Fast biodegradable rolling fluid compositions, methods of making and use thereof

Abstract

The application provides a quick biodegradable rolling liquid composition and a preparation method and application thereof, and the rolling liquid composition comprises: 82.0-94.0 parts by weight of boundary lubricant; 3.0-9.0 parts by weight of extreme pressure anti-wear agent; 2.0-5.0 parts by weight of surfactant; and 1.0-4.0 parts by weight of anti-oxidation preservative; wherein the boundary lubricant comprises main boundary lubricant and auxiliary boundary lubricant, the main boundary lubricant is selected from one or more of oxidized rape oil, coconut oil and palm oil, the auxiliary boundary lubricant is selected from one or more of isooctyl palmitate, trimethylolpropane fatty acid ester and pentaerythritol fatty acid ester, and the weight ratio of the main boundary lubricant to the auxiliary boundary lubricant is 8-1:1. The biodegradable rolling liquid composition has good biodegradability and can be used for processing multi-material metals such as stainless steel and plain carbon steel.

Description

Technical Field

[0001] This invention belongs to the field of rolling fluid technology, and in particular relates to a rapidly biodegradable rolling fluid composition, its preparation method, and its uses. Background Technology

[0002] In the cold-rolled steel sheet processing, rolling fluid, as a process lubricant, is an essential lubricating medium, playing a role in lubrication, cooling, cleaning, and rust prevention during cold rolling. After a period of use, the performance of the rolling fluid deteriorates, and its indicators worsen, requiring replacement. The resulting waste liquid has poor biodegradability in the environment, and direct discharge causes environmental degradation. Traditional incineration methods produce large amounts of greenhouse gases such as carbon dioxide and methane. Currently, there is a need for rolling fluids with rapid biodegradability.

[0003] In recent years, patent applications concerning biodegradable rolling emulsions have been published successively. For example, Chinese patent application CN 105602674 A discloses a biodegradable rolling emulsion composition and its use for process lubrication in the cold rolling process of stainless steel strip; Chinese patent application CN 105238525 A discloses the application of a biodegradable rolling emulsion composition in the hot rolling process of aluminum alloy strip; Chinese patent application CN 114058427 A discloses a biodegradable aluminum alloy hot rolling fluid and its preparation method; and Chinese patent CN 116144416 A discloses a biodegradable anionic and nonionic mixed aluminum hot rolling fluid and its preparation method. Although these patent documents all mention the biodegradability of the rolling emulsion, they do not provide specific data on the biodegradability rate, making it impossible to assess the biodegradability and degradation rate. Furthermore, the products involved in these patent documents are all used for single-metal processing and lack adaptability to multi-metal materials.

[0004] Therefore, it is still necessary to develop a biodegradable rolling fluid product that meets the technical requirements of current high-efficiency rolling mills for rolling fluids and has rapid biodegradability. Summary of the Invention

[0005] To address the aforementioned problems in the prior art, this invention proposes a rapidly biodegradable rolling fluid composition, its preparation method, and its applications. The biodegradable rolling fluid composition of this invention has good biodegradability and can be used to process various metal materials such as stainless steel and carbon steel.

[0006] The objective of this invention is achieved through the following technical solutions.

[0007] In a first aspect, the present invention provides a rapidly biodegradable rolling fluid composition, the rolling fluid composition comprising:

[0008]

[0009] The boundary lubricant includes a primary boundary lubricant and a secondary boundary lubricant. The primary boundary lubricant is selected from one or more of oxidized rapeseed oil, coconut oil, and palm oil. The secondary boundary lubricant is selected from one or more of isooctyl palmitate, trimethylolpropane fatty acid ester, and pentaerythritol fatty acid ester. The weight ratio of the primary boundary lubricant to the secondary boundary lubricant is 8 to 1:1.

[0010] According to the rolling fluid composition provided by the present invention, the weight ratio of the primary boundary lubricant and the secondary boundary lubricant can be 8:1, 7:1, 6:1, 5:1, 4:1, 3:1, 2:1, 1.5:1, 1:1 or a range thereof.

[0011] According to the rolling fluid composition provided by the present invention, the primary boundary lubricant is palm oil and the secondary boundary lubricant is pentaerythritol fatty acid ester.

[0012] The rolling fluid composition provided by the present invention further includes 0 to 10 parts by weight of a Group IV base oil as the boundary lubricant. For example, the Group IV base oil may be a PAO base oil.

[0013] According to the rolling fluid composition provided by the present invention, the extreme pressure anti-wear agent is selected from one or more of acidic phosphate esters, phosphites, alcohol ether phosphate esters, phosphate ester amine salts, sulfurized olefins, sulfurized fatty acid esters, sulfurized fatty oils, and nitrogen-containing borate esters.

[0014] In some embodiments, the extreme pressure anti-wear agent is selected from at least two, for example three to four, of acidic phosphate esters, phosphites, ammonium salts of phosphate esters, sulfurized fatty acid esters, or nitrogen-containing borate esters.

[0015] In some preferred embodiments, the extreme pressure anti-wear agent includes a primary extreme pressure anti-wear agent and a secondary extreme pressure anti-wear agent. The primary extreme pressure anti-wear agent is selected from acidic phosphate esters, phosphites, and ammonium salts of phosphate esters. The secondary extreme pressure anti-wear agent is selected from sulfurized fatty acid esters and nitrogen-containing borate esters. The weight ratio of the primary extreme pressure anti-wear agent to the secondary extreme pressure anti-wear agent is 1:(0.4-5), preferably 1:(1.5-3.5).

[0016] In some specific embodiments, the primary extreme pressure anti-wear agent comprises 1-2 parts by weight of acidic phosphate ester, 0-0.5 parts by weight of phosphite ester and 0.5-1 parts by weight of ammonium phosphate ester, and the secondary extreme pressure anti-wear agent comprises 5-6 parts by weight of sulfurized fatty acid ester.

[0017] The rolling fluid composition provided by the present invention, wherein the surfactant is selected from at least two of low HLB alkylphenol polyoxyethylene ether, high HLB alkylphenol polyoxyethylene ether, low HLB alkoxylated fatty alcohol, high HLB alkoxylated fatty alcohol, alcohol ester type surfactant, polymeric surfactant, fatty alcohol ether carboxylic acid, quaternary ammonium salt type surfactant, low HLB tallow amine polyoxyethylene ether, and high HLB tallow amine polyoxyethylene ether, preferably selected from at least two of low HLB alkylphenol polyoxyethylene ether, high HLB alkylphenol polyoxyethylene ether, alcohol ester type surfactant, polymeric surfactant, low HLB tallow amine polyoxyethylene ether, and high HLB tallow amine polyoxyethylene ether.

[0018] In this invention, the term "low HLB value" refers to an HLB value ≤ 7; the term "high HLB value" refers to an HLB value > 7.

[0019] Examples of alcohol ester surfactants suitable for use in this invention include alcohol ester surfactants with designation S-8; and / or examples of polymeric surfactants suitable for use in this invention include polymeric surfactants with designation A07.

[0020] In some embodiments, the surfactant includes a primary surfactant and a secondary surfactant; the primary surfactant is selected from low HLB alkylphenol polyoxyethylene ether, high HLB alkylphenol polyoxyethylene ether, low HLB tallow amine polyoxyethylene ether, high HLB tallow amine polyoxyethylene ether acid phosphate ester; the secondary surfactant is selected from alcohol ester type surfactants and polymeric surfactants; the mass ratio of the primary surfactant to the secondary surfactant is 1:(0.05-1), preferably 1:(0.06-0.5).

[0021] In some specific embodiments, the main surfactant comprises 0.5 to 1 part by weight of low HLB value alkylphenol polyoxyethylene ether and 2 to 3 parts by weight of high HLB value alkylphenol polyoxyethylene ether; the auxiliary surfactant comprises 0.2 to 0.5 parts by weight of polymeric surfactant and 0 to 1 part by weight of alcohol ester type surfactant.

[0022] The rolling fluid composition provided by the present invention comprises, wherein the antioxidant and corrosion inhibitor is selected from at least two of shielded phenolic antioxidants, amine antioxidants, sodium petroleum sulfonate, barium dinonylnaphthalene sulfonate, benzotriazole and its derivatives, thiadiazole derivatives, long-chain dicarboxylic acids, or hydroxyl tricarboxylic acids. Preferably, the antioxidant and corrosion inhibitor is selected from at least two of shielded phenolic antioxidants, sodium sulfonate, barium dinonylnaphthalene sulfonate, benzotriazole and its derivatives, long-chain dicarboxylic acids, and amine antioxidants.

[0023] In some embodiments, the antioxidant preservative includes a primary antioxidant preservative and a secondary antioxidant preservative; the primary antioxidant preservative is selected from sodium sulfonate, barium dinonylnaphthalenesulfonate, and benzotriazole and their derivatives, and the secondary antioxidant preservative is selected from shielded phenolic antioxidants, long-chain dicarboxylic acids, and amine antioxidants; the weight ratio of the primary antioxidant preservative to the secondary antioxidant preservative is 1:(0.1-1.5), preferably 1:(0.5-1.5), and more preferably 1:(0.5-1).

[0024] The rolling fluid composition provided by the present invention is wherein the rolling fluid composition does not contain organosiloxanes.

[0025] In some embodiments, the rolling fluid composition comprises a boundary lubricant, an extreme pressure anti-wear agent, a surfactant, and an antioxidant / corrosion inhibitor.

[0026] In a second aspect, the present invention provides a method for preparing a rapidly biodegradable rolling fluid composition according to the first aspect, wherein the preparation method includes the following steps:

[0027] S1: Heat and stir the extreme pressure anti-wear agent and boundary lubricant to obtain a mixture;

[0028] S2: Add surfactant and antioxidant preservative to the mixture obtained in step S1, heat and stir, and cool to room temperature to obtain cold rolling liquid composition.

[0029] According to the preparation method provided by the present invention, the heating and stirring conditions in steps S1 and S2 each independently include: a temperature of 45-55°C; and / or a stirring rate of 300-500 rpm; and / or a stirring time of 0.5-2 h.

[0030] Thirdly, the present invention provides the application of the rapidly biodegradable rolling fluid composition of the first aspect or the rolling fluid composition prepared by the second aspect in the field of lubrication of cold rolling processes for carbon steel and stainless steel.

[0031] According to the application provided by the present invention, the rapidly biodegradable rolling fluid composition is used in the form of an emulsion, preferably the emulsion is prepared by diluting the rapidly biodegradable rolling fluid composition with demineralized water; preferably, the concentration of the rapidly biodegradable rolling fluid composition in the emulsion is 0.5 to 8% by weight.

[0032] All of the above-mentioned raw materials used in this invention can be prepared in-house or purchased commercially; this invention does not impose any particular limitations on them.

[0033] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0034] (1) The cold rolling fluid composition of the present invention has good biodegradability, meets the requirements for rapid biodegradation, and is more in line with current environmental, safety, health and low-carbon requirements. The cold rolling fluid composition of the present invention, through the compounding and synergistic effect of its components, exhibits excellent performance, particularly good extreme pressure lubrication and antioxidant / corrosion resistance, which can meet the requirements of cold rolling processes for stainless steel and plain carbon steel. For example, according to the rapid biodegradability of chemicals carbon dioxide generation test in GB / T 21856-2008, it meets the requirements for rapid biodegradation rate.

[0035] (2) The comprehensive performance of the rapid biodegradable rolling fluid composition provided by the present invention can meet the requirements of rolling process development for rolling fluid. It can be used in industrial applications for lubrication of cold rolling process in single-stand cold rolling mills and continuous rolling mills for stainless steel or carbon steel. In particular, it has achieved good technical results in single-stand reversible rolling mills and continuous rolling mills. Detailed Implementation

[0036] The present invention will be further described below with reference to specific embodiments, but this does not constitute any limitation on the present invention.

[0037] Example 1

[0038] This embodiment provides a rapidly biodegradable rolling fluid composition, its preparation method, and its application. Raw materials are prepared according to the component weight proportions in Table 1, with specific details as follows:

[0039] S1: Add boundary lubricant and extreme pressure anti-wear agent to a reaction vessel with a stirrer, heat and stir at 50±5℃ for 1h to obtain a mixture, wherein the stirring rate is 400rpm;

[0040] S2: Add surfactant and antioxidant preservative to the mixture obtained in step S1 in sequence, stir at 50±5℃ until all additives are dissolved (1h), cool to room temperature to obtain cold rolling liquid composition, wherein the stirring rate is 400rpm.

[0041] The cold rolling fluid composition prepared in Example 1 was diluted with demineralized water to a weight percentage concentration of 2.5% emulsion, and used for process lubrication of stainless steel rolling on a 1780mm 18-roll 5-stand mill, achieving good application results; wherein the maximum rolling pressure of the mill is 1800 tons and the maximum rolling speed is 300m / min.

[0042] Example 2

[0043] This embodiment provides a rapidly biodegradable rolling fluid composition, its preparation method, and its application. Raw materials are prepared according to the component weight parts in Table 1, with specific details as follows:

[0044] S1: Add boundary lubricant and extreme pressure anti-wear agent to a reaction vessel with a stirrer, heat and stir at 50±5℃ for 1h to obtain a mixture, wherein the stirring rate is 400rpm;

[0045] S2: Add surfactant and antioxidant preservative to the mixture obtained in step S1 in sequence, stir at 50±5℃ until all additives are dissolved (1h), cool to room temperature to obtain cold rolling liquid composition, wherein the stirring rate is 400rpm.

[0046] The cold rolling fluid composition prepared in Example 2 was diluted with demineralized water to an emulsion with a weight percentage concentration of 3.0%, and used for process lubrication of plain carbon steel rolled on a 1500mm six-roll reversible rolling mill, achieving good application results; wherein the maximum rolling pressure of the rolling mill is 1500 tons and the maximum rolling speed is 1200m / min.

[0047] Examples 3-6

[0048] The rapidly biodegradable rolling fluid composition was prepared according to the formulation in Table 1 using the same method as in Example 1.

[0049] Table 1. Formulations (parts by weight) of the compositions in Examples 1-6

[0050]

[0051]

[0052] Comparative Example 1

[0053] The rolling fluid composition was prepared according to the formulation disclosed in Example 1 of document CN 105602674 A, and the specific formulation is shown in Table 2.

[0054] Table 2 Comparative Example 1 Rolling Fluid Composition Formulation

[0055] Palm oil - 44.45 parts by weight Trimethylolpropane oleate - 30 portions by weight Oleic acid - 5 parts by weight Sulfated fatty acid esters S11 8 portions by weight Phosphate CN3 2 parts by weight Alkylphenol polyoxyethylene ether NP7 5 parts by weight Dodecanedioic acid - 2 parts by weight Octyl diphenylamine - 0.5 parts by weight Di-tert-butyl-p-cresol - 1 part by weight organosiloxanes M5 0.05 parts by weight Chloromethylisothiazolinone - 2 parts by weight

[0056] Comparative Example 2

[0057] A commercially available cold rolling compound composition of brand name QH EVEROLL S, purchased from Quaker Hofton, was used as a control.

[0058] Comparative Example 3

[0059] The formulation and preparation method are basically the same as in Example 1, except that the amount of palm oil is adjusted to 48.3 parts by weight and the amount of acidic phosphate ester is adjusted to 11 parts by weight.

[0060] Comparative Example 4

[0061] The formulation and preparation method are basically the same as in Example 1, except that the amount of pentaerythritol tetraoleate is adjusted to 58.3 parts by weight and the amount of palm oil is adjusted to 30 parts by weight.

[0062] Comparative Example 5

[0063] The formulation and preparation method are basically the same as in Example 1, except that the amount of acidic phosphate ester is adjusted to 5 parts by weight and the amount of sulfurized fatty acid ester is adjusted to 1 part by weight.

[0064] Performance testing

[0065] The properties of the rolling fluid compositions of each embodiment and comparative example were measured according to the following method, and the results are shown in Table 3.

[0066] 1. Extreme pressure lubrication performance

[0067] Extreme pressure lubrication performance represents the load-bearing capacity of the lubricating film formed by the lubricant. According to the test standard GB / T3142-2019, the maximum non-seize load (PB) value of the tested oil is measured. The higher the PB value, the greater the strength of the lubricating film, the stronger its load-bearing capacity, and the better its lubrication performance. In the testing method, the PB value is classified into 57 grades, ranging from 98N (10kg) to 7845 (800kg). The PB value grades involved in this invention belong to the following ranges: 1020N (104kg), 1069N (109kg), 1118N (114kg), 1167N (119kg), 1236N (126kg), 1294N (132kg), and 1363N (139kg).

[0068] 2. Biodegradability

[0069] Biodegradation rate represents the ability of a lubricant to biodegrade upon contact with an inoculum within a specified time. The 28-day biodegradation rate of chemicals is tested according to GB / T 21856-2008 "Test for Rapid Biodegradability of Chemicals - Carbon Dioxide Generation Test," with higher values ​​indicating a higher biodegradation rate. Specifically, according to GB / T 27850-2011 "General Rules for Rapid Biodegradability of Chemicals," a 60% pass rate within a 10-day observation period during the 28-day test period is considered rapidly biodegradable.

[0070] Table 3. Performance of the cold rolling melt compositions in Examples 1-6 and Comparative Examples 1-2

[0071]

[0072] As shown in Table 3, the cold rolling fluid compositions in Examples 1-6 outperformed those in Comparative Examples 1-5 in the biodegradability experiment, with Examples 1 and 2 exhibiting the best results. Furthermore, Examples 1-6 all achieved a 60% pass rate during a 10-day observation period, demonstrating rapid biodegradability, which is superior to Comparative Examples 1-5. The maximum non-seize load PB of the cold rolling fluid compositions in Examples 1-6 ranged from 1167 to 1294 N, all superior to the comparative examples, indicating better extreme pressure lubrication performance.

[0073] It is believed that the present invention achieves excellent performance through the synergistic combination of its components. For example, the present invention uses a specific boundary lubricant with good biodegradability, and the combination of different types of extreme pressure anti-wear agents, especially the synergistic effect of ammonium phosphate salt and other sulfurized extreme pressure agents, can effectively improve the PB value, achieving superior extreme pressure performance with lower addition amounts (and allowing for increased boundary lubricant dosage). Simultaneously, the rational use of antioxidants and corrosion inhibitors gives the rolling fluid composition of the present invention better rust and corrosion prevention capabilities, meeting the processing requirements of various materials such as carbon steel and stainless steel, and exhibiting greater applicability.

[0074] In summary, the cold rolling fluid composition of this invention exhibits excellent biodegradability, meeting the requirements for rapid biodegradation and better aligning with current environmental, safety, health, and low-carbon requirements. Through the synergistic combination of its components, the cold rolling fluid composition of this invention demonstrates superior performance, particularly excellent extreme pressure lubrication and antioxidant / corrosion-resistant properties, thus satisfying the cold rolling processes of stainless steel and carbon steel. The comprehensive performance of this composition meets the requirements of rolling process development for rolling fluids and can be used in industrial applications for lubrication of cold rolling processes in single-stand cold rolling mills and continuous rolling mills for stainless steel or carbon steel.

[0075] Any numerical value mentioned in this invention, if there is only a two-unit interval between any minimum and any maximum value, includes all values ​​that increase by one unit each time from the minimum to the maximum value. For example, if the amount of a component, or the value of a process variable such as temperature, pressure, or time, is stated as 50-90, in this specification it means specifically listing values ​​such as 51-89, 52-88… and 69-71 and 70-71, etc. For non-integer values, it may be appropriately considered that a unit is 0.1, 0.01, 0.001, or 0.0001. These are merely some specifically specified examples. In this application, in a similar manner, all possible combinations of numerical values ​​between the listed minimum and maximum values ​​are considered to have been disclosed.

[0076] It should be noted that the embodiments described above are only for explaining the present invention and do not constitute any limitation on the present invention. The present invention has been described with reference to typical embodiments, but it should be understood that the words used therein are descriptive and explanatory terms, not limiting terms. Modifications can be made to the present invention within the scope of the claims, and revisions can be made to the present invention without departing from the scope and spirit of the present invention. Although the present invention described herein relates to specific methods, materials, and embodiments, it does not mean that the present invention is limited to the specific examples disclosed herein; on the contrary, the present invention can be extended to all other methods and applications with the same function.

Claims

1. A rapidly biodegradable rolling fluid composition, characterized in that, The rolling fluid composition comprises the following components: Boundary lubricant: 82.0–94.0 parts by weight; Extreme pressure anti-wear agent 3.0–9.0 parts by weight; Surfactant 2.0–5.0 parts by weight; Antioxidant and preservative: 1.0–4.0 parts by weight; The boundary lubricant includes a primary boundary lubricant and a secondary boundary lubricant. The primary boundary lubricant is selected from one or more of oxidized rapeseed oil, coconut oil, and palm oil. The secondary boundary lubricant is selected from one or more of isooctyl palmitate, trimethylolpropane fatty acid ester, and pentaerythritol fatty acid ester. The weight ratio of the primary boundary lubricant to the secondary boundary lubricant is 8 to 1:

1. The extreme pressure anti-wear agent includes a primary extreme pressure anti-wear agent and a secondary extreme pressure anti-wear agent. The primary extreme pressure anti-wear agent includes 1-2 parts by weight of acidic phosphate ester, 0-0.5 parts by weight of phosphite ester and 0.5-1 parts by weight of ammonium phosphate ester, and the secondary extreme pressure anti-wear agent includes 5-6 parts by weight of sulfurized fatty acid ester. The surfactant comprises a primary surfactant and a secondary surfactant; the primary surfactant comprises 0.5-1 parts by weight of a low HLB value alkylphenol polyoxyethylene ether and 2-3 parts by weight of a high HLB value alkylphenol polyoxyethylene ether; the secondary surfactant comprises 0.2-0.5 parts by weight of a polymeric surfactant and 0-1 parts by weight of an alcohol ester surfactant; wherein, low HLB value means HLB value ≤ 7; high HLB value means HLB value > 7; According to GB / T 27850-2011 "General Rules for Rapid Biodegradability of Chemicals", the rolling fluid composition that achieves a 60% pass rate during a 28-day test period and a 10-day observation period is considered a rapidly biodegradable rolling fluid composition.

2. The rolling fluid composition according to claim 1, characterized in that, The primary boundary lubricant is palm oil, and the secondary boundary lubricant is pentaerythritol fatty acid ester.

3. The rolling fluid composition according to claim 1 or 2, characterized in that, The antioxidant and preservative agent is selected from at least two of the following: shielding phenolic antioxidants, amine antioxidants, sodium petroleum sulfonate, barium dinonylnaphthalene sulfonate, benzotriazole and its derivatives, thiadiazole derivatives, long-chain dicarboxylic acids, or organic tricarboxylic acids.

4. The rolling fluid composition according to claim 3, characterized in that, The antioxidant and preservative are selected from at least two of the following: shielding phenolic antioxidants, sodium petroleum sulfonate, barium dinonylnaphthalene sulfonate, benzotriazole and its derivatives, long-chain dicarboxylic acids, and amine antioxidants.

5. The rolling fluid composition according to claim 3, characterized in that, The antioxidant preservative is a primary antioxidant preservative and a secondary antioxidant preservative; the primary antioxidant preservative is selected from sodium petroleum sulfonate, barium dinonylnaphthalene sulfonate, and benzotriazole and its derivatives, and the secondary antioxidant preservative is selected from shielded phenolic antioxidants, long-chain dicarboxylic acids and amine antioxidants, and the weight ratio of the primary antioxidant preservative to the secondary antioxidant preservative is 1:(0.1~1.5).

6. The rolling fluid composition according to claim 5, characterized in that, The weight ratio of the primary antioxidant preservative to the secondary antioxidant preservative is 1:(0.5~1.5).

7. The rolling fluid composition according to claim 6, characterized in that, The weight ratio of the primary antioxidant preservative to the secondary antioxidant preservative is 1:(0.5~1).

8. A method for preparing the rolling fluid composition according to any one of claims 1-7, wherein, The preparation method includes the following steps: S1: Heat and stir the extreme pressure anti-wear agent and boundary lubricant to obtain a mixture; S2: Add surfactant and antioxidant preservative to the mixture obtained in step S1, heat and stir, and cool to room temperature to obtain the rolling liquid composition.

9. The preparation method according to claim 8, characterized in that, The heating and stirring conditions in steps S1 and S2 each include independently: The temperature is 45~55℃; and / or the stirring rate is 300-500 rpm; and / or the stirring time is 0.5-2h.

10. The application of the rolling fluid composition according to any one of claims 1-7 in the field of lubrication of cold rolling processes for carbon steel and stainless steel.

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