Preparation method of composite antifoaming agent 1#: Stir the above-mentioned silicon antifoaming agent, non-silicon antifoaming agent, cosolvent and environmentally friendly solvent oil at 38°C with a magnetic stirrer for 1 hour until the components are evenly mixed to obtain a composite antifoaming agent composition.

[0038] Example 2 Composite antifoaming agent 2# and its preparation method

[0039] Components of composite antifoaming agent 2#, in parts by weight:

[0040] Silicone antifoaming agent: 10 parts of T901 silicone antifoaming agent with a viscosity (25°C) of 15-30 mm2 / s;

[0041] Non-silicone anti-foaming agent: 5 parts of 9188 non-silicone anti-foaming agent with a Brookfield viscosity (25°C) of 100-600cps;

[0042] Cosolvent: 1 part petroleum ether;

[0043] Environmentally friendly solvent oil: 84 parts of aviation kerosene.

[0044] Preparation method of composite antifoaming agent 2#: Stir the above-mentioned silicon antifoaming agent, non-silicon antifoaming agent, cosolvent and environmentally friendly solvent oil at 38°C with a magnetic stirrer for 1 hour until the components are evenly mixed to prepare a composite antifoaming agent composition.

[0045] Example 3 Composite antifoaming agent 3# and its preparation method

[0046] Components of composite antifoaming agent 3#, in parts by weight:

[0047] Silicone antifoaming agent: 14 parts of T901 silicone antifoaming agent with a viscosity (25°C) of 15-30 mm2 / s;

[0048] Non-silicone antifoaming agent: 10 parts of 9138 non-silicone antifoaming agent with a Brookfield viscosity (25°C) of 60,000 to 136,000 cps;

[0049] Solvent: 1 part Span 80;

[0050] Environmentally friendly solvent oil: 75 parts of Class I base oil.

[0051] Preparation method of composite antifoaming agent 3#: Stir the above-mentioned silicon antifoaming agent, non-silicon antifoaming agent, cosolvent and environmentally friendly solvent oil at 38°C with a magnetic stirrer for 1 hour until the components are evenly mixed to obtain a composite antifoaming agent composition.

[0052] Example 4 Composite antifoaming agent 4# and its preparation method

[0053] Components of composite antifoaming agent 4#, in parts by weight:

[0054] Silicone antifoaming agent: 14 parts viscosity (25°C) 15-30 mm 2 / s T901 silicon antifoaming agent;

[0055] Non-silicone antifoaming agent: 10 parts of 9188 non-silicone antifoaming agent with a Brookfield viscosity (25°C) of 100-600 cps;

[0056] Solvent: 1 part Span 80;

[0057] Environmentally friendly solvent oil: 75 parts of Class I base oil.

[0058] Preparation method of composite antifoaming agent 4#: Stir the above-mentioned silicon antifoaming agent, non-silicon antifoaming agent, cosolvent and environmentally friendly solvent oil at 38°C with a magnetic stirrer for 1 hour until the components are evenly mixed to obtain a composite antifoaming agent composition.

[0059] Comparative Examples 1 to 3 Composite antifoaming agents A, B, C and their preparation methods

[0060] Composite antifoaming agents A, B and C were prepared according to the steps of preparing composite antifoaming agent 1# in Example 1, except that one or more components in the formula of composite antifoaming agent 1# were missing. The compositions of composite antifoaming agents A, B and C are shown in Table 1.

[0061] Table 1 Composition of components of Example 1 and Comparative Examples 1 to 3

[0062] Number of copies Silicone antifoaming agent Non-silicone antifoaming agent Solvent Solvent oil Composite antifoaming agent 1# 10 pieces of T901 5 copies 9138 1 part petroleum ether 84 parts of aviation kerosene Composite antifoaming agent A 10 pieces of T901 - - 90 parts of aviation kerosene Composite antifoaming agent B - 5 copies 9138 - 95 parts of aviation kerosene Composite antifoaming agent C - - 1 part petroleum ether 99 parts of aviation kerosene

[0063] Comparative Example 4

[0064] This comparative example is the commercially available finished product antifoaming agent MS-575 from Mengqingxin, which is a composite antifoaming agent blended with a silicon-based antifoaming agent and a non-silicon-based antifoaming agent.

[0065] Comparative Example 5

[0066] This comparative example is the commercially available finished product antifoaming agent BAN155 from Mengqingxin, which is a composite antifoaming agent blended with a silicone antifoaming agent and a non-silicone antifoaming agent.

[0067] Comparative Example 6

[0068] This comparative example is the commercially available finished product formula No. 2 composite antifoaming agent (Jinzhou No. 2) of Jinzhou Shengda, which is a composite antifoaming agent blended with a silicon-based antifoaming agent and a non-silicon-based antifoaming agent.

[0069] Comparative Example 7

[0070] This comparative example is the commercially available finished product formula No. 3 composite antifoaming agent (Jinzhou No. 3) of Jinzhou Shengda, which is a composite antifoaming agent blended with a silicon-based antifoaming agent and a non-silicon-based antifoaming agent.

[0071] Application Examples

[0072] This application example provides a method for preparing a medium-speed engine oil composition for a ship, and the specific details are as follows:

[0073] The composite antifoaming agents 1#, 2#, 3#, 4# prepared in the above Examples 1 to 4 and the antifoaming agents of Comparative Examples 1 to 7 were weighed and added to Great Wall 4012 marine medium-speed diesel engine oil, with the added amount being 0.08% by weight of the marine medium-speed engine oil. The mixture was stirred at 58° C. for 15 to 60 min until the antifoaming agent was evenly dispersed in the marine medium-speed engine oil, and the transparency of the oil was observed.

[0074] The marine medium speed engine oil obtained in the application example was subjected to a composition foam tendency test, and the specific test method is as follows:

[0075] Using a lubricating oil foam performance tester, various marine medium-speed engine oil compositions obtained according to the corresponding examples of the standard method of GB / T 12579 "Lubricating Oil Foam Property Determination Method" were tested for foam performance, and the anti-foam stability of the medium-speed engine oil added with the anti-foaming agent composition was investigated by the static storage method. The medium-speed engine oil composition was stored at room temperature, and the changes in the foam performance of the medium-speed engine oil composition were recorded over time. The smaller the foam volume generated by the oil product and the more it can be completely defoamed within the specified time, the better the anti-foam performance of the marine medium-speed engine oil. The test results are shown in Table 2:

[0076] Table 2 Test results of Examples 1 to 4 and Comparative Examples 1 to 7

[0077]

[0078] Table 2 shows that the composite antifoaming agents 1#, 2#, 3#, and 4# prepared in Examples 1-4 have a small foaming volume and can eliminate the foam within the specified time, and have excellent antifoaming effects; as the storage time increases, the antifoaming property and antifoaming stability of the medium-speed engine oil added with the composition of T901 and 9188 are the best, followed by the medium-speed engine oil added with the composition of T901 and 9138. Comparison of the composite antifoaming agent 1# prepared in Example 1 and the composite antifoaming agents A, B, and C prepared in Comparative Examples 1, 2, and 3 shows that the antifoaming performance of the composite antifoaming agent composition prepared by each component is better than that of each single component. The foaming volume of Comparative Examples 4, 5, 6, and 7 has exceeded the index of the oil product and there is foam that has not been eliminated, which cannot meet the requirements. Although the foaming volume of Comparative Examples 5 and 7 is small, some foam has not been eliminated within the specified time, and as the storage time increases, the antifoaming property gradually deteriorates, and the antifoaming index of the oil product cannot be met. Compared with Examples 1-4 and Comparative Examples 4-7, the anti-foaming effect in medium-speed engine oil is good, and the anti-foaming stability is also good as the storage time increases.

[0079] In summary, the composite antifoaming agent composition of the present invention and the existing composite antifoaming agents on the market utilize the characteristics of good antifoaming properties of silicon-type antifoaming agents in small doses and good dispersion stability of non-silicon-type antifoaming agents, and improve the dispersion stability of the antifoaming agent by adding a co-solvent, thereby improving the antifoaming performance of the lubricating oil, and achieving better technical effects.

[0080] It should be noted that the above embodiments can be freely combined as needed. The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered as the protection scope of the present invention.

Claims

1. A composite antifoaming agent, characterized in that: The composition comprises the following components by weight: 1 to 20 parts of silicon-based antifoaming agent, 1 to 15 parts of non-silicon-based antifoaming agent, 1 to 5 parts of cosolvent, and 65 to 95 parts of solvent oil; The viscosity of the silicon antifoaming agent (25°C) is 10 to 10000 mm 2 / s; The non-silicon antifoaming agent has a Brookfield viscosity (25° C.) of 100 to 150,000 cps.

2. The composite antifoaming agent according to claim 1, characterized in that The co-solvent is selected from at least one of Span 80, ethanol, ethylene glycol, cyclohexane, benzene, xylene, petroleum ether and acetone.

3. The composite antifoaming agent composition according to claim 1 or 2, characterized in that: The solvent oil is selected from at least one of Class I base oil, Class II base oil, No. 20 solvent oil, aviation kerosene, D40, D60, D80, and D90.

4. The method for preparing the composite antifoaming agent according to any one of claims 1 to 3, characterized in that: include: The silicone antifoaming agent, non-silicone antifoaming agent and co-solvent are mixed with solvent oil to obtain the product.

5. The preparation method according to claim 4, characterized in that: The preparation method comprises the steps of: S1: mixing a silicon-based antifoaming agent, a non-silicone-based antifoaming agent and solvent oil to obtain a mixture; S2: Mixing the mixture obtained in step S1 with a co-solvent to obtain the composite antifoaming agent.

6. The preparation method according to claim 4 or 5, characterized in that: In the step S1, the mixing method is stirring, preferably the stirring rate is 300-400 rpm, the stirring time is 0.25-1 h; and / or the mixing temperature is 30-45°C.

7. The preparation method according to claim 4 or 5, characterized in that: In the step S2, the mixing method is stirring, preferably the stirring rate is 300-400 rpm, the stirring time is 0.25-1 h; and / or the mixing temperature is 30-45°C.

8. Use of the composite antifoaming agent composition according to any one of claims 1 to 3 or the composite antifoaming agent prepared by the preparation method according to any one of claims 4 to 7 in the field of marine lubricating oil.

9. Marine lubricating oil, characterized in that: The invention relates to a composite antifoaming agent comprising the composite antifoaming agent according to any one of claims 1 to 3 or the composite antifoaming agent prepared by the preparation method according to any one of claims 4 to 7.

10. The marine lubricating oil according to claim 9, characterized in that: In the marine lubricating oil, the mass fraction ratio of the composite antifoaming agent is 0.02% to 0.2%.

Images