阅读说明：本技术 一种复合防老剂的合成方法 (Synthetic method of composite anti-aging agent ) 是由 任磊 陶建青 黄伟 何志勇 于 2019-08-29 设计创作，主要内容包括：本发明提供了一种复合防老剂的合成方法。以2-辛酮、4-氨基二苯胺为基本原料,在铂碳催化剂,固定床中连续缩合加氢反应,控制一定的反应条件,得到防老剂688,本发明方法使用更高效的催化剂来生产防老剂688,减少反应原料2-辛酮转化为2-辛醇的比例,提高反应原料的利用率,降低反应液的处理难度。防老剂688与防老剂TMQ氮气保护并加热的条件下按一定比例进行复配,生产防老剂8PPD。(The invention provides a synthetic method of a composite anti-aging agent. The method uses a more efficient catalyst to produce the anti-aging agent 688, reduces the proportion of the reaction raw material 2-octanone converted into 2-octanol, improves the utilization rate of the reaction raw material and reduces the treatment difficulty of the reaction liquid. The antioxidant 688 and the antioxidant TMQ are compounded according to a certain proportion under the conditions of nitrogen protection and heating to produce the antioxidant 8 PPD.)

1. A synthetic method of a composite anti-aging agent is characterized by comprising the following steps: 2-octanone and 4-aminodiphenylamine are used as basic raw materials, and are subjected to continuous condensation hydrogenation reaction in a fixed bed in the presence of a noble metal catalyst to obtain an anti-aging agent 688, and the anti-aging agent 688 and an anti-aging agent TMQ are mixed and compounded in proportion to obtain the anti-aging agent 8 PPD.

2. The synthesis process as claimed in claim 1, wherein the noble metal catalyst is platinum-carbon catalyst.

3. The synthesis method according to claim 2, wherein the content of platinum metal in the catalyst is 0.1% to 0.3%.

4. The synthesis method according to claim 2, wherein the carrier in the catalyst has a specific surface area of 800-1200 m²Per g, suctionThe water rate is more than 60 percent.

5. The synthesis method according to claim 1, wherein 2-octanone is added to 4-aminodiphenylamine in an amount at least sufficient to completely dissolve 4-aminodiphenylamine, and the space velocity of the reaction liquid is 0.10-0.15 h^-1。

6. The synthesis method of claim 1, wherein the condensation hydrogenation reaction is carried out at a temperature of 120 ℃ to 150 ℃ and a reaction pressure of 0.6MPa to 1.0 MPa.

7. The synthesis method according to claim 1, wherein the ratio of hydrogen to oil fed to the condensation hydrogenation reaction, that is, the ratio of the volume flow rate of hydrogen to the volume flow rate of the raw material, is 200 to 500.

8. The method of claim 1, wherein the weight ratio of antioxidant 688 to antioxidant TMQ is 4: 1-5: 1.

9. the synthesis method of claim 1, wherein the combination of the antioxidant 688 and the antioxidant TMQ is performed under the protection of nitrogen and under heating.

10. The method of claim 9, wherein the heating temperature is controlled to be 95 ℃ to 120 ℃.

Technical Field

The invention relates to a synthesis method of an antioxidant 688 and a compounding method of an antioxidant 8PPD, belonging to the field of fine chemical engineering.

Background

Antioxidant 688, also known as antioxidant OPPD, is chemically known as N-sec-octyl-N' -phenyl p-phenylenediamine. Dark tan viscous liquid. Density 1.003. Freezing point 10 ℃. The boiling point is 430 ℃. The antiozonants for natural rubber and synthetic rubber also have good protection effect on flex cracking. Good compatibility with rubber and low volatility. It is suitable for tyre, sealing rubber strip, rubber pipe, rubber belt and various industrial rubber products.

The anti-aging agent, N-sec-octyl-N' -phenyl-p-phenylenediamine, was first produced by American ring oil chemical company, and the trade mark of the anti-aging agent is UOP688, which was authorized by the trademark in 6 months in 1962.

The US3366684A patent describes the synthesis of an antioxidant 688 by charging 138 g of purified 4-aminodiphenylamine, 384 g of 2-octanone, 2 g of a silica-based nickel catalyst containing 63% nickel in a 1 liter stirred autoclave and reacting at 160 c and 750-1000psi of hydrogen pressure for 4 hours. The product was distilled at 250 ℃ at 25 mm Hg, 33.7% of the ketone was reduced to alcohol and 87.7% was present in the distillation residue. After 4 ml thiodipropionic acid containing 0.0516 g of catalyst modifier was added and reacted under the same conditions, 9.7% of the ketone was converted into alcohol, and the distillation residue was 100% of the target product.

CN105348114B introduces a method for synthesizing an antioxidant 688 by a fixed bed, wherein a copper catalyst participates in the synthesis, and a final product is obtained by separation. The method prepares the antioxidant 688 with high efficiency, and has the main defects that in a reaction product, the ratio of 2-octanol to 2-octanone is about 4: 1, namely a large amount of 2-octanone as a raw material is converted into 2-octanol, which causes the waste of the raw material and brings certain difficulty to the subsequent recovery of the raw material.

The antioxidant 8PPD is a compound of the antioxidant 688 and the antioxidant TMQ, is dark brown viscous liquid and has the density of about 1.00-1.03 g/cm³(25 ℃) and a viscosity of about 1700-2200 mPa ℃. (25 ℃). The product is a polluting anti-aging agent, has the characteristics of ketoamine anti-aging agents and p-phenylenediamine anti-aging agents, has protective effects on heat, oxygen, ozone and natural aging, has outstanding high-temperature service performance and waterproof extraction performance, and has good compatibility with rubber. It is widely used as rubber anti-aging agent, especially as stabilizer in butadiene styrene rubber. Can also be used in rubber products such as wires and cables, can replace armor prevention, butyl prevention and RD prevention in equal amount, but has obviously excellent comprehensive protection performanceThe later aging performance is close to that of the antioxidant 4010NA and the antioxidant 6 PPD.

CN1142515A discloses a production method of composite antioxidant 8PPD, which takes antioxidant 688, antioxidant RD (TMQ) and a carrier as raw materials, and carries out compound production under certain conditions, wherein the heating temperature is 150-180 ℃, and the method mainly relates to a method for preparing the additive carrier.

Disclosure of Invention

The invention aims to produce the antioxidant 688 by using a more efficient catalyst, and synthesize the antioxidant 8PPD by compounding the antioxidant 688 and the antioxidant TMQ.

The main technical scheme of the invention is as follows: the synthetic method of the composite anti-aging agent comprises the following steps: 2-octanone and 4-aminodiphenylamine are used as basic raw materials, and are subjected to continuous condensation hydrogenation reaction in a fixed bed in the presence of a noble metal catalyst to obtain an anti-aging agent 688, and the anti-aging agent 688 and an anti-aging agent TMQ are mixed and compounded in proportion to obtain the anti-aging agent 8 PPD.

Typically, the noble metal catalyst used in the present invention is a platinum carbon catalyst.

The content of the metal platinum in the catalyst is 0.1% -0.3%.

The carrier in the catalyst has a specific surface area of 800-1200 m²The water absorption rate of the coconut shell activated carbon is more than 60 percent.

The synthesis method comprises the steps of adding 2-octanone into 4-aminodiphenylamine, wherein the addition amount of the 2-octanone at least meets the requirement of completely dissolving the 4-aminodiphenylamine, and the feeding airspeed of reaction liquid is 0.10-0.15 h^-1。

The synthesis method has the advantages that the condensation hydrogenation reaction is controlled at the temperature of 120-150 ℃ and the reaction pressure of 0.6-1.0 MPa.

The synthesis method is characterized in that the ratio of hydrogen to oil fed in the condensation hydrogenation reaction, namely the ratio of the volume flow of hydrogen to the volume flow of the raw material is 200-500.

In the synthesis method, the weight ratio of the antioxidant 688 to the antioxidant TMQ is 4: 1-5: 1.

according to the synthesis method, the anti-aging agent 688 and the anti-aging agent TMQ are compounded under the conditions of nitrogen protection and heating, and the heating temperature is controlled to be 95-120 ℃.

The invention has the advantages of

The antioxidant 688 is produced by using a more efficient catalyst, and the antioxidant 688 and the antioxidant TMQ are compounded to synthesize the antioxidant 8 PPD.

The invention utilizes the noble metal catalyst to produce the anti-aging agent 688, can improve the utilization rate of the reaction raw material 2-octanone, and reduce the treatment difficulty of the reaction residual liquid.

Compared with the prior art, the method for compounding and synthesizing the anti-aging agent 8PPD by adopting the synthesis method is simple and has lower temperature.

Detailed Description

The technical solution of the present invention is further described below with reference to examples, and the scope of the present invention is not limited to the following specific embodiments.

Example 1

On a fixed bed in a laboratory, 100ml of platinum-carbon catalyst with platinum content of 0.1 percent is filled in a fixed bed layer, and the mol ratio of the raw materials of 2-octanone and 4-aminodiphenylamine is 4.5: 1 is prepared into solution, the raw materials are pumped in according to set conditions and react under certain conditions, and the space velocity of the reaction liquid is 0.10h^-1The reaction pressure is 0.6MPa, the reaction temperature is 120 ℃, and the reaction solution 1# is collected for gas chromatographic analysis, and the content of the anti-aging agent 688 and the alcohol conversion degree of the raw material 2-octanone are analyzed.

Example 2

On a fixed bed in a laboratory, 100ml of platinum-carbon catalyst with platinum content of 0.1 percent is filled in a fixed bed layer, and the mol ratio of the raw materials of 2-octanone and 4-aminodiphenylamine is 4.5: 1 is prepared into solution, the raw materials are pumped in according to set conditions and react under certain conditions, and the space velocity of the reaction liquid is 0.12h^-1The reaction pressure is 0.8MPa, the reaction temperature is 135 ℃, and the reaction solution 2# is collected for gas chromatographic analysis, and the content of the anti-aging agent 688 and the alcohol conversion degree of the raw material 2-octanone are analyzed.

Example 3

On a fixed bed in a laboratory, 100ml of platinum-carbon catalyst with platinum content of 0.1 percent is filled in a fixed bed layer, and the mol ratio of the raw materials of 2-octanone and 4-aminodiphenylamine is 4.5: 1 preparing into solution, pumping raw materials into a certain strip according to set conditionsThe reaction is carried out under the condition that the space velocity of the reaction liquid is 0.15h^-1The reaction pressure is 1.0MPa, the reaction temperature is 150 ℃, and the reaction liquid 3# is collected for gas chromatographic analysis, and the content of the anti-aging agent 688 and the alcohol conversion degree of the raw material 2-octanone are analyzed.

Example 4

On a fixed bed in a laboratory, 100ml of platinum-carbon catalyst with platinum content of 0.2 percent is filled in a fixed bed layer, and the mol ratio of the raw materials of 2-octanone and 4-aminodiphenylamine is 4.5: 1 is prepared into solution, the raw materials are pumped in according to set conditions and react under certain conditions, and the space velocity of the reaction liquid is 0.10h^-1The reaction pressure is 0.6MPa, the reaction temperature is 120 ℃, and the reaction solution 4# is collected for gas chromatographic analysis, and the content of the anti-aging agent 688 and the alcohol conversion degree of the raw material 2-octanone are analyzed.

Example 5

On a fixed bed in a laboratory, 100ml of platinum-carbon catalyst with platinum content of 0.2 percent is filled in a fixed bed layer, and the mol ratio of the raw materials of 2-octanone and 4-aminodiphenylamine is 4.5: 1 is prepared into solution, the raw materials are pumped in according to set conditions and react under certain conditions, and the space velocity of the reaction liquid is 0.12h^-1The reaction pressure is 0.8MPa, the reaction temperature is 135 ℃, and the reaction solution 2# is collected for gas chromatographic analysis, and the content of the anti-aging agent 688 and the alcohol conversion degree of the raw material 2-octanone are analyzed.

Example 6

On a fixed bed in a laboratory, 100ml of platinum-carbon catalyst with platinum content of 0.2 percent is filled in a fixed bed layer, and the mol ratio of the raw materials of 2-octanone and 4-aminodiphenylamine is 4.5: 1 is prepared into solution, the raw materials are pumped in according to set conditions and react under certain conditions, and the space velocity of the reaction liquid is 0.15h^-1The reaction pressure is 1.0MPa, the reaction temperature is 150 ℃, and the reaction liquid 3# is collected for gas chromatographic analysis, and the content of the anti-aging agent 688 and the alcohol conversion degree of the raw material 2-octanone are analyzed.

Example 7

On a fixed bed in a laboratory, 100ml of platinum-carbon catalyst with platinum content of 0.3 percent is filled in a fixed bed layer, and the mol ratio of the raw materials of 2-octanone and 4-aminodiphenylamine is 4.5: 1 is prepared into solution, the raw materials are pumped in according to set conditions and react under certain conditions, and the space velocity of the reaction liquid is 0.10h^-1The reaction pressure is 0.6MPa, the reaction temperature is 120 ℃, and the reaction solution 4# is collected for gas chromatographic analysis, and the content of the anti-aging agent 688 and the alcohol conversion degree of the raw material 2-octanone are analyzed.

Example 8

On a fixed bed in a laboratory, 100ml of platinum-carbon catalyst with platinum content of 0.3 percent is filled in a fixed bed layer, and the mol ratio of the raw materials of 2-octanone and 4-aminodiphenylamine is 4.5: 1 is prepared into solution, the raw materials are pumped in according to set conditions and react under certain conditions, and the space velocity of the reaction liquid is 0.12h^-1The reaction pressure is 0.8MPa, the reaction temperature is 135 ℃, and the reaction solution 2# is collected for gas chromatographic analysis, and the content of the anti-aging agent 688 and the alcohol conversion degree of the raw material 2-octanone are analyzed.

Example 9

On a fixed bed in a laboratory, 100ml of platinum-carbon catalyst with platinum content of 0.3 percent is filled in a fixed bed layer, and the mol ratio of the raw materials of 2-octanone and 4-aminodiphenylamine is 4.5: 1 is prepared into solution, the raw materials are pumped in according to set conditions and react under certain conditions, and the space velocity of the reaction liquid is 0.15h^-1The reaction pressure is 1.0MPa, the reaction temperature is 150 ℃, and the reaction liquid 3# is collected for gas chromatographic analysis, and the content of the anti-aging agent 688 and the alcohol conversion degree of the raw material 2-octanone are analyzed.

TABLE 1 results of fixed bed synthesis of antioxidant 688

Serial number	RT%	688%	Conversion rate/%	Selectivity is/%	2-octanone%	2-octanol%
							1	2.21	96.25	97.79	98.43	94.6	5.4
2	1.51	97.03	98.49	98.52	97.2	2.8
							3	1.89	96.43	98.11	98.29	97.6	2.4
4	0.39	99.21	99.61	99.60	99.2	0.8
							5	0.56	98.79	99.44	99.35	99.6	0.4
6	0.21	99.54	99.79	99.75	99.5	0.5
							7	0.86	98.54	99.14	99.39	98.2	1.8
8	0.92	98.31	99.08	99.22	98.5	1.5
							9	0.77	98.62	99.23	99.39	98.0	2.0

Comparative example

The feeding molar ratio of the 2-octanone to the 4-aminodiphenylamine is 5: 1, space velocity of 0.17h^-1The reaction pressure is 1.10MPa, a copper catalyst is used, the set temperature of the reactor is 185 ℃, and the ratio of 2-octanone to 2-octanol alcohol in the reaction liquid is 15: 85, a large amount of the reaction material, 2-octanone, was converted to 2-octanol.

Example 10

Adding 80g of the antioxidant 688 and 20g of the antioxidant TMQ into a thick-walled flask, slowly introducing nitrogen, setting the heating temperature to 100 ℃, slowly starting stirring, and maintaining the heating stirring for 1.5 hours. After the heating is finished, the heating is removed, and nitrogen is introduced to naturally cool the glass. The viscosity at 25 ℃ was determined to be 1920 m.pa.S.

The synthesis method of the invention adopts the noble metal catalyst to produce the antioxidant 688, which can improve the utilization rate of the reaction raw material 2-octanone and reduce the treatment difficulty of the reaction residual liquid. Compared with the prior art, the method for compounding and synthesizing the anti-aging agent 8PPD by adopting the synthesis method is simple and has lower temperature.