CN102659606B - Preparation method of alkylated diphenylamine antioxidant with high color stability - Google Patents
Preparation method of alkylated diphenylamine antioxidant with high color stability Download PDFInfo
- Publication number
- CN102659606B CN102659606B CN201210137193.6A CN201210137193A CN102659606B CN 102659606 B CN102659606 B CN 102659606B CN 201210137193 A CN201210137193 A CN 201210137193A CN 102659606 B CN102659606 B CN 102659606B
- Authority
- CN
- China
- Prior art keywords
- pentanoic
- antioxidant
- color
- diphenylamine
- luster
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Anti-Oxidant Or Stabilizer Compositions (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Lubricants (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to a preparation method of an alkylated diphenylamine antioxidant with high color stability, belonging to the technical field of chemical engineering of production of synthetic material antioxidants. In the process of preparing and storing the alkylated diphenylamine antioxidant product, a small amount of functional antioxidant with high color stability is added to improve the color stability. The method is implemented in a way that: an atlapulgite catalyst, diphenylamine, styrene, dimerized isobutylene, nonylene and alpha-methylstyrene alkylating reagent are subjected to catalytic alkylation reaction to prepare the alkylated diphenylamine antioxidant product; and in the preparation process, a heat stabilizer and a color protection-color reduction agent method is utilized to obtain the alkylated diphenylamine antioxidant product with high color stability. The product is still light yellow after being stored in a closed white glass bottle at the indoor temperature of 10-35 DEG C for 6 months.
Description
Technical field
The invention belongs to the chemical technology field that synthetic materials oxidation inhibitor is produced, be specifically related to the preparation method of the stable alkylated diphenylamine antioxidant product of a kind of color and luster.
Background technology
Pentanoic, as oxidation inhibitor, has the volatilization of being easy to, and the defect that antioxygen persistence is poor is general by adding the group that relative molecular mass is large to improve.It is found that pentanoic and corresponding active olefin carry out alkylated reaction, available product has good antioxygen property.As, pentanoic and vinylbenzene, nonene, Diisobutylene, alpha-methyl styrene etc. carry out alkylated reaction, generate corresponding alkylated diphenylamine product, be widely used in rubber tyre, various rubber item, lubricating oil, for replacing contaminative and other stronger amines antioxidants of toxicity, as diaryl secondary amine antioxidant, p phenylenediamine type antioxidant, aldehyde-amine condensate class anti-aging agent, ketoamine condenses class anti-aging agent etc.; In addition, alkylated diphenylamine kind antioxidant has the high anti-oxidation usefulness of amine antioxidants, the possibility that has again alternative phenolic antioxidant, people in succession develop with alkylated diphenylamine kind antioxidant and substitute phenolic antioxidant for this reason, and preparation is used in light color or white polymer without phenol oxidation inhibitor.
Alkylated diphenylamine kind antioxidant product has heat-tinting problem, need in process of production to use nitrogen protection blocking oxygen, make it to reduce as much as possible heat-tinting degree under heated condition, make product can have a good appearance luster, especially high boiling point, the styrenated diphenylamine oxidation inhibitor of liquid state, nonylated diphenylamine oxidation inhibitor, P, the octylated diphenylamine oxidation inhibitor that P-dioctyl diphenylamines content is less than 25%, in product preparation process, there is no treating process, the color relation of end reaction liquid is the color of product, good situation is simple faint yellow, almost there is deep yellow, or even light brown or dark-brown, another kind of solid state, as 4-(Α, Α-dimethyl benzyl) pentanoic and 4, 4 '-bis-(Α, Α-dimethyl benzyl) pentanoic is main mixture solid particle oxidation inhibitor, P, the octylated diphenylamine mixture oxidation inhibitor that P-dioctyl diphenylamines content is greater than 80%, in product preparation process, there is no solvent recrystallization treating process, reaction solution is through the simple distillation of comparatively high temps, the light constituent that remove portion is relative, stay product in still kettle through overcooling, after granulation, be corresponding alpha-methyl styrene diphenylamines mixture oxidation inhibitor, octylated diphenylamine mixture oxidation inhibitor solids product, owing to distilling through excessive temperature in production process, the situation that resulting solid particulate product is good is light brown or dark-brown.
No matter be the styrenated diphenylamine of liquid state in addition, nonylated diphenylamine, octylated diphenylamine oxidation inhibitor, or alpha-methyl styrene diphenylamines mixture, octylated diphenylamine mixture oxidation inhibitor solids product, in natural storage process, can to dark color, be developed by original light color, As time goes on develop into gradually dark-brown, when this class alkylated diphenylamine antioxidant product is added in polymkeric substance, can there is the evolution process of color equally in product itself, cause the look of polymkeric substance dirty, therefore, the absolute factor of puzzlement alkylated diphenylamine antioxidant product widespread use and result of use is initial stage color and the color after one period of shelf lives of product, and still there is the evolution process of color in product in polymkeric substance.
The appearance color of this class alkylated diphenylamine antioxidant product represents its product rank and commercial value conventionally.
Solve initial stage color and the storage colour-change problem of alkylated diphenylamine antioxidant product, the quality of improving product significantly, improves application performance and expands use range and commercial value undoubtedly.
US:2943112 discloses that to take sulfuric acid and atlapulgite be catalyzer, and Diisobutylene and pentanoic carry out catalyzed reaction, prepare octylated diphenylamine mixture; US:3496230 discloses with AlCl
3for catalyzer, nonene and pentanoic carry out catalyzed reaction, prepare liquid nonylated diphenylamine mixture; US:4263456 discloses take atlapulgite as catalyzer, and vinylbenzene and pentanoic carry out catalyzed reaction, preparation liquid styrene diphenylamines mixture; US:4163757 discloses usings sulfuric acid dipping natural montmorillonite as catalyzer, carries out catalyzed reaction, preparation liquid styrene diphenylamines mixture with vinylbenzene and pentanoic; Chinese patent CN:101353445A discloses take atlapulgite as catalyzer, and vinylbenzene and pentanoic carry out catalyzed reaction, preparation liquid styrene diphenylamines mixture; Chinese patent CN:1288000A discloses take atlapulgite as catalyzer, in autoclave, Diisobutylene and pentanoic are raw material, at 170-180 ℃, pressure 0.30-0.50MPa, atlapulgite, are that catalyzer, Resorcinol are that stopper carries out catalyzed reaction and prepares liquid octylated diphenylamine mixture; Chinese patent CN:102320983A discloses take atlapulgite as catalyzer, and in autoclave, Diisobutylene and pentanoic are that raw material carries out catalyzed reaction and prepares liquid octylated diphenylamine mixture; Chinese patent CN:101538208A discloses take atlapulgite as catalyzer, alpha-methyl styrene, pentanoic is that raw material carries out catalyzed reaction, the reaction solution obtaining under reduced pressure, through 200 ~ 250 ℃ of pyrogenic distillations, obtain 4-(Α, Α-dimethyl benzyl) pentanoic and 4,4 '-bis-(Α, Α-dimethyl benzyl) diphenylamine compound solid particulate oxidation inhibitor, product is exposed in air grizzle gradually.The common weak point of these public technologies is colour stability problems in the time of could not solving product initial stage color and product stock.
In order to solve the coloring problem of alkylated diphenylamine antioxidant product, people turn one's attention to the functional oxidation inhibitor that interpolation has height colour stability on a small quantity and improve the colour stable in alkylated diphenylamine product preparation and storage process, participate in the collaborative antioxygenation of bringing into play simultaneously.One class has the oxidation inhibitor of catching carbon radicals, as: antioxidant of bisphenol monoacryate, dialkyl group azanol kind antioxidant, benzofuranone kind antioxidant, not only the color and luster of product self is highly stable, and Product Activity is high, can in lower concentration range, show good antioxidant effect, after mixing with hindered amines stablizer, there is good colour stability, in storage process, also there will not be metachromatism.
Summary of the invention
The present invention existingly prepares that alkylated diphenylamine antioxidant product color is partially dark for overcoming, product colour deepens gradually in storage process, the method for selecting to add thermo-stabilizer, the Bao Se-agent of losing lustre make product produce and storage process in colour stable.
Bao Se of the present invention-the agent of losing lustre is antioxidant of bisphenol monoacryate, dialkyl group azanol kind antioxidant, benzofuranone kind antioxidant; Thermo-stabilizer is comprised of with Hinered phenols antioxidant and phosphite ester kind antioxidant antioxidant of bisphenol monoacryate, dialkyl group azanol kind antioxidant, benzofuranone kind antioxidant.
The alkylated diphenylamine liquid antioxidant product preparation method that color and luster of the present invention is stable, according to following step, carry out:
(1) activated bauxite catalyst, pentanoic, organic solvent are added in synthesis reaction vessel in proportion, under nitrogen protection, stir, be warming up to 80 ~ 82 ℃, reflux dewatering, then organic solvent is removed in distillation;
(2) be warming up to 135 ~ 165 ℃ of temperature of reaction, under constant temperature of reaction, drip alkylating reagent, dropwise, insulation reaction, reaction finishes rear solids removed by filtration catalyzer, obtains alkylated diphenylamine liquid antioxidant;
(3) under nitrogen protection, stir, heat up, add in proportion Bao Se-lose lustre agent and make it to be dissolved in completely in alkylated diphenylamine liquid antioxidant, obtain the stable alkylated diphenylamine liquid antioxidant product of color and luster of the present invention.
Described in step (1), organic solvent is hexane, heptane, octane, octane-iso, hexanaphthene, methylcyclohexane;
Activated bauxite catalyst add-on described in step (1) is by the mass ratio of itself and pentanoic, pentanoic: activated bauxite catalyst (mass ratio)=1:0.1 ~ 0.18; Organic solvent add-on is by the mass ratio of itself and pentanoic, pentanoic: organic solvent (mass ratio)=1:1.0 ~ 1.5;
Described in step (2), alkylating reagent refers to vinylbenzene, Diisobutylene, nonene; Alkylating reagent add-on is by the molar ratio computing of itself and pentanoic, pentanoic: alkylating reagent (mol ratio)=1:2.1 ~ 2.8
The alkylated diphenylamine liquid antioxidant obtaining described in step (2) refers to styrenated diphenylamine liquid antioxidant, octylated diphenylamine liquid antioxidant, nonylated diphenylamine liquid antioxidant; The stable alkylated diphenylamine liquid antioxidant product of color and luster refers to the stable nonylated diphenylamine liquid antioxidant product of color and luster stable styrenated diphenylamine liquid antioxidant, color and luster stable octylated diphenylamine liquid antioxidant, color and luster.
Bao Se described in step (the 3)-agent of losing lustre refers to 2-[1-(2-hydroxyl-3,5-di-tert-butyl-phenyl)-methyl]-4,6-di-tert-butyl-phenyl acrylate, 2-[1-(2-hydroxyl-3,5-bis-tertiary amyl phenyl)-ethyl]-4,6-bis-tertiary amyl phenyl acrylate, 2-tertiary butyl-6-(3-tertiary butyl-2-hydroxy-5-methyl base phenyl)-4-methylphenol acrylate; N, two (octadecyl) azanols of N-, N, the two lauryl azanols of N-, N, two (tetradecyl) azanols of N-, N, two (hexadecyl) azanols of N-, N-hexadecyl-N-octadecyl azanol,, N-heptadecyl-N-octadecyl azanol, N, N prepared by two (h-tallow) amine direct oxidations of N-, N-dialkyl group azanol product, N, N-dibenzyl hydroxylamine; 5,7-di-t-butyl-3-(4-methyl) 3 hydrogen-benzofuran-2-ones, 5,7-di-t-butyl-3-(3,4-dimethyl) 3 hydrogen-benzofuran-2-ones, 5,7-di-t-butyl-3-(2,4-dimethyl) 3 hydrogen-benzofuran-2-ones or, 5,7-di-t-butyl-3-(2,3-dimethyl) 3 hydrogen-benzofuran-2-ones.
The temperature that is warming up to temperature of reaction described in step (3) is 85 ~ 90 ℃ and adds the Bao Se-agent of losing lustre; The add-on of the Bao Se-agent of losing lustre is by the mass ratio of itself and pentanoic, pentanoic: the Bao Se-agent of losing lustre (mass ratio)=1:0.02 ~ 0.025;
The alkylated diphenylamine solid antioxidant product preparation method that color and luster of the present invention is stable, according to following step, carry out:
(1) activated bauxite catalyst, pentanoic, organic solvent are added in synthesis reaction vessel in proportion, under nitrogen protection, stir, be warming up to 80 ~ 82 ℃, reflux dewatering, then organic solvent is removed in distillation;
(2) be warming up to 135 ~ 170 ℃ of temperature of reaction, under constant temperature of reaction, drip alkylating reagent, dropwise, insulation reaction, reaction finishes rear solids removed by filtration catalyzer, adds in proportion thermo-stabilizer, underpressure distillation under nitrogen protection, deviate from light constituent, obtain alkylated diphenylamine oxidation inhibitor;
(3) under nitrogen protection, stir, cooling, adds in proportion Bao Se-lose lustre agent and makes it to be dissolved in completely in alkylated diphenylamine oxidation inhibitor, granulation, is cooled to 20 ~ 25 ℃ and obtains the stable alkylated diphenylamine solid antioxidant product of color and luster of the present invention.
Described in step (1), organic solvent is hexane, heptane, octane, octane-iso, hexanaphthene, methylcyclohexane;
Activated bauxite catalyst add-on described in step (1) is by the mass ratio of itself and pentanoic, pentanoic: activated bauxite catalyst (mass ratio)=1:0.1 ~ 0.18; Organic solvent add-on is by the mass ratio of itself and pentanoic, pentanoic: organic solvent (mass ratio)=1:1.0 ~ 1.5;
The add-on of thermo-stabilizer described in step (2) is by the mass ratio of itself and pentanoic, pentanoic: thermo-stabilizer (mass ratio)=1:0.05 ~ 0.06;
Described in step (2), alkylating reagent refers to alpha-methyl styrene, Diisobutylene; Alkylated diphenylamine solid antioxidant refers to 4-(Α, Α-dimethyl benzyl) pentanoic and 4,4 '-bis-(Α, Α-dimethyl benzyl) diphenylamine compound solid particulate oxidation inhibitor, P, the octylated diphenylamine mixture oxidation inhibitor that P-dioctyl diphenylamines content is greater than 80%; The stable alkylated diphenylamine solid antioxidant product of color and luster refers to the stable 4-(Α of color and luster, Α-dimethyl benzyl) pentanoic and 4,4 '-bis-(Α, Α-dimethyl benzyl) the stable P of diphenylamine compound solid particulate oxidation inhibitor and color and luster, the octylated diphenylamine mixture solid particle oxidation inhibitor that P-dioctyl diphenylamines content is greater than 80%.
Alkylating reagent add-on described in step (2) is by the molar ratio computing of itself and pentanoic, pentanoic: alkylating reagent (mol ratio)=1:2.1 ~ 2.8
The temperature of the cooling described in step (3) is 110 ~ 130 ℃ and adds the Bao Se-agent of losing lustre; The add-on of the Bao Se-agent of losing lustre is by the mass ratio of itself and pentanoic, pentanoic: the Bao Se-agent of losing lustre (mass ratio)=1:0.02 ~ 0.035.
Thermo-stabilizer described in step (3) refers to three kinds of antioxidant mixtures that Bao Se-lose lustre agent and Hinered phenols antioxidant and phosphite ester kind antioxidant form, and it consists of the Bao Se-agent of losing lustre: Hinered phenols antioxidant: phosphite ester kind antioxidant (mass ratio)=1.0:1.0:1.0; Hinered phenols antioxidant refers to β-(4-hydroxyl-3,5-di-tert-butyl-phenyl) the positive octadecyl ester of propionic acid, four (β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester, 2,2,-methylene-bis (4,6-DI-tert-butylphenol compounds), 2,2 ,-ethylene two (4,6-di-tert-pentyl phenol), 2,2 ,-ethylene two (4,6-DI-tert-butylphenol compounds); Phosphite ester kind antioxidant refers to two (different tridecanol base) pentaerythritol diphosphites; Two (stearyl alcohol base) pentaerythritol diphosphites, phosphorous acid (three nonyl phenyl) ester, tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester.
In step (2), alkylating reagent and pentanoic add the color and luster that a small amount of stopper is conducive to improve the selectivity of object product and reduces alkylated reaction liquid in carrying out catalytic alkylation reaction process, stopper of the present invention is 2,6-di-t-butyl-4-methylphenol; 2,2 '-ethylene two (4,6-di-tert-pentyl phenol); 2,2 '-ethylene two (4,6-DI-tert-butylphenol compounds); 2,2 '-methylene-bis (4,6-di-tert-pentyl phenol); 2,2 '-methylene-bis (4,6-DI-tert-butylphenol compounds); 2,2 '-methylene-bis(4-ethyl-6-t-butyl phenol); 2,2 '-methylene-bis (4-methyl-6-tert-butylphenol).β-(4-hydroxyl-3,5-di-tert-butyl-phenyl) positive octadecyl ester of propionic acid, four (β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester.
advantage of the present invention
1, in preparing liquid alkyl diphenylamine antioxidant product process by adding the Bao Se of the present invention-agent of losing lustre, solved liquid alkyl diphenylamine antioxidant product deposit with use procedure in coloring problem; In preparing solid alkylation pentanoic antioxidant product process by adding thermo-stabilizer of the present invention, solved the dark problem of solid alkylation pentanoic antioxidant product color and luster, by adding the Bao Se of the present invention-agent of losing lustre, solved solid alkylation pentanoic antioxidant product deposit with use procedure in coloring problem.
2, the thermo-stabilizer of the present invention adding in alkylated diphenylamine antioxidant product, Bao Se-lose lustre agent and original product have good synergistic effect, except having the Bao Se-effect of losing lustre, also can improve anti-oxidant efficiency.
3, solve initial stage color and the storage colour-change problem of alkylated diphenylamine antioxidant product, significantly promoted quality and the commercial value of product, improved alkylated diphenylamine antioxidant product application performance and expanded use range.
Embodiment
Vinylbenzene used in the present invention, Diisobutylene, nonene, alpha-methyl styrene, pentanoic, thermo-stabilizer, the Bao Se-agent of losing lustre, stopper, organic solvent are commercially available prod, and specification is industrial top grade product.
According to known technological method Kaolinite Preparation of Catalyst FS:
Take 100 grams of polynites, be placed in 1000mL with the four-hole boiling flask of agitator, thermometer, dropping funnel, reflux exchanger, add 500 grams of water, slowly start agitator, polynite can be dispersed in water more uniformly.Then add 9 grams of AlCl
3, at 50～55 ℃, stir 5 hours.After stopping stirring, at room temperature precipitate static ageing 24 hours.Remove by filter the aqueous solution, solids is washed with water to pH=6～7, then at 110～130 ℃, vacuum-drying 5 hours, obtains catalyzer FS.
Following non-limiting example 1 ~ 3; Comparative example 1 ~ 3, is used for the present invention that explains, rather than limits the invention, and in the protection domain of spirit of the present invention and claim, any modification and change that the present invention is made, all belong to protection scope of the present invention.
embodiment 1
In the GST-2 type 2000mL stainless steel cauldron with magnetic stirring apparatus, reflux water-dividing device, Diisobutylene feed pot, add 300 grams of pentanoic, 45 grams of catalyzer FS, 1.5 gram 2,6-di-t-butyl-4-methylphenol, 400 grams of hexanaphthenes.Heat up; carry out reflux dewatering to 80 ~ 82 ℃; carry out 1 hour; then steam the hexanaphthene in reaction solution; normal temperature is down in nitrogen protection, adds 230 grams of Diisobutylenes, with the air in the abundant replacement reaction kettle of nitrogen; start stirring; heating, makes temperature in the kettle in still rise to 160 ~ 170 ℃, still internal pressure 0.2 ~ 0.25 MPa; insulation reaction 10 hours; add 80 grams of Diisobutylenes, 160 ~ 170 ℃ of insulation reaction 15 hours, add 40 grams of Diisobutylenes; 160 ~ 170 ℃ of insulation reaction 20 hours, reaction finishes.Cooling, add 500 grams of hexanaphthenes, 60 ~ 70 ℃ of filtrations, remove solid catalyst, collect filtrate in still kettle, steam hexanaphthene, under nitrogen protection, vacuum-0.095MPa, deviate from part unreacting material for 140 ~ 150 ℃, cooling, obtain light yellow viscous liquid, both octylated diphenylamine liquid antioxidant, its temperature is maintained to 85 ~ 90 ℃, add Bao Se-agent 2-[1-(2-hydroxyl-3 of losing lustre, 5-bis-tertiary amyl phenyl)-ethyl]-4, 7.5 grams of 6-bis-tertiary amyl phenyl acrylate, fully stir completely and dissolve, cooling, obtain light yellow viscous liquid, both the stable octylated diphenylamine liquid antioxidant product of color and luster.Product is in airtight white glass bottle, and 10 ~ 35 ℃ of storages of room temp 6 months are still faint yellow.
comparative example 1
According to embodiment 1 same procedure (the not Jia Baose-agent of losing lustre), make octylated diphenylamine liquid antioxidant product.Product is in airtight white glass bottle, and 10 ~ 35 ℃ of storages of room temp become light brown for 1 month, within 6 months, become dark-brown.
embodiment 2
In reaction flask at 500mL with agitator, thermometer, water trap and reflux exchanger, dropping funnel, nitrogen conduit, add 60 grams of pentanoic, 8 grams of catalyzer FS, four (β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester is 0.3 gram, 80 grams of hexanaphthenes.Nitrogen replacement also stirs, heats up under nitrogen protection, carries out reflux dewatering to 80 ~ 82 ℃, carries out 1 hour; then steam the hexanaphthene in reaction solution, then be warming up to 135 ~ 138 ℃, start to drip 81 grams of vinylbenzene; within 3 hours, add, 138 ℃ of insulation reaction 2 hours, reaction finishes.Cooling; add 100 grams of hexanaphthenes; 60 ~ 70 ℃ of filtrations, remove solid catalyst, distillation filtrate; steam hexanaphthene; under nitrogen protection, vacuum-0.095MPa, deviates from part unreacting material for 140 ~ 150 ℃; cooling; obtain light yellow viscous liquid, both styrenated diphenylamine liquid antioxidant, maintained 85 ~ 90 ℃ by its temperature; add the Bao Se-agent N of losing lustre; 1.3 grams of N-dibenzyl hydroxylamines, fully stir completely and dissolve, cooling; obtain light yellow viscous liquid, both the stable styrenated diphenylamine liquid antioxidant product of color and luster.Product is in airtight white glass bottle, and 10 ~ 35 ℃ of storages of room temp 6 months are still faint yellow.
comparative example 2
According to embodiment 2 same procedure (the not Jia Baose-agent of losing lustre), make styrenated diphenylamine liquid antioxidant product.Product is in airtight white glass bottle, and 10 ~ 35 ℃ of storages of room temp become light brown for 1 month, within 6 months, become dark-brown.
embodiment 3
In reaction flask at 500mL with agitator, thermometer, water trap and reflux exchanger, dropping funnel, nitrogen conduit, add 60 grams of pentanoic, 10 grams of catalyzer FS, stopper four (β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester is 0.3 gram, 85 grams of hexanaphthenes.Nitrogen replacement also stirs, heats up under nitrogen protection, carries out reflux dewatering to 80 ~ 82 ℃, carries out 1 hour; then steam the hexanaphthene in reaction solution, then be warming up to 135 ~ 138 ℃, start to drip 100 grams of alpha-methyl styrenes; within 4 hours, add, 135 ~ 138 ℃ of insulation reaction 4 hours, reaction finishes.Add 100 grams of hexanaphthenes, 60 ~ 70 ℃ of filtrations, remove solid catalyst, collect filtrate in still kettle, add 3 grams of thermo-stabilizers, steam hexanaphthene, under nitrogen protection, vacuum-0.095MPa, deviate from light constituent for 200 ~ 230 ℃, be cooled to 85 ~ 90 ℃, add the Bao Se-agent 5 of losing lustre, 2.0 grams of 7-di-t-butyl-3-(4-methyl) 3 hydrogen-benzofuran-2-ones, fully stir completely and dissolve, granulation, be cooled to 20 ~ 25 ℃ and obtain faint yellow solid particle, be the stable 4-(Α of color and luster, Α-dimethyl benzyl) pentanoic and 4, 4 '-bis-(Α, Α-dimethyl benzyl) diphenylamine compound solid particulate antioxidant product.Product is in airtight white glass bottle, and 10 ~ 35 ℃ of storages of room temp 6 months are still faint yellow.
comparative example 3
According to embodiment 3 same procedure (not adding thermo-stabilizer, the Bao Se-agent of losing lustre), make light brown 4-(Α, Α-dimethyl benzyl) pentanoic and 4,4 '-bis-(Α, Α-dimethyl benzyl) diphenylamine compound solid particulate antioxidant product.Product is in airtight white glass bottle, and 10 ~ 35 ℃ of storages of room temp 6 months, become dark-brown by light brown.
Claims (8)
1. the stable alkylated diphenylamine liquid antioxidant product preparation method of color and luster, is characterized in that carrying out according to following step:
(1) activated bauxite catalyst, pentanoic, organic solvent are added in synthesis reaction vessel in proportion, under nitrogen protection, stir, be warming up to 80 ~ 82 ℃, reflux dewatering, then organic solvent is removed in distillation;
(2) be warming up to 135 ~ 165 ℃ of temperature of reaction, under constant temperature of reaction, drip alkylating reagent, dropwise, insulation reaction, reaction finishes rear solids removed by filtration catalyzer, obtains alkylated diphenylamine liquid antioxidant;
(3) under nitrogen protection, stir, heat up, add in proportion Bao Se-lose lustre agent and make it to be dissolved in completely in alkylated diphenylamine liquid antioxidant, obtain the stable alkylated diphenylamine liquid antioxidant product of color and luster of the present invention;
Described in step (1), organic solvent is hexane, heptane, octane, octane-iso, hexanaphthene, methylcyclohexane;
Activated bauxite catalyst add-on described in step (1) is by the mass ratio of itself and pentanoic, pentanoic: activated bauxite catalyst (mass ratio)=1:0.1 ~ 0.18; Organic solvent add-on is by the mass ratio of itself and pentanoic, pentanoic: organic solvent (mass ratio)=1:1.0 ~ 1.5.
2. the stable alkylated diphenylamine liquid antioxidant product preparation method of color and luster according to claim 1, is characterized in that described in step (2), alkylating reagent refers to vinylbenzene, Diisobutylene, nonene; Alkylating reagent add-on is by the molar ratio computing of itself and pentanoic, pentanoic: alkylating reagent (mol ratio)=1:2.1 ~ 2.8;
The alkylated diphenylamine liquid antioxidant obtaining described in step (2) refers to styrenated diphenylamine liquid antioxidant, octylated diphenylamine liquid antioxidant, nonylated diphenylamine liquid antioxidant; The stable alkylated diphenylamine liquid antioxidant product of color and luster refers to the stable nonylated diphenylamine liquid antioxidant product of color and luster stable styrenated diphenylamine liquid antioxidant, color and luster stable octylated diphenylamine liquid antioxidant, color and luster.
3. the stable alkylated diphenylamine liquid antioxidant product preparation method of color and luster according to claim 1, it is characterized in that the Bao Se described in step (the 3)-agent of losing lustre refers to 2-[1-(2-hydroxyl-3,5-di-tert-butyl-phenyl)-methyl]-4,6-di-tert-butyl-phenyl acrylate, 2-[1-(2-hydroxyl-3,5-bis-tertiary amyl phenyl)-ethyl]-4,6-bis-tertiary amyl phenyl acrylate, 2-tertiary butyl-6-(3-tertiary butyl-2-hydroxy-5-methyl base phenyl)-4-methylphenol acrylate; N, two (octadecyl) azanols of N-, N, the two lauryl azanols of N-, N, two (tetradecyl) azanols of N-, N, two (hexadecyl) azanols of N-, N-hexadecyl-N-octadecyl azanol,, N-heptadecyl-N-octadecyl azanol, N, N prepared by two (h-tallow) amine direct oxidations of N-, N-dialkyl group azanol product, N, N-dibenzyl hydroxylamine; 5,7-di-t-butyl-3-(4-methyl) 3 hydrogen-benzofuran-2-ones, 5,7-di-t-butyl-3-(3,4-dimethyl) 3 hydrogen-benzofuran-2-ones, 5,7-di-t-butyl-3-(2,4-dimethyl) 3 hydrogen-benzofuran-2-ones or, 5,7-di-t-butyl-3-(2,3-dimethyl) 3 hydrogen-benzofuran-2-ones;
The temperature that is warming up to temperature of reaction described in step (3) is 85 ~ 90 ℃ and adds the Bao Se-agent of losing lustre; The add-on of the Bao Se-agent of losing lustre is by the mass ratio of itself and pentanoic, pentanoic: the Bao Se-agent of losing lustre (mass ratio)=1:0.02 ~ 0.025.
4. the stable alkylated diphenylamine solid antioxidant product preparation method of color and luster, is characterized in that carrying out according to following step:
(1) activated bauxite catalyst, pentanoic, organic solvent are added in synthesis reaction vessel in proportion, under nitrogen protection, stir, be warming up to 80 ~ 82 ℃, reflux dewatering, then organic solvent is removed in distillation;
(2) be warming up to 135 ~ 170 ℃ of temperature of reaction, under constant temperature of reaction, drip alkylating reagent, dropwise, insulation reaction, reaction finishes rear solids removed by filtration catalyzer, adds in proportion thermo-stabilizer, underpressure distillation under nitrogen protection, deviate from light constituent, obtain alkylated diphenylamine oxidation inhibitor;
(3) under nitrogen protection, stir, cooling, adds in proportion Bao Se-lose lustre agent and makes it to be dissolved in completely in alkylated diphenylamine oxidation inhibitor, granulation, is cooled to 20 ~ 25 ℃ and obtains the stable alkylated diphenylamine solid antioxidant product of color and luster of the present invention.
5. the stable alkylated diphenylamine solid antioxidant product preparation method of color and luster according to claim 4, is characterized in that described in step (1), organic solvent is hexane, heptane, octane, octane-iso, hexanaphthene, methylcyclohexane;
Activated bauxite catalyst add-on described in step (1) is by the mass ratio of itself and pentanoic, pentanoic: activated bauxite catalyst (mass ratio)=1:0.1 ~ 0.18; Organic solvent add-on is by the mass ratio of itself and pentanoic, pentanoic: organic solvent (mass ratio)=1:1.0 ~ 1.5.
6. the stable alkylated diphenylamine solid antioxidant product preparation method of color and luster according to claim 4, the add-on that it is characterized in that thermo-stabilizer described in step (2) is by the mass ratio of itself and pentanoic, pentanoic: thermo-stabilizer (mass ratio)=1:0.05 ~ 0.06;
Described in step (2), alkylating reagent refers to alpha-methyl styrene, Diisobutylene; Alkylated diphenylamine solid antioxidant refers to 4-(Α, Α-dimethyl benzyl) pentanoic and 4,4 '-bis-(Α, Α-dimethyl benzyl) diphenylamine compound solid particulate oxidation inhibitor, P, the octylated diphenylamine mixture oxidation inhibitor that P-dioctyl diphenylamines content is greater than 80%; The stable alkylated diphenylamine solid antioxidant product of color and luster refers to the stable 4-(Α of color and luster, Α-dimethyl benzyl) pentanoic and 4,4 '-bis-(Α, Α-dimethyl benzyl) the stable P of diphenylamine compound solid particulate oxidation inhibitor and color and luster, the octylated diphenylamine mixture solid particle oxidation inhibitor that P-dioctyl diphenylamines content is greater than 80%;
Alkylating reagent add-on described in step (2) is by the molar ratio computing of itself and pentanoic, pentanoic: alkylating reagent (mol ratio)=1:2.1 ~ 2.8.
7. the stable alkylated diphenylamine solid antioxidant product preparation method of color and luster according to claim 4, the temperature that it is characterized in that the cooling described in step (3) is 110 ~ 130 ℃ and adds the Bao Se-agent of losing lustre; The add-on of the Bao Se-agent of losing lustre is by the mass ratio of itself and pentanoic, pentanoic: the Bao Se-agent of losing lustre (mass ratio)=1:0.02 ~ 0.035;
Thermo-stabilizer described in step (2) refers to three kinds of antioxidant mixtures that Bao Se-lose lustre agent and Hinered phenols antioxidant and phosphite ester kind antioxidant form, and it consists of the Bao Se-agent of losing lustre: Hinered phenols antioxidant: phosphite ester kind antioxidant (mass ratio)=1.0:1.0:1.0; Hinered phenols antioxidant refers to β-(4-hydroxyl-3,5-di-tert-butyl-phenyl) the positive octadecyl ester of propionic acid, four (β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester, 2,2,-methylene-bis (4,6-DI-tert-butylphenol compounds), 2,2 ,-ethylene two (4,6-di-tert-pentyl phenol), 2,2 ,-ethylene two (4,6-DI-tert-butylphenol compounds); Phosphite ester kind antioxidant refers to two (different tridecanol base) pentaerythritol diphosphites; Two (stearyl alcohol base) pentaerythritol diphosphites, phosphorous acid (three nonyl phenyl) ester, tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester.
8. the stable alkylated diphenylamine solid antioxidant product preparation method of color and luster according to claim 4, it is characterized in that alkylating reagent and pentanoic add a small amount of stopper in carrying out catalytic alkylation reaction process in step (2), described stopper is 2,6-di-t-butyl-4-methylphenol; 2,2 '-ethylene two (4,6-di-tert-pentyl phenol); 2,2 '-ethylene two (4,6-DI-tert-butylphenol compounds); 2,2 '-methylene-bis (4,6-di-tert-pentyl phenol); 2,2 '-methylene-bis (4,6-DI-tert-butylphenol compounds); 2,2 '-methylene-bis(4-ethyl-6-t-butyl phenol); 2,2 '-methylene-bis (4-methyl-6-tert-butylphenol);
β-(4-hydroxyl-3,5-di-tert-butyl-phenyl) positive octadecyl ester of propionic acid, four (β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210137193.6A CN102659606B (en) | 2012-05-07 | 2012-05-07 | Preparation method of alkylated diphenylamine antioxidant with high color stability |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210137193.6A CN102659606B (en) | 2012-05-07 | 2012-05-07 | Preparation method of alkylated diphenylamine antioxidant with high color stability |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102659606A CN102659606A (en) | 2012-09-12 |
| CN102659606B true CN102659606B (en) | 2014-04-09 |
Family
ID=46769219
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210137193.6A Active CN102659606B (en) | 2012-05-07 | 2012-05-07 | Preparation method of alkylated diphenylamine antioxidant with high color stability |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102659606B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105732400A (en) * | 2014-12-12 | 2016-07-06 | 中国石油天然气股份有限公司 | Preparation method for (para, para)-diisopropylphenyl diphenylamine product |
| CN107556524A (en) * | 2017-09-29 | 2018-01-09 | 镇江市星耀智能装备有限公司 | A kind of age resistor for wood-plastic composite panel |
| CN109369418A (en) * | 2018-10-10 | 2019-02-22 | 河南师范大学 | A kind of continuous synthesis technology and synthesizer of energy saving and environment friendly alkyl benzene amine class I liquid I antioxidant |
| EP3868737A4 (en) * | 2018-10-16 | 2022-10-05 | China Petroleum & Chemical Corporation | Phenolic derivative, preparation method therefor and use thereof |
| CN111676081A (en) * | 2020-06-28 | 2020-09-18 | 安徽威驰化工有限责任公司 | Antioxidant for reducing environmental pollution of lubricating oil and preparation method thereof |
| CN112759523B (en) * | 2021-02-19 | 2022-10-21 | 河南正佳能源环保股份有限公司 | Styryl diphenylamine antioxidant and preparation method thereof |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3496230A (en) * | 1966-02-17 | 1970-02-17 | American Cyanamid Co | Process for mixture of mono- and dialkyl-diphenylamines |
| US4263456A (en) * | 1976-12-02 | 1981-04-21 | The Goodyear Tire & Rubber Company | Process of preparing styrenated diphenylamine |
| SG65759A1 (en) * | 1997-06-06 | 1999-06-22 | Ciba Sc Holding Ag | Nonylated diphenylamines |
| CN100393693C (en) * | 2005-06-16 | 2008-06-11 | 广州合成材料研究院 | Method for preparing antioxidant of bisphenol mono acrylic ester |
| US8828916B2 (en) * | 2006-12-28 | 2014-09-09 | Chevron Oronite Company Llc | Method to prepare nonylated diphenylamine using recycle sequential temperatures |
| CN102320983A (en) * | 2011-06-14 | 2012-01-18 | 江苏飞亚化学工业有限责任公司 | A kind of preparation method of liquid octylated diphenylamine oxidation inhibitor |
-
2012
- 2012-05-07 CN CN201210137193.6A patent/CN102659606B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN102659606A (en) | 2012-09-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102659606B (en) | Preparation method of alkylated diphenylamine antioxidant with high color stability | |
| CA2607967C (en) | Ortho-nitrosophenols as polymerization inhibitors | |
| CN100586919C (en) | Polymerization inhibitor, composition containing the same and process for producing easily polymerizable compound with the polymerization inhibitor | |
| TWI436975B (en) | Production of ethylenically unsaturated acids or esters thereof | |
| CN101704948A (en) | Method for synthesizing dendritic phenolic antioxidant | |
| CA2835880A1 (en) | Synergistic combination for inhibiting polymerization of vinyl monomers | |
| US5562863A (en) | Methods and compositions for inhibiting vinyl aromatic monomer polymerization | |
| CN102101847A (en) | Method for preparing N-methyl-N'-(2-chloroethyl)piperazine | |
| KR20010079775A (en) | Styrene monomer polymerization inhibition using substituted dihydroxyarenes and nitroxides | |
| CN102584601B (en) | Preparation method of alkylated diphenylamine antioxidant product | |
| CN105985224A (en) | Synthetic method of semi-hindered bisphenol-type antioxidant | |
| CN106944142B (en) | A kind of preparation method of composite catalyst and nonyl diphenylamine | |
| CN104119217A (en) | 2,6-di-tert-butyl-4-(-4-fluorobenzylidene)-2,5-cyclohexadiene-1-one and preparation method thereof | |
| CN1911939A (en) | Preparation method of phosphite ester kind antioxidant | |
| US2700682A (en) | Ketimines and process of preparing same | |
| US2789912A (en) | Deactivating catalytic effect of metals | |
| AU2013277509B2 (en) | Antimicrobial compounds | |
| CN109608392B (en) | Stilbene similar compound and preparation method and application thereof | |
| RU2290394C1 (en) | Composition for inhibiting of styrene thermopolymerization and method for production thereof | |
| CN112939740A (en) | Production process of efficient environment-friendly antioxidant | |
| CN108484529B (en) | A kind of synthetic method of N, N '-di-2-ethylhexylphosphine oxide morpholine | |
| US2199828A (en) | Process for stabilizing organic heavy metal salts | |
| JP6916164B2 (en) | Method for preparing a stabilized organophosphorus compound solution | |
| RU2349622C2 (en) | Phenylenediamine composition, soluble in water, and method of stabilising ethylenically unsaturated compounds and monomers | |
| AU2013277511B2 (en) | Heterocyclic antimicrobial compounds for use in water - containing systems |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C56 | Change in the name or address of the patentee | ||
| CP02 | Change in the address of a patent holder |
Address after: 213016 Baiyun District, Changzhou, Jiangsu Patentee after: Changzhou University Address before: Gehu Lake Road Wujin District 213164 Jiangsu city of Changzhou province No. 1 Patentee before: Changzhou University |
|
| TR01 | Transfer of patent right |
Effective date of registration: 20191213 Address after: 213311 building 7, No. 8-2, Dutou street, Daitou Town, Liyang, Changzhou City, Jiangsu Province Patentee after: Liyang Chang Technology Transfer Center Co., Ltd. Address before: 213016 Baiyun Road, bell tower area, Changzhou, Jiangsu Patentee before: Changzhou University |
|
| TR01 | Transfer of patent right |