A method of inhibiting the polymerization of unsaturated compounds

 

(57) Abstract:

Usage: the invention relates to the petrochemical industry, in particular to the processes of inhibition of polymerization of unsaturated compounds. The invention is: to prevent polymerization of unsaturated compounds in the process of storage, transportation and receiving inhibitory add the mixture in an amount of 0.5 to 1,000 ppm consisting of hydroxylamine derivatives and aminophenol at a ratio(10 90) (90 10). 1 table.

The invention relates to the petrochemical industry, in particular to the process of inhibiting polymerization vinylaromatic and diene compounds in the process of receiving, storage and transport.

Known use as inhibitor 3,5-di-tert-butyl-4-hydroxy-N, N-dimethylbenzylamine [1] which is well prevents the polymerization of isoprene and vinylpyridine, but not effective enough in styrene.

It is also known the use of derivatives of N,N-dialkylhydroxylamines, the effectiveness of which is enhanced by joint application or tertiary allylpyrocatechol [2]

The closest in technical essence to the present invention is a method of using mixtures of derivatives of the HN and/or mono - or di-tert-alkylhydroquinones [3] quoted in the mass ratio (10-90): (90-10) in an amount of 0.5 to 1000 ppm per vinylaromatic connection. The efficiency shown in the mixtures dibenzylhydroxylamine with 2,5-di-tert-butylhydroquinone and 4-tert-butylpyrocatechol taken in the ratio 50: 50 weight percent and a total concentration of 500 ppm based on the styrene. To create more severe conditions of inhibitor in styrene additionally add the sodium hydroxide and benzoyl peroxide. The polymerization is carried out at 90aboutC for 120 minutes

When using 2,5-di-tert-butylhydroquinone as acomponent of dibenzylhydroxylamine number forming happened polymer was 0.01 wt. and when using 4-tert-butylpyrocatechol of 0.08 wt.

The invention consists in the use as inhibitor mixture on the derivatives of hydroxylamine (GAA) and aminophenol in their mass ratio (10-90):(90-10) in an amount of 0.5 to 1000 ppm in the calculation of the unsaturated compound.

As derivatives of PGA using the compounds of formula

R1R2NOH, where R1and R2hydrogen, alkyl groups with normal or branched carbon chains having from 20 to 10 (preferably 2-6) carbon atoms, aryl or arylalkyl group having the structural formula

R3n where R3Allenova groupa with normal or branched chain, having 1-6 carbon atoms;

n takes on the values 0 or 1.

R1and R2together with the nitrogen atom can form cycles, such as N-hydroxymorphinan, N-hydroxypiperidine.

Preferably R1and R2alkyl, phenyl or aromatic radicals. R3has 1-6 carbon atoms, R4the hydrogen. When n is equal to 0, fenelonov group is directly linked to the nitrogen atom.

You can apply derivatives of hydroxylamine and with a large number of carbon atoms, but the above give quite satisfactory results.

Derivatives of hydroxylamine are, for example, N,N-diethylhydroxylamine, N, N-ethylbutylamine, N, N-dibutylethanolamine, N,N-2-ethylbutyraldehyde, N,N-diphenylhydrazine, N,N-dibenzylhydroxylamine, N-phenyl-N-(3-phenylpropyl)hydroxylamine, N,N-bis-(3-phenyl-propyl)hydroxylamine.

As aminophenol use of compounds of formula

HOCH2-NR7R8where R5, R6hydrogen, the same or different alkyl, aryl group with 1-10 carbon atoms;

R7, R8the same or different alkyl groups with 1-5 carbon atoms.

Preferably, R5and R6

You can use as acomponent inhibitory system as individual substances and mixtures based on them, consisting of two or more components.

In the invention, the relative concentrations GAA and aminophenol changes in the range of 10-90 wt. for PGA and within 90-10 wt. for aminophenol calculated on the total weight of these compounds.

The inhibitory concentration of the mixture is 0.5-1000 ppm (preferably 5-500 ppm) per monomer.

Inhibiting effective mixture to prevent polymerization of unsaturated monomers in their selection by distillation at temperatures up to 150aboutC and above. Maybe its application in the presence of other additives such as corrosion inhibitors.

Inhibitory composition serves in any way. The most convenient to serve in a solvent that is compatible with the monomer, for example kerosene, lower alkanes (hexane), aromatic solvents (toluene, benzene), alcohols, ketones and other Possible dissolution inhibitor in the monomer avoid being hit by DOPOLNITEL.

When the inhibition of polymerization vinylaromatic compounds of this mixture exhibits a synergistic effect and the inhibition efficiency of industrial polymerization inhibitors, as evidenced by the examples.

The invention is illustrated by the following examples, in which as vinylaromatic monomer is styrene, and Gidropress telebasel is added to create a more stringent conditions for testing the effectiveness of the inhibiting composition. For diene hydrocarbon samples are isoprene and industrial sobrenatural faction.

P R I m e R 1. In a glass dilatometer, pre-washed with ethyl alcohol and dried with nitrogen injected styrene, nezapravlennaya stabilizer, add 200 ppm of gidroperekisi telebasel in the form of a 25 wt. solution in ethylbenzene. The dilatometer thermostatic at 120aboutWith in a silicone bath 180 minutes the Amount of polymer in the solution with a content up to 3 wt. determine the values method. Higher contents of polymer definition produced by the gravimetric method based on maintaining attachment of the polymer solution under an infrared lamp at 180-200aboutC to constant weight. The content of the polymer (x) donkey drying, g;

m1weight Bucca, g;

m2weight buxa with the sample, ,

The amount of polymer is 40.5 wt.

P R I m m e R 2. In the conditions of example 1 is introduced into the calculation of the monomer 500 ppm of a mixture of dibenzylhydroxylamine (DBGA) with 2,5-di-tert-butylhydroquinone (TBG), taken in a weight ratio of 1/1. The amount of polymer is of 11.2 wt.

P R I m e R s 3 and 4. In the conditions of example 1 administered 250 and 500 ppm N,N-diethylhydroxylamine (DEG) per monomer. The amount of polymer is relevant - ment of 19.2 and 8.3 wt.

P R I m e R 5. In the conditions of example 1 administered 500 ppm of dibenzylhydroxylamine per monomer. The amount of polymer is 15.8 wt.

P R I m e R 6. In terms of polymer 1 is introduced into the calculation of the monomer 500 ppm 3,5-di-tert-butyl-4-hydroxy-N, N-dimethylbenzylamine (OHMS). The number of polymer respectively to 29.5 wt.

P R I m e R s 7 and 8. In the conditions of example 1 is introduced into the calculation of the monomer 250 and 500 ppm of a mixture of DEG/OM, taken in a weight ratio of 1/1. The amount of polymer is respectively 12 and 6.5 wt.

P R I m e R s 9 and 10. In the conditions of example 1 is introduced into the calculation of the monomer 600 and 750 ppm of a mixture of DEG/3,5-di-isopropyl-4-hydroxy-N, N-diethylbenzamide (OM), taken in weighty sootnoshenia 1 is introduced into the calculation of the monomer 500 ppm of a mixture of dibenzylhydroxylamine (DBGA)/Ω, taken in a weight ratio of 1/1. The amount of polymer is, respectively, 4.8 wt.

P R I m e R 12. In pre-washed with alcohol and dried glass vial administered 3 g of iron filings, 10 ml of isoprene and add one drop of water to initiate the formation of polymer. Ampoule zakolerovat, sealed and thermostatic under 100aboutC for 24 h after incubation, the ampoule is opened and examined for the content of polymer compounds. For this purpose the contents of the ampoule quantitatively transferred using benzene, suspended in a porcelain Cup, planted ethyl alcohol polymer and dried at 40aboutC, under vacuum until constant weight.

The amount of polymer (x) in percent is calculated by the formula

x=(m1/m) 100% where m1the polymer mass, g;

m the mass of the source of isoprene, ,

The amount of polymer is 2.05 wt.

P R I m e R s 13 and 14. In the conditions of example 12 in the ampoule is introduced into the calculation of the monomer 500 ppm of a mixture of DEG/OM, taken in a weight ratio of 1/1 and 2/1. The amount of polymer, respectively 0,072 and of 0.014 wt.

P R I m e R 15. In the conditions of example 12 instead of isoprene take industrial isoprene fraction of the next status the mouths of 0.1 Water methanol, CEC - lamentation, other 0,2

The amount of polymer is to 1.67 wt.

P R I m e R 16. In the conditions of example 15 in the ampoule is introduced into the calculation of the weight fractions of 300 ppm of a mixture of DEG/OM, taken in a weight ratio of 1/1. The amount of polymer is 0,021 wt.

The results presented in the table.

P R I m e R 17. The inhibitory efficiency of the system during storage. In a flat-bottomed glass flask of 250 ml, pre-washed with ethyl alcohol and dried with nitrogen injected with 150 ml trademarks of styrene, not tucked stabilizer, add 0,5 ppm of a mixture of N-(n-hexylphenyl)-N-ethylhydroxylamine (GPAGE) with 3-methyl-5-n-isopropylbenzyl-4-hydroxy-N,N-dimethylbenzylamine (OM), taken in a ratio of 9/1, cover tightly capped and stored under normal conditions for 2 months. The polymer defined in the conditions of example 1, no.

P R I m e R 18. In the conditions of example 17 add 0,5 ppm of LLEGA. The number of polymer amounts to 0.016 wt.

P R I m e R 19. In the conditions of example 17 add 0,5 ppm OM. The amount of polymer is 0,018 wt.

P R I m e R 20. In the conditions of example 1 is introduced into the calculation of the monomer 100 ppm N-(10-phenyldeca)-N-deceleration (FDHA). The amount of the polymer has been, N-demoversionen (OM). The amount of polymer is 31.3 wt.

P R I m e R 22. In the conditions of example 1 is introduced into the calculation of the monomer 1000 ppm mixture FDHA/OM taken in a weight ratio of 1/9. The amount of polymer is of 20.3 wt.

P R I m e R 23. In a round bottom glass flask of 250 ml, equipped with a reverse refrigerator water injected 100 ml of product industrial dehydration methylphenylcarbinol the following composition, wt. styrene 76,11, ethylbenzene 0,58-methylsterol 0,02, benzaldehyde 0,22, acetophenone 20,68, methylphenylcarbinol 1,35, light hydrocarbons 0,83, heavy residue of 0.2. In addition enter in the calculation of the monomer 500 ppm of a mixture of N-phenylhydroxylamine (PHA)/AM taken in a weight ratio of 1/5. The flask thermostatic at 120aboutWith over 180 min. Number of polymer, as defined in the conditions of example 11, 1.2 wt.

A METHOD of INHIBITING the POLYMERIZATION of UNSATURATED COMPOUNDS by introducing 0.5 to 1000 ppm by weight of the monomer mixture of inhibitors, including derivatives hydroxyamine and aminophenol in their mass ratio 10 90 90 10, characterized in that as a derivative of hydroxylamine use of compounds of General formula

R1R2NOH,

where R1,R2H, C2<
< / BR>
where R3-CH2oCC10H20;

R4H, CH3oC C6H13;

n 0; 1,

as aminophenol use of compounds of General formula

< / BR>
where R5, R6-H, alkali or C1C10-arily;

R7, R8CH3C5H11.

 

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