CN115181025A - N-phenyl-N' - (p-alkylphenyl) p-phenylenediamine and preparation method and application thereof - Google Patents
N-phenyl-N' - (p-alkylphenyl) p-phenylenediamine and preparation method and application thereof Download PDFInfo
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- CN115181025A CN115181025A CN202210763036.XA CN202210763036A CN115181025A CN 115181025 A CN115181025 A CN 115181025A CN 202210763036 A CN202210763036 A CN 202210763036A CN 115181025 A CN115181025 A CN 115181025A
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- phenylenediamine
- phenyl
- alkylphenyl
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- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- ATGUVEKSASEFFO-UHFFFAOYSA-N p-aminodiphenylamine Chemical compound C1=CC(N)=CC=C1NC1=CC=CC=C1 ATGUVEKSASEFFO-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000011973 solid acid Substances 0.000 claims abstract description 18
- 239000003054 catalyst Substances 0.000 claims abstract description 17
- 229920001971 elastomer Polymers 0.000 claims abstract description 13
- 239000005060 rubber Substances 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 8
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 8
- ZZMVLMVFYMGSMY-UHFFFAOYSA-N 4-n-(4-methylpentan-2-yl)-1-n-phenylbenzene-1,4-diamine Chemical compound C1=CC(NC(C)CC(C)C)=CC=C1NC1=CC=CC=C1 ZZMVLMVFYMGSMY-UHFFFAOYSA-N 0.000 claims abstract description 5
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 36
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 29
- 239000000463 material Substances 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 22
- 238000010992 reflux Methods 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 12
- 235000006408 oxalic acid Nutrition 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 9
- 239000003930 superacid Substances 0.000 claims description 9
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 8
- 239000008096 xylene Substances 0.000 claims description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- ISAVYTVYFVQUDY-UHFFFAOYSA-N 4-tert-Octylphenol Chemical compound CC(C)(C)CC(C)(C)C1=CC=C(O)C=C1 ISAVYTVYFVQUDY-UHFFFAOYSA-N 0.000 claims description 5
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 239000006227 byproduct Substances 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 238000000354 decomposition reaction Methods 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 238000005292 vacuum distillation Methods 0.000 claims description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
- 229920005668 polycarbonate resin Polymers 0.000 claims 1
- 239000004431 polycarbonate resin Substances 0.000 claims 1
- 125000003944 tolyl group Chemical group 0.000 claims 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 abstract description 17
- 230000000694 effects Effects 0.000 abstract description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 7
- 238000002845 discoloration Methods 0.000 abstract description 7
- 230000003628 erosive effect Effects 0.000 abstract description 7
- 230000003068 static effect Effects 0.000 abstract description 7
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 230000007547 defect Effects 0.000 abstract description 3
- 229910052742 iron Inorganic materials 0.000 abstract description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 abstract description 2
- 230000003712 anti-aging effect Effects 0.000 description 18
- 239000003795 chemical substances by application Substances 0.000 description 17
- PIBIAJQNHWMGTD-UHFFFAOYSA-N 1-n,3-n-bis(4-methylphenyl)benzene-1,3-diamine Chemical compound C1=CC(C)=CC=C1NC1=CC=CC(NC=2C=CC(C)=CC=2)=C1 PIBIAJQNHWMGTD-UHFFFAOYSA-N 0.000 description 9
- 239000000126 substance Substances 0.000 description 8
- -1 aryl alkyl p-phenylenediamine Chemical compound 0.000 description 7
- 238000001816 cooling Methods 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- 239000004594 Masterbatch (MB) Substances 0.000 description 5
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- RNVCVTLRINQCPJ-UHFFFAOYSA-N o-toluidine Chemical compound CC1=CC=CC=C1N RNVCVTLRINQCPJ-UHFFFAOYSA-N 0.000 description 4
- 238000013508 migration Methods 0.000 description 3
- 230000005012 migration Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000004636 vulcanized rubber Substances 0.000 description 3
- JJYPMNFTHPTTDI-UHFFFAOYSA-N 3-methylaniline Chemical compound CC1=CC=CC(N)=C1 JJYPMNFTHPTTDI-UHFFFAOYSA-N 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- MDZBMZIJIUEQJS-UHFFFAOYSA-N 1-n,4-n-bis(2-methylphenyl)benzene-1,4-diamine Chemical compound CC1=CC=CC=C1NC(C=C1)=CC=C1NC1=CC=CC=C1C MDZBMZIJIUEQJS-UHFFFAOYSA-N 0.000 description 1
- QFTSXPJTPSOVJG-UHFFFAOYSA-N 4-n-(2-methylphenyl)-1-n-phenylbenzene-1,4-diamine Chemical compound CC1=CC=CC=C1NC(C=C1)=CC=C1NC1=CC=CC=C1 QFTSXPJTPSOVJG-UHFFFAOYSA-N 0.000 description 1
- VWNMIDRTNPTBJH-UHFFFAOYSA-N 4-n-(2-methylphenyl)benzene-1,4-diamine Chemical compound CC1=CC=CC=C1NC1=CC=C(N)C=C1 VWNMIDRTNPTBJH-UHFFFAOYSA-N 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- UTGQNNCQYDRXCH-UHFFFAOYSA-N N,N'-diphenyl-1,4-phenylenediamine Chemical compound C=1C=C(NC=2C=CC=CC=2)C=CC=1NC1=CC=CC=C1 UTGQNNCQYDRXCH-UHFFFAOYSA-N 0.000 description 1
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 1
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methylaniline Chemical compound CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000010074 rubber mixing Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
- C07C209/14—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of hydroxy groups or of etherified or esterified hydroxy groups
- C07C209/18—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of hydroxy groups or of etherified or esterified hydroxy groups 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C211/00—Compounds containing amino groups bound to a carbon skeleton
- C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
- C07C211/54—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to two or three six-membered aromatic rings
- C07C211/55—Diphenylamines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention discloses N-phenyl-N '- (p-alkylphenyl) p-phenylenediamine and a preparation method and application thereof, wherein 4-aminodiphenylamine and p-alkylphenol are condensed and post-treated under the catalysis of a solid acid catalyst to obtain the N-phenyl-N' - (p-alkylphenyl) p-phenylenediamine. The preparation method is simple, clean and environment-friendly, and can avoid the defect that a large amount of iron mud is generated in the traditional ferric trichloride catalysis process. The obtained N-phenyl-N' - (p-alkylphenyl) p-phenylenediamine can be used as a rubber antioxidant, can achieve good static or dynamic ozone erosion resistance and yield resistance when being used together with the antioxidant 4020, can make up the problem of poor later-stage protection effect of the antioxidant, and can solve the problem of discoloration on the basis of keeping good ozone resistance of the sidewall rubber.
Description
Technical Field
The invention relates to N-phenyl-N' - (p-alkylphenyl) p-phenylenediamine and a preparation method and application thereof, belonging to the technical field of fine chemical engineering.
Background
The anti-aging agent DTPD is a mixture which is mainly prepared from aniline, o-toluidine, mixed dimethylaniline or mixed methylaniline and hydroquinone through condensation, neutralization, washing and rectification separation, and mainly comprises N-phenyl-N ' - (o-methylphenyl) p-phenylenediamine, N ' -bis (o-methylphenyl) p-phenylenediamine and N, N ' -bis (phenyl) p-phenylenediamine. According to the data of the relationship between the molecular structure and the effectiveness of the p-phenylenediamine anti-aging agent, the dialkyl p-phenylenediamine is more than the aryl alkyl p-phenylenediamine and more than the diaryl p-phenylenediamine, wherein the dialkyl p-phenylenediamine has the best protective effect at the initial stage but is easy to migrate out and has poor protective effect at the later stage; the diaryl p-phenylenediamine resists migration and has a certain long-acting property, but the total protection effect is poor, and the aryl alkyl p-phenylenediamine has the best comprehensive performance.
The most representative product of aryl alkyl p-phenylenediamine is the anti-aging agent 4020, although the comprehensive performance is the best, the migration resistance is still not achieved, the anti-aging agent DTPD is a compound mixed product obtained by condensing and washing hydroquinone, o-toluidine, aniline, m-toluidine and the like, the anti-aging agent DTPD has the characteristic of migration resistance, can make up the defects that the anti-aging effect of the anti-aging agent 4020 and the like in the early stage is good and the effect of the anti-aging agent in the later stage is slightly poor, has the flexibility resistance and has a certain long-acting effect, particularly the later-stage protection effect, and is usually matched with the anti-aging agent 4020 in a tire for use.
N, N' -bis (o-methylphenyl) p-phenylenediamine in the anti-aging agent DTPD has great influence on the synthesis or protection effect due to steric hindrance of methyl, and has higher cost and increased market popularization difficulty. And DTPD is a compound mixed product, ferric trichloride is needed as a catalyst in the production process, a large amount of salt-containing organic wastewater and iron mud are generated, and the environmental pollution is serious.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides N-phenyl-N' - (p-alkylphenyl) p-phenylenediamine, which has single component and simple preparation, can replace the antioxidant DTPD and the antioxidant 4020 to achieve good static or dynamic ozone erosion resistance and yield resistance, can make up the problem of poor later protection effect of the antioxidant, and can solve the problem of discoloration on the basis of keeping good ozone resistance of the sidewall rubber.
The specific technical scheme of the invention is as follows:
an N-phenyl-N' - (p-alkylphenyl) p-phenylenediamine having the formula:
Preferably, R is tert-butyl or tert-octyl.
Furthermore, the N-phenyl-N' - (p-alkylphenyl) p-phenylenediamine is prepared by condensing 4-aminodiphenylamine and p-alkylphenol under the catalysis of a solid acid catalyst, and has the following reaction formula:
further, the invention also provides a preparation method of the N-phenyl-N' - (p-alkylphenyl) p-phenylenediamine, which comprises the following steps:
(1) Mixing 4-aminodiphenylamine, p-alkylphenol, a solid acid catalyst and a solvent, heating for reflux reaction, and continuously separating out water generated during the reaction until no water is generated any more;
(2) After the reaction is finished, removing the solid acid catalyst by heating decomposition or filtration, and removing the solvent, unreacted raw materials and byproducts from the rest materials to obtain the N-phenyl-N' - (p-alkylphenyl) p-phenylenediamine.
Further, the solid acid catalyst is solid super acid or oxalic acid. The solid super acid includes but is not limited to SO4 2- /ZrO、SO4 2- /TiO、SO4 2- /Fe 2 O 3 Or WO3/ZrO 2 . All solid super acids can be purchased in the market.
Further, when the solid acid catalyst is solid super acid, the solid super acid is removed from the reaction material by a filtration mode, and when the solid acid catalyst is oxalic acid, the reacted material is heated to 180 ℃ or above to decompose the oxalic acid.
Furthermore, the dosage of the solid acid catalyst is 3-4% of the mass of the 4-aminodiphenylamine.
Further, the p-alkylphenol is preferably p-tert-butylphenol or p-tert-octylphenol.
Further, the molar ratio of the p-alkylphenol to the 4-aminodiphenylamine is 1-2:1, the molar ratio is preferably 1.1.
Further, the temperature of the reflux reaction is 100 to 150 ℃, preferably 120 to 150 ℃.
Further, the solvent is an organic solvent capable of generating an azeotrope with water, such as toluene, benzene, xylene, and the like.
Further, the solvent, unreacted raw materials and byproducts in the materials are removed by vacuum distillation or rectification.
The invention further provides an application of the N-phenyl-N' - (p-alkylphenyl) p-phenylenediamine as a rubber anti-aging agent.
Furthermore, the invention also provides an anti-aging agent composition, which comprises the N-phenyl-N' - (p-alkylphenyl) p-phenylenediamine and the anti-aging agent 4020. The combination of the two can achieve good static or dynamic ozone erosion resistance and flexibility resistance, can make up the problem of slightly poor later protection effect of the anti-aging agent, and can solve the problem of discoloration of the sidewall rubber on the basis of keeping good ozone resistance.
Further, the molar ratio of N-phenyl-N' - (p-alkylphenyl) p-phenylenediamine to antioxidant 4020 was (1~2): 2.
The invention has the following beneficial effects:
1. the N-phenyl-N' - (p-alkyl phenyl) p-phenylenediamine is a high-purity single component, has a proper melting point and good compatibility with rubber, and avoids the problem of poor compatibility of DTPD and rubber. The compatibility of the N-phenyl-N' - (p-alkylphenyl) p-phenylenediamine and the anti-aging agent 4020 can achieve good static or dynamic ozone erosion resistance and yield resistance, can make up the problem of poor later protection effect of the anti-aging agent, and can solve the problem of discoloration on the basis of keeping good ozone resistance of the sidewall rubber.
2. The raw materials of the N-phenyl-N' - (p-alkyl phenyl) p-phenylenediamine are conventional chemicals in the market, are convenient to purchase and easy to obtain, and have the advantages of simple preparation process, low cost and low industrial popularization difficulty.
3. The preparation method of the invention adopts solid acid as the catalyst, and the catalyst can be removed by filtration or pyrolysis, so that the method does not produce iron-containing sludge, and is clean and environment-friendly.
Detailed description of the invention
The present invention is described in detail below with reference to specific examples, but the use and purpose of these exemplary embodiments are merely to exemplify the present invention, and do not set forth any limitation on the actual scope of the present invention in any form, and the scope of the present invention is not limited thereto.
Example 1
Putting 101.33 g of 4-aminodiphenylamine, 90.88 g of p-tert-butylphenol, 3.5 g of oxalic acid and 350 ml of toluene into a four-neck flask, heating to a reflux state, keeping the reflux reaction at the temperature of 120 ℃ for 2 hours until no water is generated, stopping the reaction, continuously heating to 180 ℃ to decompose the oxalic acid, removing the solvent toluene in vacuum, rectifying and removing incompletely reacted materials and micromolecule substances, pouring out the materials in the flask, and cooling to obtain 172.83 g of the invention, wherein the yield is 99.3 percent calculated by 4-aminodiphenylamine and the softening point is 90.8 ℃.
Example 2
101.33 g of 4-aminodiphenylamine, 90.88 g of p-tert-butylphenol and 3.5 g of SO4 2- Adding ZrO and 350 ml toluene into a four-neck flask, heating to reflux state at 120 deg.C, maintaining reflux reaction at the temperature for 2 hr until no water is formed, filtering while hot to obtain solid acid SO4 2- Filtering out ZrO, removing solvent toluene from the filtrate in vacuum, then rectifying and removing unreacted materials and micromolecular substances, pouring out the materials in the flask and cooling to obtain the sample 171.44 g, wherein the yield is 98.5 percent by using 4-aminodiphenylamine and the softening point is 89.4 ℃.
Example 3
101.33 g of 4-aminodiphenylamine, 90.88 g of p-tert-butylphenol and 4 g of WO3/ZrO 2 And 350 ml of xylene are put into a four-neck flask, heated to a reflux state at a reaction temperature of 110 ℃, kept at the reflux temperature for 2 hours until no water is generated to stop the reaction, and filtered while hot to obtain the solid acid WO3/ZrO 2 Filtering, removing solvent xylene from the filtrate in vacuum, then rectifying and removing unreacted materials and micromolecular substances, pouring out the materials in the flask and cooling to obtain the sample 171.09 g, wherein the yield is 98.3 percent by using 4-aminodiphenylamine and the softening point is 89.8 ℃.
Example 4
101.33 g of 4-aminodiphenylamine, 124.82 g of p-tert-octylphenol, 4 g of WO3/ZrO 2 And 800 ml of toluene are put into a four-neck flask and heated toRefluxing at 130 deg.C for 3 hr until no water is formed, filtering to remove WO3/ZrO 2 Filtering, removing the solvent toluene from the filtrate in vacuum, then rectifying and removing the materials and small molecular substances which are not completely reacted, pouring out the materials in the flask and cooling to obtain the sample 200.19 g of the invention, wherein the yield is 97.7 percent by taking 4-aminodiphenylamine as a reference, and the softening point is 90.5 ℃.
Example 5
101.33 g of 4-aminodiphenylamine, 124.82 g of p-tert-octylphenol, 4 g of oxalic acid and 800 ml of xylene are put into a four-neck flask, heated to a reflux state, the reaction temperature is 120 ℃, the reflux reaction is kept for 2 hours until no water is generated, the reaction is stopped until no water is generated, the temperature is continuously increased to 190 ℃ to completely decompose the oxalic acid, then the solvent xylene is removed in vacuum, finally the materials which are not completely reacted and the micromolecule substances are removed by rectification, the materials in the flask are poured out and cooled, 201.83 g of the sample is obtained, the yield is 98.5 percent by the 4-aminodiphenylamine, and the softening point is 85.7 ℃.
Example 6
101.33 g of 4-aminodiphenylamine, 124.82 g of p-tert-octylphenol, 4 g of SO4 2- Adding ZrO and 800 ml toluene into a four-neck flask, heating to reflux state at 120 deg.C, maintaining reflux reaction for 2 hr until no water is generated, filtering while hot to obtain solid acid SO4 2- Filtering out ZrO, removing solvent toluene from the filtrate in vacuum, then rectifying and removing unreacted materials and micromolecular substances, pouring out the materials in the flask and cooling to obtain the sample 198.35 g, wherein the yield is 96.8 percent by using 4-aminodiphenylamine and the softening point is 86.4 ℃.
Example 7
Putting 101.33 g of 4-aminodiphenylamine, 71.37 g of p-methylphenol, 4 g of oxalic acid and 500 ml of xylene into a four-neck flask, heating to a reflux state, keeping the reflux reaction at 110 ℃ for 2 hours until no water is generated, stopping the reaction, continuously heating to 200 ℃ to decompose the oxalic acid completely, then removing the solvent xylene in vacuum, finally removing unreacted materials and micromolecule substances by rectification, pouring out the materials in the flask and cooling to obtain 149.1 g of a sample of the invention, wherein the yield is 98.8 percent by using 4-aminodiphenylamine and the softening point is 88.3 ℃.
To verify the properties of the samples of the above examples, a comparison of the application properties in rubber was made as follows:
1. sizing material formula
A first stage: NR 45 parts, BR 55 parts, N330 30 parts, znO-80.375 parts and SA 2 parts;
and (2) second stage: 1.875 parts of S-80, 1 part of NS-80, 1.5 parts of H3241 and 3 parts of anti-aging agent. The antioxidant was the sample of example 1, the sample of example 5, the sample of example 7, antioxidant DTPD, antioxidant 4020 in a molar ratio of 1:1, and the mixture of example 5.
2. Rubber mixing process
The rubber material is mixed by adopting a two-stage mixing process.
The first mixing process was carried out in a 1.5L internal mixer: banburying parameters: the initial temperature is 80 ℃, and the rotation speed is 50r min < -1 >; the charging sequence is as follows: putting natural rubber and butadiene rubber into an internal mixer for 20s, carrying out press mixing for 60s, lifting for 10s, adding carbon black, zinc oxide and stearic acid, carrying out press mixing for 45s, carrying out press mixing for 10s, carrying out mixing for 40s, cleaning for 10s, carrying out press mixing for 30s, carrying out press mixing for 10s, carrying out 20s rubber discharging by pressing the lifting for 10s (the rubber discharging temperature is 135 +/-5 ℃).
The two-stage mixing process is carried out on an open mill, and comprises the following steps: one section of master batch, sulfur, an accelerant and an anti-aging agent, wherein the left and right 3/4 of the master batch are respectively cut for 2 times, the master batch is passed through the cutter for 6 times, the master batch is rolled for 6 times, and the master batch is placed at a roller spacing of 4mm for a piece to be tested.
3. Vulcanizate Property testing
The vulcanized rubber ozone aging resistance experiment static stretching experiment is tested according to GB7762-87, the vulcanized rubber ozone aging resistance experiment dynamic stretching experiment is tested according to GB/T13642-92, the vulcanized rubber flex crack resistance experiment is tested according to GB/T13934-1992, and the test results are respectively shown in the following tables 1-5:
4. conclusion of the experiment
The results in tables 1-5 above show that:
1. the dynamic ozone corrosion resistance, static ozone corrosion resistance, flexibility resistance and discoloration resistance of the samples of the embodiment 1, the embodiment 5 and the embodiment 7 are better than those of DTPD;
2. the 8h dynamic ozone resistance of the invention in the embodiment 1, the embodiment 5 and the embodiment 7 is slightly lower than 4020, and the 48h dynamic ozone resistance is equivalent to 4020; the antistatic ozone erosion performance is slightly lower than 4020 in 8h and 72h, and is higher than 4020 after 168 h;
3. the discoloration resistance and the flexing resistance of the invention in the embodiment 1, the embodiment 5 and the embodiment 7 are all better than 4020;
4. in addition, it can be seen that the combination of the invention of example 5 and 4020 according to the molar ratio of 1:1 is superior to that of example 5 or 4020 alone in dynamic ozone erosion resistance, static ozone erosion resistance, discoloration resistance and flexibility resistance.
Claims (10)
1. The N-phenyl-N' - (p-alkylphenyl) p-phenylenediamine is characterized in that: having a formula as described below:
2. A preparation method of N-phenyl-N' - (p-alkylphenyl) p-phenylenediamine is characterized by comprising the following steps:
(1) Mixing 4-aminodiphenylamine, p-alkylphenol, a solid acid catalyst and a solvent, heating for reflux reaction, and continuously separating out water generated during the reaction until no water is generated any more;
(2) After the reaction is finished, removing the solid acid catalyst by heating decomposition or filtration, and removing the solvent, unreacted raw materials and byproducts from the rest materials to obtain the N-phenyl-N' - (p-alkylphenyl) p-phenylenediamine.
3. The method for preparing a polycarbonate resin composition according to claim 2, wherein: the solid acid catalyst is solid super acid or oxalic acid; preferably, the solid super acid comprises SO4 2- /ZrO、SO4 2- /TiO、SO4 2- /Fe 2 O 3 Or WO3/ZrO 2 (ii) a Preferably, the dosage of the solid acid catalyst is 3-4% of the mass of the 4-aminodiphenylamine.
4. The method of claim 3, wherein: when the solid acid catalyst is solid super acid, the solid super acid is removed from the reaction material by a filtration mode, and when the solid acid catalyst is oxalic acid, the reacted material is heated to 180 ℃ or above to decompose the oxalic acid.
5. The method of claim 2, wherein: the p-alkylphenol is p-tert-butylphenol or p-tert-octylphenol; preferably, the molar ratio of p-alkylphenol to 4-aminodiphenylamine is 1~2:1, preferably 1.1.
6. The method of claim 2, wherein: the temperature of the reflux reaction is 100 to 150 ℃, and preferably 120 to 150 ℃.
7. The method of claim 2, wherein: the solvent is an organic solvent which can generate azeotropy with water; preferably, the solvent is toluene, benzene or xylene.
8. The method of claim 2, wherein: removing the solvent, unreacted raw materials and byproducts in the materials by vacuum distillation or rectification.
9. The use of N-phenyl-N' - (p-alkylphenyl) p-phenylenediamine, according to claim 1, as a rubber antioxidant.
10. An antioxidant composition, which is characterized in that: comprising N-phenyl-N' - (p-alkylphenyl) p-phenylenediamine, as set forth in claim 1, and an antioxidant 4020.
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