EA-053298-B1 - AGING RETARDANT BASED ON POLYALKYL-PARA-PHENYLENEDIAMINE, AN INTERMEDIATE COMPOUND FOR ITS PRODUCTION AND A METHOD FOR ITS PRODUCTION

EA053298B1EA 053298 B1EA053298 B1EA 053298B1EA-053298-B1

Abstract

A polyalkyl-paraphenylenediamine-based aging retarder with a structure represented by formula I, an intermediate compound for its preparation, and a method for producing said aging retarder are proposed. The polyalkyl-paraphenylenediamine-based aging retarder exhibits high resistance to thermal-oxidative aging and high resistance to aging under ultraviolet radiation.

Inventors

Син Цзиньгуо
Гуо Сянъюнь
Лян Гань
Чжан Цзяцян
Тан Чжиминь

Assignees

СЕННИКС КО., ЛТД.

Dates

Publication Date: 20260504
Application Date: 20221121
Priority Date: 20221110

Claims (8)

(1) carrying out a condensation reaction of a compound of formula A and a compound of formula B in the presence of a first catalyst to form a condensation product comprising a compound of formula C, a compound of formula C, or both of these compounds, and reducing the condensation product in the presence of H 2 and a second catalyst to form a compound of formula II: second catalyst H 2 (P) ; 1. Compound of formula I: (I), where each Ri independently represents H, a C1-C18 hydrocarbon group, or a C3-C18 alicyclic hydrocarbon group, and is an integer ranging from 1 to 5; each of R2 , R3, R4, and R5 is independently AND or methyl, and two or three of R2 , R3, R4, and R5 are AND; when three of R2 , R3 , R4 , and R5 are AND, R2 is not AND; when two of R2 , R3, R4, and R5 are AND, R2 and R4 are not AND; and each of R 6 , R 7 independently represents a C1-C18 hydrocarbon group or a C3-C18 aliphatic hydrocarbon group, or R 6 together with R 7 forms a C3-C18 aliphatic ring.
(2) carrying out a reductive alkylation reaction of a compound of formula II with a compound of formula D in the presence of H 2 and a third catalyst to form a compound of formula I: (II) (D) (I) where R b R 2 , R 3 , R 4 , R 5 , R 6 and R 7 in formulas A, B, C, C, D, II and I have the meanings specified in paragraph 1; wherein the first catalyst is selected from one or more of the following substances: an alkali metal hydroxide, an alkali metal alkoxide, a quaternary ammonium base, a combination of an alkali metal hydroxide and a tetraalkylammonium halide; the second catalyst is a porous metal catalyst or a supported metal catalyst, wherein the porous metal catalyst is one or more of the following: Raney nickel, Raney cobalt, or Raney copper; the metal in the supported metal catalyst is one or more of the following: nickel, cobalt, - 19053298 copper, platinum, palladium, ruthenium or rhodium, and the support in the supported metal catalyst is one or more of the following: carbon, alumina, silica gel or a molecular sieve; the third catalyst is a supported metal catalyst, wherein the metal in the supported metal catalyst is one or more of the following metals: nickel, cobalt, copper, platinum, palladium, ruthenium or rhodium, and the support in the supported metal catalyst is one or more of the following substances: carbon, alumina, silica gel or a molecular sieve; in step (1), the molar ratio of the compound of formula A to the compound of formula B is from 2:1 to 15:1; at stage (1), the condensation reaction temperature is from 40 to 90C, and the degree of vacuum is from -0.09 to -0.99 MPa; at stage (1), the temperature in the reaction of the condensation product and H2 is from 40 to 120C, and the hydrogen pressure is from 0.5 to 5 MPa; in step (2), the molar ratio of the compound of formula D to the compound of formula II is from 1:1 to 15:1; in step (2), the reaction temperature is from 40 to 150C, and the reaction pressure is from 0.5 to 5 MPa. 2. The compound according to claim 1, wherein each Ri independently represents H or C1-C8 alkyl, and is equal to 1 or 2, each of R 6 , R 7 independently represents C1-C8 alkyl or C3-C8 cycloalkyl, or 1% together with R 7 forms a C3-C8 aliphatic ring.
3. A method for producing a compound according to claim 1, comprising:
4. The method according to claim 3, having one or more of the following characteristics: in step (1), the molar ratio of the compound of formula A to the compound of formula B is from 4:1 to 10:1; at stage (1) the condensation reaction temperature is from 65 to 85C; at stage (1), the temperature in the reaction of the condensation product and H2 is from 60 to 90C, and the hydrogen pressure is from 0.5 to 2.5 MPa.
5. A rubber mixture comprising a compound according to claim 1 or 2 and a diene elastomer.
6. A rubber product comprising a rubber mixture according to paragraph 5 and which is a tire, rubber footwear, sealing strip, sound-insulating panel or shock-absorbing panel.
7. A method for increasing the resistance to thermal-oxidative aging of rubber or a rubber product, wherein the method includes adding a compound according to paragraph 1 or 2 to the rubber or rubber product.
8. A method for increasing the resistance to aging under the influence of UV radiation of rubber or a rubber product, wherein the method includes adding a compound according to paragraph 1 or 2 to the rubber or rubber product.

Description

Field of technology The present invention relates to the field of aging retarders based on paraphenylenediamine, in particular, aging retarders based on polyalkyl-para-phenylenediamine, to intermediate compounds for their production and to a method for their production. State of the art Currently, para-phenylenediamine-based ageing retarders, which are widely used in rubber products, particularly tires, provide effective protection against ozone, very good protection against bending stress and general ageing, such as exposure to oxygen and elevated temperatures, and also exhibit a high protective effect against the effects of harmful metals such as copper and manganese. For example, the ageing retarder 6PPD, chemically named K-(1,3-dimethylbutyl)-K-phenyl-para-phenylenediamine, is a highly effective ageing retarder for rubber. Published Chinese Patent Application CN 113072741 A describes an environmentally friendly antiaging agent based on para-phenylenediamine and a method for producing it. The environmentally friendly antiaging agent based on para-phenylenediamine described in this document has the following structure: R 1 wherein the aging retarder does not convert to quinone derivatives during the aging process if the following specific conditions are met: at least one of x and w is 1, at least one of y and z is 1, and if x and z are both equal to 1, then y and w are not both equal to 0. The method of preparation presented in this patent application is as follows: first, aniline and para-bromonitrobenzene having the appropriate substituent(s) enter into a CN coupling reaction. The resulting coupling reaction product is subjected to reduction in the presence of a catalyst under a hydrogen atmosphere, yielding an intermediate product. The intermediate reaction product, in the presence of an aldehyde or ketone, is subjected to reductive amination in the presence of a catalyst, yielding an aging retarder based on para-phenylenediamine. This method requires the use of expensive bromide and catalysts based on an organophosphorus complex of a noble metal, the degree of conversion and yield in the reaction are low, separation and purification are difficult, and wastewater containing metal bromides is formed, meaning this method is not suitable for industrial production. In the production of para-phenylenediamine-based aging retarders, an important intermediate is 4-aminodiphenylamine, which is formed in the condensation and reduction reactions of aniline or its derivatives with nitrobenzene under alkaline conditions. Furthermore, this compound can also be obtained by the C-N coupling reaction of aniline and para-halogenated nitrobenzene in the presence of a palladium coordination compound with triphenylphosphorus, which acts as a catalyst, resulting in anilinonitrobenzene, which is then reduced by hydrogenation. Thus, there is a need to create an aging retarder based on paraphenylenediamine, which has a new structure, and to develop an environmentally friendly method for its production. The essence of the invention To overcome the shortcomings of current technology, the present invention provides a para-phenylenediamine-based aging retarder with a novel structure that exhibits high resistance to thermal-oxidative aging and UV aging. The present invention also relates to a method for producing an environmentally friendly para-phenylenediamine-based aging retarder that is consistent with the Green Agenda and does not generate waste. The present invention also relates to an intermediate compound for producing the para-phenylenediamine-based aging retarder. In particular, the present invention relates to a compound of formula I: H i 6 R4 NR 7 r 5 n (I), - 1 053298 where each Ri is independently selected from H, a C1-C18 hydrocarbon group, or a C3-C18 alicyclic hydrocarbon group; and is an integer ranging from 1 to 5; each of R 2 , R3, R4, R5 is independently selected from H, a C1-C18 hydrocarbon group or a C3-C18 alicyclic hydrocarbon group, and at least one of R 2 , R3, R4, R5 is not H; each of R^, R 7 is independently selected from a C1-C18 hydrocarbon group, a C3-C18 alicyclic hydrocarbon group, or FQ together with R 7 forms a C3-C18 aliphatic ring. In one or more embodiments, each Ri in formula I is independently H or C1C8 alkyl. In one or more embodiments, a in formula I may be 1 or 2. In one or more embodiments, each of R 2 , R 3 , R4 and R 5 in formula I is independently H or C1-C8 alkyl. In one or more embodiments of formula I, two or three of R 2 , R 3 , R4, R 5 are H. In one or more embodiments, each of R^ and R 7 in formula I is independently C1C8 alkyl or C3-C8 cycloalkyl, or R^ together with R 7 forms a C3-C8 aliphatic ring. The present invention also relates to a method for preparing a compound having formula I, wherein the method comprises the following steps: (1) carrying out a condensation reaction of a compound of formula A and a compound of formula B, in the presence of a first catalyst to form a