CN113072741B - Environment-friendly p-phenylenediamine anti-aging agent and preparation method and application thereof - Google Patents
Environment-friendly p-phenylenediamine anti-aging agent and preparation method and application thereof Download PDFInfo
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- C07C209/10—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of halogen atoms with formation of amino groups bound to carbon atoms of six-membered aromatic rings or from amines having nitrogen atoms bound to carbon atoms of six-membered aromatic rings
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- C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
- C07C209/36—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst
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Abstract
The invention discloses an environment-friendly p-phenylenediamine anti-aging agent, a preparation method and application thereof. The p-phenylenediamine anti-aging agent with the structure shown in the formula (I) has good anti-aging performance, does not generate high-toxicity quinone products, and has the functions of ozone, heat and oxygen aging protection; the rubber vulcanized rubber using the environment-friendly p-phenylenediamine anti-aging agent has excellent physical properties and aging resistance, and is environment-friendly and non-toxic, and the rubber residues are subjected to toxicity detection, and high-toxicity quinone products are not detected.
Description
Technical Field
The invention relates to the technical field of mechanical engineering pumps, in particular to a pump shaft connecting device of a sliding vane pump.
Background
Rubber is gradually aged due to its structure change under the action of oxygen, ozone, acid, alkali, water, etc. in the air or under the action of heat, ultraviolet rays, mechanical force, etc. to deteriorate its physical properties. The most effective method for preventing rubber fatigue aging is to add a certain amount of anti-aging agent, and the anti-aging agent plays a role by improving the stability of structural change in the rubber fatigue process.
The most widely used type of antioxidant at present is p-phenylenediamine; for example, the rubber antioxidant 4020, which is chemically N- (1, 3-dimethylbutyl) -N' -phenyl-p-phenylenediamine, is a highly efficient rubber antioxidant as the antioxidants 4010NA and 4010 belong to the p-phenylenediamine class. The p-phenylenediamine anti-aging agent can be applied to tires and cables of transportation tools and rubber products for waterproof engineering, has excellent protective performance, and can protect ozone, flexion aging, oxygen, heat and other general aging; it also has good protection effect on harmful metals such as copper, manganese and the like.
31 hundred million tires are newly produced in the world every year, and the number of tires in the world is huge in addition to the quantity of the retained tires; debris from the friction of a huge amount of tires against the ground will pose a threat to the environment and human health, the impact of which can be even comparable to that of micro-plastics in the sea. More feasibly, the antioxidants in these tire chips become more toxic in the natural environment through "mutation"; according to the report in journal of Science in 2020, the product of reaction of p-phenylenediamine antioxidants with ozone in natural environment is probably lethal toxin, professor team of Edward P.Kolodziej of Washington university (Science,2020-12-3.DOI:10.1126/science.abd6951) studied the half lethal concentration LC of 6 PPD-quinone conversion product 6 PPD-quinone of anti-aging agent 6PPD50The concentration of the quinone derivative is only 0.79 plus or minus 0.16 mu g/L, the half lethal concentration of tire filtrate is 0.82 plus or minus 0.27 mu g/L, and the quinone generated by ozone aging of the p-phenylenediamine anti-aging agent is the substance with the highest toxicity in the tire. Therefore, the development of an environment-friendly anti-aging agent is urgently needed, the anti-aging agent is prevented from generating quinone by ozone aging, and the harm of tire rubber residues to the environment and human health is reduced.
Disclosure of Invention
In order to solve the problems, the invention provides the environment-friendly p-phenylenediamine anti-aging agent and the preparation method and the application thereof.
The technical scheme adopted by the invention is as follows:
an environment-friendly p-phenylenediamine anti-aging agent has a structure shown in formula (I):
in the formula (I), R1、R1’Is selected from C1-C18Or a chain or alicyclic hydrocarbon group of (3) or H, R2、R3Is selected from C1-C18Is a chain hydrocarbon group orR2And R3Formation of an alicyclic ring, R4、R5Is selected from C1-C18With a chain hydrocarbon radical of (2) or R4And R5Forming an alicyclic ring; x is 0 or 1, y is 0 or 1, z is 0 or 1, w is 0 or 1, and at least one of x and w is 1, and at least one of y and z is 1.
Preferably, the structure of formula (I) is
Wherein R is1、R1’Is selected from C1-C18Or a chain or alicyclic hydrocarbon group of (3) or H, R2、R3Is selected from C1-C18With a chain hydrocarbon group of (2) or R2And R3Forming an alicyclic ring.
Preferably, the structure of formula (I) is
Wherein R is1、R1’Is selected from C1-C18Or a chain hydrocarbon or alicyclic hydrocarbon of (3) or H, R3、R5Is selected from C1-C18A chain hydrocarbon group of (2).
Preferably, the structure of formula (I) is
Wherein R is1、R1’Is selected from C1-C18Or a chain or alicyclic hydrocarbon group of (2) or H, R2、R3Is selected from C1-C18With a chain hydrocarbon radical of (2) or R2And R3Formation of an alicyclic ring, R4、R5Is selected from C1-C18A chain hydrocarbon group of (2).
Preferably, the structure of formula (I) is:
wherein R is1、R1’Is selected from C1-C18Or a chain or alicyclic hydrocarbon group of (2) or H, R2、R3Is selected from C1-C18With a chain hydrocarbon group of (2) or R2And R3Formation of an alicyclic ring, R4、R5Is selected from C1-C18With a chain hydrocarbon radical of (2) or R4And R5Forming an alicyclic ring.
When the existing p-phenylenediamine anti-aging agent reacts with ozone, p-benzoquinone is easily generated on a benzene ring of p-phenylenediamine, because 4 positions left after p-amino substitution on the benzene ring of the p-phenylenediamine are in a relatively electron-rich activated state, the p-benzoquinone is easily oxidized into the p-benzoquinone by ozone or oxygen in the atmosphere, and the p-benzoquinone is a substance with high toxicity. According to the environment-friendly p-phenylenediamine anti-aging agent provided by the invention, the benzene ring of p-phenylenediamine is subjected to substitution end sealing, so that the condition that the para position is exposed simultaneously is avoided, and the p-phenylenediamine anti-aging agent is not oxidized to generate p-benzoquinone with high toxicity; therefore, the rubber tire adopting the environment-friendly p-phenylenediamine anti-aging agent is friendly to the environment and human health after the rubber residue generated in the using process or aging.
The invention also provides a preparation method of the environment-friendly p-phenylenediamine anti-aging agent shown as the formula (I), aniline and p-bromonitrobenzene with corresponding substituent groups are subjected to C-N coupling reaction, the obtained coupling product is subjected to reduction reaction in a hydrogen atmosphere under a catalytic condition to obtain a reaction intermediate, and the reaction intermediate and aldehyde or ketone are subjected to reductive amination reaction under a catalytic condition to obtain the p-phenylenediamine anti-aging agent.
Preferably, the C-N coupling reaction is carried out in an inert atmosphere, and the molar ratio of the aniline to the p-bromonitrobenzene with corresponding substituent groups is 1: 1.0-1.2; the catalyst of the C-N coupling reaction is a palladium catalyst selected from Pd2(dba)3(Tris (dibenzylideneacetone) dipalladium), Pd (OAc)2(Palladium acetate), Pd (PPh)3)4(tetrakis (triphenylphosphine) palladium) or Pd (acac)2(bis (acetylacetonato) palladium (II)); the ligand of the palladium catalyst is selected from phosphine ligand XPhos (2-dicyclohexylphosphine-2 ',4',6 '-triisopropylbiphenyl), phosphine ligand SPhos (2-dicyclohexylphosphine-2', 6 '-dimethoxy-1, 1' -biphenyl) or phosphine ligand BINAP (2,2 '-bisdiphenylphosphino-1, 1' -binaphthyl); the alkali added in the C-N coupling reaction is selected from K2CO3、Cs2CO3t-BuOK or t-BuONa; the reaction solvent of the C-N coupling reaction is selected from isopropanol, methanol, tert-butanol or 1, 4-dioxane; the reaction temperature of the C-N coupling reaction is 70-120 ℃;
preferably, the catalyst for the reduction reaction is a platinum carbon catalyst, wherein the amount of the platinum carbon is 5-20% of the mass of the p-bromonitrobenzene with the corresponding substituent; the hydrogen pressure of the reduction reaction is 0.05-1MPa, and the reaction temperature is 50-100 ℃;
the molar ratio of the reaction intermediate to aldehyde or ketone is 1:1.5-2, the reaction temperature of the reductive amination reaction is 130-170 ℃, the reaction pressure is 2-5 MPa, and the catalyst is a platinum carbon catalyst.
The catalyst for the reduction reaction and the reductive amination reaction can be not only a platinum carbon catalyst, but also a metal catalyst selected from VIII group metals in the periodic table of elements, such as Ni, Pd, Ru and the like; the catalyst may be a copper-based catalyst.
Preferably, the molar ratio of the aniline to the p-bromonitrobenzene with corresponding substituent is 1:1.1, and the palladium catalyst is Pd2(dba)3The ligand of the palladium catalyst is XPhos, and the alkali added in the C-N coupling reaction is K2CO3The reaction solvent of the C-N coupling reaction is isopropanol, and the reaction temperature of the C-N coupling reaction is 110 ℃.
The dosage of the platinum-carbon catalyst for the reduction reaction is 10 percent of the mass of the p-bromonitrobenzene with the corresponding substituent, the hydrogen pressure of the reduction reaction is 0.2MPa, and the reaction temperature is 80 ℃.
The general reaction formula is as follows:
the invention also provides application of the environment-friendly p-phenylenediamine antioxidant shown in the formula (I) in rubber mixing or vulcanization, wherein the antioxidant is applied to natural rubber or synthetic rubber, mixed by a conventional mixing method and vulcanized to obtain vulcanized rubber.
Compared with the existing p-phenylenediamine anti-aging agent, the environment-friendly p-phenylenediamine anti-aging agent provided by the invention has good anti-aging performance, does not generate highly toxic quinone products, and has the functions of ozone, heat and oxygen aging protection; the rubber vulcanized rubber using the environment-friendly p-phenylenediamine anti-aging agent has excellent physical properties and aging resistance, rubber residues are subjected to toxicity detection, high-toxicity quinonization products are not detected, and the rubber vulcanized rubber is environment-friendly and non-toxic.
Detailed Description
The following detailed description of the invention refers to specific embodiments thereof for better understanding by those skilled in the art.
Comparative example 1
Under an inert gas nitrogen atmosphere, 15.2g (0.066mol, 1.1eq) of 2, 5-dimethyl-4-nitrobromobenzene and 0.552g (0.0006mol, 1%) of Pd were added to a 500mL three-necked flask2(dba)3，1.416g(0.003mol，5％)XPhos，16.58g(0.12mol，2eq)K2CO3And 5.58g (0.06mol) of aniline in 250mL of isopropanol, then placing the mixture at 110 ℃ for reflux reaction for 24 hours, filtering the reaction system, extracting and separating liquid, washing an organic phase by saturated saline solution, drying the organic phase by anhydrous sodium sulfate, and removing the solvent by a rotary evaporator to obtain a crude intermediate. In a hydrogen atmosphere, adding the obtained crude intermediate into 1L of ethanol, adding 1.52g of platinum-carbon catalyst (containing 0.076g of platinum), reacting for 24h under the conditions that the hydrogen pressure is 0.2MPa and the temperature is 80 ℃; cooling to room temperature after reaction, filtering, washing filter cake with hot ethanol, removing solvent with rotary evaporator, performing column chromatography with 400 mesh silica gel powder, eluting with petroleum ether and ethyl acetate, and gradient elutingThe sexual selection range is petroleum ether: ethyl acetate (volume ratio) is 10: 1-3: 1, and 9.32g of reaction intermediate 2, 5-dimethyl-4-amino-p-phenylenediamine is obtained.
9.29g (0.038mol) of reaction intermediate 2, 5-dimethyl-4-amino-p-phenylenediamine, 7.53g (0.075mol) of methyl isobutyl ketone and 0.96g of platinum carbon catalyst (containing 0.048g of platinum) are reacted in a hydrogen atmosphere, the reaction system is heated from room temperature to 150 ℃ within 1h, then hydrogen is pressurized to about 2.94MPa, the temperature and the pressure are kept stable, after 2h of reaction, hydrogen is discharged from an autoclave, the normal pressure is restored, meanwhile, the reaction system is cooled to room temperature, the catalyst and the activated carbon in the reaction liquid are filtered, a crude product is separated by a high-efficiency liquid chromatography to obtain 12g of a new compound, and the new compound is characterized as a compound (an anti-aging agent D-1) by a nuclear magnetic resonance spectrum, and the data are as follows:1H NMR(600MHz,CDCl3)δ7.23(t,J＝7.9Hz,2H),6.88(d,J＝7.9Hz,2H),6.82(t,J＝7.2Hz,1H),6.75(s,1H),6.28(s,1H),5.40(s,1H),3.60-3.50(m,1H),3.32(s,1H),2.16(s,6H),1.88-1.78(m,1H),1.57-1.48(m,1H),1.36-1.26(m,1H),1.22(d,J＝6.2Hz,3H),1.01(d,J＝6.6Hz,3H),0.99(d,J＝6.6Hz,3H).13C NMR(150MHz,CDCl3)δ146.48,144.16,132.17,129.28,122.63,119.70,118.67,114.78,47.15,47.06,25.21,23.12,22.69,21.21,18.53.
the structural formula of the compound (antioxidant D-1) is as follows:
the reaction formula of the above reaction is shown below:
example 1
Under an inert gas nitrogen atmosphere, 15.2g (0.066mol, 1.1eq) of 3, 5-dimethyl-4-nitrobromobenzene and 0.552g (0.0006mol, 1%) of Pd were added into a 500mL three-necked flask2(dba)3，1.416g(0.003mol，5％)XPhos，16.58g(0.12mol，2eq)K2CO3And 5.58And g (0.06mol) aniline is dispersed in 250mL isopropanol, then the mixture is placed at the temperature of 110 ℃ for reflux reaction for 24 hours, the reaction system is filtered, extracted and separated, the organic phase is washed by saturated saline solution, dried by anhydrous sodium sulfate, and the solvent is removed by a rotary evaporator to obtain a crude intermediate. In a hydrogen atmosphere, adding the obtained crude intermediate into 1L of ethanol, adding 1.52g of platinum-carbon catalyst (containing 0.076g of platinum), reacting for 24h under the conditions that the hydrogen pressure is 0.2MPa and the temperature is 80 ℃; cooling to room temperature after the reaction is finished, filtering, washing a filter cake by hot ethanol, removing a solvent by a rotary evaporator, and performing column chromatography separation by using 400-mesh silica gel powder, wherein an eluent system comprises petroleum ether and ethyl acetate, and a gradient elution polarity selection range comprises the following steps: ethyl acetate (volume ratio) is 10: 1-3: 1, and 9.45g of reaction intermediate 3, 5-dimethyl-4-amino-p-phenylenediamine is obtained.
9.29g (0.038mol) of reaction intermediate 3, 5-dimethyl-4-amino-p-phenylenediamine, 7.53g (0.075mol) of methyl isobutyl ketone and 0.96g of platinum-carbon catalyst (containing 0.048g of platinum) are reacted in a hydrogen atmosphere, the reaction system is heated to 150 ℃ from room temperature within 1h, then hydrogen is pressurized to about 2.94MPa, the temperature and the pressure are kept stable, after 2h of reaction, hydrogen is discharged from an autoclave, the normal pressure is restored, meanwhile, the reaction system is cooled to room temperature, the catalyst and activated carbon in the reaction liquid are filtered, the crude product is separated by high performance liquid chromatography, and 12.5g of new compound is obtained, and the new compound is characterized as a target compound (antioxidant O-1) by nuclear magnetic resonance spectrum, and the data are as follows:1H NMR(600MHz,CDCl3)δ7.23(t,J＝7.9Hz,2H),6.88(d,J＝7.9Hz,2H),6.82(t,J＝7.2Hz,1H),6.75(s,2H),5.40(s,1H),3.61-3.49(m,1H),3.32(s,1H),2.16(s,6H),1.87-1.78(m,1H),1.57-1.50(m,1H),1.36-1.28(m,1H),1.22(d,J＝6.2Hz,3H),1.01(d,J＝6.6Hz,3H),0.99(d,J＝6.6Hz,3H).13C NMR(150MHz,CDCl3)δ146.49,144.18,132.17,129.29,122.51,119.71,118.69,114.82,47.15,47.06,25.21,23.12,22.69,21.21,18.53.
the structural formula of the target compound (antioxidant O-1) is as follows:
the reaction formula of the above reaction is shown below:
example 2
Under an inert gas nitrogen atmosphere, 15.2g (0.066mol, 1.1eq) of 2, 3-dimethyl-4-nitrobromobenzene and 0.552g (0.0006mol, 1%) of Pd were added into a 500mL three-necked flask2(dba)3，1.416g(0.003mol，5％)XPhos，16.58g(0.12mol，2eq)K2CO3And 5.58g (0.06mol) of aniline in 250mL of isopropanol, then placing under reflux at 110 ℃ for 24 hours, filtering the reaction system, extracting and separating, washing the organic phase with saturated saline solution, drying with anhydrous sodium sulfate, and removing the solvent with a rotary evaporator to obtain a crude intermediate. Adding the obtained crude intermediate into 1L of ethanol in a hydrogen atmosphere, adding 1.52g of a platinum carbon catalyst (containing 0.076g of platinum), reacting at 80 ℃ for 24h under the hydrogen pressure of 0.2MPa, cooling to room temperature after the reaction is finished, filtering, washing a filter cake with hot ethanol, removing a solvent by using a rotary evaporator, performing column chromatography separation by using 400-mesh silica gel powder, wherein the eluent system comprises petroleum ether and ethyl acetate, and the gradient elution polarity selection range is petroleum ether: ethyl acetate (volume ratio) is 10: 1-3: 1, and 9.4g of reaction intermediate 2, 3-dimethyl-4-amino-p-phenylenediamine is obtained.
9.29g (0.038mol) of the reaction intermediate 2, 3-dimethyl-4-amino-p-phenylenediamine and 7.53g (0.075mol) of methyl isobutyl ketone, 0.96g of a platinum carbon catalyst (containing 0.048g of platinum) were reacted under a hydrogen atmosphere, and the reaction system was elevated from room temperature to 150 ℃ over 1h, then hydrogen was pressurized to about 2.94MPa, and the temperature and pressure were kept constant. After reacting for 2h, discharging hydrogen from an autoclave, recovering normal pressure, simultaneously cooling a reaction system to room temperature, filtering out a catalyst and active carbon in a reaction liquid, separating a crude product by high performance liquid chromatography to obtain a new compound 12g, and characterizing the new compound as a target compound (an anti-aging agent O-2) by nuclear magnetic resonance spectrum, wherein the data are as follows:1H NMR(600MHz,CDCl3)δ7.22(t,J＝7.9Hz,2H),6.87(d,J＝7.9Hz,2H),6.82(t,J＝7.2Hz,1H),6.70(d,J＝8.2Hz,1H),6.28(d,J＝8.2Hz,1H),5.40(s,1H),3.60-3.50(m,1H),3.32(s,1H),2.16(s,6H),1.86-1.77(m,1H),1.56-1.50(m,1H),1.35-1.28(m,1H),1.22(d,J＝6.2Hz,3H),1.01(d,J＝6.6Hz,3H),0.99(d,J＝6.6Hz,3H).13C NMR(150MHz,CDCl3)δ146.49,144.17,132.17,129.41,129.29,119.92,118.69,116.30,114.82,106.83,47.15,47.06,25.21,23.12,22.69,21.21,18.52,18.50.
the structural formula of the target compound (the anti-aging agent O-2) is as follows:
the reaction formula of the above reaction is shown below:
example 3
Under an inert gas nitrogen atmosphere, 16.11g (0.066mol, 1.1eq) of 2,3, 5-trimethyl 4-nitrobromobenzene and 0.552g (0.0006mol, 1%) of Pd were added to a 500mL three-necked flask2(dba)3，1.416g(0.003mol，5％)XPhos，16.58g(0.12mol，2eq)K2CO3And 5.58g (0.06mol) of aniline in 250mL of isopropanol, then placing the mixture at 110 ℃ for reflux reaction for 24 hours, filtering the reaction system, extracting and separating liquid, washing an organic phase by saturated saline solution, drying by anhydrous sodium sulfate, and removing the solvent by a rotary evaporator to obtain a crude intermediate. Adding the obtained crude intermediate into 1L ethanol, adding 1.52g of platinum carbon catalyst (containing 0.076g of platinum), reacting at 80 ℃ for 24h under the hydrogen pressure of 0.2MPa, cooling to room temperature after the reaction is finished, filtering, washing a filter cake by hot ethanol, removing a solvent by using a rotary evaporator, and performing column chromatography separation by using 400-mesh silica gel powder, wherein the eluent system comprises petroleum ether and ethyl acetate, and the gradient elution polarity selection range is petroleum ether: ethyl acetate (volume ratio) is 10: 1-3: 1, and 6.8g of 2,3, 5-trimethyl-4-amino-p-phenylenediamine is obtained.
Mixing 6.6g (0.026mol) of 2,3, 5-trisMethyl-4-amino-p-phenylenediamine and 5.21g (0.050mol) of methyl isobutyl ketone, 0.66g of platinum carbon catalyst (platinum 0.033g) are reacted under hydrogen atmosphere, the reaction system is raised from room temperature to 150 ℃ within 1h, then hydrogen is pressurized to about 2.94MPa, and the temperature and the pressure are kept stable. After reacting for 2h, discharging hydrogen from an autoclave, recovering normal pressure, simultaneously cooling a reaction system to room temperature, filtering out a catalyst and active carbon in a reaction liquid, separating a crude product by high performance liquid chromatography to obtain 8.5g of a new compound, and characterizing the new compound as a target compound (an anti-aging agent O-3) by nuclear magnetic resonance spectrum, wherein the data are as follows:1H NMR(600MHz,CDCl3)δ7.21(t,J＝7.9Hz,2H),6.86(d,J＝7.9Hz,2H),6.82(t,J＝7.2Hz,1H),6.63(s,1H),5.40(s,1H),3.60-3.50(m,1H),3.32(s,1H),2.16(s,9H),1.85-1.77(m,1H),1.55-1.48(m,1H),1.34-1.25(m,1H),1.22(d,J＝6.2Hz,3H),1.01(d,J＝6.6Hz,3H),0.99(d,J＝6.6Hz,3H).13C NMR(150MHz,CDCl3)δ146.48,144.16,132.16,129.27,126.41,119.62,119.53,118.68,116.24,114.81,47.15,47.06,25.21,23.12,22.69,21.21,18.52,18.49,18.48.
the structural formula of the target compound (antioxidant O-3) is as follows:
the reaction formula of the above reaction is shown below:
example 4
17.1g (0.066mol, 1.1eq) of 2,3,5, 6-tetramethyl-4-nitrobromobenzene, 0.552g (0.0006mol, 1%) of Pd were charged in a 500mL three-necked flask under an inert gas nitrogen atmosphere2(dba)3，1.416g(0.003mol，5％)XPhos,16.58g(0.12mol，2eq)K2CO3And 5.58g (0.06mol) of aniline in 250mL of isopropanol, then placing the mixture at 110 ℃ for reflux reaction for 24 hours, filtering the reaction system, extracting and separating the liquid, washing the organic phase with saturated saline, drying the organic phase with anhydrous sodium sulfate, and using the anhydrous sodium sulfateRemoving the solvent by a rotary evaporator to obtain a crude intermediate. Adding the obtained crude intermediate into 1L ethanol, adding 1.52g of platinum carbon catalyst (containing 0.076g of platinum), reacting at 80 ℃ for 24h under the hydrogen pressure of 0.2MPa, cooling to room temperature after the reaction is finished, filtering, washing a filter cake by hot ethanol, removing a solvent by using a rotary evaporator, and performing column chromatography separation by using 400-mesh silica gel powder, wherein the eluent system comprises petroleum ether and ethyl acetate, and the gradient elution polarity selection range is petroleum ether: ethyl acetate (volume ratio) 10: 1-3: 1, to obtain 8.65g of 2,3,5, 6-tetramethyl-4-amino-p-phenylenediamine.
7.88g (0.029mol) of 2,3,5, 6-tetramethyl-4-amino-p-phenylenediamine and 5.81g (0.058mol) of methyl isobutyl ketone, 0.79g of platinum carbon catalyst (containing 0.04g of platinum) are reacted under a hydrogen atmosphere, the reaction system is raised from room temperature to 150 ℃ within 1h, then hydrogen is pressurized to about 2.94MPa, and the temperature and the pressure are kept stable. After reacting for 2h, discharging hydrogen from an autoclave, recovering normal pressure, simultaneously cooling a reaction system to room temperature, filtering out a catalyst and active carbon in a reaction liquid, separating a crude product by high performance liquid chromatography to obtain 10g of a new compound (O-4), and characterizing the new compound as a target compound (an anti-aging agent O-4) by nuclear magnetic resonance spectrum, wherein the data are as follows:1H NMR(600MHz,CDCl3)δ7.20(t,J＝7.9Hz,2H),6.85(d,J＝7.9Hz,2H),6.80(t,J＝7.2Hz,1H),5.40(s,1H),3.60-3.50(m,1H),3.32(s,1H),2.16(s,12H),1.85-1.75(m,1H),1.56-1.48(m,1H),1.34-1.26(m,1H),1.22(d,J＝6.2Hz,3H),1.01(d,J＝6.6Hz,3H),0.99(d,J＝6.6Hz,3H).13C NMR(150MHz,CDCl3)δ146.44,144.13,132.11,129.27,126.33,118.66,114.79,113.25,47.15,47.06,25.21,23.12,22.69,21.21,18.48.
the structural formula of the target compound (antioxidant O-4) is as follows:
the reaction formula of the above reaction is shown below:
example 5
Under an inert gas nitrogen atmosphere, 16.11g (0.066mol, 1.1eq) of 2,3, 6-trimethyl 4-nitrobromobenzene and 0.552g (0.0006mol, 1%) of Pd were added to a 500mL three-necked flask2(dba)3，1.416g(0.003mol，5％)XPhos，16.58g(0.12mol，2eq)K2CO3And 5.58g (0.06mol) of aniline in 250mL of isopropanol, then placing the mixture at 110 ℃ for reflux reaction for 24 hours, filtering the reaction system, extracting and separating liquid, washing an organic phase by saturated saline solution, drying by anhydrous sodium sulfate, and removing the solvent by a rotary evaporator to obtain a crude intermediate. Adding the obtained crude intermediate into 1L of ethanol, adding 1.52g of platinum-carbon catalyst (containing 0.076g of platinum), reacting at 80 ℃ for 24h under the hydrogen pressure of 0.2MPa, cooling to room temperature after the reaction is finished, filtering, washing a filter cake with hot ethanol, removing the solvent by using a rotary evaporator, and performing column chromatography separation by using 400-mesh silica gel powder, wherein the eluent system comprises petroleum ether and ethyl acetate, and the gradient elution polarity selection range is petroleum ether: ethyl acetate (volume ratio) is 10: 1-3: 1, and 6.75g of 2,3, 5-trimethyl-4-amino-p-phenylenediamine is obtained.
6.6g (0.026mol) of 2,3, 6-trimethyl-4-amino-p-phenylenediamine and 5.21g (0.050mol) of methyl isobutyl ketone, 0.66g of platinum carbon catalyst (0.033 g of platinum therein) were reacted under a hydrogen atmosphere, and the reaction system was elevated from room temperature to 150 ℃ over 1 hour, then hydrogen was pressurized to about 2.94MPa, and the temperature and pressure were kept stable. After reacting for 2h, discharging hydrogen from an autoclave, recovering normal pressure, simultaneously cooling a reaction system to room temperature, filtering out a catalyst and active carbon in a reaction liquid, separating a crude product by a high performance liquid chromatography to obtain 8g of a new compound, and characterizing the new compound as a target compound (an anti-aging agent O-5) by a nuclear magnetic resonance spectrum, wherein the data is as follows:1H NMR(600MHz,CDCl3)δ7.21(t,J＝7.9Hz,2H),6.86(d,J＝7.9Hz,2H),6.82(t,J＝7.2Hz,1H),6.58(s,1H),5.40(s,1H),3.60-3.50(m,1H),3.32(s,1H),2.16(s,9H),1.85-1.77(m,1H),1.55-1.48(m,1H),1.34-1.25(m,1H),1.22(d,J＝6.2Hz,3H),1.01(d,J＝6.6Hz,3H),0.99(d,J＝6.6Hz,3H).13C NMR(150MHz,CDCl3)δ146.49,144.18,132.17,129.28,126.46,119.62,119.54,118.68,116.26,114.76,47.15,47.06,25.21,23.12,22.69,21.21,18.52,18.49,18.48.
the structural formula of the target compound (the anti-aging agent O-5) is as follows:
the reaction formula of the above reaction is shown below:
example 6
Under an inert gas nitrogen atmosphere, 15.2g (0.066mol, 1.1eq) of 3, 5-dimethyl-4-nitrobromobenzene, 0.183g (0.0006mol, 1%) of Pd (acac)21.231g (0.003mol, 5%) of SPhos, 11.53g (0.12mol, 2eq) of t-BuONa and 5.58g (0.06mol) of aniline were dispersed in 250mL of t-butanol, and then the mixture was refluxed at 120 ℃ for 24 hours, and the reaction system was filtered, extracted, separated, and the organic phase was washed with saturated brine, dried over anhydrous sodium sulfate, and the solvent was removed by a rotary evaporator to obtain a crude intermediate. In a hydrogen atmosphere, adding the obtained crude intermediate into 1L of ethanol, adding 3.04g of platinum-carbon catalyst (containing 0.152g of platinum), reacting for 24h at 50 ℃ under the hydrogen pressure of 1 MPa; cooling to room temperature after the reaction is finished, filtering, washing a filter cake by hot ethanol, removing a solvent by a rotary evaporator, and performing column chromatography separation by using 400-mesh silica gel powder, wherein an eluent system comprises petroleum ether and ethyl acetate, and the gradient elution polarity selection range is petroleum ether: ethyl acetate (volume ratio) is 10: 1-3: 1, and 8.95g of reaction intermediate 3, 5-dimethyl-4-amino-p-phenylenediamine is obtained.
8.80g (0.036mol) of reaction intermediate 3, 5-dimethyl-4-amino-p-phenylenediamine, 5.42g (0.054mol) of methyl isobutyl ketone and 0.88g of platinum carbon catalyst (containing 0.044g of platinum) are reacted in a hydrogen atmosphere, the reaction system is heated to 130 ℃ from room temperature within 1h, then the hydrogen is pressurized to about 5MPa, the temperature and the pressure are kept stable, after 2h of reaction, the hydrogen is discharged from an autoclave, the normal pressure is restored, meanwhile, the reaction system is cooled to room temperature, the catalyst and the activated carbon in the reaction liquid are filtered, the crude product is separated by a high performance liquid chromatography, 10.5g of a new compound is obtained, and the new compound is characterized as a target compound (an anti-aging agent O-1) by a nuclear magnetic resonance spectrum.
Example 7
13.82g (0.06mol, 1eq) of 3, 5-dimethyl-4-nitrobromobenzene, 0.135g (0.0006mol, 1%) of Pd (OAc) were added under an inert gas nitrogen atmosphere to a 500mL three-necked flask2，1.868g(0.003mol，5％)BINAP，39.1g(0.12mol，2eq)Cs2CO3And 5.58g (0.06mol) of aniline were dispersed in 250mL of 1, 4-dioxane, and then allowed to stand at 90 ℃ for reaction for 24 hours, and the reaction system was filtered, followed by extraction and liquid separation, washing of the organic phase with saturated brine, drying with anhydrous sodium sulfate, and removal of the solvent with a rotary evaporator to obtain a crude intermediate. In a hydrogen atmosphere, adding the obtained crude intermediate into 1L ethanol, adding 0.7g of platinum carbon catalyst (containing 0.035g of platinum), reacting for 24h under the hydrogen pressure of 0.2MPa and the temperature of 100 ℃; cooling to room temperature after the reaction is finished, filtering, washing a filter cake by hot ethanol, removing a solvent by a rotary evaporator, and performing column chromatography separation by using 400-mesh silica gel powder, wherein an eluent system comprises petroleum ether and ethyl acetate, and the gradient elution polarity selection range is petroleum ether: ethyl acetate (volume ratio) is 10: 1-3: 1, and 7.6g of reaction intermediate 3, 5-dimethyl-4-amino-p-phenylenediamine is obtained.
7.33g (0.03mol) of reaction intermediate 3, 5-dimethyl-4-amino-p-phenylenediamine, 5.42g (0.054mol) of methyl isobutyl ketone and 0.74g of platinum carbon catalyst (containing 0.037g of platinum) are reacted in a hydrogen atmosphere, the reaction system is heated to 170 ℃ from room temperature within 1h, then the hydrogen is pressurized to about 2MPa, the temperature and the pressure are kept stable, after 2h of reaction, the hydrogen is discharged from an autoclave, the normal pressure is recovered, meanwhile, the reaction system is cooled to room temperature, the catalyst and the activated carbon in the reaction liquid are filtered, the crude product is separated by a high performance liquid chromatography, 9.1g of a new compound is obtained, and the new compound is a target compound (antioxidant O-1) characterized by a nuclear magnetic resonance spectrum.
Example 8
Under an inert gas nitrogen atmosphere, 16.58g (0.072mol, 1.2eq) of 3, 5-bis (methylene chloride) is added into a 500mL three-necked flaskMethyl-4-nitrobromobenzene, 0.693g (0.0006mol, 1%) Pd (PPh)3)41.416g (0.003mol, 5%) of XPhos, 13.47g (0.12mol, 2eq) of t-BuOK and 5.58g (0.06mol) of aniline were dispersed in 250mL of methanol, and then the mixture was left to stand at 70 ℃ for reflux reaction for 24 hours, and the reaction system was filtered, extracted, separated, the organic phase was washed with saturated brine, dried over anhydrous sodium sulfate, and the solvent was removed by a rotary evaporator to obtain a crude intermediate. Adding the obtained crude intermediate into 1L ethanol in hydrogen atmosphere, adding 1.66g of platinum-carbon catalyst (containing 0.083g of platinum), reacting at 80 ℃ for 24h under the hydrogen pressure of 0.05 MPa; cooling to room temperature after the reaction is finished, filtering, washing a filter cake by hot ethanol, removing a solvent by a rotary evaporator, and performing column chromatography separation by using 400-mesh silica gel powder, wherein an eluent system comprises petroleum ether and ethyl acetate, and a gradient elution polarity selection range comprises the following steps: ethyl acetate (volume ratio) is 10: 1-3: 1, and 5.6g of reaction intermediate 3, 5-dimethyl-4-amino-p-phenylenediamine is obtained.
4.89g (0.02mol) of reaction intermediate 3, 5-dimethyl-4-amino-p-phenylenediamine, 4.02g (0.04mol) of methyl isobutyl ketone and 0.49g of platinum carbon catalyst (containing 0.025g of platinum) are reacted in a hydrogen atmosphere, the reaction system is heated from room temperature to 140 ℃ within 1h, then hydrogen is pressurized to about 4MPa, the temperature and the pressure are kept stable, after 2h of reaction, hydrogen is discharged from an autoclave, the normal pressure is restored, meanwhile, the reaction system is cooled to room temperature, the catalyst and the activated carbon in the reaction liquid are filtered, the crude product is separated by a high performance liquid chromatography method, and 6.2g of new compound is obtained and is characterized as a target compound (antioxidant O-1) by a nuclear magnetic resonance spectrum.
Example 9
The existing anti-aging agent 4020 and the anti-aging agents D-1, O-2, O-3 and O-4 prepared above are respectively applied to the raw isoprene rubber, the raw isoprene rubber is mixed and vulcanized by a conventional mixing method and a formula (detailed in Table 1), the performance of the obtained corresponding rubber is detected, and the detection result is shown in Table 2.
A common mixing process adopts two-stage mixing, wherein the rotation speed is set to 80rpm during the first-stage mixing, raw isoprene rubber is put into an internal mixer to be broken for 30s, then 2/3 carbon black N234 is added to be mixed for 1min, the rest 1/3 carbon black N234 is added, cleaning is carried out after mixing for 30s, stearic acid, zinc oxide and an anti-aging agent are added after mixing for 1min, cleaning is carried out after mixing for 30s, and rubber is discharged at 150 ℃ after mixing for 1 min; standing the primary master batch for more than 4h, and then performing secondary mixing; and during the second-stage mixing, setting the rotation speed to be 50rpm, putting the first-stage master batch into an internal mixer, breaking the rubber for 30s, adding the accelerator and sulfur, cleaning after mixing for 30s, continuously mixing for 1min, and discharging the rubber at the rubber discharge temperature of not more than 100 ℃ to obtain the final rubber.
Vulcanizing the final rubber compound on a flat vulcanizing machine, wherein the vulcanization temperature is 150 ℃, and the vulcanization time of the tensile, tearing and dynamic performance test sample is (tc90+5) min; the vulcanization time of the elasticity, hardness, density and compression heat generation test specimens was (tc90+10) min.
TABLE 1 compounding recipe for rubber materials with different anti-aging agents
| Comparative size 1 | Comparative size 2 | M-1 | M-2 | M-3 | M-4 | |
| Isoprene rubber | 100 | 100 | 100 | 100 | 100 | 100 |
| Carbon Black N234 | 50 | 50 | 50 | 50 | 50 | 50 |
| Zinc oxide | 4 | 4 | 4 | 4 | 4 | 4 |
| Stearic acid | 2 | 2 | 2 | 2 | 2 | 2 |
| Anti-aging agent 4020 | 1 | |||||
| Anti-aging agent D-1 | 1 | |||||
| Anti-aging agent O-1 | 1 | |||||
| Antioxidant O-2 | 1 | |||||
| Antioxidant O-3 | 1 | |||||
| Antioxidant O-4 | 1 | |||||
| Accelerator TBBS | 1.2 | 1.2 | 1.2 | 1.2 | 1.2 | 1.2 |
| Sulfur | 1 | 1 | 1 | 1 | 1 | 1 |
| Total up to | 159.2 | 159.2 | 159.2 | 159.2 | 159.2 | 159.2 |
Wherein, the comparative rubber material 1 and the comparative rubber material 2 are respectively rubber material formulas added with the anti-aging agent 4020 and the anti-aging agent D-1 prepared in the comparative example 1, and the M-1, the M-2, the M-3 and the M-4 are respectively rubber material formulas added with the anti-aging agents O-1, O-2, O-3 and O-4 prepared in the examples 1 to 4.
TABLE 2 elastomeric/vulcanizate Properties
As can be seen from table 2, the p-phenylenediamine anti-aging agent provided by the invention can achieve the same or even better physical properties as the prior anti-aging agent 4020 when applied to isoprene rubber.
Aging the vulcanized rubber compound of M-1, M-2, M-3 and M-4, extracting, and detecting the extract by ultra-high performance liquid chromatography-high resolution tandem mass spectrometry (UPLC-HRMS/MS) to obtain no quinone compound; aging the vulcanized rubber compounds of the comparative rubber compound 1 and the comparative rubber compound 2, extracting, and detecting the extract to detect the quinone compound; therefore, the environment-friendly p-phenylenediamine anti-aging agent provided by the invention does not generate high-toxicity quinone transformation products in rubber residues, and is an environment-friendly rubber auxiliary agent.
Examples 10-18 were prepared as in example 1, and the structural formula of the obtained antioxidant is shown in the following table:
the environment-friendly p-phenylenediamine anti-aging agent provided by the invention, and the preparation method and the application thereof are introduced in detail. The principles and embodiments of the present invention are explained herein using specific examples, which are presented only to assist in understanding the method and central concepts of the present invention. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
Claims (10)
1. An environment-friendly p-phenylenediamine anti-aging agent is characterized by having a structure shown in a formula (I):
in the formula (I), R1、R1’Is selected from C1-C18Or a chain or alicyclic hydrocarbon group of (2) or H, R2、R3Is selected from C1-C18With a chain hydrocarbon radical of (2) or R2And R3Formation of an alicyclic ring, R4、R5Is selected from C1-C18With a chain hydrocarbon radical of (2) or R4And R5Forming an alicyclic ring; x is 0 or 1, y is 0 or 1, z is 0 or 1, w is 0 or 1, and at least one of x and w is 1, and at least one of y and z is 1, wherein when x and z are both 1, y and w are not both 0.
2. The environment-friendly p-phenylenediamine anti-aging agent according to claim 1, wherein said structure of formula (I) is
Wherein R is1、R1’Is selected from C1-C18Or a chain or alicyclic hydrocarbon group of (2) or H, R2、R3Is selected from C1-C18With a chain hydrocarbon group of (2) or R2And R3Forming an alicyclic ring.
3. The environment-friendly p-phenylenediamine anti-aging agent according to claim 1, wherein said structure of formula (I) is
Wherein R is1、R1’Is selected from C1-C18Or a chain hydrocarbon or alicyclic hydrocarbon of (3) or H, R3、R5Is selected from C1-C18A chain hydrocarbon group of (1).
4. The environment-friendly p-phenylenediamine anti-aging agent according to claim 1, wherein said structure of formula (I) is
Wherein R is1、R1’Is selected from C1-C18Or a chain or alicyclic hydrocarbon group of (3) or H, R2、R3Is selected from C1-C18With a chain hydrocarbon radical of (2) or R2And R3Formation of an alicyclic ring, R4、R5Is selected from C1-C18A chain hydrocarbon group of (2).
5. The environment-friendly p-phenylenediamine anti-aging agent according to claim 1, wherein said structure of formula (I) is:
wherein R is1、R1’Is selected from C1-C18Or a chain or alicyclic hydrocarbon group of (3) or H, R2、R3Is selected from C1-C18With a chain hydrocarbon group of (2) or R2And R3Formation of an alicyclic ring, R4、R5Is selected from C1-C18With a chain hydrocarbon group of (2) or R4And R5Forming an alicyclic ring.
6. A preparation method of the environment-friendly p-phenylenediamine anti-aging agent according to any one of claims 1 to 5, characterized in that aniline and p-bromonitrobenzene with corresponding substituent groups are subjected to C-N coupling reaction, the obtained coupled product is subjected to reduction reaction in a hydrogen atmosphere under a catalytic condition to obtain a reaction intermediate, and the reaction intermediate and aldehyde or ketone are subjected to reductive amination reaction under a catalytic condition to obtain the p-phenylenediamine anti-aging agent.
7. The preparation method of the environment-friendly p-phenylenediamine anti-aging agent as claimed in claim 6, wherein the C-N coupling reaction is carried out in an inert atmosphere, and the molar ratio of the aniline to p-bromonitrobenzene having corresponding substituent groups is 1: 1.0-1.2; the catalyst of the C-N coupling reaction is a palladium catalyst selected from Pd2(dba)3、Pd(OAc)2、Pd(PPh3)4Or Pd (acac)2(ii) a The ligand of the palladium catalyst is selected from phosphine ligand XPhos, phosphine ligand SPhos or phosphine ligand BINAP; the alkali added in the C-N coupling reaction is selected from K2CO3、Cs2CO3t-BuOK or t-BuONa; the reaction solvent of the C-N coupling reaction is selected from isopropanol, methanol, tert-butanol or 1, 4-dioxane; the reaction temperature of the C-N coupling reaction is 70-120 ℃.
8. The method for preparing the environment-friendly p-phenylenediamine anti-aging agent according to claim 6, wherein the catalyst for the reduction reaction is a platinum carbon catalyst, and the amount of the platinum carbon catalyst is 5-20% of the mass of the p-bromonitrobenzene with the corresponding substituent group; the hydrogen pressure of the reduction reaction is 0.05-1MPa, and the reaction temperature is 50-100 ℃;
the molar ratio of the reaction intermediate to aldehyde or ketone is 1:1.5-2, the reaction temperature of the reductive amination reaction is 130-170 ℃, the reaction pressure is 2-5 MPa, and the catalyst is a platinum carbon catalyst.
9. The method for preparing the environment-friendly p-phenylenediamine anti-aging agent as claimed in claim 7 or 8, wherein the molar ratio of the aniline to the p-bromonitrobenzene with corresponding substituent group is 1:1.1, and the palladium catalyst is Pd2(dba)3The ligand of the palladium catalyst is XPhos, and the alkali added in the C-N coupling reaction is K2CO3The reaction solvent of the C-N coupling reaction is isopropanol, and the reaction temperature of the C-N coupling reaction is 110 ℃;
the dosage of the platinum-carbon catalyst for the reduction reaction is 10 percent of the mass of the p-bromonitrobenzene with the corresponding substituent, the hydrogen pressure of the reduction reaction is 0.2MPa, and the reaction temperature is 80 ℃.
10. The use of the environment-friendly p-phenylenediamine anti-aging agent as claimed in any one of claims 1 to 5 in rubber mixing or vulcanization, wherein the anti-aging agent is applied to natural rubber or synthetic rubber, and a vulcanized rubber is obtained after mixing and vulcanization.
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