Finish rolling emulsified oil, preparation method and rolling emulsified liquid containing finish rolling emulsified oil

Abstract

The invention discloses finish rolling emulsified oil, a preparation method and rolling emulsified liquid containing the finish rolling emulsified oil. The finish rolling emulsified oil is prepared from the following components in parts by weight: 88 to 90 parts of base oil, 1.5 to 2 parts of phosphate polyoxyethylene polyoxypropylene ether, 1.5 to 2.3 parts of nitrogen-containing polymer, 0.3 to 0.4 part of antioxidant, 2 to 2.9 parts of nonionic surfactant, 3 to 5 parts of extreme pressure agent and 0.2 to 0.3 part of antirust agent. The rolling emulsion based on the finish rolling emulsified oil has good oil film release capacity and continuous good oil film release capacity in the rolling process, and an adjusting agent needs to be additionally added after 1-2 months to stabilize the bath solution state, so that the adjusting period of the emulsion is effectively prolonged.

Description

TECHNICAL FIELD

[0001] The present application relates to a finish rolling emulsified oil, and also relates to a preparation method of the finish rolling emulsified oil and a rolling emulsion containing the finish rolling emulsified oil. BACKGROUND

[0002] As a key process medium for steel and non-ferrous metal rolling, the rolling emulsion is currently mainly applied in the cold rolling link in the form of oil-in-water (O / W), and its core functions are cooling, lubrication and rust prevention between processes. The cooling function requires quickly taking away the heat of the rolling deformation zone to avoid affecting the precision due to the thermal deformation of the strip; the lubrication function reduces the friction coefficient by forming a stable oil film between the roller and the strip, thereby reducing the energy consumption and equipment loss; the rust prevention function is used to ensure that the strip does not rust in a short time after rolling. The three functions together determine the surface quality and production efficiency of the rolled strip, and are crucial to the production of high-precision rolling products such as cold rolled sheets.

[0003] The finish rolling emulsified oil is compounded by a base oil, a surfactant, an extreme pressure additive and other additives. The surfactant is the core of the product performance, which determines the dispersed particle size and dispersion stability of the oil in water, and also has an important influence on the oil film release process in the rolling deformation zone, thereby affecting the lubricating capacity of the emulsion.

[0004] The existing rolling emulsion can meet the needs of conventional production, but in the finish rolling production, there are higher requirements for the plate surface quality, and the problems in the application process are: on the one hand, the oil film is released slowly in the rolling deformation process, and uneven oil film is easy to cause color difference of the plate surface, reducing the quality of the plate, on the other hand, the oil film release capacity is poor, and the surfactant (regulator) needs to be supplemented within 7 days in the tank liquid circulation process; since the product performance is sensitive to the concentration of the surfactant, and the consumption rates of various surfactants are uneven, the oil film release capacity will decrease significantly after 3-6 months of use, thereby being difficult to meet the processing needs of high surface quality. SUMMARY

[0005] The present application aims to provide a finish rolling emulsified oil with good oil film release capacity and capable of continuously maintaining good oil film release capacity, and another object of the present application is to provide a preparation method of the finish rolling emulsified oil and a rolling emulsion containing the finish rolling emulsified oil.

[0006] Technical scheme: The finish rolling emulsified oil provided by the present application comprises the following components in parts by weight: 88-90 parts of base oil, 1.5-2 parts of phosphate ester polyoxyethylene polyoxypropylene ether, 1.5-2.3 parts of nitrogen-containing polymer, 0.3-0.4 parts of antioxidant, 2-2.9 parts of non-ionic surfactant, 3-5 parts of extreme pressure agent and 0.2-0.3 parts of rust inhibitor.

[0007] The structural general formula of the phosphate ester polyoxyethylene polyoxypropylene ether is: ; R1 is a C10-C20 saturated or unsaturated aliphatic hydrocarbon group; x and z are both integers between 1 and 15; x+z is an integer between 10 and 30; y is an integer between 1 and 10.

[0008] The nitrogen-containing polymer is a polyoxyethylene amine, and its structural formula is: ; R is a C16-C18 saturated or unsaturated aliphatic hydrocarbon group; n and m are both positive integers, and n+m is an integer between 8 and 14.

[0009] The addition ratio of the phosphate ester polyoxyethylene polyoxypropylene ether and the nitrogen-containing polymer is specifically that the molar amount of phosphate (P-OH) in the phosphate ester polyoxyethylene polyoxypropylene ether to the molar amount of nitrogen (N) in the nitrogen-containing polymer is 0.5-0.9. At this ratio, the finish rolling emulsified oil can achieve a sustained and good oil film releasing capacity. Too high or too low a ratio will result in weakening or loss of the oil film releasing capacity.

[0010] The antioxidant is at least one of 2,6-di-tert-butyl-p-cresol or octylated diphenylamine. The non-ionic surfactant is at least two of sorbitan fatty acid ester, C12-C14 fatty alcohol polyoxyethylene ether or octylphenol polyoxyethylene ether; wherein the number of ethylene oxide in the C12-C14 fatty alcohol polyoxyethylene ether or octylphenol polyoxyethylene ether is 6-8. The extreme pressure agent is a combination of sulfurized lard oil and phosphate ester; the mass ratio of the sulfurized lard oil to the phosphate ester is 1:2-3. The rust inhibitor is at least one of benzotriazole, methylbenzotriazole or imidazoline-based rust inhibitor. The base oil is a homogeneous mixture of at least two of stearate, diisooctyl adipate, refined coconut oil (RBD coconut oil) or refined palm oil (24-degree palm oil).

[0011] The preparation method of the above finish rolling emulsified oil comprises the following steps: (1) warm the base oil to 70-90℃ according to the formula amount; add the antioxidant and the rust inhibitor to the base oil according to the formula amount, uniformly stir until the antioxidant and the rust inhibitor are completely dissolved, and adjust the temperature to 50-65℃; (2) then add the extreme pressure agent, the phosphate ester polyoxyethylene polyoxypropylene ether, the nitrogen-containing polymer and the non-ionic surfactant to the oil liquid of step (1) according to the formula amount, uniformly stir to obtain the finish rolling emulsified oil.

[0012] The rolling emulsion containing the finishing rolling emulsifying oil comprises the following components in percentage by mass: 0.5-5% of the finishing rolling emulsifying oil and 95-99.5% of deionized water; the finishing rolling emulsifying oil is dispersed into the deionized water to form an emulsion system, and rolling is carried out in the form of the emulsion.

[0013] Advantages: Compared with the prior art, the rolling emulsion based on the finishing rolling emulsifying oil has the following remarkable advantages: the rolling emulsion has good oil film releasing capacity in the rolling process, thus having high lubricating performance and high plate surface cleaning performance (referring to YB / T 4302-2012 method, testing plate surface single-side residual oil < 250 mg / m 2 , the plate surface is clean after annealing), and can effectively prolong the adjustment period of the emulsion (1-2 months for adding additional adjustment agent) and improve the service life of the emulsion to 1-2 years. BRIEF DESCRIPTION OF DRAWINGS

[0014] Figure 1 The infrared spectrum of the phosphate ester polyoxyethylene ether polyoxypropylene ether prepared in Example 2. DETAILED DESCRIPTION

[0015] Example 1 The finishing rolling emulsifying oil comprises the following components in parts by weight: refined coconut oil 10 parts; refined palm oil 80 parts; phosphate ester polyoxyethylene polyoxypropylene ether 2 parts, R1 in the structure is C14 monounsaturated hydrocarbon, and x, y, z are respectively 12, 8, and 12 (the product model is P-EPE2000, and the structural formula is C 14 H 29 -O-(EO) 12 -(PO)8-(EO) 12 -P(=O)(OH)2); polyoxyethylene amine 1.5 parts, R in the structure is C16 saturated hydrocarbon, and the value of n+m is 10; 2,6-di-tert-butyl-p-cresol 0.4 parts; C14 fatty alcohol polyoxyethylene ether 2.5 parts, the number of ethylene oxide is 6; sorbitol polyether-30 tetraoleate 0.4 parts; phosphate ester 2 parts; sulfurized lard oil 1 part; imidazoline antirust agent 0.2 parts.

[0016] The preparation method of the finishing rolling emulsifying oil comprises the following steps: (1) The formula amount of base oil is heated to 80℃; the formula amount of antioxidant and antirust agent is added into the base oil, and uniformly stirred until the antioxidant and antirust agent are completely dissolved, and the temperature is adjusted to 60℃; (2) Then, the formula amount of extreme pressure agent, phosphate ester polyoxyethylene polyoxypropylene ether, polyoxyethylene amine, and non-ionic surfactant are sequentially added into the oil liquid of step (1), and uniformly stirred to obtain the finishing rolling emulsifying oil.

[0017] Example 2 The finish rolling emulsified oil comprises the following components in parts by weight: 5 parts of stearate; 3 parts of diisooctyl adipate; 80 parts of refined palm oil; 2 parts of phosphate ester polyoxyethylene polyoxypropylene ether, wherein R1 is C14 monounsaturated hydrocarbon, and x, y, z are 5, 2, and 8 respectively (structure formula: C 14 H 29 -O-(EO)5-(PO)2-(EO)8-P(=O)(OH)2); polyoxyethylene amine 2.3 parts, wherein R is C18 monounsaturated hydrocarbon, and n+m is 14; 2,6-di-tert-butyl-p-cresol 0.4 parts; C14 fatty alcohol polyoxyethylene ether 1.0 part, with 8 ethylene oxides; octylphenol polyoxyethylene ether 0.6 part, with 7 ethylene oxides; sorbitol polyether-30 tetraoleate 0.4 part; phosphate ester 3.5 parts; sulfurized lard oil 1.5 parts; imidazoline antirust agent 0.2 parts; methylbenzotriazole 0.1 part.

[0018] The preparation method of the finish rolling emulsified oil comprises the following steps: (1) The base oil in the formula amount is heated to 80℃; the antioxidant and the antirust agent in the formula amount are added into the base oil, and stirred uniformly until the antioxidant and the antirust agent are completely dissolved, and the temperature is adjusted to 60℃; (2) Then, the extreme pressure agent, the phosphate ester polyoxyethylene polyoxypropylene ether, the polyoxyethylene amine, and the non-ionic surfactant in the formula amount are sequentially added into the oil liquid in step (1), and stirred uniformly to obtain the finish rolling emulsified oil.

[0019] The preparation method of the phosphate ester polyoxyethylene polyoxypropylene ether in the embodiment is as follows: (1.1) In a reaction kettle, tetradecanol and the catalyst potassium hydroxide are mixed, heated to 100~130℃, and vacuum dehydrated to form an alcohol potassium active initiator; the mixture is kept at 100~130℃, and the ethylene oxide is slowly introduced (firstly added) under nitrogen protection; the system temperature is kept, and the propylene oxide is slowly introduced; the system temperature is kept, and the measured ethylene oxide is slowly introduced (secondly added); after the reaction is completed, the product is obtained through neutralization, decolorization, and filtration; wherein, the molar ratio of tetradecanol: the first added ethylene oxide: the propylene oxide: the second added ethylene oxide is 1:5:2:8; (1.2) Add the product from step (1.1) to the reactor. Under high-speed stirring and with the temperature controlled below 25°C, add phosphorus pentoxide in three batches at a molar ratio of 2.4:1 for the product from step (1.1). After adding phosphorus pentoxide, gradually increase the temperature to the esterification reaction temperature of 65°C to carry out the esterification reaction for 10 hours to obtain the esterified product. Separate and purify the monoesters in the esterified product obtained in step (1.2) by washing with water, neutralizing with saturated sodium carbonate, extracting with dichloromethane or ethyl acetate, and acidifying to obtain phosphate ester polyoxyethylene ether polyoxypropylene ether.

[0020] Depend on Figure 1 It can be seen that the product is at 2720cm -1 The absorption peak near the point is the stretching vibration of P-OH; 1240 cm⁻¹ -1 The absorption peak appears; it is the vibrational absorption peak of P=O, in the range of 1000~1150 cm⁻¹. -1 The absorption bands between these peaks are relatively broad, consistent with the POC absorption bands of phosphate monoesters; combined with these characteristic peaks, the presence of phosphate ester groups is confirmed. The product's absorption bands are between 2900 and 2820 cm⁻¹. -1 There is an absorption peak of CH stretching vibration at 1370 cm⁻¹. -1 The vibratory peak of -CH2- is located near 1100 cm⁻¹. -1 The broad peaks nearby represent the asymmetric stretching vibrations of COC. These characteristic peaks confirm the chain structure of polyoxyethylene and polyoxypropylene. Therefore, the structure of the reaction product, phosphate ester polyoxyethylene ether polyoxypropylene ether, is C. 14 H 29 -O-(EO)5-(PO)2-(EO)8-P(=O)(OH)2.

[0021] Example 3 This invention relates to a refined milling emulsified oil comprising the following components in parts by weight: 4 parts stearate; 3 parts diisooctyl adipate; 12 parts refined coconut oil; 70 parts refined palm oil; 2 parts phosphate ester polyoxyethylene polyoxypropylene ether, wherein R1 in the structure is a C14 monounsaturated hydrocarbon, and x, y, and z are 5, 2, and 8, respectively; 1.7 parts polyoxyethylene amine, wherein R in the structure is a C18 monounsaturated hydrocarbon, and n+m is 8; 0.3 parts 2,6-di-tert-butyl-p-cresol; 0.1 parts octyl diphenylamine; 1.0 part C14 fatty alcohol polyoxyethylene ether, with an ethylene oxide number of 8; 0.6 parts octylphenol polyoxyethylene ether, with an ethylene oxide number of 7; 0.4 parts sorbitol polyether-30 tetraoleate; 2.5 parts phosphate ester; 1.5 parts sulfurized lard; 0.2 parts imidazoline rust inhibitor; and 0.1 parts methylbenzotriazole.

[0022] The preparation method of the above-mentioned finishing emulsified oil includes the following steps: (1) The formula amount of base oil is heated to 80℃; the formula amount of antioxidant, rust inhibitor is added to the base oil, and stirred uniformly until the antioxidant, rust inhibitor is completely dissolved, and the temperature is adjusted to 60℃; (2) Then the formula amount of extreme pressure agent, phosphate ester polyoxyethylene polyoxypropylene ether, polyoxyethylene amine, non-ionic surfactant is added to the oil liquid of step (1) in turn, and stirred uniformly to obtain the finish rolling emulsified oil.

[0023] Comparative example 1 A finish rolling emulsified oil, comprising the following components in parts by weight: refined coconut oil 10 parts; refined palm oil 80 parts; phosphate ester polyoxyethylene polyoxypropylene ether 1.5 parts, R1 in the structure is C14 monounsaturated hydrocarbon, x, y, z values are 12, 8, 12 (P-EPE2000); polyoxyethylene amine 2 parts, R in the structure is C16 saturated hydrocarbon, n+m value is 10; 2,6-di-tert-butyl-p-cresol 0.4 parts; C14 fatty alcohol polyoxyethylene ether 2.5 parts, the number of ethylene oxide is 6; sorbitol polyether-30 tetraoleate 0.4 parts; phosphate ester 2 parts; sulfurized lard 1 part; imidazoline type rust inhibitor 0.2 parts.

[0024] The preparation method of the above-mentioned finish rolling emulsified oil, comprising the following steps: (1) The formula amount of base oil is heated to 80℃; the formula amount of antioxidant, rust inhibitor is added to the base oil, and stirred uniformly until the antioxidant, rust inhibitor is completely dissolved, and the temperature is adjusted to 60℃; (2) Then the formula amount of extreme pressure agent, phosphate ester polyoxyethylene polyoxypropylene ether, polyoxyethylene amine, non-ionic surfactant is added to the oil liquid of step (1) in turn, and stirred uniformly to obtain the finish rolling emulsified oil.

[0025] Comparative example 2 The finish rolling emulsified oil of the present application, comprising the following components in parts by weight: refined coconut oil 10 parts; refined palm oil 80 parts; phosphate ester polyoxyethylene polyoxypropylene ether 2 parts, R1 in the structure is C14 monounsaturated hydrocarbon, x, y, z values are 12, 8, 12 (P-EPE2000); polyoxyethylene amine 1.5 parts, R in the structure is C16 saturated hydrocarbon, n+m value is 10; 2,6-di-tert-butyl-p-cresol 0.4 parts; C14 fatty alcohol polyoxyethylene ether 2.5 parts, the number of ethylene oxide is 6; sorbitol polyether-30 tetraoleate 0.4 parts; phosphate ester 2 parts; sulfurized lard 1 part; imidazoline type rust inhibitor 0.2 parts.

[0026] The preparation method of the above-mentioned finish rolling emulsified oil, comprising the following steps: (1) The formula amount of base oil is heated to 80℃; the formula amount of antioxidant, rust inhibitor is added to the base oil, and stirred uniformly until the antioxidant, rust inhibitor is completely dissolved, and the temperature is adjusted to 60℃; (2) Then, the formula amount of extreme pressure agent, polyoxyethylene amine, phosphate ester polyoxyethylene polyoxypropylene ether, and non-ionic surfactant are sequentially added into the oil liquid of step (1), and stirred uniformly to obtain the finish rolling emulsified oil.

[0027] Comparative Example 3 The finish rolling emulsified oil of the present application comprises the following components in parts by weight: refined coconut oil 10 parts; refined palm oil 80 parts; phosphate ester polyoxyethylene polyoxypropylene ether 2 parts, wherein R1 in the structure is C14 monounsaturated hydrocarbon, and x, y, z are respectively 12, 8, 12 (P-EPE2000); polyoxyethylene amine 1.5 parts, wherein R in the structure is C16 saturated hydrocarbon, and the value of n+m is 10; 2,6-di-tert-butyl-p-cresol 0.4 parts; C14 fatty alcohol polyoxyethylene ether 2.5 parts, wherein the number of ethylene oxide is 6; sorbitol polyether-30 tetraoleate 0.4 parts; phosphate ester 2 parts; sulfurized lard oil 1 part; imidazoline type anti-rust agent 0.2 parts.

[0028] The preparation method of the finish rolling emulsified oil comprises the following steps: (1) The formula amount of base oil is heated to 80℃; the formula amount of antioxidant and anti-rust agent is added into the base oil, and stirred uniformly until the antioxidant and anti-rust agent are completely dissolved, and the temperature is adjusted to 60℃; (2) Then, the formula amount of extreme pressure agent, non-ionic surfactant, phosphate ester polyoxyethylene polyoxypropylene ether, and polyoxyethylene amine are sequentially added into the oil liquid of step (1), and stirred uniformly to obtain the finish rolling emulsified oil.

[0029] Evaluation of oil film rapid release capacity: the emulsion stability test is used to evaluate the oil film release capacity, and the lower the emulsion stability coefficient, the faster the oil film release. The emulsion stability coefficient should be stable between 30% and 70%, and if it is too high, the oil film release is slow, the rolling mill cleanliness is poor, the emulsion lubricating capacity is insufficient, and the plate surface quality is reduced; if it is too low, the oil film release is too fast, the plate surface is oily, and the plate surface quality is poor.

[0030] The finish rolling emulsified oils prepared in Examples 1-3 and Comparative Examples 1-3 are used to prepare rolling emulsions, and 30g of the finish rolling emulsified oil prepared in Examples 1-3 and Comparative Examples 1-3 is added into 6 parts of 970g deionized water to prepare 3wt.% oil-water emulsion.

[0031] 500mL of emulsion is taken and placed in a 1L separatory funnel, and after being placed in a 60℃ oven for 2h, 100mL of lower layer emulsion is discharged, the lower layer emulsion is dried with a halogen moisture meter, the oil content x% is tested, and the emulsion stability coefficient=x / 3*100% is tested, which is repeated for 3 times. After three tests, the emulsion stability of Examples 1-3 and Comparative Examples 1-3 is shown in Table 1.

[0032] Table 1

[0033] Examples 1-3 meet the performance requirements, and the stability of Comparative Example 1 is too high, and the test results of Comparative Examples 2-3 fluctuate greatly.

[0034] The oil-water emulsion of 20 L of the finishing emulsion oil based on Examples 1-3 and Comparative Examples 1-3 was prepared in the above manner, and the mass concentration of the emulsion was 3%. After the emulsion was circulated in a circulating test machine for 72 h, the 304 stainless steel was rolled by a small rolling mill for 200 m. After rolling, the above emulsion stability test was performed, and the emulsion stability of Examples 1-3 and Comparative Examples 1-3 was repeated three times, as shown in Table 2.

[0035] Table 2

[0036] Examples 1-3 meet the performance requirements, and the stability of Comparative Example 1 is too high, and the stability of Comparative Examples 2-3 meets the requirements.

[0037] The emulsion oil prepared in Example 1 was mixed with 19.4 L of water to prepare an oil-water emulsion of about 20 L at a concentration of 3 wt.%. The emulsion was circulated in a circulating test machine at a temperature of 60°C, and was used for rolling lubrication in a small rolling mill. When the liquid level was lower than 18 L, 2 L of the emulsion was discharged to a liquid level of 16 L, and the emulsion stability coefficient of the discharged emulsion was tested. An oil-water emulsion of about 4 L at a concentration of 3 wt.% was prepared using 120 g of the emulsion oil prepared in Example 1 and 3.88 L of water as a supplement, and was added as a supplement. If the ESI does not meet the requirements, additional adjusting agents need to be added to stabilize the tank liquid. The experiment was repeated multiple times to simulate the aging of the emulsion during rolling production, and each addition can simulate about 1.5 days of production consumption.

[0038] The emulsion stability coefficient changes of the emulsion based on the emulsion oil of Example 1 and the existing commercial rolling emulsion products A (SL97-CR) and B (TC-1) in the experiment are shown in Table 3: when the stability coefficient is > 70% or < 30%, additional adjusting agents need to be added to maintain the performance of the rolling emulsion.

[0039] Table 3

[0040] As can be seen from Table 3, the rolling emulsion based on the emulsion oil of the present application has a longer adjusting agent addition period.

Claims

1. A refined milling emulsified oil, characterized in that, It includes the following components in parts by weight: 88-90 parts base oil, 1.5-2 parts phosphate ester polyoxyethylene polyoxypropylene ether, 1.5-2.3 parts nitrogen-containing polymer, 0.3-0.4 parts antioxidant, 2-2.9 parts nonionic surfactant, 3-5 parts extreme pressure agent, and 0.2-0.3 parts rust inhibitor.

2. The refining emulsified oil according to claim 1, characterized in that: The general structural formula of the phosphate ester polyoxyethylene polyoxypropylene ether is: ； R1 is a C10~C20 saturated or unsaturated aliphatic hydrocarbon group; x and z are integers between 1 and 15; x+z is an integer between 10 and 30; y is an integer between 1 and 10.

3. The finishing emulsified oil according to claim 1, characterized in that: The nitrogen-containing polymer is polyoxyethylene amine, and its structural formula is: ； R is a C16~C18 saturated or unsaturated aliphatic hydrocarbon group; n and m are both positive integers, and n+m takes the value of an integer from 8 to 14.

4. The finishing emulsified oil according to claim 1, characterized in that: The antioxidant is at least one of 2,6-di-tert-butyl-p-cresol or octyl diphenylamine.

5. The refining emulsified oil according to claim 1, characterized in that: The nonionic surfactant is at least two of sorbitol polyether-30 tetraoleate, C12-C14 fatty alcohol polyoxyethylene ether, or octylphenol polyoxyethylene ether; wherein, in C12-C14 fatty alcohol polyoxyethylene ether and octylphenol polyoxyethylene ether, the number of ethylene oxides is 6-8.

6. The finishing emulsified oil according to claim 1, characterized in that: The extreme pressure agent is a combination of sulfurized lard and phosphate ester; the mass ratio of sulfurized lard to phosphate ester is 1:2~3.

7. The finishing emulsified oil according to claim 1, characterized in that: The rust inhibitor is at least one of benzotriazole, methylbenzotriazole, or imidazoline rust inhibitors.

8. The finishing emulsified oil according to claim 1, characterized in that: The base oil is a homogeneous mixture formed from at least two of stearate, diisooctyl adipate, refined coconut oil, or refined palm oil.

9. The method for preparing the refining emulsified oil according to claim 1, characterized in that, Includes the following steps: (1) Heat the base oil of the formula amount to 70~90℃; add the antioxidant and rust inhibitor of the formula amount to the base oil, stir evenly until the antioxidant and rust inhibitor are completely dissolved, and adjust the temperature to 50~65℃; (2) Then add the extreme pressure agent, phosphate ester polyoxyethylene polyoxypropylene ether, nitrogen-containing polymer and nonionic surfactant in the formula amount to the oil in step (1) and stir evenly to obtain fine rolling emulsified oil.

10. A rolling emulsion containing the finishing emulsified oil of claim 1, characterized in that: It includes the following components by weight percentage: 0.5-5% refined mill emulsified oil and 95-99.5% deionized water.

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