Method for preparing plasticizer for automobile rubber shock pad

Abstract

The invention discloses a method for preparing a plasticizer for an automobile rubber shock pad, and relates to the technical field of plasticizers for automobiles. The method comprises the following steps: by taking solvent extract oil in an extraction tower as a raw material, carrying out hydrofining at 200-240 DEG C by adopting a hydrotreating resin catalyst, and carrying out reduced pressure distillation on the hydrogenated oil to obtain the rubber plasticizer for the rubber shock pad. The hydrotreating resin catalyst is obtained through reaction of aminophosphonic acid resin / nickel, 2, 3-ethylene oxide dicarboxylic acid palladium and 4, 4 '-diaminobiphenyl-2, 2'-dicarboxylic acid palladium. The resin immobilized palladium / nickel catalyst adopted in the method has good stability and reusability, the loss and cost of the catalyst can be reduced, the dispersity and stability of the catalyst are enhanced, the catalytic effect is improved, the hydrogenation reaction of the solvent extract oil is promoted, and the hydrogenation yield is improved.

Description

Technical Field

[0001] The invention relates to the technical field of automobile plasticizers, in particular to a method for preparing a plasticizer for an automobile rubber shock-absorbing pad. Background Art

[0002] The rapid development of China's automobile industry has promoted the development of other related supporting industries in my country, especially the rubber industry. Rubber shock-absorbing products are mainly installed in engines, car bodies, air conditioners and car suspension systems. They are mainly used to reduce vibration and noise during car driving and improve the stability, safety and comfort of car control. With the continuous improvement of the comprehensive performance of modern automobiles, higher and higher requirements are placed on the performance and quality of rubber shock-absorbing products. The main requirement is that shock-absorbing products should have excellent shock-absorbing and damping performance, dynamic fatigue resistance and ultra-long life durability. Automobile rubber shock-absorbing products mainly include air springs, front and rear engine suspension pads, flexible couplings, and rubber bushings and gaskets of various shapes. Special shock absorbers with excellent performance are also installed in each tire support on high-end cars.

[0003] Plasticizers are widely used in rubber products due to their good effects, small dosage, fast absorption speed, good compatibility with rubber, and low volatility. Petroleum-based plasticizers are one of the most commonly used plasticizers in rubber processing. They have good plasticizing effects, abundant sources, and low costs. Petroleum-based plasticizers are made by selecting appropriate crude oil for atmospheric and vacuum distillation. The main varieties include operating oil, third-line oil, transformer oil, engine oil, light and heavy oil, paraffin, vaseline, asphalt, and petroleum resin.

[0004] Heavy aromatic oil hydrorefining catalyst and method for producing BTX from heavy aromatic oil (Chinese patent application number: CN202011185527.8) The heavy aromatic oil hydrorefining catalyst includes a metal active component and a carrier for loading the metal active component, wherein the carrier is prepared by mixing and calcining natural sponge powder and aluminum hydroxide dry rubber powder, and the metal active component includes a metal oxide; the pore volume of the heavy aromatic oil hydrorefining catalyst is 0.9-1.3 ml / g, and the specific surface area is 150-350 m 2 / g, crushing strength is 300N·cm -1 The heavy aromatic oil hydrorefining catalyst prepared by the present invention has the advantages of large specific surface area and good activity; at the same time, the method of the present invention converts cheap and inferior heavy aromatic oil into high value-added liquefied gas and triphenylene products, which significantly improves the comprehensive economy of the reforming device.

[0005] A method for preparing a low-viscosity green rubber plasticizer (Chinese patent application number: CN201610451477.0). The method comprises the following steps: using kaolin to refine cycloalkane-minus-one fraction oil, and obtaining refined oil after removing the kaolin; distilling and cutting the refined oil to remove light components and heavy components, thereby obtaining a low-viscosity green rubber plasticizer. The physical and chemical parameters of the low-viscosity green rubber plasticizer are as follows: chromaticity not higher than 1.1; pour point not lower than -30°C; C A The value is not less than 16%; the benzo[a]pyrene content is less than 1 mg / kg.

[0006] In addition to the need to further improve the product yield of the plasticizer prepared in the above public information and prior art, plasticizer C A The value is also poor and the process is complicated. Summary of the invention

[0007] The main purpose of the present invention is to provide a method for preparing a plasticizer for automobile rubber shock-absorbing pads, so as to overcome the shortcomings of the prior art.

[0008] In order to achieve the above-mentioned invention object, the technical solution adopted by the present invention includes: The embodiment of the present invention provides a method for preparing a plasticizer for an automobile rubber shock-absorbing pad, and the operating steps are as follows: The solvent extracted oil in the extraction tower is used as raw material, and a hydrogenation resin catalyst is used to carry out hydrogenation refining at 200-240°C. The hydrogenated oil is distilled under reduced pressure to obtain a rubber plasticizer for a rubber shock-absorbing pad.

[0009] Preferably, the solvent in the extraction tower is a mixture of furfural and N-methylpyrrolidone, and the mass ratio thereof is furfural:N-methylpyrrolidone=(1-9):9.

[0010] Preferably, the addition ratio of the hydrotreating resin catalyst is 10-20% by volume of the hydrotreating reactor.

[0011] Preferably, the preparation method of the hydrotreating resin catalyst is: S1: Add 1000-1500 parts by weight of a 0.05-0.5 mol / L nickel nitrate aqueous solution into a reaction kettle 1, then add 100-120 parts of an aminophosphonic acid resin, stir at 30-40° C. for 10-30 h, then filter, wash, and dry to obtain a product 1; S2: Add 0.5-1.5 parts of palladium chloride, 0.03-0.06 parts of 4,4'-diaminobiphenyl-2,2'-dicarboxylic acid and 1000-1500 parts of ethanol into reactor 2 by weight, stir at 30-40°C for 20-50 h, then add 6-12 parts of 2,3-ethylene oxide dicarboxylic acid, stir at 60-70°C for 60-100 minutes, then add 100-160 parts of product 1 and 2-5 parts of potassium hydroxide, stir at the temperature for 100-140 minutes, then filter, wash and vacuum dry to obtain a hydrogenation resin catalyst.

[0012] Preferably, the aminophosphonic acid resin is Purolite S940.

[0013] Preferably, the volume ratio of hydrogen to oil during the hydrotreating process is (800-1600):1.

[0014] Preferably, the hydrogen oil volume space velocity during the hydrofining process is 0.1-2 / h.

[0015] Preferably, the hydrogen partial pressure during the hydrotreating process is 10-20 MPa.

[0016] Preferably, the rubber plasticizer for rubber shock-absorbing pads can be used in the automotive industry.

[0017] Technical effects: First, aminophosphonic acid resin / nickel reacts with 2,3-oxirane dicarboxylic acid palladium to undergo amino-epoxy reaction, and 4,4'-diaminobiphenyl-2,2'-dicarboxylic acid palladium reacts with 2,3-oxirane dicarboxylic acid palladium to undergo amino-epoxy reaction, to obtain a palladium / nickel ion complex immobilized on the resin by complexation. Subsequently, in the hydrogenation process, hydrogen is used to reduce the palladium / nickel element immobilized on the resin to a hydrogenation catalyst, which can improve the hydrogenation yield of solvent-extracted oil.

[0018] The aminophosphonic acid resin / nickel and palladium 2,3-oxirane dicarboxylate undergo an amino-epoxy reaction, and a similar reaction occurs between palladium 4,4'-diaminobiphenyl-2,2'-dicarboxylate and palladium 2,3-oxirane dicarboxylate to form a resin-supported palladium / nickel ion complex. During the hydrogenation process, the resin-supported palladium / nickel ion complex is reduced by hydrogen to a supported palladium / nickel hydrogenation catalyst. The supported palladium / nickel hydrogenation catalyst plays a catalytic role in the hydrogenation reaction. The palladium and nickel elements have high hydrogenation activity and can effectively convert the carbon-carbon double bonds in the oil into single bonds, thereby increasing the hydrogen yield of the oil. The resin-supported palladium / nickel catalyst has good stability and reusability, which can reduce the loss and cost of the catalyst. The aminophosphonic acid resin can complex palladium and nickel ions, enhance the dispersibility and stability of the catalyst, and improve the catalytic effect. It promotes the hydrogenation reaction of the solvent-extracted oil and improves the hydrogenation yield. DETAILED DESCRIPTION

[0019] In view of the deficiencies in the prior art, the inventor of this case, after long-term research and extensive practice, was able to propose the technical solution of the present invention. The technical solution, its implementation process and principle, etc. will be further explained as follows.

[0020] Example 1 A method for preparing a plasticizer for an automobile rubber shock-absorbing pad, the operating steps of the method are as follows: The solvent extracted oil in the extraction tower is used as raw material, and a hydrogenation resin catalyst is used to carry out hydrogenation refining at 200°C. The hydrogenated oil is distilled under reduced pressure to obtain a rubber plasticizer for a rubber shock-absorbing pad.

[0021] The solvent in the extraction tower is a mixture of furfural and N-methylpyrrolidone, and the mass ratio of furfural to N-methylpyrrolidone is 1:9.

[0022] The addition ratio of the hydrotreating resin catalyst is: 10% by volume of the hydrotreating reactor.

[0023] The preparation method of the hydrotreating resin catalyst: S1: Add 1000 g of 0.05 mol / L nickel nitrate aqueous solution into reaction kettle 1, then add 100 g of aminophosphonic acid resin, stir at 30° C. for 10 h, then filter, wash, and dry to obtain product 1; S2: Add 0.5g palladium chloride, 0.03g 4,4'-diaminobiphenyl-2,2'-dicarboxylic acid, and 1000g ethanol into reactor 2, stir at 30°C for 20h, then add 6g 2,3-ethylene oxide dicarboxylic acid, stir at 60°C for 60 minutes, then add 100g product 1,2g potassium hydroxide, keep warm and stir for 100 minutes, then filter, wash, and vacuum dry to obtain a hydrogenation treatment resin catalyst.

[0024] The aminophosphonic acid resin is Purolite S940.

[0025] The volume ratio of hydrogen to oil in the hydrotreating process is 800:1.

[0026] The hydrogen oil volume space velocity during the hydrofining process is 0.1 / h.

[0027] The hydrogen partial pressure during the hydrotreating process is 10 MPa.

[0028] Example 2 A method for preparing a plasticizer for an automobile rubber shock-absorbing pad, the operating steps of the method are as follows: The solvent extracted oil in the extraction tower is used as raw material, and a hydrogenation resin catalyst is used to carry out hydrogenation refining at 220°C. The hydrogenated oil is distilled under reduced pressure to obtain a rubber plasticizer for a rubber shock-absorbing pad.

[0029] The solvent in the extraction tower is a mixture of furfural and N-methylpyrrolidone, and the mass ratio of furfural to N-methylpyrrolidone is 3:9.

[0030] The addition ratio of the hydrotreating resin catalyst is: 15% by volume of the hydrotreating reactor.

[0031] Preferably, the preparation method of the hydrotreating resin catalyst is: S1: Add 1200 g of 0.15 mol / L nickel nitrate aqueous solution into reaction kettle 1, then add 110 g of aminophosphonic acid resin, stir at 35°C for 20 h, then filter, wash, and dry to obtain product 1; S2: Add 1g palladium chloride, 0.04g 4,4'-diaminobiphenyl-2,2'-dicarboxylic acid, and 1250g ethanol into reactor 2, stir at 35°C for 35h, then add 8g 2,3-ethylene oxide dicarboxylic acid, stir at 65°C for 80 minutes, then add 120g product 1,3g potassium hydroxide, stir at this temperature for 120 minutes, then filter, wash, and vacuum dry to obtain a hydrogenation resin catalyst.

[0032] The aminophosphonic acid resin is Purolite S940.

[0033] The volume ratio of hydrogen to oil in the hydrotreating process is 1200:1.

[0034] The hydrogen oil volume space velocity during the hydrofining process is 0.5 / h.

[0035] The hydrogen partial pressure during the hydrotreating process is 15 MPa.

[0036] Example 3 A method for preparing a plasticizer for an automobile rubber shock-absorbing pad, the operating steps of the method are as follows: The solvent extracted oil in the extraction tower is used as raw material, and a hydrogenation resin catalyst is used to carry out hydrogenation refining at 220°C. The hydrogenated oil is distilled under reduced pressure to obtain a rubber plasticizer for a rubber shock-absorbing pad.

[0037] The solvent in the extraction tower is a mixture of furfural and N-methylpyrrolidone, and the mass ratio of the mixture is furfural:N-methylpyrrolidone=6:9.

[0038] The addition ratio of the hydrotreating resin catalyst is: 15% by volume of the hydrotreating reactor.

[0039] The preparation method of the hydrotreating resin catalyst: S1: Add 1400 g of 0.35 mol / L nickel nitrate aqueous solution into reaction kettle 1, then add 110 g of aminophosphonic acid resin, stir at 35°C for 20 h, then filter, wash, and dry to obtain product 1; S2: Add 1g palladium chloride, 0.05g 4,4'-diaminobiphenyl-2,2'-dicarboxylic acid, and 1250g ethanol into reactor 2, stir at 35°C for 40h, then add 10g 2,3-ethylene oxide dicarboxylic acid, stir at 65°C for 80min, then add 140g product 1, 4g potassium hydroxide, keep warm and stir for 130min, then filter, wash, and vacuum dry to obtain a hydrogenation resin catalyst.

[0040] The aminophosphonic acid resin is Purolite S940.

[0041] The volume ratio of hydrogen to oil in the hydrotreating process is 1400:1.

[0042] The hydrogen-to-oil volume space velocity during the hydrofining process is 1 / h.

[0043] The hydrogen partial pressure during the hydrotreating process is 15 MPa.

[0044] Example 4 A method for preparing a plasticizer for an automobile rubber shock-absorbing pad, the operating steps of the method are as follows: The solvent extracted oil in the extraction tower is used as raw material, and a hydrogenation resin catalyst is used to carry out hydrogenation refining at 240°C. The hydrogenated oil is distilled under reduced pressure to obtain a rubber plasticizer for a rubber shock-absorbing pad.

[0045] The solvent in the extraction tower is a mixture of furfural and N-methylpyrrolidone, and the mass ratio thereof is furfural:N-methylpyrrolidone=1:1.

[0046] The addition ratio of the hydrotreating resin catalyst is: 20% by volume of the hydrotreating reactor.

[0047] The preparation method of the hydrotreating resin catalyst: S1: Add 1500 g of 0.5 mol / L nickel nitrate aqueous solution into reaction kettle 1, then add 120 g of aminophosphonic acid resin, stir at 40° C. for 30 h, then filter, wash, and dry to obtain product 1; S2: Add 1.5g palladium chloride, 0.06g 4,4'-diaminobiphenyl-2,2'-dicarboxylic acid, and 1500g ethanol into reactor 2, stir at 40°C for 50 h, then add 12g 2,3-ethylene oxide dicarboxylic acid, stir at 70°C for 100 minutes, then add 160g product 1,5g potassium hydroxide, keep warm and stir for 140 minutes, then filter, wash, and vacuum dry to obtain a hydrogenation resin catalyst.

[0048] The aminophosphonic acid resin is Purolite S940.

[0049] The volume ratio of hydrogen to oil in the hydrotreating process is 1600:1.

[0050] The hydrogen-to-oil volume space velocity during the hydrofining process is 2 / h.

[0051] The hydrogen partial pressure during the hydrotreating process is 20 MPa.

[0052] Comparative Example 1 A method for preparing a plasticizer for an automobile rubber shock-absorbing pad, the operating steps of the method are as follows: The solvent extracted oil in the extraction tower is used as raw material, and a hydrogenation resin catalyst is used to carry out hydrogenation refining at 200°C. The hydrogenated oil is distilled under reduced pressure to obtain a rubber plasticizer for a rubber shock-absorbing pad.

[0053] The solvent in the extraction tower is a mixture of furfural and N-methylpyrrolidone, and the mass ratio of furfural to N-methylpyrrolidone is 1:9.

[0054] The addition ratio of the hydrotreating resin catalyst is: 10% by volume of the hydrotreating reactor.

[0055] The preparation method of the hydrotreating resin catalyst: S1: Add 1000 g of 0.05 mol / L nickel nitrate aqueous solution into reaction kettle 1, then add 100 g of aminophosphonic acid resin, stir at 30° C. for 10 h, then filter, wash, and dry to obtain product 1; S2: Add 0.5g palladium chloride and 1000g ethanol into reactor 2, stir at 30°C for 20h, then add 6g 2,3-ethylene oxide dicarboxylic acid, stir at 60°C for 60min, then add 100g product 1,2g potassium hydroxide, stir at this temperature for 100min, then filter, wash, and vacuum dry to obtain a hydrogenation resin catalyst.

[0056] The aminophosphonic acid resin is Purolite S940.

[0057] The volume ratio of hydrogen to oil in the hydrotreating process is 800:1.

[0058] The hydrogen oil volume space velocity during the hydrofining process is 0.1 / h.

[0059] The hydrogen partial pressure during the hydrotreating process is 10 MPa.

[0060] Comparative Example 2 A method for preparing a plasticizer for an automobile rubber shock-absorbing pad, the operating steps of the method are as follows: The solvent extracted oil in the extraction tower is used as raw material, and a hydrogenation resin catalyst is used to carry out hydrogenation refining at 200°C. The hydrogenated oil is distilled under reduced pressure to obtain a rubber plasticizer for a rubber shock-absorbing pad.

[0061] The solvent in the extraction tower is a mixture of furfural and N-methylpyrrolidone, and the mass ratio of furfural to N-methylpyrrolidone is 1:9.

[0062] The addition ratio of the hydrotreating resin catalyst is: 10% by volume of the hydrotreating reactor.

[0063] The preparation method of the hydrotreating resin catalyst: S1: Add 1000 g of 0.05 mol / L nickel nitrate aqueous solution into reaction kettle 1, then add 100 g of aminophosphonic acid resin, stir at 30° C. for 10 h, then filter, wash, and dry to obtain product 1; S2: Add 0.03g 4,4'-diaminobiphenyl-2,2'-dicarboxylic acid and 1000g ethanol into reactor 2, stir at 30°C for 20h, then add 6g 2,3-ethylene oxide dicarboxylic acid, stir at 60°C for 60min, then add 100g product 1,2g potassium hydroxide, keep warm and stir for 100min, then filter, wash, and vacuum dry to obtain a hydrogenation treatment resin catalyst.

[0064] The aminophosphonic acid resin is Purolite S940.

[0065] The volume ratio of hydrogen to oil in the hydrotreating process is 800:1.

[0066] The hydrogen oil volume space velocity during the hydrofining process is 0.1 / h.

[0067] The hydrogen partial pressure during the hydrotreating process is 10 MPa.

[0068] Evaluation of the embodiment: Performance Testing The rubber plasticizers obtained in Examples 1-4 and Comparative Examples 1-2 were tested as follows: 1) Yield (relative to solvent extracted oil), % 2) Density at 20℃, g / cm 3 : Tested in accordance with GB / T 1884; 3) Kinematic viscosity at 100℃, mm 2 / s: Tested in accordance with GB / T 265; 4) Open cup flash point, °C: Tested in accordance with GB / T 3536; 5) CA value, %: tested in accordance with SH / T 0725; 6) Aniline point, °C: Tested in accordance with GB / T 262; 7) BaP content, mg / kg: tested according to the first method of SN / T 1877.3-2007; 8) PAHs content, mg / kg: tested in accordance with SN / T 1877.3-2007 method 1.

[0069] The test results are shown in Table 1: Table 1 The plasticizers prepared in the above examples and comparative examples are used to prepare rubber shock-absorbing pads, and the preparation method is as follows: 50kg of hydrogenated nitrile rubber, 35kg of polyurethane rubber, 45kg of butadiene rubber, 6kg of fiber, 6kg of carbon black, 2kg of defoaming agent, 4kg of paraffin, 5kg of stearic acid, 4kg of sulfur, 2kg of accelerator tetraethylthiuram disulfide, 5kg of plasticizer and 4kg of anti-aging agent p-phenylenediamine.

[0070] The rubber shock-absorbing pad is tested for performance. The specific testing method is as follows: Mechanical properties test: XL-250A tensile testing machine was used to test in accordance with GB / T528.

[0071] The specific test results are shown in Table 2: Table 2 It should be understood that the above embodiments are only for illustrating the technical concept and features of the present invention, and their purpose is to enable people familiar with the technology to understand the content of the present invention and implement it accordingly, and they cannot be used to limit the protection scope of the present invention. Any equivalent changes or modifications made according to the spirit of the present invention should be included in the protection scope of the present invention.

Claims

1. A method for preparing a plasticizer for an automobile rubber shock-absorbing pad, the operating steps of which are: The solvent extracted oil in the extraction tower is used as raw material, and a hydrogenation resin catalyst is used to carry out hydrogenation refining at 200-240°C. The hydrogenated oil is subjected to vacuum distillation to obtain a rubber plasticizer for a rubber shock-absorbing pad; The hydrogenation treatment resin catalyst is obtained by reacting aminophosphonic acid resin / nickel, 2,3-oxirane dicarboxylate palladium and 4,4'-diaminobiphenyl-2,2'-dicarboxylate palladium.

2. A method for preparing a plasticizer for automotive rubber shock-absorbing pads according to claim 1, characterized in that: The solvent in the extraction tower is a mixture of furfural and N-methylpyrrolidone, and the mass ratio thereof is furfural:N-methylpyrrolidone=(1-9):

9.

3. The method for preparing a plasticizer for automobile rubber shock-absorbing pad according to claim 1, characterized in that: The addition ratio of the hydrotreating resin catalyst is: 10-20% by volume of the hydrotreating reactor.

4. The method for preparing a plasticizer for automobile rubber shock-absorbing pad according to claim 1, characterized in that: The preparation method of the hydrotreating resin catalyst: S1: Add 1000-1500 parts by weight of a 0.05-0.5 mol / L nickel nitrate aqueous solution into a reaction kettle 1, then add 100-120 parts of an aminophosphonic acid resin, stir at 30-40° C. for 10-30 h, then filter, wash, and dry to obtain a product 1; S2: Add 0.5-1.5 parts of palladium chloride, 0.03-0.06 parts of 4,4'-diaminobiphenyl-2,2'-dicarboxylic acid and 1000-1500 parts of ethanol into reactor 2 by weight, stir at 30-40°C for 20-50 h, then add 6-12 parts of 2,3-ethylene oxide dicarboxylic acid, stir at 60-70°C for 60-100 minutes, then add 100-160 parts of product 1 and 2-5 parts of potassium hydroxide, stir at the temperature for 100-140 minutes, then filter, wash and vacuum dry to obtain a hydrogenation resin catalyst.

5. A method for preparing a plasticizer for automobile rubber shock-absorbing pad according to claim 4, characterized in that: The aminophosphonic acid resin is Purolite S940.

6. The method for preparing a plasticizer for automobile rubber shock-absorbing pad according to claim 1, characterized in that: The volume ratio of hydrogen to oil in the hydrotreating process is (800-1600):

1.

7. The method for preparing a plasticizer for automobile rubber shock-absorbing pad according to claim 1, characterized in that: The hydrogen oil volume space velocity in the hydrofining process is 0.1-2 / h.

8. The method for preparing a plasticizer for automobile rubber shock-absorbing pad according to claim 1, characterized in that: The hydrogen partial pressure during the hydrofining process is 10-20 MPa.

9. The method for preparing a plasticizer for automobile rubber shock-absorbing pad according to claim 1, characterized in that: The rubber plasticizer for the rubber shock-absorbing pad can be used in the automobile industry.

Images