Aluminum foil rolling oil with ultralow oil content and preparation method thereof
By preparing aluminum foil rolling oil containing thiazole carbon nanotube polymer, the problems of poor lubricity and wear resistance during aluminum foil rolling are solved, low oil content and high oil film strength are achieved, and it is suitable for high cleanliness fields.
Patent Information
- Application Number
- CN202511031371.0
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-07-25
- Publication Date
- 2025-09-26
AI Technical Summary
Existing aluminum foil rolling oil has problems such as poor lubricity, low oil film strength, poor wear resistance and corrosion resistance during the rolling process, resulting in a high amount of residual oil on the surface of the aluminum foil, affecting product quality and performance.
A composition containing 80-90% base oil, 9-15% rolling oil additives and 1-5% thiazole carbon nanotube polymer is used to prepare ultra-low oil content aluminum foil rolling oil through hydrogenation refining and ultrasonic dispersion technology. The special molecular structure of thiazole carbon nanotube polymer and the high thermal conductivity of carbon nanotubes are utilized to form a stable oil film to reduce residue on the aluminum foil surface.
The aluminum foil has extremely low oil content on the surface, high oil film strength, excellent wear resistance and corrosion resistance, ensuring the surface smoothness and conductive properties of the aluminum foil. It is suitable for high-cleanliness fields such as food packaging and medicinal aluminum foil.
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Abstract
Description
Technical Field
[0001] The invention relates to the technical field of lubricating oils, in particular to an ultra-low oil content aluminum foil rolling oil and a preparation method thereof. Background Art
[0002] Aluminum foil generally refers to a rolled product with a thickness of less than 0.2mm and a rectangular cross-section. It is lightweight, airtight, and has good wrapping properties. It can protect against light, moisture, odor, and pollution, making it an excellent packaging and decorative material. The production of aluminum foil involves multiple steps such as melting, hot rolling, and cold rolling. Among them, rolling the aluminum strip into aluminum foil through mechanical cold rolling is the most critical step. During the cold rolling process, special rolling lubricants are required to ensure a smooth surface and clean, cool, and lubricate the rolling process. Modern aluminum foil rolling mills run at very high speeds, and the surface of the aluminum foil just rolled has varying degrees of oil. If the rolling oil viscosity is high and the product has a large amount of oil, residue will remain on the surface of the aluminum foil after annealing, causing oil spots or oil stickiness, which will reduce the bonding strength of the aluminum foil product with other substances. This will limit the application of materials that need to be directly coated on the surface of the aluminum foil. Therefore, the preparation of an aluminum foil rolling oil with ultra-low oil content is of great practical significance.
[0003] Animal and vegetable oils were the earliest rolling lubricants used, primarily composed of stearic acid, oleic acid, and palmitic acid. They offer excellent lubrication, high oil film strength, and a low friction coefficient, but they also suffer from poor oxidation stability, are prone to deterioration during use, and the free organic acids released at high temperatures are highly corrosive to metals. During annealing, they can easily leave oil spots on metal surfaces, affecting product quality. Traditional aluminum foil rolling oils use mineral oil as a base oil, with lubrication properties enhanced by the addition of extreme pressure agents, oiliness enhancers, and antioxidants. However, existing technologies require reducing the amount of additives to minimize oil carryover, which can weaken the oil film strength, leading to increased roll wear and increased surface roughness. After rolling, an oil film remains on the surface of aluminum foil. Traditional oil films have low surface tension, which indirectly increases the surface contact angle. High levels of residual oil on the foil surface (e.g., >30 mg / m²) can easily lead to annealing oil spots and carbide deposition, affecting the foil's surface finish and electrical conductivity.
[0004] During the cold rolling process of aluminum foil, the working rolls of the foil rolling mill come into contact with the aluminum foil. The aluminum foil is thinned to the target thickness according to different rolling passes. The deformation heat and friction heat of the metal increase the temperature of the rolled piece and the rolls. This is more prominent when the processing rate is large, the rolling speed is high, and the pressure is high. In order to obtain sufficient lubrication effect to ensure the smooth progress of aluminum foil rolling, the following requirements must be met: the base oil must have appropriate viscosity, good antioxidant properties, a suitable friction coefficient, a strong oil film, no damage under high pressure, uniform adhesion, and no corrosion to the rolled piece and rolls; it must not evaporate easily during annealing and not easily cause oil spots on the product surface; it must be low in sulfur, low in aromatics, non-toxic, odorless, and abundant in resources. Currently, existing rolling lubricants have problems such as poor lubricity, low oil film strength, poor wear resistance, and poor corrosion resistance. The present invention, through the collaborative innovation of base oil and additives, breaks through the contradiction between the oil volume and performance of traditional aluminum foil rolling oils, and has significant economic and social benefits. Summary of the Invention
[0005] The purpose of the present invention is to overcome the shortcomings of the existing technology and provide an ultra-low oil content aluminum foil rolling oil and a preparation method thereof. The ultra-low oil content, high lubricity and environmental protection can meet the needs of high cleanliness fields such as food packaging and medicinal aluminum foil.
[0006] To achieve the above object, the technical solution adopted by the present invention is: An aluminum foil rolling oil with ultra-low oil content comprises the following components by mass fraction: 80-90% of base oil, 9-15% of rolling oil additive and 1-5% of thiazole carbon nanotube polymer ester.
[0007] Among them, the base oil is C12 or C13 normal alkane that has been hydrorefined and precisely fractionated.
[0008] Among them, the rolling oil additives include 35-45% dioctyl sebacate, 20-30% extreme pressure agent, 15-20% non-ionic emulsifier, 8-12% co-emulsifier, and 3-5% antioxidant.
[0009] Wherein, the antioxidant is 2,6-di-tert-butyl-p-cresol or bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite.
[0010] The preparation method of aluminum foil rolling oil with ultra-low oil content is as follows: add a nonionic emulsifier and an emulsifier co-emulsifier to the base oil, stir evenly, then add dioctyl sebacate, an extreme pressure agent and an antioxidant, stir at 35-50°C for 30-40 minutes, then add thiazole carbon nanotube polymer, and disperse in an ultrasonic disperser with a power of 20-30KHz for 10-20 minutes to obtain aluminum foil rolling oil with ultra-low oil content.
[0011] Furthermore, the extreme pressure agent is any one of diethyl dithiophosphate, dodecyl diphenyl phosphate or di-n-butyl phosphite.
[0012] Furthermore, the nonionic emulsifier is nonylphenol polyoxyethylene ether; and the auxiliary emulsifier is a mixture of oleic acid, triethanolamine and n-propanol in a mass ratio of 1:1:1.
[0013] Furthermore, the preparation method of thiazole carbon nanotube polymer ester is carried out according to the following steps: Step (1): under a nitrogen atmosphere, 2-amino-6-methoxybenzothiazole and N,N-dimethylformamide were added to a reaction flask, and after stirring evenly, 4,4'-(1,1,3,3-tetramethyldisiloxane-1,3-diyl)dibutyric acid, HATU and triethylamine were added, and the mixture was stirred for reaction. After the reaction was completed, the mixture was cooled to room temperature, extracted with ethyl acetate and deionized water, and the organic phase was purified by column chromatography (DCM / MeOH=20:1), and concentrated and dried to obtain a dimethoxythiazole organosilicon monomer.
[0014] Step (2): Add dimethoxythiazole organosilicon monomer and dichloromethane to a reaction flask under a nitrogen atmosphere, stir evenly, then add boron tribromide, react at 0-20°C for 12-24 hours, extract with ethyl acetate and deionized water, concentrate the organic phase, and dry to obtain thiazole organosilicon diol monomer. The preparation reaction formula is as follows:
[0015] Step (3): under nitrogen atmosphere, add adipic acid, propylene glycol, hydroxylated carbon nanotubes and thiazole organosilicon diol monomer to the reaction flask, stir and heat in an oil bath at 200-220°C until almost no fraction is generated, add a catalyst and a thermal stabilizer, continue the reaction for 3-8 hours, and distill under reduced pressure to obtain thiazole carbon nanotube polymer.
[0016] Furthermore, in step (1), the ratio of 2-amino-6-methoxybenzothiazole, 4,4'-(1,1,3,3-tetramethyldisiloxane-1,3-diyl)dibutyric acid, HATU, and triethylamine is 1 mol: (1.02-1.1) mol: (2.4-2.8) mol: (2.6-3) mol.
[0017] Furthermore, in step (1), the reaction temperature is 40-60° C., and the reaction time is 8-16 h.
[0018] Furthermore, in step (2), the ratio of dimethoxythiazole organosilicon monomer to boron tribromide is 1 mol: (3.2-4.5) mol.
[0019] Furthermore, in step (3), the ratio of adipic acid, propylene glycol, hydroxylated carbon nanotubes, and thiazole organosilicon diol monomer is 100 g: (45-60) g: (15-20) g: (2-10) g.
[0020] Furthermore, in step (3), the catalyst is tetrabutyl titanate and the thermal stabilizer is triphenyl phosphite.
[0021] By adopting the above technical solution, the beneficial effects of the present invention are: (1) Good antioxidant properties: The rolling oil prepared by the present invention is uniform and transparent, and the oil film strength reaches up to 362.6N. It can maintain the minimum rollable thickness under a smaller wear spot diameter. The rolling additives contain fatty acids, fatty alcohols and esters with polar groups, which can be firmly adsorbed on the metal surface, realize the separation of the roller and the aluminum foil, and play a lubricating role. The rolling base oil is a C12 or C13 normal alkane, and the chain angle and chain length of its carbon atoms are symmetrical structures, with directionality and a tight directional arrangement. It is very firmly adsorbed on the surface of the aluminum foil and is not easy to produce oxidation reaction.
[0022] (2) Excellent wear resistance and corrosion inhibition performance, high oil film strength: Thiazole carbon nanotube polymer contains long-chain fatty acids, which are similar to dioctyl sebacate in rolling additives. Carbon nanotubes can convert sliding friction into rolling friction. When in contact with the friction surface, the polar groups in the polymer generate chemical adsorption force with the aluminum surface, and the non-polar groups attract each other in the opposite direction to form a multi-molecular layer, so that the oil film can withstand huge rolling pressure in the vertical direction, and convert the dry friction between the roller and the rolled piece into internal friction between the oil film molecules. The wear spot diameter is greatly reduced, achieving the purpose of lubrication; at the same time, the thermal conductivity of carbon nanotubes is much higher than that of traditional additives, which can quickly conduct rolling heat and prevent the oil film from breaking; in addition, silicone has a low surface tension, which can improve the spreading ability of rolling oil, making it easier for rolling oil to form an oil film on the friction pair surface, and the film-forming ability is stronger, that is, the oil film can bear greater pressure, so that the aluminum foil can be rolled thinner.
[0023] (3) The amount of oil on the surface of the aluminum foil is extremely low: the rolling oil of the present application has basically no residue on the surface of the aluminum foil after use, because the thiazole carbon nanotube polymer has a special molecular structure, and the carbon nanotube component therein has high strength and good lubricity. Its high thermal conductivity can accelerate the diffusion of friction heat, avoid local overheating and oil film rupture, maintain stable lubrication conditions, promote the uniform spreading of the oil film on the surface of the aluminum foil, form a complete and dense oil film, reduce local oil accumulation caused by uneven oil film, and thus reduce the overall oil content; the sulfur and nitrogen atoms in the thiazole group can undergo chemical adsorption with the surface of the aluminum foil to form chemical bonds, so that the oil film is more firmly attached to the surface of the aluminum foil, ensuring the integrity of the oil film, and can reduce the shedding and splashing of the oil film during rolling, and reduce the amount of oil remaining on the surface of the aluminum foil. DETAILED DESCRIPTION
[0024] The compounds of the present invention and their preparation methods and applications are further described in detail below with reference to specific examples. The present invention can be implemented in many different forms and is not limited to the embodiments described herein. On the contrary, the purpose of providing these embodiments is to provide a more thorough and comprehensive understanding of the disclosure of the present invention. Unless otherwise indicated, the raw materials and reagents used in this application are all commercially available products or can be prepared by known methods.
[0025] Preparation of hydroxylated carbon nanotubes: 6 g of carbon nanotubes were mixed with 200 mL of concentrated sulfuric acid and magnetically stirred at room temperature for 24 h. Then, 200 mL of concentrated nitric acid was added and the mixture was refluxed at 140°C for 30 min. The mixture was then washed with distilled water several times, filtered, and dried to obtain hydroxylated carbon nanotubes.
[0026] 2-Amino-6-methoxybenzothiazole, CAS number is 1747-60-0.
[0027] 4,4'-(1,1,3,3-tetramethyldisiloxane-1,3-diyl)dibutyric acid, CAS number 3353-68-2.
[0028] Example 1
[0029] (1) Under nitrogen atmosphere, 35 mmol of 2-amino-6-methoxybenzothiazole and 140 mL of N,N-dimethylformamide were added to the reaction flask. After stirring evenly, 37.1 mmol of 4,4'-(1,1,3,3-tetramethyldisiloxane-1,3-diyl)dibutyric acid, 91 mmol of HATU and 98 mmol of triethylamine were added. The mixture was reacted at 50 °C for 12 h, cooled to room temperature, extracted with ethyl acetate and deionized water, and the organic phase was purified by column chromatography (DCM / MeOH = 20:1). After concentration and drying, the dimethoxythiazole organosilicon monomer was obtained.
[0030] (2) Under nitrogen atmosphere, 30 mmol of dimethoxythiazole organosilicon monomer and 195 mL of dichloromethane were added to the reaction flask. After stirring evenly, 114 mmol of boron tribromide was added and the mixture was reacted at 10°C for 16 h. The mixture was extracted with ethyl acetate and deionized water. The organic phase was concentrated and dried to obtain the thiazole organosilicon diol monomer.
[0031] (3) Under nitrogen atmosphere, 100 g of adipic acid, 50 g of propylene glycol, 15 g of hydroxylated carbon nanotubes and 2 g of thiazole organosilicon diol monomer were added to the reaction flask, and the mixture was stirred and heated in an oil bath at 210 °C until almost no fraction was generated. 0.8 g of tetrabutyl titanate and 0.05 g of triphenyl phosphite were added, and the reaction was continued for 5 h. The mixture was then distilled under reduced pressure to obtain thiazole carbon nanotube polymer.
[0032] (4) 9 g of rolling oil additive was added to 90 g of C12 normal alkane, wherein the rolling oil additive included 18% of nonylphenol polyoxyethylene ether, 12% of emulsifier (oleic acid, triethanolamine and n-propanol in a mass ratio of 1:1:1), 40% of dioctyl sebacate, 25% of diethyl dithiophosphate and 5% of 2,6-di-tert-butyl-p-cresol, and stirred at 45 °C for 35 min. Then, 1 g of thiazole carbon nanotube polymer was added and dispersed in an ultrasonic disperser with a power of 25 kHz for 15 min to obtain aluminum foil rolling oil with ultra-low oil content.
[0033] Example 2
[0034] (1) Under nitrogen atmosphere, 200 mmol of 2-amino-6-methoxybenzothiazole and 600 mL of N,N-dimethylformamide were added to the reaction flask. After stirring evenly, 204 mmol of 4,4'-(1,1,3,3-tetramethyldisiloxane-1,3-diyl)dibutyric acid, 480 mmol of HATU and 520 mmol of triethylamine were added. The mixture was reacted at 60 °C for 8 h. After cooling to room temperature, the mixture was extracted with ethyl acetate and deionized water. The organic phase was purified by column chromatography (DCM / MeOH = 20:1) and concentrated to dryness to obtain dimethoxythiazole organosilicon monomer.
[0035] (2) Under nitrogen atmosphere, 180 mmol of dimethoxythiazole organosilicon monomer and 900 mL of dichloromethane were added to the reaction flask. After stirring evenly, 576 mmol of boron tribromide was added. The mixture was reacted at 20°C for 12 h. The mixture was extracted with ethyl acetate and deionized water. The organic phase was concentrated and dried to obtain the thiazole organosilicon diol monomer.
[0036] (3) Under nitrogen atmosphere, 100 g of adipic acid, 45 g of propylene glycol, 16 g of hydroxylated carbon nanotubes and 4 g of thiazole organosilicon diol monomer were added to the reaction flask, and the mixture was stirred and heated in an oil bath at 220 °C until almost no fraction was generated. 0.8 g of tetrabutyl titanate and 0.05 g of triphenyl phosphite were added, and the reaction was continued for 3 h. The mixture was then distilled under reduced pressure to obtain thiazole carbon nanotube polymer.
[0037] (4) 10 g of rolling oil additive was added to 88 g of C13 normal alkane, wherein the rolling oil additive included 15% of nonylphenol polyoxyethylene ether, 8% of emulsifier (oleic acid, triethanolamine and n-propanol in a mass ratio of 1:1:1), 44% of dioctyl sebacate, 30% of dodecyl diphenyl phosphate and 3% of bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, and the mixture was stirred at 50 °C for 30 min. Then, 2 g of thiazole carbon nanotube polymer was added and the mixture was dispersed in an ultrasonic disperser with a power of 30 kHz for 10 min to obtain aluminum foil rolling oil with ultra-low oil content.
[0038] Example 3
[0039] (1) Under nitrogen atmosphere, 80 mmol of 2-amino-6-methoxybenzothiazole and 400 mL of N,N-dimethylformamide were added to the reaction flask. After stirring evenly, 88 mmol of 4,4'-(1,1,3,3-tetramethyldisiloxane-1,3-diyl)dibutyric acid, 224 mmol of HATU and 240 mmol of triethylamine were added. The mixture was reacted at 40 °C for 16 h. After cooling to room temperature, the mixture was extracted with ethyl acetate and deionized water. The organic phase was purified by column chromatography (DCM / MeOH = 20:1) and concentrated to dryness to obtain dimethoxythiazole organosilicon monomer.
[0040] (2) Under nitrogen atmosphere, 60 mmol of dimethoxythiazole organosilicon monomer and 480 mL of dichloromethane were added to the reaction flask. After stirring evenly, 270 mmol of boron tribromide was added and the mixture was reacted at 0°C for 24 h. The mixture was extracted with ethyl acetate and deionized water. The organic phase was concentrated and dried to obtain the thiazole organosilicon diol monomer.
[0041] (3) Under nitrogen atmosphere, 100 g of adipic acid, 60 g of propylene glycol, 18 g of hydroxylated carbon nanotubes and 6 g of thiazole organosilicon diol monomer were added to the reaction flask, and the mixture was stirred and heated in an oil bath at 200 °C until almost no fraction was generated. 0.8 g of tetrabutyl titanate and 0.05 g of triphenyl phosphite were added, and the reaction was continued for 8 h. The mixture was then distilled under reduced pressure to obtain thiazole carbon nanotube polymer.
[0042] (4) 12 g of rolling oil additive was added to 85 g of C12 normal alkane, wherein the rolling oil additive included 20% of nonylphenol polyoxyethylene ether, 12% of co-emulsifier (oleic acid, triethanolamine and n-propanol in a mass ratio of 1:1:1), 35% of dioctyl sebacate, 30% of di-n-butyl phosphite and 3% of 2,6-di-tert-butyl-p-cresol, and stirred at 35 °C for 40 min. Then, 3 g of thiazole carbon nanotube polymer was added and dispersed in an ultrasonic disperser with a power of 20 kHz for 20 min to obtain aluminum foil rolling oil with ultra-low oil content.
[0043] Example 4
[0044] (1) Under nitrogen atmosphere, 120 mmol of 2-amino-6-methoxybenzothiazole and 540 mL of N,N-dimethylformamide were added to the reaction flask. After stirring evenly, 125 mmol of 4,4'-(1,1,3,3-tetramethyldisiloxane-1,3-diyl)dibutyric acid, 306 mmol of HATU and 340 mmol of triethylamine were added. The mixture was reacted at 45 °C for 15 h. After cooling to room temperature, the mixture was extracted with ethyl acetate and deionized water. The organic phase was purified by column chromatography (DCM / MeOH = 20:1) and concentrated to dryness to obtain dimethoxythiazole organosilicon monomer.
[0045] (2) Under nitrogen atmosphere, 105 mmol of dimethoxythiazole organosilicon monomer and 590 mL of dichloromethane were added to the reaction flask. After stirring evenly, 400 mmol of boron tribromide was added and the mixture was reacted at 5°C for 20 h. The mixture was extracted with ethyl acetate and deionized water. The organic phase was concentrated and dried to obtain the thiazole organosilicon diol monomer.
[0046] (3) Under nitrogen atmosphere, 100 g of adipic acid, 48 g of propylene glycol, 19 g of hydroxylated carbon nanotubes and 8 g of thiazole organosilicon diol monomer were added to the reaction flask, and the mixture was stirred and heated in an oil bath at 205 °C until almost no fraction was generated. 0.8 g of tetrabutyl titanate and 0.05 g of triphenyl phosphite were added, and the reaction was continued for 7 h. The mixture was then distilled under reduced pressure to obtain thiazole carbon nanotube polymer.
[0047] (4) 14 g of rolling oil additive was added to 82 g of C13 normal alkane, wherein the rolling oil additive included 20% of nonylphenol polyoxyethylene ether, 8% of co-emulsifier (oleic acid, triethanolamine and n-propanol in a mass ratio of 1:1:1), 38% of dioctyl sebacate, 30% of diethyl dithiophosphate and 4% of bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, and the mixture was stirred at 40 °C for 40 min. Then, 4 g of thiazole carbon nanotube polymer was added and dispersed in an ultrasonic disperser with a power of 28 kHz for 18 min to obtain aluminum foil rolling oil with ultra-low oil content.
[0048] Example 5
[0049] (1) Under nitrogen atmosphere, 100 mmol of 2-amino-6-methoxybenzothiazole and 350 mL of N,N-dimethylformamide were added to the reaction flask. After stirring evenly, 108 mmol of 4,4'-(1,1,3,3-tetramethyldisiloxane-1,3-diyl)dibutyric acid, 265 mmol of HATU and 290 mmol of triethylamine were added. The mixture was reacted at 60 °C for 16 h. After cooling to room temperature, the mixture was extracted with ethyl acetate and deionized water. The organic phase was purified by column chromatography (DCM / MeOH = 20:1) and concentrated to dryness to obtain dimethoxythiazole organosilicon monomer.
[0050] (2) Under nitrogen atmosphere, 85 mmol of dimethoxythiazole organosilicon monomer and 580 mL of dichloromethane were added to the reaction flask. After stirring evenly, 325 mmol of boron tribromide was added and the mixture was reacted at 5°C for 24 h. The mixture was extracted with ethyl acetate and deionized water. The organic phase was concentrated and dried to obtain the thiazole organosilicon diol monomer.
[0051] (3) Under nitrogen atmosphere, 100 g of adipic acid, 52 g of propylene glycol, 20 g of hydroxylated carbon nanotubes and 10 g of thiazole organosilicon diol monomer were added to the reaction flask, and the mixture was stirred and heated in an oil bath at 220 °C until almost no fraction was generated. 0.8 g of tetrabutyl titanate and 0.05 g of triphenyl phosphite were added, and the reaction was continued for 5 h. The mixture was then distilled under reduced pressure to obtain thiazole carbon nanotube polymer.
[0052] (4) 15 g of rolling oil additive was added to 80 g of C12 normal alkane, wherein the rolling oil additive included 16% of nonylphenol polyoxyethylene ether, 10% of co-emulsifier (oleic acid, triethanolamine and n-propanol in a mass ratio of 1:1:1), 41% of dioctyl sebacate, 28% of dodecyl diphenyl phosphate and 5% of 2,6-di-tert-butyl-p-cresol, and stirred at 45 °C for 35 min. Then, 5 g of thiazole carbon nanotube polymer was added and dispersed in an ultrasonic disperser with a power of 30 kHz for 20 min to obtain aluminum foil rolling oil with ultra-low oil content.
[0053] Comparative Example 1 (1) Under nitrogen atmosphere, 100 g of adipic acid, 50 g of propylene glycol and 2 g of thiazole organosilicon diol monomer (prepared in Example 1) were added to a reaction flask, and the mixture was stirred and heated in an oil bath at 210°C until almost no fraction was generated. 0.8 g of tetrabutyl titanate and 0.05 g of triphenyl phosphite were added, and the reaction was continued for 5 h. The mixture was then distilled under reduced pressure to obtain a thiazole-based polymer.
[0054] (2) 9 g of rolling oil additive was added to 90 g of C12 normal alkane, wherein the rolling oil additive included 18% of nonylphenol polyoxyethylene ether, 12% of co-emulsifier (oleic acid, triethanolamine and n-propanol in a mass ratio of 1:1:1), 40% of dioctyl sebacate, 25% of diethyl dithiophosphate and 5% of 2,6-di-tert-butyl-p-cresol, and stirred at 45 °C for 35 min. Then, 1 g of thiazolyl polymer was added and dispersed in an ultrasonic disperser with a power of 25 kHz for 15 min to obtain aluminum foil rolling oil.
[0055] Comparative Example 2 (1) Under nitrogen atmosphere, 100 g of adipic acid, 50 g of propylene glycol, and 15 g of hydroxylated carbon nanotubes were added to a reaction flask. The mixture was stirred and heated in an oil bath at 210 °C until almost no fraction was generated. 0.8 g of tetrabutyl titanate and 0.05 g of triphenyl phosphite were added, and the reaction was continued for 5 h. The mixture was then distilled under reduced pressure to obtain a carbon nanotube-based polymer.
[0056] (2) 9 g of rolling oil additive was added to 90 g of C12 normal alkane, wherein the rolling oil additive included 18% of nonylphenol polyoxyethylene ether, 12% of co-emulsifier (oleic acid, triethanolamine and n-propanol in a mass ratio of 1:1:1), 40% of dioctyl sebacate, 25% of diethyl dithiophosphate and 5% of 2,6-di-tert-butyl-p-cresol, and stirred at 45 °C for 35 min. Then, 1 g of carbon nanotube-based polymer was added and dispersed in an ultrasonic disperser with a power of 25 kHz for 15 min to obtain aluminum foil rolling oil.
[0057] Comparative Example 3 To 90 g of C12 normal alkane, 10 g of a rolling oil additive was added, wherein the rolling oil additive included 18% of nonylphenol polyoxyethylene ether, 12% of an emulsifier (oleic acid, triethanolamine and n-propanol in a mass ratio of 1:1:1), 40% of dioctyl sebacate, 25% of diethyl dithiophosphate and 5% of 2,6-di-tert-butyl-p-cresol. The mixture was stirred at 45°C for 35 min and dispersed in an ultrasonic disperser with a power of 25 kHz for 15 min to obtain aluminum foil rolling oil.
[0058] Appearance of rolling oil: Obtained by visual inspection at room temperature.
[0059] Oil film strength test: refer to GB / T 3142 Determination of load-bearing capacity of lubricants (four-ball method), speed is 1450r / min, running time is 10s.
[0060] Wear resistance test: refer to SH / T 0189 lubricating oil anti-wear performance test method, speed is 950-1450r / min, load is 225N, running time is 60min, wear spot diameter is measured on an optical microscope.
[0061] Corrosion resistance test: Tested in accordance with GB / T 5096, under the conditions of copper sheet corrosion (100°C, 3h).
[0062] Minimum rollable thickness: An industrial rolling test was conducted on a two-roll irreversible, intermittent rolling mill with a roll diameter of 530 mm, a roll length of 1550 m, a main motor power of 300 kW, a rolling speed of 40 m / min, and a 1160 industrial pure aluminum plate (200 × 200 × 0.5) mm rolled sample. Six passes were performed, with the last two passes being pressed against each other. The minimum rollable thickness of the aluminum foil after rolling was directly measured using a spiral micrometer.
[0063] Table 1 Basic performance test of rolling oil Rolling oil appearance (room temperature) Oil film strength (N) Wear spot diameter (mm) Copper corrosion (level) Minimum rollable thickness (μm) Example 1 Uniform and transparent 274.4 0.641 2b 15 Example 2 Uniform and transparent 303.8 0.523 2a 12 Example 3 Uniform and transparent 333.2 0.455 1b 8 Example 4 Uniform and transparent 352.8 0.420 1a 4 Example 5 Uniform and transparent 362.6 0.406 1a 3 Comparative Example 1 Uniform and transparent 269.5 0.818 2b 16 Comparative Example 2 Uniform and transparent 259.7 0.652 2e 18 Comparative Example 3 Uniform and transparent 230.3 1.021 3a 22 The oil film formed by the rolling oil during the rolling process can separate the rollers and the rolled piece; it can be seen from the test results in the above table that with the increase of the content of thiazole carbon nanotube polymer ester, the basic performance of the rolling oil is significantly improved. The rolling oils prepared in the embodiments are all in a uniform and transparent oil body state, the oil film strength can reach up to 362.6N, and it can maintain the minimum rollable thickness under a smaller wear spot diameter, indicating that the prepared rolling oil has good performance. This is because, on the one hand, the rolling additives contain fatty acids, fatty alcohols and esters with polar groups, which can be firmly adsorbed on the metal surface to achieve the separation of the rollers and the aluminum foil and play a lubricating role. The rolling base oil is a C12 or C13 normal alkane, the chain angle and chain length of its carbon atoms are symmetrical structures, with directionality and a tight directional arrangement. It is very firmly adsorbed on the surface of the aluminum foil and is not easy to produce oxidation reactions; on the other hand, the thiazole carbon nanotube polymer ester Rice tube polymer contains long-chain fatty acids, which are similarly compatible with dioctyl sebacate in rolling additives. Carbon nanotubes can convert sliding friction into rolling friction. When in contact with the friction surface, the polar groups in the polymer generate chemical adsorption force with the aluminum surface, and the non-polar groups attract each other in the opposite direction to form a multi-molecular layer, so that the oil film can withstand huge rolling pressure in the vertical direction, and the dry friction between the roller and the rolled piece is converted into internal friction between the oil film molecules, and the wear spot diameter is greatly reduced, achieving the purpose of lubrication; at the same time, the thermal conductivity of carbon nanotubes is much higher than that of traditional additives, which can quickly conduct rolling heat and prevent the oil film from rupturing; in addition, silicone has a low surface tension, which can improve the spreading ability of rolling oil, making it easier for rolling oil to form an oil film on the surface of the friction pair, and the film-forming ability is stronger, that is, the oil film can withstand greater pressure, so that the aluminum foil can be rolled thinner. Comparative Example 1 does not contain carbon nanotubes and has poor wear resistance; Comparative Example 2 does not contain thiazole groups and has poor corrosion resistance; Comparative Example 3 does not contain any modifier and has the worst overall performance.
[0064] Test for the amount of oil on the surface of aluminum foil: Aluminum foil rolled with the rolling oils of the examples and comparative examples was cut into 7 cm × 7 cm specimens and placed upright in beakers. The surface of the aluminum foil was eluted with carbon tetrachloride via a fine dropper (carbon tetrachloride can dissolve the grease on the surface of the aluminum foil), and the elution liquid was continuously transferred to a 50 mL volumetric flask until the scale line was reached. The solution was shaken and the carbon tetrachloride extract was transferred to a 4 cm quartz cuvette. The absorbance of the solution was tested by infrared method to calculate the amount of oil on the surface of the aluminum foil.
[0065] Table 2 Test of oil content on aluminum foil surface <![CDATA[Oil content (mg / m 2 )]]> Example 1 18 Example 2 12 Example 3 8 Example 4 4 Example 5 3 Comparative Example 1 23 Comparative Example 2 26 Comparative Example 3 35 From the test results in the table above, it can be seen that with the increase of the content of thiazole carbon nanotube polymer, the amount of oil on the aluminum foil surface is significantly reduced. The amount of oil in Example 5 is only 3 mg / m 2 , which shows that the rolling oil of the present application leaves basically no residue on the surface of the aluminum foil after use. This is because the thiazole carbon nanotube polymer has a special molecular structure, and the carbon nanotube component therein has high strength and good lubricity. Its high thermal conductivity can accelerate the diffusion of frictional heat, avoid local overheating and oil film rupture, maintain stable lubrication conditions, promote the uniform spreading of the oil film on the surface of the aluminum foil, form a complete and dense oil film, reduce local oil accumulation caused by uneven oil film, and thus reduce the overall oil content; the sulfur and nitrogen atoms in the thiazole group can undergo chemical adsorption with the surface of the aluminum foil to form chemical bonds, so that the oil film is more firmly attached to the surface of the aluminum foil, ensuring the integrity of the oil film, and can reduce the shedding and splashing of the oil film during rolling, and reduce the amount of oil remaining on the surface of the aluminum foil.
[0066] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.
Claims
1. A method for preparing ultra-low oil content aluminum foil rolling oil, characterized in that: The ultra-low oil content aluminum foil rolling oil comprises the following components by mass fraction: 80-90% base oil, 9-15% rolling oil additive and 1-5% thiazole carbon nanotube polymer ester; The base oil is C12 or C13 normal alkane that has been hydrorefined and precisely fractionated; The rolling oil additive includes 35-45% of dioctyl sebacate, 20-30% of extreme pressure agent, 15-20% of nonionic emulsifier, 8-12% of co-emulsifier, and 3-5% of antioxidant; The antioxidant is 2,6-di-tert-butyl-p-cresol or bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite; The preparation method of the ultra-low oil content aluminum foil rolling oil comprises the following steps: adding a nonionic emulsifier and an emulsifier co-emulsifier to a base oil, stirring evenly, then adding dioctyl sebacate, an extreme pressure agent and an antioxidant, stirring at 35-50° C. for 30-40 minutes, then adding thiazole carbon nanotube polymer, and dispersing in an ultrasonic disperser with a power of 20-30 kHz for 10-20 minutes to obtain the ultra-low oil content aluminum foil rolling oil.
2. The method for preparing the ultra-low oil content aluminum foil rolling oil according to claim 1, characterized in that: The extreme pressure agent is any one of diethyl dithiophosphate, dodecyl diphenyl phosphate or di-n-butyl phosphite.
3. The method for preparing the ultra-low oil content aluminum foil rolling oil according to claim 1, characterized in that: The nonionic emulsifier is nonylphenol polyoxyethylene ether; the auxiliary emulsifier is prepared by compounding oleic acid, triethanolamine and n-propanol in a mass ratio of 1:1:
1.
4. The method for preparing the ultra-low oil content aluminum foil rolling oil according to claim 1, characterized in that: The preparation method of the thiazole carbon nanotube polymer is carried out according to the following steps: Step (1), under a nitrogen atmosphere, add 2-amino-6-methoxybenzothiazole and N,N-dimethylformamide to a reaction flask, stir evenly, add 4,4'-(1,1,3,3-tetramethyldisiloxane-1,3-diyl)dibutyric acid, HATU and triethylamine, stir and react, after the reaction is completed, cool to room temperature, extract with ethyl acetate and deionized water, purify the organic phase by column chromatography, and concentrate and dry to obtain a dimethoxythiazole organosilicon monomer; Step (2), under a nitrogen atmosphere, add dimethoxythiazole organosilicon monomer and dichloromethane to a reaction flask, stir evenly, add boron tribromide, react at 0-20°C for 12-24h, extract with ethyl acetate and deionized water, concentrate the organic phase, and dry to obtain thiazole organosilicon diol monomer; Step (3): under nitrogen atmosphere, add adipic acid, propylene glycol, hydroxylated carbon nanotubes and thiazole organosilicon diol monomer to the reaction flask, stir and heat in an oil bath at 200-220°C until almost no fraction is generated, add a catalyst and a thermal stabilizer, continue the reaction for 3-8 hours, and distill under reduced pressure to obtain thiazole carbon nanotube polymer.
5. The method for preparing the ultra-low oil content aluminum foil rolling oil according to claim 4, characterized in that: In the step (1), the ratio of 2-amino-6-methoxybenzothiazole, 4,4'-(1,1,3,3-tetramethyldisiloxane-1,3-diyl)dibutyric acid, HATU, and triethylamine is 1 mol: (1.02-1.1) mol: (2.4-2.8) mol: (2.6-3) mol.
6. The method for preparing the ultra-low oil content aluminum foil rolling oil according to claim 4, characterized in that: In step (1), the reaction temperature is 40-60° C. and the reaction time is 8-16 h.
7. The method for preparing the ultra-low oil content aluminum foil rolling oil according to claim 4, characterized in that: In the step (2), the ratio of dimethoxythiazole organosilicon monomer to boron tribromide is 1 mol: (3.2-4.5) mol.
8. The method for preparing the ultra-low oil content aluminum foil rolling oil according to claim 4, characterized in that: In the step (3), the ratio of adipic acid, propylene glycol, hydroxylated carbon nanotubes, and thiazole organosilicon diol monomer is 100 g: (45-60) g: (15-20) g: (2-10) g.
9. The method for preparing ultra-low oil content aluminum foil rolling oil according to claim 4, characterized in that: In step (3), the catalyst is tetrabutyl titanate and the thermal stabilizer is triphenyl phosphite.
10. An ultra-low oil content aluminum foil rolling oil, characterized in that: The method is obtained by the preparation method according to any one of claims 1 to 9.