Method for stabilizing halogenated paraffins

FIELD: chemical technology.

SUBSTANCE: invention relates to technology manufacturing halide-substituted hydrocarbons, in particular, to stabilization of halogenated paraffins that are used as plasticizers, antipyrenes and special additives for polymeric materials and rubber mixtures, and in leather industry and in manufacturing depressants and lubricants also. Method is carried out by addition of stabilizing system comprising epoxy-compound and chelate compound forming chelate with iron ions. Stabilizing system comprises additionally acceptor of hydrogen chloride as a stabilizing agent that represents aliphatic carboxylic acid ketene comprising carbon number in chain in the ranges (C10-C23) and alkaline-earth metal of the 2-d group of periodic system in the following ratio of components as measured for the parent halogenated paraffin, wt.-%: chelate compound, 0.03-0.50; acceptor of hydrogen chloride as a stabilizing agent, 0.05-0.30; epoxy-compound, 0.20-0.80. Addition of indicated components of stabilizing system to halogenated paraffin is carried out simultaneously or successively at temperature in the ranges 40-90oC. Stabilizing system can comprise additionally also antioxidant - a stabilizing agent of phenol type representing sterically hindered di- or trialkylphenol or its derivative, or their mixtures taken in the mount 0.01-0.15 wt.-%. Addition of indicated antioxidant - stabilizing agent is carried out before blowing or steaming acid mixtures at temperature in the ranges 40-90oC in common or separately with chelate compound. Halogenated paraffin represents chlorinated paraffin with mass part of chlorine in the ranges 12-75%. Invention provides enhancing quality of stabilized halogenated paraffins by indices "color index" and "mass part of acids", reducing consumption norm of epoxy-compound.

EFFECT: improved stabilizing method.

8 cl, 1 tbl, 16 ex

 

The invention relates to the production technology galijasevic hydrocarbons, in particular to the stabilization of halogenated paraffins, which are used as plasticizers, flame retardants and special additives for polymeric materials and rubber compounds, and also in the leather industry and the production of depreciation and lubricants.

A method of obtaining a highly chlorinated paraffins by the reaction of chlorinated paraffin wax with one or more connection - acceptor hydrogen chloride, taken in an amount of 0.1-20% by weight of chloroparaffin, at a temperature of 10-250°mainly 50-100°C [Patent GB No. 2040284, IPC4C 07 C 17/42, publ. 1980).

The disadvantages of this method are the relatively high rate of acceptor of hydrogen chloride and, as a consequence, the decrease of the technical characteristics and properties of the target products, and the relatively low thermal stability of such chlorinated paraffin wax containing impurities of iron ions (Lewis acids).

Known method of stabilizing chlorinated paraffins, including the introduction of a stabilizing agent containing epoxysilane, BHT and vaseline at the following content of components in the calculation of the stabilized chloroparaffin, wt.%:

BHT0,2-1,0
Vaseline0,02-0,08
Epoxysilane0,2-1,5

[Ed. the certificate of the USSR No. 1496211, IPC507 With 19/01, 17/42, publ. 20.07.1999]. The total content of the components of the stabilizing system is 0.42-2,58% by weight of chloroparaffin.

The disadvantages of this method of stabilization is the relatively high rate of BHT is 2,6-di-tert-butyl-4-METHYLPHENOL (0.2 to 1.0 wt.%), high sensitivity stable thus of chlorinated paraffin wax to the presence of iron ions and other Lewis acids at elevated temperatures and the related increase in color and acidity of the product and reducing its thermal stability due to the secondary processes of dehydrocorydaline and degradation catalyzed by Lewis acids.

The closest in technical essence and the achieved effect to the proposed method is highly allocation of paraffin from its solution in a chlorinated organic solvent, based on the joint use of conventional stabilizer (epoxy resin, compounds of magnesium or glycols), taken in an amount of 1.0 to 1.6% by weight of chloroparaffin and compounds forming complexes with iron (amines or phosphates), taken in an amount of 0.01-0.1% by weight of chloroparaffin [Ed. the certificate of the USSR No. 535269. IPC207 With 19/02, publ. 15.11.1976]. This is the first example of the use of the integrated stabilizing system epoxysilane - complexing agents for effective stabilization of halogenated paraffins, in particular, in the process providing high paraffins from their solutions.

The disadvantages of this method are the narrow range of application of a stabilizing system epoxysilane - complexing agents, limited solely by the allocation process (or stabilization when selected) high (solid) paraffins from their solutions, as well as the relatively high rate of epoxysilane and obtain the target product with a relatively high chroma and high residual acidity.

The objective of the proposed method of stabilization is to improve the quality of the stabilized halogenated paraffins indicators "chroma" and "mass fraction of acids (acidity), the decrease of expenditure norms epoxysilane, as well as the expansion of the scope of a stabilizing system for stabilizing various halogenated paraffins, both liquid and solid.

This is achieved by the stabilization of halogenated paraffins is carried out by introducing a stabilizing system containing epoxysilane and connection-complexing agents forming a complex with iron ions, and optionally containing stabilizer acceptor of hydrogen chloride, as to the th use ketene aliphatic carboxylic acid With 10-C23or salt of aliphatic carboxylic acid With10-C23and alkaline earth metal of group 2 of the periodic table, in the following ratio of components in the calculation of the original halogenoacetyl, wt.%:

connection-kompleksoobrazovatel forming a complex with iron ions,0,03-0,50
stabilizer - acceptor hydrogen chloride0,05-0,30
epoxysilane0,20-0,80,

moreover, the introduction of these components of the stabilizing system in a halogenated paraffin carried out simultaneously or sequentially at a temperature of paraffin in the range of 40-90°C.

Preferred is the introduction of components of the stabilizing system in the following sequence: (a) before Stripping or Stripping acidic impurities from the original raw halogenated paraffin enter the connection-complexing agents; b) after Stripping or Stripping acidic impurities introduced separately or as a mixture of the remaining components of the stabilizing system.

Most appropriate for the proposed method is used as soedineniya-complexing agents forming a complex with iron ions, ether orthophosphoric acid selected from the group, enabling the nd: trialkylphosphates, mainly tributyl phosphate, dialkylphosphate, dialkylammonium, mainly dibutyltindilaurate, alkyldithiofosfaat, triarylphosphite, mainly tricresylphosphate or dirtypantylover, or mixtures thereof.

The proposed method is more preferable as ketene aliphatic carboxylic acids with the number of carbon atoms in the chain within10-C23to use diketene stearic and/or palmitic acid, or mixtures of these Ketanov.

Similar technical result of the proposed method when used as salts of aliphatic carboxylic acids with the number of carbon atoms in the chain within10-C23and alkaline earth metal of group 2 of the periodic table calcium stearate or magnesium, or barium, or a mixture of these salts or stearates.

The most high quality and stability of halogenated paraffins obtained using the proposed method of stabilizing the system, optionally containing antioxidant is a phenolic stabilizer type that represents a sterically hindered di - or dialkylphenol or its derivative, or a mixture thereof, in the following ratio of the components of the stabilizing system based on halogenated paraffin, wt.%:

connection-complexing agents forming whom the Lex ions

iron0,03-0,50
stabilizer - acceptor hydrogen chloride0,05-0,30
epoxysilane0,20-0,80
antioxidant phenolic stabilizer type0,01-0,15,

with the introduction of this antioxidant stabilizer in halogenated paraffin is carried out before the Stripping or Stripping acidic impurities at a temperature in the range of 40-90°together With or separately from the connection-complexing agents.

Most appropriate for the proposed method to use as an antioxidant stabilizer is a phenolic type compound selected from the group comprising: 2,6-di-tert-butyl-4-METHYLPHENOL, 2,6-di-tert-butylphenol, bis(4-hydroxy-3,5-di-tert-butylmethylether), three(2,4-di-tert-butylphenyl)FOSFA, di(4-tert-butylphenyl)(2,6-di-tert-butylphenyl)FOSFA, pentaerythritol-Tetra-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, tetrakis-(2,4-di-tert-butylphenyl)-4,4'-diferentiated or mixtures thereof.

The proposed method of stabilizing halogenated paraffins most preferably used for the stabilization of chlorinated paraffins with a mass fraction of chlorine in the range 12-75%.

The expected technical result is achieved due to sovokupnogo the significant what's characteristics as follows. Connection-complexing agents with the introduction of the original halogenated paraffin (SE) in the specified number of forms stable and, as a rule, medicationbuy complex with iron ions or other Lewis acids contained in the SE, and thereby deactivates the known catalytic activity of these impurities in the reactions of dehydrohalogenation (dihydrochloride) and destruction, especially at the stage of Stripping or Stripping acidic impurities at elevated temperatures, as well as in the selection and retention of SE. The optimal number of complexing agents (0.03 to 0.50 wt.%) is determined by the nature of the original paraffin content of halogen and Lewis acids (primarily iron compounds) in the SE. Higher stabilization effect (preservation of colors and reducing acidity SE) is achieved by the introduction of complexing agents in the raw GP before Stripping or Stripping acidic impurities due to the deactivation of the Lewis acids under conditions of elevated temperatures and by preventing the formation of stable complexes between Lewis acids and hydrogen halides contained in the raw.

The introduction of a stabilizing system of additional stabilizer - acceptor of hydrogen chloride in the specified number of permits already in the process of stabilization of SE at temperatures from 40 to 90°maximum is also and quickly neutralize contained acidic impurities, mainly hydrogen chloride, with the formation of a sufficiently inert and stable reaction products and obtaining halogenated paraffins with acidity in terms of hydrogen chloride (Hcl) from 0.007 wt.% prior to the absence. The decrease of the residual acidity of SE less than 0.007 wt.% (HCl), achieved in this way can significantly reduce the likelihood of reactions dehydrohalogenation (dihydrochloride), which, as you know, the autocatalytic nature and is accompanied by an increase in color and decrease thermal stability of the halogenated paraffins. While the introduction of this acceptor in the SE is more preferable to carry out after Stripping or Stripping acidic impurities, i.e. with a minimum acidity of SE, although it is possible and the immediate introduction of this component of the stabilizing system in the original raw before Stripping (Stripping), which reduces its duration and stabilizes the color SE.

Using epoxysilane as a necessary component of the proposed stabilizirawe system in the amount of 0,20-0,80 wt.% and putting it simultaneously or sequentially with other components allows to achieve high thermal stability of the product due to the effective binding of the hydrogen halides at temperatures above 100°and prevent the autocatalytic dehydrogenase the financing of SOEs in these conditions, and to ensure the stability of its properties during storage and processing. It is the presence of epoxysilane as one of the components of the stabilizing system ensures high quality halogenated paraffins in terms of "stability".

Introduction in the proposed stabilizing system stabilizer-antioxidant fenolio type in an amount of 0.01 to 0.15% by weight of SE before Stripping or Stripping acidic impurities leads to the binding of reactive radicals contained in the raw SE after halogenation, inactive radicals and defines the high stability of SE to the radical dehydrohalogenating and oxidation of the product, including the selection and storage. The consequence of this is getting after Stripping (Stripping) acidic impurities halogenated paraffin with a low color and acidity, that is a product of higher quality.

Thus, more effective stabilization of SE is achieved due to the complex, interrelated actions of all components of the proposed three - and four-stabilizing systems, where each component or components selectively neutralize the negative factors that reduce the quality and stability of SE: decontamination of Lewis acids complexing agents; reduced to the slodnosti SE and catalytic activity Hcl stabilizer - the Hcl acceptor; effective neutralization of the hydrogen halides formed at high temperatures, and providing the necessary thermal stability of epoxysilane; decontamination reactive radicals by antioxidant stabilizer and improving the sustainability of SE to a radical oxidation.

Specified temperature range (40-90° (C) for the introduction of the stabilizing system provides rapid and effective dispersion and activity of components in raw halogenated paraffin, as a liquid or dissolved in an organic solvent, and in addition, it is technically feasible, because the raw SE after halogenation and/or Stripping usually has a temperature above 40°C. At lower temperatures the SE have a high viscosity, making it difficult to disperse.

A more preferred variant of the sequential introduction of GP first complexing agents, and then other components due to the fact that this ensures the most effective decontamination of Lewis acids at maximum concentrations of halogenated contained in the raw, and prevented the increase in color (darkening) of the product in the process of Stripping or Stripping acidic impurities. A similar effect can also be achieved by simultaneous (joint or separate) the introduction of the raw SE of complexing agents and antioxidant stabilizer with the only difference being that last stabilizes color and reduces the acidity due to the deactivation of reactive radicals and prevent radical dehydrohalogenation and oxidation of the target product.

These intervals are the mass fractions of components in the SE are the best, because at lower values the effect of each component becomes significantly lower and at higher values of unreasonably increased expenses components or worsen certain technical properties of some halogenated paraffins.

The preferred use as a connection-complexing agents ester of orthophosphoric acid, selected from the above group, due to the good compatibility of phosphates with SE, their low volatility, high thermal and chemical stability, the known properties of flame retardants and plasticizers and other physico-chemical properties. You can use other complexing agents, such as derivatives of ethylenediaminetetraacetic or 1-hydroxyethylidenediphosphonic acids, certain amines and amides, however, these compounds are less universal and less chemically inert.

Offered as the most preferred Ketanov aliphatic carboxylic acids with carbon chain length From10-C23 diketene stearic and/or palmitic acid, or mixtures thereof are very efficient acceptors of hydrogen chloride and other halides at temperatures from 40 to 90°and more active acceptors than epoxy compounds. Similar properties are also mainly used as salts of aliphatic carboxylic acids With10-C23and alkaline earth metals of group 2 of the periodic table stearates of calcium or magnesium, or barium, or a mixture of these salts or stearates. In the General case as appropriate Ketanov or salts of aliphatic carboxylic acids with the number of carbon atoms With10-C23the proposed method can be used any compounds of this type, which are more reactive towards hydrogen halides at 40-90°than epoxysilane, and who do not have a significant impact on technical parameters and properties of the target galogenarenov in a specified number (from 0.05 to 0.30 wt.%).

The use of antioxidant phenolic stabilizer type sterically constrained di - or dialkylphenol or its derivative, or mixtures thereof due to the high antioxidant activity and the relative availability of these compounds produced on an industrial scale, in particular 2,6-di-t is et-butyl-4-METHYLPHENOL (BHT, Agidol-1), 2,6-di-tert-butylphenol (Agidol-0), bis(4-hydroxy-3,5-di-tert-butylmethylether) (antioxidant MB-1, Ionox-220), three(2,4-di-tert-butylphenyl)phosphite (Stator-24, Irgafos-168), di(4-tert-butylphenyl)(2,6-di-tert-butylphenyl)phosphite, pentaerythritol-Tetra-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (Irganox-1010), tetrakis-(2,4-di-tert-butylphenyl)-4,4'-differentitate (Irgafos-PEPQ) or mixtures thereof. Fundamentally the proposed method, the other sterically obstructed di - and dialkylphenols or their derivatives, other than those specified above, but also has high antioxidant and stabilizing action, for example 2,2'-methylene-bis(4-methyl-6-tert-butylphenol), 2,2'-thio-bis(4-methyl-6-tert-butylphenol), 2,4,6-tri-tert-butylphenol, 2,4-di-tert-butylphenol.

The proposed method is illustrated by the following examples. In all examples, the number stabilized halogenated paraffin is 100,0, the Mass fraction of acids (acidity) in the samples of SE before Stripping acidic impurities were 0.02-0.1% in terms of Hcl. As epoxysilane used well-known epoxy stabilizers, for example epoxydodecane resin grades ED-16, ED-18 ED-20 ED-22 and others; epoxydecane vegetable oil or other epoxysilane. As stabilizers of hydrogen chloride acceptors used di is Ateny stearic and palmitic acid, technical stearates of calcium, magnesium and barium, calcium and magnesium salts of synthetic fatty acids (FFA) with the number of carbon atoms within10-C23. As a connection-complexing agents used in the first place, tributyl phosphate, triisobutylene, three(2-ethylhexyl)phosphate, di(2-ethylhexyl)phosphate, dibutyltindilaurate, butyldiphenylsilyl, tricresylphosphate, dirtypantylover, cresyldiphenyl, triphenyl, and the disodium salt of ethylenediaminetetraacetic acid. As the antioxidant of the phenolic stabilizer of the type used compound from the group specified above, or a mixture of such compounds, with the introduction of the antioxidant in the SE was carried out before Stripping (Stripping) acidic impurities at 40-90°together, i.e. in the form of a mixture, or separately with complexing agents. The duration of the dispersion of the components in the SE was determined visually - until a homogeneous liquid (solution) and ranged from 10 to 40 minutes.

Example 1 (standard methods for the stabilization of SE after Stripping or Stripping acidic impurities)

In a glass reactor equipped with a reflux condenser, a thermometer, a mechanical stirrer and a gas-feeding tube placed in 100.0 g of crude halogenated (chlorinated or brominated) paraffin with a mass fraction of chlorine (bromine) before the lah 12-55%, the obtained liquid-phase radical halogenoalkanes and past the Stripping acidic impurities inert gas to the mass fraction (M. D.) acids in terms of Hcl not more than 0.02%, are added simultaneously in the form of a pre-prepared mixture or sequentially one after the other components of the stabilizing system: 0.03 g of tributyl phosphate or dibutyltindilaurate, 0.05 g of diketene stearic acid or calcium stearate, and 0.20 g epoxidizing soybean oil, stirred the mixture at 40-90°C for 20-60 minutes and get stable SE with the indices specified in the table. The definition of indicators hereinafter is performed by standard methods described in the technical specifications 6-01-16-90 with ISM. 1, THE 6-01-5-63-94 with ISM. 1, 2 and THE 2493-211-05763458-97.

Example 2 (standard methods for the stabilization of liquid SE without prior Stripping or Stripping acidic impurities)

The stabilization is carried out analogously to example 1, with the difference that as the source of SE directly use the raw SE after synthesis with the acidity of from 0.01 to 0.10 wt.% HCl and M. D. halogen, mainly chlorine, within 12-60%. Add to crude under stirring at a temperature of 40-90°With 0.2 g of dirtypantylover or tricresylphosphate, are Stripping acidic impurities inert gas (nitrogen) and then enter the remaining components of the stabilizing system: 0,30 d is Ketanov stearic and palmitic acid and 0.5 g of epoxidations resin ED-20 or ED-22, or epoxidizing soybean oil. After 10-40 minutes stirring receive stable chloroparaffin with the indices specified in the table.

Example 3 (method for high paraffin)

In a glass reactor described in example 1 is placed 154-222,4 g 45-65%-aqueous solution of chloroparaffin with a mass fraction of chlorine in the range 60-75% in carbon tetrachloride or other inert organic solvent (reaction mass after chlorination of paraffin to Stripping acidic impurities) and under stirring at a temperature of 40-90°injected With 0.5 g of complexing agents selected from the above group, such as tributyl phosphate or tricresylphosphate, and hold at the same temperature of the Stripping acid impurities inert gas (nitrogen) or Stripping with some part of the solvent. Then, the resulting solution of chloroparaffin at 40-90°administered separately or in a mixture of 0.2 g of stabilizer - acceptor of hydrogen chloride, for example, diketene stearic acid or calcium stearate or magnesium, or barium, and 0.5 g epoxidizing vegetable oil or epoxidations resin ED-20 or ED-22, stirred the mixture for 10 to 40 minutes and then emit stable chloroparaffin from the solution by conventional means. Get the product of the indices specified in the table.

Other examples of stabilization done is implemented according to the methods of examples 1, 2 or 3 using the same or other above-mentioned components shown in the table. In examples 2, 4, 11 and 13 the data on stabilization as chlorinated and brominated paraffins. In other examples data

for chlorinated paraffins. The table also presents the example of stabilization of high paraffin prototype (example 16) using as components of the stabilizing system of epoxidations resin ED-20 and triethyl phosphate.

Table

Examples of stabilizing halogenated paraffins (SE) for the proposed method
No. if measureMass fraction (ppm) halogen in the DPP,%Ppm of complexing agents, % SEPpm acceptor Hcl, % SEPpm of epoxysilane, % SEPpm of antioxidant, % SEThe total number of the camera. system,%The method of stabilization for exampleThe color on the iodine scale, mg I2/100 cm3Memorial plaques acids in terms of Hcl, %Thermostability at 175°S, Hcl, %.
112-140,030,050,20-0,2817 0,0005-
228-320,030,050,80-0,88260,00040,08
370,60,500,200,50-1,20350,00060,09
445-490,200,300,50-1,0013no0,10
541-440,300,150,40-0,85250,00030,11
645-490,100,300,80-1,2012no0,06
772,20,500,050,80-1,35350,00060,09
848-520,200,150,200,010,5621no0,12/td>
950-540,300,050,600,010,96210,00050,09
1024-290,030,100,200,010,3422is 0.00020,18
1145-490,030,300,700,151,1822no0,11
1223-260,500,150,300,101,0025no0,14
1339-420,200,050,600,151,00230,00030,13
1471,10,500,050,800,051,40360,00070,08
1575,00,500,300,200,151,1537is 0.00020,10
1670,60,10-1,50-1,60the placeholder80,0050,11

In all these examples get halogenated, mainly chlorinated paraffins, which due to their technical characteristics and properties fully comply with various brands of industrial products.

From the presented examples, it follows that the proposed method of stabilization compared to the prototype allows to reduce the mass fraction of acids in the SE in terms of Hcl no less than 7 times, to improve the quality of SE in terms of "color", reduce the expenditure rate epoxysilane 1.25-8 times and significantly expand the range of industrial applications stabilizing system containing complexing agents.

1. Method of stabilizing halogenated paraffins by introducing a stabilizing system containing epoxysilane and connection-complexing agents forming a complex with iron ions, wherein the stabilizing system further comprises a stabilizer acceptor of hydrogen chloride, which is used as ketene aliphatic carboxylic acids with the number of carbon atoms in the chain within10-C23or salt of aliphatic carbon is acid with the number of carbon atoms in the chain within 10-C23and alkaline earth metal of group 2 of the periodic table, in the following ratio of components in the calculation of the original halogenated paraffin, wt.%:

Connection-complexing agents forming a complex with iron ions, of 0,03 0,50

Stabilizer - acceptor hydrogen chloride 0,05-0,30

Epoxysilane 0,20-0,80

moreover, the introduction of these components of the stabilizing system in a halogenated paraffin carried out simultaneously or sequentially at a temperature of paraffin in the range of 40-90C.

2. The method according to claim 1, characterized in that the introduction of the components of the stabilizing system is carried out in the following sequence: (a) before Stripping or Stripping acidic impurities from the original raw halogenated paraffin enter the connection-complexing agents; b) after Stripping or Stripping acidic impurities introduced separately or as a mixture of the remaining components of the stabilizing system.

3. The method according to claims 1 and 2, characterized in that the connection quality-of complexing agents forming a complex with iron ions, use ether orthophosphoric acid selected from the group comprising trialkylphosphates, mainly tributyl phosphate, dialkylphosphate, dialkylammonium, mainly dibutyltindilaurate, alkyldithiofosfaat, triarylphosphite, the advantage is but tricresylphosphate or dirtypantylover, or mixtures thereof.

4. The method according to any one of claims 1 to 3, characterized in that as ketene aliphatic carboxylic acids with the number of carbon atoms in the chain within10-C23use diketene stearic and/or palmitic acid, or mixtures of these Ketanov.

5. The method according to any one of claims 1 to 3, characterized in that salts of aliphatic carboxylic acids with the number of carbon atoms in the chain within10-C23and alkaline earth metal of group 2 of the periodic table use calcium stearate or magnesium, or barium, or a mixture of these salts or stearates.

6. The method according to any one of claims 1 to 5, characterized in that the stabilizing system further comprises an antioxidant is a phenolic stabilizer type that represents a sterically hindered di - or dialkylphenol or its derivative, or a mixture thereof, in the following ratio of the components of the stabilizing system based on halogenated paraffin, wt.%:

Connection-complexing agents forming a complex with iron ions, of 0,03 0,50

Stabilizer - acceptor hydrogen chloride 0,05-0,30

Epoxysilane 0,20-0,80

Antioxidant phenolic stabilizer type 0,01-0,15

with the introduction of this antioxidant stabilizer in halogenated paraffin is carried out before the blow-off or what tarkay acidic impurities at a temperature in the range of 40-90C jointly or separately with the connection-complexing agents.

7. The method according to p. 6, characterized in that the antioxidant is a phenolic stabilizer of the type used as a compound selected from the group comprising 2,6-di-tert-butyl-4-METHYLPHENOL, 2,6-di-tert-butylphenol, bis(4-hydroxy-3,5-di-tert-butylmethylether), three(2,4-di-tert-butylphenyl)FOSFA, di(4-tert-butylphenyl)(2,6-di-tert-butylphenyl)FOSFA, pentaerythritol-Tetra-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, tetrakis-(2,4-di-tert-butylphenyl)-4,4'-diphenylene-diphosphite or mixtures thereof.

8. The method according to any one of claims 1 to 7, characterized in that the halogenated paraffin is a chlorinated paraffin with a mass fraction of chlorine in the range 12-75%.



 

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FIELD: chemical technology.

SUBSTANCE: invention relates to technology manufacturing halide-substituted hydrocarbons, in particular, to stabilization of halogenated paraffins that are used as plasticizers, antipyrenes and special additives for polymeric materials and rubber mixtures, and in leather industry and in manufacturing depressants and lubricants also. Method is carried out by addition of stabilizing system comprising epoxy-compound and chelate compound forming chelate with iron ions. Stabilizing system comprises additionally acceptor of hydrogen chloride as a stabilizing agent that represents aliphatic carboxylic acid ketene comprising carbon number in chain in the ranges (C10-C23) and alkaline-earth metal of the 2-d group of periodic system in the following ratio of components as measured for the parent halogenated paraffin, wt.-%: chelate compound, 0.03-0.50; acceptor of hydrogen chloride as a stabilizing agent, 0.05-0.30; epoxy-compound, 0.20-0.80. Addition of indicated components of stabilizing system to halogenated paraffin is carried out simultaneously or successively at temperature in the ranges 40-90oC. Stabilizing system can comprise additionally also antioxidant - a stabilizing agent of phenol type representing sterically hindered di- or trialkylphenol or its derivative, or their mixtures taken in the mount 0.01-0.15 wt.-%. Addition of indicated antioxidant - stabilizing agent is carried out before blowing or steaming acid mixtures at temperature in the ranges 40-90oC in common or separately with chelate compound. Halogenated paraffin represents chlorinated paraffin with mass part of chlorine in the ranges 12-75%. Invention provides enhancing quality of stabilized halogenated paraffins by indices "color index" and "mass part of acids", reducing consumption norm of epoxy-compound.

EFFECT: improved stabilizing method.

8 cl, 1 tbl, 16 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method of stabilising organochlorine solvents selected from perchloroethylene, trichloroethylene, dichloroethylene and chloroform, in which the stabiliser is used in amount of 0.01-1.0% of the weight of the stabilised organochlorine solvent. The stabiliser used is epoxidated soya bean oil, or a stabilising system consisting of 95.55-98.90 wt % epoxidated soya bean oil, 0.10-0.40 wt % urotropin, 1.00-4.00 wt % ethanol and 0.00-0.10 wt % epichlorohydrin, or a stabilising system consisting of 50.0-96.0 wt % epoxidated soya bean oil and 4.0-50.0 wt % ethanol.

EFFECT: highly efficient stabilisation of organochlorine solvents, availability and low cost of stabiliser components and relatively low environmental hazard.

10 tbl

FIELD: chemistry.

SUBSTANCE: target product represents 1,2-epoxydodecane and combined with it 1,2-dodecanediol, in a weight ratio of 3:1. The catalytic oxidation of 1-dodecen with sodium hypochlorite is carried out with the application of the catalyst KBr for 10 h in the presence of a solvent - acetonitrile, with a volume ratio 1-dodecene:acetonitrile, equal to 1:815.

EFFECT: increased rate of carrying out the reaction and an increase of the target product output.

3 dwg, 2 tbl, 5 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method for catalytic gas-phase fluorination of a product of 1,1,1,2,3-pentachloropropane and/or 1,1,2,2,3-pentachloropropane into a 2,3,3,3-tetrafluoropropene product. The method comprises the following steps: (i) contacting 1,1,1,2,3-pentachloropropane (HCC 240db) and/or 1,1,2,2,3-pentachloropropane (HCC 240aa) with hydrogen fluoride HF in a gas phase in the presence of a fluorination catalyst in conditions that are sufficient for obtaining a reaction mixture containing 2,3,3,3-tetrafluoropropene (1234yf); (ii) dividing the reaction mixture into a first stream containing 2,3,3,3-tetrafluoropropene (1234yf), and a second stream containing 2-chloro-3,3,3-trifluoro-1-propene (1233xf) and 1,1,1,2,2-pentafluoropropane (245cb); (iii) recycling at least a portion of the second stream at least partially to step (i).

EFFECT: use of the present method enables to obtain an end product in a single reaction step, which ensures acceptable process performance.

21 cl, 4 tbl, 7 ex, 2 dwg

FIELD: chemical technology.

SUBSTANCE: invention relates to technology manufacturing halide-substituted hydrocarbons, in particular, to stabilization of halogenated paraffins that are used as plasticizers, antipyrenes and special additives for polymeric materials and rubber mixtures, and in leather industry and in manufacturing depressants and lubricants also. Method is carried out by addition of stabilizing system comprising epoxy-compound and chelate compound forming chelate with iron ions. Stabilizing system comprises additionally acceptor of hydrogen chloride as a stabilizing agent that represents aliphatic carboxylic acid ketene comprising carbon number in chain in the ranges (C10-C23) and alkaline-earth metal of the 2-d group of periodic system in the following ratio of components as measured for the parent halogenated paraffin, wt.-%: chelate compound, 0.03-0.50; acceptor of hydrogen chloride as a stabilizing agent, 0.05-0.30; epoxy-compound, 0.20-0.80. Addition of indicated components of stabilizing system to halogenated paraffin is carried out simultaneously or successively at temperature in the ranges 40-90oC. Stabilizing system can comprise additionally also antioxidant - a stabilizing agent of phenol type representing sterically hindered di- or trialkylphenol or its derivative, or their mixtures taken in the mount 0.01-0.15 wt.-%. Addition of indicated antioxidant - stabilizing agent is carried out before blowing or steaming acid mixtures at temperature in the ranges 40-90oC in common or separately with chelate compound. Halogenated paraffin represents chlorinated paraffin with mass part of chlorine in the ranges 12-75%. Invention provides enhancing quality of stabilized halogenated paraffins by indices "color index" and "mass part of acids", reducing consumption norm of epoxy-compound.

EFFECT: improved stabilizing method.

8 cl, 1 tbl, 16 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to manufacturing chloro-containing hydrocarbons, in particular, tert.-butyl chloride used for preparing addition agents and as activator for dehydrogenation catalysts. Method for preparing involves interaction gaseous isobutylene and hydrogen chloride in the presence of catalyst in the amount 0.02-0.3 wt.-% of parent reagents mass. Water is used as a catalyst. Process is carried out at volume rate of feeding reagents from 1400 h-1 to 1500 h-1, at temperature from 0oC to -5oC and in the mole ratio isobutylene : hydrogen chloride = (1.01-1.015):1 in the bubbling reactor. Method provides elevating yield of tert.-butyl chloride up to 99.2-99.5 wt.-%.

EFFECT: improved preparing method, enhanced yield.

2 cl, 1 tbl, 4 ex

FIELD: industrial organic synthesis.

SUBSTANCE: invention is dealing with production of chlorohydrocarbons exhibiting plasticizing properties in polymer compositions in production of synthetic building materials, varnishes and paints, artificial films and leathers, in rubber industry, and as fire-retardant additives in polymers. Process comprises chlorination of waste obtained in production of C14-C32 fraction by ethylene-α-olefin oligomerization. Chlorination is accomplished in two steps: addition chlorination at 35-55°C followed by substitution chlorination at 40-105°C. Chlorohydrocarbons thus obtained can, in particular, be used as secondary plasticizer in polyvinylchloride compositions.

EFFECT: reduced expenses due to using production waste.

4 tbl, 30 ex

FIELD: chemical industry, in particular method for production of value products from lower alkanes.

SUBSTANCE: claimed method includes passing of gaseous reaction mixture containing at least one lower alkane and elementary chlorine through catalytic layer. Used catalyst represents geometrically structured system comprising microfiber with diameter of 5-20 mum. Catalyst has active centers having in IR-spectra of adsorbed ammonia absorption band with wave numbers in region of ν = 1410-1440 cm-1, and contains one platinum group metal as active component, and glass-fiber carrier. Carrier has in NMR29Si-specrum lines with chemical shifts of -100±3 ppm (Q3-line) and -110±3 ppm (Q4-line) in integral intensity ratio Q3/Q4 from 0.7 to 1.2; in IR-specrum it has absorption band of hydroxyls with wave number of ν = 3620-3650 cm-1 and half-width of 65-75 cm-1, and has density, measured by BET-method using argon thermal desorption, SAr = 0.5-30 m2/g, and specific surface, measured by alkali titration, SNa = 10-250 m2/g in ratio of SAr/SNa = 5-30.

EFFECT: method of increased yield.

3 cl, 4 ex

FIELD: chemistry, in particular utilization of chlorine-containing waste.

SUBSTANCE: claimed method includes passing of organochlorine compound vapors blended with oxygen-containing reaction gaseous mixture through catalyst layer providing oxidation of starting organochlorine compounds. Said catalyst represents geometrically structured system from microfibers with length of 5-20 mum. Catalyst has active centers which are characterized by presence of absorption band in absorbed ammonia IR-spectrum with wave number ν = 1410-1440 cm-1; contains platinum group metal as active ingredient; and glass fiber carrier. Said carrier in NMR29Si-spectrum has lines with chemical shifts of -100±3 ppm (Q3-line) and -110±3 ppm (Q4-line) in integral intensity ratio of Q3/Q4 = 0.7-1.2; in IR-spectrum it has hydroxyl absorption band with wave number ν = 3620-1440 cm-1 and half-width of 65-75 cm-1; has specific surface, measured by BET using argon thermal absorption: SAr = 0.5-30 m2/g; surface area, measured by alkali titration: SNa = 10-250 m2/g, wherein SNa/SAr = 5-30.

EFFECT: selective oxidation of starting organochlorine compounds to safe and easily utilizing substances without toxic by-product formation.

3 cl, 4 ex

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