CS224167B1 - Method of manufacture of mixed peroxides and/or mixtures of peroxides - Google Patents

Description

The invention relates to a process for the production of mixed organic peroxides and / or organic peroxide mixtures of the desired composition in solvents, depending on the optimum application needs,

224 167

224 167 resp. from optimal reaction conditions for their application, in particular for initiation in non-radical reactions such as polymerizations, copolymers and the like.

It is known to produce dialkyl peroxydicarbonates from alkyl chloroformates, hydrogen peroxide and sodium hydroxide at temperatures of -10 to +30 ° C at pH 8 to 14 with stirring, the use of hydrogen halides as hydrogenation agents, e.g. carbon tetrachloride (MS 1 265 154; MS 1 259 325), followed by diethyl ether (U.S. Pat.

374,789) and aromatic hydrocarbons (Hungarian Patent 153,373; quoted in Antonovsky V.L., Organičkskije perekisnyje Initiators, pp. 249-253, IzdateTstvo Khimija, Moscow (1972)). However, in addition to many advantages, the disadvantage of the anhydrous polyhaloalkanes is that they also act as efficient carriers, especially by incorporating them into macromelecules (e.g., polyvinyl chloride) to reduce their thermal stability. High pressure vapor diethyl ether makes it difficult to handle solutions and is more sensitive to hydroperoxide formation.

Also interesting is the synthesis of mixed organic peroxides from alkyl chloroformates as well as acyl chlorides and hydrogen peroxide with sodium hydroxide at -10 to +10 ° C. The organic peroxides formed at about 1 ° C are extracted with petroleum ether. Anionic surfactants such as sodium lauryl sulphate or sodium dodecylbenzenesulphonate (Austrian patent 292 659) may be added to the aqueous solution to improve phase contact. · The disadvantage is the limited solubility of the mixed organic peroxides formed, the high vapor pressure of petroleum ether, the rapid decrease in yields from rising 1% at 1 ° C to 57% at 25 ° C and 50.4% at 38 ° C. In general, in the synthesis of percarbonates from chloroformates and hydrogen peroxide in an alkaline medium, a solvent is usually added to the reaction medium, which is then removed by extraction.

- 3 224 167 with water or under vacuum, resp. recrystallization, e.g. from pentane (U.S. Pat. No. 3,499,919).

Interesting is the solution (Čs. Aut. Certificate 175 908) for the production of organic peroxides from the raw materials, ie. j. acyl chlorides, alkyl chloroformates, hydrogen peroxide and alkali metal hydroxides, respectively. alkali metal peroxides, in the form of solutions in organic solvents. However, it prefers dosing of acyl chlorides and alkyl chloroformates into an aqueous solution of alkali metal peroxides, thereby achieving lower yields of organic peroxides. These drawbacks are overcome and the advantages of the known methods are utilized by the method of the present invention.

According to the invention, there is provided a process for the preparation of mixed peroxides and / or mixtures of peroxides of the general formula

0

1 | ii

R '- C - 00 - C - R' in which

R 6 is alkyl, alkoxy, straight or branched chain having 2 to 18 carbon atoms, C 8 H 11 CH 8 O-, halogenated alkyls to C 1-4, cyclohexyl, alkylcyclohexyl C 1-4 alkyl; to C 1-4, benzyl, phenyl, halogenated phenyl _,.

R 'and phenyl, halogenated phenyl, benzyl, alkylbenzyl, cyclohexyl, alkylcyclohexyl C? to C ₁₂ alkyl group in straight or branched chain of carbon number 2 to 20, alkoxy group of carbon number 4-18, vinyl, crotyl, ₂ CH = CHCH ₂ O in the form of solutions in organic solvents at temperatures of -20 to + 60 ° C, by reacting the carboxylic acid halides of the formula R'COX and / or the halogenated carboxylic acid esters of the formula R »OCOX in which X = a chlorine or bromine atom with hydrogen peroxide in an alkaline medium and / or an alkali metal peroxide

224 167 alkaline earth peroxide, from effective mixing, possibly also with the aid of auxiliary substances, is carried out by adding to the aqueous solution of the alkali metal peroxide or a mixture of alkali metal peroxides simultaneously or intermittently interrupting it or at least two or more continually * COX and / or R'OCOX and an organic solvent, or vice versa, an aqueous alkali metal peroxide solution is added to a mixture of at least two different substances of the formulas li'COX and / or R''OCOX and an organic solvent boiling above 70 ° C or a mixture of alkali metal peroxides, the temperature of the reaction medium being maintained at a temperature of -10 to + 50 ° C, preferably of 0 to 30 G, wherein, as a rule, either at least 90 alkali metal peroxides or 90 organic compounds of the general formula reaί 'are reacted. and / or R * OCOX are separated by 10 to 100 aqueous phases, being present in the organic phase the mixture of organic peroxides is optionally treated by physical or physicochemical methods such as drying, distilling off the by-products under reduced pressure, freeze-drying, the addition of water-removing agents or adsorbing agents.

Advantages of the process according to the invention are both high yields of organic peroxides and the possibility of preparing mixed peroxides and mixtures of organic peroxides with different half-lives, which enables the optimum utilization of generated radicals in free radicals. syntheses and processes, such as e.g. in the polymerization of vinyl inonomers, ethylene and the like. Furthermore, the fact that simultaneously with the solution of dganic peroxides, the necessary solvents (e.g. paraffinic or isoparaffinic oils for high-pressure ethylene polymerization) are introduced into the reaction medium of free radical reactions (polyinerization, copolymerization, cleavage, etc.); trichlorethylene

- 5 224 167 slurry polymerization of vinyl chloride, modifiers (e.g. higher fatty alcohols), possibly comonomers, etc. Last but not least, the advantage is not only the safety of the production of organic peroxide solutions, but also their handling and the fact that the presence of water are readily separated from the crude reaction products by alkali metal or earth halides ·

The auxiliaries in the preparation of the mixed and / or organic peroxide mixtures according to the invention are, on the one hand, inhibitors or radical scavengers (nitroaromatic compounds such as nitrobenzene, dinitrobenzene, nitrotoluene, phenols, polyphenols, phenothiazine, hydroxyl amine and the like). such as magnesium sulfate, calcium carbonate, magnesium carbonate and the like, post-active agents such as nonionic surfactants, hydroxyalkylcelluloses such as hydroxyethyloeluloza, alkylhydroxyalkylcelluloses such as e.g. methylhydroxypropylcellulose, anionic surfactants and the like ·

Suitable organic solvents having a boiling point above 70 ° C are, in particular, aromatic hydrocarbons, in which the organic peroxides are finally well dissolved, most preferably from the technical-economic point of view, and toluene, xylenes, ethylbenzene, kiaene, diisopropylbenzenes, diethylbenzenes and the like. alkanic, alkane and naphthenic hydrocarbons having carbon numbers greater than 6, but in particular greater than 9, then saturated but also unsaturated alcohols. Both chlorinated hydrocarbons and smith can be used. these are least suitable for most of the possible applications.

Treatment by physical or physicochemical methods is also understood to mean treatment in an applicable, most often transportable form, such as treatment of a solution of a peroxide mixture, e.g. concentration to desired value, addition of stabilizers, preparation of aqueous emulsions from organic peroxide solutions, including possible addition of additional peroxides, removal of liquid and possibly solid impurities, moisture (eg mixed peroxides are to be used for high pressure polymerization of ethyl), o224 167

- 6 inert atmosphere, addition of dyes to differentiate different types of peroxide solutions and handling fluids, including packaging, etc. The production method according to the invention can be carried out batchwise, semi-continuously or continuously.

Further details and advantages of the production method according to the invention are evident from the examples.

Example 1

ABOUT

To a 1 dm glass reactor equipped with a stirrer (250 rpm), a thermometer and a coolant coolant and inlets for component addition and an outlet valve at the bottom of the reactor was charged 1.2 moles of 2-ethylhexyl chloroformate (231.2 g as

100%) and 0.3 mol of benzoyl chloride (42.2 g as 100%) of 3 and 150 cm xylenes. In a separate vessel, an aqueous solution of 1 mol.dm < -1 > * * is prepared in an amount of 1 dm < -1 > by mixing 0.8 dm ^{< RTI ID =} 0.0 > ^{J < / RTI &gt}; 20 wt. as a stabilizer, 163.3 g of aqueous sodium hydroxide solution with conc. 49% (2 moles) and 113.4 g of hydrogen peroxide with conc. 30% wt. (1 mol). While stirring the contents of the glass reactor, a first portion of 500 cm @ 3 of an aqueous sodium peroxide solution is added thereto at a rate such that the reaction temperature does not exceed 30 ° C. After 80 min from the start of the addition of aqueous sodium peroxide, the reaction mixture is cooled to 20 ° C and the stirring is stopped. The separated lower aqueous phase was separated.

Stirring and cooling are then started again and a second 500 cm @ 3 portion of aqueous sodium peroxide solution is added. The reaction temperature is maintained at 30 ° C for 100 min from the start of the second portion of sodium peroxide. The reactor contents are then cooled to 20 ° C, stirring is stopped, the lower aqueous layer and the upper organic phase containing a solution of three organic peroxides are separated.

- 7 224 167 (C ₆ H ₅ CO-OO-COC ₆ H ₅ , CH ₃ CH ₂ CH ₂ CH ₂ CHCH ₂ OC-OO-COC ₆ H ₅ ^C 2 ^H 5 ch ₃ ch ₂ ch ₂ ch ₂ oco- o-cooch ₂ ch-ch ₂ ch ₂ ch ₃ ) ^C 2 ^H 5 and in xylene is analyzed. A mixture of said peroxides of conc. 65.2 wt. (calculated as pure di-2-ethylhexyl * 5 peroxydicarbonate), respectively. 1.76 mol.dm ^{J of} xylene. Then the solution is diluted with xylene to conc. 50% by weight, calculated as di-2-ethylhexylperoxydicarbonate, corresponding to a concentration of 1.35 mol / ml of organic peroxides.

The yield of organic peroxides per consumed 2-ethylhexyl chloroformate and benzoyl chloride was 89.3%. The xylene initiator solution thus obtained, either immediately after preparation or after dilution, can be stabilized by the addition of known inhibitors such as phenol and its derivatives, nitro compounds and the like, and also colored to distinguish similar solutions.

Example 2 *

80 moles (15.414 kg as 100%) of 2-ethylhexyl chloroformate, 20 moles are charged to a 100dm 2 glass reactor equipped with a stirrer, a cooling coil and a thermowell, as well as reaction component addition openings at the top of the lid and with a bottom outlet. (2.811 kg as 100%) benzoyl chloride and 10 g of xylene. In a separate vessel, e and peroxide aqueous solution of sodium du 5 • mixing the components: 50 dm ^J demineralized water, 0.65 dm ^ aqueous solution of magnesium sulfate on the cone. 10% wt.

(= 65 g), 10.61 kg of aqueous sodium hydroxide solution with conc. 49% (" 5,199 kg as 100%, i.e. 130 moles) and 7.37 kg peroxide in an amount of 30% by weight. (= 2.210 kg as 100%, i.e. 65 moles). The total amount of aqueous sodium peroxide solution is thus 65 dm ^ and the concentration is 1.0 mol.dm ^J Na ₂ 0 ₂ ·

An aqueous sodium peroxide solution is added to a glass reactor containing benzoyl chloride, 2-ethylhexyl chloroformate and xylene with the agitator running, so that the reaction temperature does not exceed 30 ° C. * 120 min. with the phase. The yield of the mixture of peroxides was 93.1% (34.5 dm · 50% by weight, calculated on di-2-ethylhexylperoxydicarbonate).

Example 3

The procedure is similar to that of Example 2, except that instead of 10 dm xylene, 20 dm 2 of medicinal mineral oil is used, the above-obtained solution of three organic peroxides in mineral oil is dried with phosphorus pentoxide, which is then separated and peroxide in mineral oil. stabilizes with 0.1 wt. dinitrobenzene.

The peroxide yield is 91.1

Example 4

The procedure is similar to that of Example 2, except that xylene as solvent is not added at the start of the reaction, but only 40 minutes after the start of the addition of aqueous sodium peroxide solution. The total reaction time is 50 min and the total yield of organic peroxides in the range is 91.8% calculated on di-2-ethylhexylperoxydicarbonate ·

- 9 Example 5

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The procedure is similar to that of Example 2, except that the entire batch of aqueous sodium peroxide solution is metered into the stirrer reactor first. To this, with stirring, is added a solution of 2-ethylhexyl chloroformate, and benzoyl chloride in xylene, taking care that the temperature does not exceed 30 ° C. · After 60 minutes the reaction is complete. The yield of organic peroxides is 88.6% (calculated on the chloroformate and benzoyl chloride used).

Example 6

In a stainless steel container, 80 dmM of an aqueous solution of sodium peroxide at a concentration of 1.5 mol / ml are prepared by mixing 240 moles of sodium hydroxide in the form of an aqueous solution of conc. 49% in an amount of 19.6 kg, followed by 120 moles of hydrogen peroxide in the form of an aqueous solution of conc. 30% wt. in an amount of 13.6 kg and 0.08 kg of magnesium sulfate in the form of an aqueous solution with conc. 10% wt. (800 cm @ 3 of solution), followed by a 4 daP aqueous solution of methyl hydroxypropylcellulose with conc. 2 wt. and 50 dmM of demineralized water.

100 moles of benzoyl chloride <2.4 .mu.l and 100 moles of chloro-chlorobenzoyl chloride are metered into the glass reactor and the reactor contents are stirred. An aqueous solution of peroxide, sodium is then added so that the temperature does not rise to 30 ° C. After the addition of 80 .mu.M sodium peroxide was added, the mixture was allowed to react for 20 minutes. The resulting mixture of dibenzoyl peroxide peroxides, di- (dichlorobenzoyl) peroxide and benzoyl dichlorobenzoyl peroxide as a suspension is separated by filtration or centrifugation. The wet powder may be further washed with methanol, fc

- 10 224 167 to adjust the moisture content. Paroxide yield 89% ·

Example 7

The procedure is similar to that of Example 6, but only 50 dm xylene is metered into the glass reactor in addition to benzoyl chloride and dichlorobenzoyl chloride. The resulting peroxide product is in the form of a xylene solution with a yield of 88.5% ·

Example 8

The procedure is similar to that of Example 6, except that the process of adding the components to the reactor is reversed. That is, to 80 diP aqueous sodium peroxide solution on the horse. Benzoyl chloride is added with stirring at a slow flow rate of 1.5 mol / ml. Peroxide mixture yield 87% ·

Example 9

The procedure is similar to that of Example 1, except that 1.2 mol of butyl chloroformate is used instead of 1.2 mol of 2-ethylhexyl chloroformate. The yield of the peroxide mixture is 90%.

Example 10

The procedure is similar to that of Example 1 except that benzyl chloroformate is used instead of 1 * 2 mol of 2-ethylhexyl chloroformate. The yield of the peroxide mixture is 70%.

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Example 11

The procedure is similar to Example 1 except that allyl chloroformate is used instead of 2-ethylhexyl chloroformate. The yield of the peroxide mixture is £8%.

Example 12

The procedure is similar to that in Example 1 except that 2,4-dichlorobenzoyl chloride is used instead of benzoyl chloride. The yield of the peroxide mixture is 92%.

Example 13

The procedure is similar to that of Example 1 except that 0.3 mol of octanoyl chloride is used instead of benzoyl chloride. The yield of the peroxide mixture is 87%.

Example 14

The procedure is similar to that of Example 1, only 0.6 mol but instead of 0.6 mol of ethyl chloroformate are used instead of 1.2 mol of 2-ethylhexyl chloroformate. Organic peroxide mixture yield 88% ·

- 12 224

The procedure is similar to that of Example 1 except that only 0.5 mol, but additionally 0.5 mol of dodecyl chloroformate and 0.2 mol of benzyl chloroformate are used instead of 1.2 mol of 2-ethylhexyl chloroformate. The yield of the mixture of organic peroxides is 67%.

Example 16

Example 15

The procedure is similar to that in Example 1, except that 1.2 mol of hexadecyl chloroformate (cetyl chloroformate) is used instead of 2-ethylhexyl chloroformate. The total reaction time is 210 min and the yield of organic peroxides reached 93% ·

Example 17

The procedure is as in Example 1, but with the difference that 1,2 mol of bucoxyethyl chloroformate is used instead of 2-ethylhexyl chloroformate. With a total reaction time of 90 min, an organic peroxide yield of 81% is achieved.

Example 18

The procedure is as in Example 1, except that 0.3 mol of 2-ethylhexanoyl chloride is used instead of benzoyl chloride. At a reaction temperature of 10 ° C and a total reaction time of 120 min, the yield of mixed and organic peroxide mixtures is 63% ·

-13 224 167

Example 19

The procedure is similar to that of Example 1, except that 2-chloroethyl chloroformate (1.2 mol) and 2-chloropropionyl chloride (0.3 mol) are used as starting chloroorganic compounds. At a reaction temperature of 10 ° C for 50 min, the yield of the mixture and the mixed organic peroxides is 74%.

Example 20

The procedure is similar to Example 1, except that 1.2 mol of cyclohexyl chloroformate and 0.3 mol of methacryloyl chloride are used in the reaction. At 0 ° C for a reaction time of 60 min, an organic peroxide yield of 79% is achieved.

Example 21

The procedure is similar to that in Example 6, except that 100 moles of hexadecyl chloroformate and 100 moles of lauroyl chloride are used in the reaction. At a temperature of 35 ° C for a reaction time of 4 h, the yield of the mixture and mixed peroxides is 88%,

Example 22

The procedure is similar to that of Example 1, except that benzyl chloroformate (1.2 mol) and cyclohexanecarbonyl chloride (0.3 mol) are used to produce mixed and organic peroxides. At 0 ° C a peroxide yield of 67% is achieved within 120 min ·

Example 23

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The procedure is similar to that in Example 1, except that 1.2 mol of 2-phenoxy-2-chloroethyl chloroformate (CH-CHg-O-COCl) and 0.3 mol of crotonyl chloride are used in the reaction.

An organic peroxide yield of 72% is achieved at 150 ° C over 150 min.

Example 24

The procedure is similar to Example 1, except that the same amount (0.3 mol) of 2-methylbeneoyl chloride is used instead of benzoyl chloride to produce the mixture and mixed organic peroxides. At 30 ° C an organic peroxide yield of 93% is achieved in 180 min ·

Example 25

The procedure is similar to that of Example 1 except that 1.5 mol of methacroyl chloride is used instead of 2-ethylhexyl chloroformate and benzoyl chloride. At 20 ° C, a yield of dimethacroyl peroxide of 92% is reached in 20 minutes and at 0 ° C in 30 minutes a yield of 90% is achieved.

Example 26

The procedure is similar to that of Example 1 except that allyl chloroformate is used instead of 1.2 mol of 2-ethylhexyl chloroformate.

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At a temperature of 20 ° C, the yield of the mixture and the mixed peroxides of 89% is achieved within 60 min. ·

Example 27

The procedure is similar to that of Example 1 except that 0.3 mol of 2-methoxybenzoyl chloride is used instead of 0.3 mol of benzoyl chloride, with a yield of mixed and peroxide mixtures of 80% at 20 ° C.

Example 28

The procedure is similar to that of Example 1 except that 0.3 mol of 2,4-dichlorobenzoyl chloride is used instead of 0.3 mol of benzoyl chloride. A yield of mixed and peroxide mixtures 84 is obtained at 0 ° C

Example 29

The procedure is similar to that of Example 1 except that 1,5 mol of 2,4-dichlorobenzoyl chloride is used instead of 2-ethylhexyl chloroformate and benzoyl chloride. At 0 ° C a yield of bis (2,4-dichlorobenzoyl) peroxide of 90% is obtained.

Example 30

The procedure is similar to that of Example 1 except that 0.3 mol of crotonoyl chloride is used instead of benzoyl chloride, at a temperature of

224 187 ° C, a yield of 83% was obtained for mega and mixed organic pens.

Example 31

The procedure is similar to that of Example 1, except that 1.5 moles of 2-chlorocapryloyl chloride are used instead of the starting chloroorganic compounds, yielding bis (2-chlorocapryloyl) peroxide at 20 ° C.

Example 32 v

The procedure is similar to that of Example 1 except that 0.3 mole of 2-chloropropionyl chloride is used instead of benzoyl chloride. At 0 [deg.] C., the yield of the peroxide mixture is obtained together with the mixed ones. peroxides 76% ·

Claims (5)

Object of the invention A process for the production of mixed peroxides and / or mixtures of peroxides of the general formula II o II R * - C - 00 - C - R »» in which R '= alkyl-C 1-6 alkoxy, the same or branched chain having 2 to 18 carbon atoms, CH 2 -CH 2 CH 2 -O-, halogenated alkyl to C 1-4, cyclohexyl, alkylcyclohexyl C? to, benzyl, phenyl, halogenated phenyl, R @ 1 = phenyl, halogenated phenyl, benzyl, alkylbenzyl, C1-6 cyclohexyl, alkylcyclohexyl C1-6 alkyl; C 1 -C ₂ , straight or branched chain alkyl having 2 to 20 carbon atoms, alkoxy having 4 to 18 carbon atoms, vinyl, methyl, CII ₂ xCHCl 2 O-, in the form of solutions in organic solvents at -20 to +60 ° C, by reaction of carboxylic acid halides of the formula R'Ό00Χ, in which X «is a chlorine or bromine atom, with hydrogen peroxide in an alkaline medium and / or an alkali metal peroxide, optionally an alkaline earth peroxide, with stirring, optionally also in conjunction with excipients, characterized in that at least two different substances of the general formula R'COX and / or R '* OCOX and organic compounds are added simultaneously or individually to the aqueous solution of the alkali metal peroxide or a mixture of alkali metal peroxides solvent, or vice versa, into a mixture of at least two different substances of the general formula R'COX and / or R''OCOX 18 224 167 and an organic solvent boiling above 70 ° C, an aqueous solution of alkali metal peroxide or a mixture of alkali metal peroxides is added, maintaining the temperature of the reaction medium at a temperature of -10 to + 50 ° C, preferably 0 to 30 ° C. as a rule, either after the reaction of at least 90 alkali metal peroxide or 90 1 ° of organic compounds of the formula 11'COX and / or R '* OCOX, 10 to 100% of the aqueous phase is separated, the organic phase present in the organic phase Peroxides optionally uprawx is a physical or physicochemical method such as drying, distilling off the by-products under reduced pressure, freeze drying, adding water-scavenging agents or adsorbing agents. 2. Process according to claim 1, characterized in that the organic solvent is unsaturated and / or aromatic hydrocarbons, preferably toluone, xylenes. 3. The method according to claim 1 or 2, characterized in that the organic solvent is naphthenes and / or paraffinic hydrogen atoms, preferably paraffinic hydrogen atoms having a carbon number of 10 to 6, 4. A process according to claim 1, optionally also 2 and 3, characterized in that the organic solvents are saturated and / or unsaturated alcohols. 5. A process according to any one of claims 1 to 4, characterized in that the organic peroxide mixture present in the organic phase is adjusted to the desired concentration with a solvent or solvent mixture.