Novel bio-based phosphite antioxidant and preparation method thereof

Abstract

The invention discloses a novel biological based phosphite ester type antioxidant and a preparation method thereof. A compound I has a structural formula as shown in the description. The novel biological based phosphite ester type antioxidant is free of nonyl phenol, large in molecular weight and green, environmental-friendly and safe. The invention provides a preparation method of the biologicalbased phosphite ester type antioxidant. The preparation method comprises the following steps: by taking biological-based cardanol as a raw material, carrying out a hydrogenation reaction so as to convert the cardanol into m-pentadecyl phenol, and further carrying out an esterification reaction on the m-pentadecyl phenol, obtained through the reaction and phosphorus trichloride in the presence of acatalyst under the action of negative pressure, thereby obtaining the biological based phosphite ester type antioxidant. The antioxidant prepared by using the method comprises three P-O bonds, has atrivalent bond P, has steric hindrance approximate to that of TNPP (Tris-Nonyl Phenyl Phosphite), has hydrolytic stability equivalent to that of TNPP, and is a good antioxidant because of a large molecular weight and high thermal resistance stability.

Description

technical field

[0001] The invention relates to an antioxidant for polymer materials, in particular to a novel bio-based phosphite antioxidant and a preparation method thereof. Background technique

[0002] During processing and long-term use, polymers are susceptible to light and heat, oxidized by oxygen in the air, lose mechanical properties, discoloration, cracks, loss of gloss and other changes, and the appearance becomes unattractive. Antioxidants need to be added to improve the processing stability and long-term stability of the polymer. Antioxidants are such a class of chemical substances, when only a small amount exists in the polymer system, they can delay or inhibit the oxidation process of the polymer, thereby preventing the aging of the polymer and prolonging its service life, also known as "Anti-aging agent".

[0003] The types of antioxidants are: hindered phenol antioxidants, phosphite antioxidants, thio antioxidants, etc.

[0004] Phosphite antioxidant is ...

Examples

Embodiment 1

[0041] The synthesis of the pentadecylphenol of embodiment 1

[0042]Add 986 grams of cardanol into a clean 2L pressure reactor, add 5 grams of Raney nickel catalyst, and replace the air in the reactor with nitrogen until the nitrogen content of the gas discharged from the outlet is ≥99.5%, and the hydrogen flow rate is controlled through the connected hydrogen cylinder. Hydrogen replacement, after the replacement, re-flow hydrogen to the pressure of about 4 MPa in the kettle, stop the hydrogen flow, close the hydrogen valve, seal the reaction kettle, gradually raise the temperature, observe the reaction pressure during the heating process, control the pressure by adjusting the heating speed to no more than 5 MPa, and keep the stirring speed at about 300r / min, heat up to about 120°C in about 2 hours, keep the reaction at the reaction temperature of 120-140°C for 3 hours, cool down to below 45°C after the reaction is completed, slowly open the vent valve, and restore the normal ...

Embodiment 2

[0043] The synthesis of the pentadecylphenol of embodiment 2

[0044] Add 986 grams of cardanol into a clean 2L pressure reactor, add 8 grams of Raney nickel catalyst, and replace the air in the reactor with nitrogen until the nitrogen content of the gas discharged from the outlet is ≥99.5%, and the hydrogen flow rate is controlled through the connected hydrogen cylinder. Hydrogen replacement, after the replacement, re-flow hydrogen to the pressure in the kettle to about 4MPa, stop the hydrogen flow, close the hydrogen valve, seal the reaction kettle, gradually raise the temperature, observe the reaction pressure during the heating process, control the pressure in the kettle to not exceed 5MPa by adjusting the heating speed, and keep stirring The speed is about 300r / min, the temperature is raised to about 110°C in about 1.5h, and the reaction is maintained at a reaction temperature of 110-130°C for 2.5 hours. The reaction product is released, transferred to a four-neck flask f...

Embodiment 3

[0045] The synthesis of the pentadecylphenol of embodiment 3

[0046] Add 986 grams of cardanol into a clean 2L pressure reactor, add 3 grams of Raney nickel catalyst, and replace the air in the reactor with nitrogen until the nitrogen content of the gas discharged from the outlet is ≥99.5%, and the hydrogen flow rate is controlled through the connected hydrogen cylinder. Hydrogen replacement, after the replacement, re-flow hydrogen until the pressure in the kettle is about 4.5MPa, stop the hydrogen flow, close the hydrogen valve, seal the reaction kettle, gradually raise the temperature, observe the reaction pressure during the heating process, control the pressure not to exceed 5.5MPa by adjusting the heating speed, and keep stirring The speed is about 300r / min, the temperature is raised to about 120°C in about 2.5h, and the reaction is maintained at a reaction temperature of 120-140°C for 3.5 hours. The reaction product is released, transferred to a four-neck flask for vacu...

technical field

[0001] The invention relates to an antioxidant for polymer materials, in particular to a novel bio-based phosphite antioxidant and a preparation method thereof. Background technique

[0002] During processing and long-term use, polymers are susceptible to light and heat, oxidized by oxygen in the air, lose mechanical properties, discoloration, cracks, loss of gloss and other changes, and the appearance becomes unattractive. Antioxidants need to be added to improve the processing stability and long-term stability of the polymer. Antioxidants are such a class of chemical substances, when only a small amount exists in the polymer system, they can delay or inhibit the oxidation process of the polymer, thereby preventing the aging of the polymer and prolonging its service life, also known as "Anti-aging agent".

[0003] The types of antioxidants are: hindered phenol antioxidants, phosphite antioxidants, thio antioxidants, etc.

[0004] Phosphite antioxidant is ...

Examples

Embodiment 1

[0041] The synthesis of the pentadecylphenol of embodiment 1

[0042]Add 986 grams of cardanol into a clean 2L pressure reactor, add 5 grams of Raney nickel catalyst, and replace the air in the reactor with nitrogen until the nitrogen content of the gas discharged from the outlet is ≥99.5%, and the hydrogen flow rate is controlled through the connected hydrogen cylinder. Hydrogen replacement, after the replacement, re-flow hydrogen to the pressure of about 4 MPa in the kettle, stop the hydrogen flow, close the hydrogen valve, seal the reaction kettle, gradually raise the temperature, observe the reaction pressure during the heating process, control the pressure by adjusting the heating speed to no more than 5 MPa, and keep the stirring speed at about 300r / min, heat up to about 120°C in about 2 hours, keep the reaction at the reaction temperature of 120-140°C for 3 hours, cool down to below 45°C after the reaction is completed, slowly open the vent valve, and restore the normal ...

Embodiment 2

[0043] The synthesis of the pentadecylphenol of embodiment 2

[0044] Add 986 grams of cardanol into a clean 2L pressure reactor, add 8 grams of Raney nickel catalyst, and replace the air in the reactor with nitrogen until the nitrogen content of the gas discharged from the outlet is ≥99.5%, and the hydrogen flow rate is controlled through the connected hydrogen cylinder. Hydrogen replacement, after the replacement, re-flow hydrogen to the pressure in the kettle to about 4MPa, stop the hydrogen flow, close the hydrogen valve, seal the reaction kettle, gradually raise the temperature, observe the reaction pressure during the heating process, control the pressure in the kettle to not exceed 5MPa by adjusting the heating speed, and keep stirring The speed is about 300r / min, the temperature is raised to about 110°C in about 1.5h, and the reaction is maintained at a reaction temperature of 110-130°C for 2.5 hours. The reaction product is released, transferred to a four-neck flask f...

Embodiment 3

[0045] The synthesis of the pentadecylphenol of embodiment 3

[0046] Add 986 grams of cardanol into a clean 2L pressure reactor, add 3 grams of Raney nickel catalyst, and replace the air in the reactor with nitrogen until the nitrogen content of the gas discharged from the outlet is ≥99.5%, and the hydrogen flow rate is controlled through the connected hydrogen cylinder. Hydrogen replacement, after the replacement, re-flow hydrogen until the pressure in the kettle is about 4.5MPa, stop the hydrogen flow, close the hydrogen valve, seal the reaction kettle, gradually raise the temperature, observe the reaction pressure during the heating process, control the pressure not to exceed 5.5MPa by adjusting the heating speed, and keep stirring The speed is about 300r / min, the temperature is raised to about 120°C in about 2.5h, and the reaction is maintained at a reaction temperature of 120-140°C for 3.5 hours. The reaction product is released, transferred to a four-neck flask for vacu...

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