CA1062282A - Method of producing 2,2'-lower alkylidene-bis(4,6-dialkylphenols) - Google Patents
Method of producing 2,2'-lower alkylidene-bis(4,6-dialkylphenols)Info
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- CA1062282A CA1062282A CA242,524A CA242524A CA1062282A CA 1062282 A CA1062282 A CA 1062282A CA 242524 A CA242524 A CA 242524A CA 1062282 A CA1062282 A CA 1062282A
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- dialkylphenol
- butylphenol
- tert
- methyl
- acetal
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Abstract
ABSTRACT OF THE DISCLOSURE
A method of producing 2,2'-lower alkylidenebis(4,6-dialkylphenols) residing in that 2,4-dialkylphenols interact with acetals in the presence of an acid catalyst at a temperature from 30°C to 140°C
with the formation of a reaction mixture containing the desired product and with subsequent separation of the desire product from said mixture, the starting reagents being taken in amounts of 1 mole of 2,4-dialkylphenol per 1-10 moles of acetal.
The method if technologically simple and accomplished with-out the formation of waste water.
A method of producing 2,2'-lower alkylidenebis(4,6-dialkylphenols) residing in that 2,4-dialkylphenols interact with acetals in the presence of an acid catalyst at a temperature from 30°C to 140°C
with the formation of a reaction mixture containing the desired product and with subsequent separation of the desire product from said mixture, the starting reagents being taken in amounts of 1 mole of 2,4-dialkylphenol per 1-10 moles of acetal.
The method if technologically simple and accomplished with-out the formation of waste water.
Description
The present invention relates to producing 2,2'-lower alkylidenebis(4,6-dialkylphenols).
2,2'-methylenebist4,6-dialkylphenols) are effective stabilizers of polymer materials. They protect almost all kinds of polymers from ageing, do not affect their colour, and are non-volatile. Thus, for example, 2,2'-methylenebis(4-methyl-6-tert.
butylphenol), the most important stabilizer of this class, is widely used to protect rubbers, resins, polyolefins, chloro- and nitrogen-containing polymers, polyoxymethylene, polystyrene and other polymers against thermal oxidation.
Known in the art are batch processes of producing 2,2'-methylene-bis(4,6-dialkylphenols) based on emulsion condensation of 2,4-dialkylphenols with a condensing agent. For example, formaldehyde is used as a condensing agent. Condensation is run in the presence of an acid catalyst, for example, sulphuric acid. The process is carried out in a water emulsion of 2,4-dial-kylphenol containing a surfactant and an organic solvent at a temperature from 75C to 90C. The main disadvantage of this process is the formation of waste water in large amounts, con-taminated with the surfactant and organic solvents.
In other sources, a method of producing 2,2'-methylene-bis(4,6-dialkylphenols) is described consisting in condensation :
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of 2,4-dialkylphenols with formaldehyde in an organic solvent at a temperature from 90~C to llO~C. The method fails to ensure the high yield of pure product. The formation of waste water is not excluded either since formaldehyde is used as a 37% aqueous solution.
;; In some methods, paraform is used as the condensing agent, but the desired product obtained in low yield and of poor quality. Condensation with trioxymethylene is performed in an aqueous solution of formic acid. Therefore, the formation of waste water is also possible.
Likewise known in the art is a method of producing 2,2'-methylenebis(4,6-dialkylphenols) by water-emulsion condensation of 2,4-dialkylphenols with a 36% aqueous solution of formaldehyde as the condensing agent.
As 2,4-dialkylphenols use is made, for example, of 4-; methyl-2-tert.butylphenol,4-ethyl-2-tert.butylphenyl, 4-ethyl-2-tert.octylphenol.
The reaction is carried out in the presence of an organic solvent, for example, heptane, chlorobenzene, a surfact-ant, and sulphuric acid as a catalyst.
The reaction temperature is maintained within a range from 30~C to 140~C, for example, 75U-9OuC.
As a result, a mixture is obtained containing the de-sired product. The mixture is neutralized with sodium hydroxide solu-:
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, . .
tion and the desired product is i~olated by known methods, suchas filtration or centrifugation. The yield of the de~ired pro-duct is 96-9~/o.
The method is disadvantageous in that waste water is used in large amount3 containing impurities of the organic solvent and the surfactant: 12,000-15,000 litres of waste water are formed per 1 ton of the desired product.
The same disadvantage is inherent in a known continuous method of producing 2,2'-methylenebis(4-methyl_6_tert~butylphenol), based on water-emul~ion condensation of 4-methyl-2-tert.butyl-phenol with formaldehyde.
It is an object of the invention to provide a method of producing a 2,2-alkylidenebis(4,6-dialkylphenol) which will pre-clude waste water formation, ensuring high yield of a high quality end product.
The present invention provides a method of producing a 2,2'-lower alkylidenebis(4,6-dialkylphenol), comprising react-ing a 2,4-dialkylphenol with an acetal in the presence of an acid catalyst at a temperature of from 30C to 140C, in a molar ratio of 1 mole of 2,4-dialkylphenol per 1 to 10 moles of acetal, with the formation of a reaction mixture containing the desired product and subsequently separating the desired product from said mixture.
The 2,2'-lower alkylidenebis(4,6-dialkylphenols) pro-duced include, by way of example, 2,2'-methylenebis(4,6-dialkyl-phenol and 2,2'-ethylidenebis(4,6-dialkylphenol).
:.
. "
~ i - 3 -As a catalyst, use can be made of sulphuric, phos-phoric, perchlori~, to~uene sulphonic and other m~neral or organic acids, as well as cation exchange resins, for example, sulphated copolymer of styrene with divinylbenzene.
The reaction can be carried out in a wide temperature range from 30 to 140C.
The reaction proceeds in an acetal medium which is both a condensing agent and a solvent. Therefore, it is taken in amounts of 1-10 moles acetal per 1 mole of 2,4-dialkylphenol (preferably 4-5 moles); stoichiometric relationship is 0.5 mole of acetal per 1 le of 2,4-dialkylphenol. Excess acetal not participating in the reaction is removed and used in sub-sequent syntheses.
As acetals it is recommended to use, for example, dimethylformal (i.e. methylal), diethylformal, dimethylacetal, diethylacetal diisopropylàcetal~ànd the likè. ~-; Condensation of 2,4-dialkylphenols with acetals allows the production of 2,2'-methylenebis(4,6-dialkylphenols) not only in a batch process, but also continuously, without the formation of waste water and waste products. The yield of 2,2'-methylenebis(4,6-dialkylphenols) obtained by this method is as high as 98%. The products are of high quality.
Thus, for-example, 2,2'-methylenebis(4-methyl-6-tert.butyl-phenol) has a melting point of no less than 128-129C.
The method is technologically simple. No new equip-ment is ~' ~
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required for its implementation.
Due to the use of acetals, the reaction proceeds in a solution. Thus, there is no need to introduce surfactants into the reaction mixture.
The proposed method is realized as follows.
2,4-dialkylphenol is dissolved in acetal and the solu-tion is stirred in the presence of catalytic amounts of an acid catalyst, for example, sulphuric, phosphoric acids, sulphates co-polymer of styrene with divinylbenzene, and the like.
The reaction may be carried out over a wide temperature range from 30 to 140C. As a result, a reaction mixture is ob-tained containing the desired product. The mixture is then cooled, the catalyst is neutralized and removed. When sulphated copolymer of styrene with divinylbenzene is used as the catalyst, it is removed from the reaction mixture just after cooling this mixture. ~ext, the unreacted acetal is distilled off from said mixture and the desired product is delivered, in the form of a melt, for flaking.
For a better understanding of the present invention specific examples are given hereinbelow by way of illustration.
Example 1 82 g of 4-methyl-2-tert.butylphenol, 200 ml of methylal, and 2.5g of concentrated sulphuric acid are put into a reactor fitted with a thermometer, a condenser, and a stirrer.
The contents of the reactor are stirred for 2 hrs at 60-70UC. Then the obtained reaction mixture is cooled to 20~C, calcium oxide is added for neutralization of sulphuric acid, and after stirring for another 20 min, the mixture is filtrated.
. ~ .
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:
~ ~ ' ' ' ' The unreacted methylal is distilled off from the filtrate. The residue is 2~2 I-methylenebis(4-methyl-6-tert.butylphenol), m.p.
128-129~C. The yield of the product is 98% of theory.
Example 2 60 g of cation-exchange resin (sulphated copolymer of styrene with divinylbenzene) and a solution of 82 g of 4-methyl-2-tert.butylphenol in 180 ml of methylal are put into the reacto.
described in Example 1. The contents of the reactor is stirred for 3 hrs at 30-70C. The obtained reaction mixture is cooled to 20UC, the catalyst is separated by filtration, and the unre-acted methylal is distilled off from the filtrate.
The product obtained is analogous to that in Example 1.
The yield is 97% of theory.
Example 3 103 g of 2,4-ditert.butylphenol, 220 ml of methylal, and 3 g of concentrated sulphuric acid are put into the reactor ~r described in Example 1. The contents of the reactor are stirred ~ for 1.5 hrs at 80-lOO~C.
Subsequent treatment of the obtained reaction mixture and isolation of the desired product are performed as specified in Example 1.
2,2'-methylenebis(4,6-ditert.butylphenol) is obtained, :-.
~ m.p. 141-142~C. The yield of the product is 98% of theory. ~ ;
c Example 4 A 30/O solution of 4-methyl-2-tert.butylphenol in methyl-al is passed through two tubular reactors in series filled with ~ -, a cation-exchange resin similar to that described in Example 2.
. 1 . ~ .
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. - - : ,:, , The temperature in the first reactor is 50-60UC, and in the second, 70-80~C. The solution is passed at a rate of 50-60 ml per hr. After the second reactor, the unreacted methylal is removed from the obtained reaction mixture. The residue is 2,2'-methylenebis(4-methyl-6-tert.butylphenol), m.p. 129-130UC.
The yield of the product is 99~/O of theory. The distilled methylal is recycled for the preparation of a solution of 4-methyl-2-tert.butylphenol.
Example 5 82 g of 4-methyl-2-tert.butylphenol, 300 ml of diethyl-formal and 2.5 g of concentrated sulphuric acid are put into the reactor described in Example 1. The contents of the reactor are stirred for 2.5 hrs at 85-95UC. Subsequent treatment of the obtained reaction mixture and separation of the desired pro-ductare performed following the procedure described in Example 1.
2,2'-methylenebis(4-methyl-6-tert.butylphenol) is , produced, m.p. 128-129C, in yield 86% of theory.
Example 6 60 g of a cation-exchange resin of the kind described in Example 2 and a solution of 82 g of 4-methyl-2-tert.butyl-phenol in 250 ml of diethylformal are put into the reactor de-scribed in Example 1. The contents of the reactor are stirred for 4 hrs at 85-95~C. Subsequent treatment of the obtained re-action mixture and isolation of the desired product are per-formed following the procedure described in Example 2.
; ~,2'-methylenebis(4-methyl-6-tert.butylphenol) is pro-duced, m.p. 128-129~C. The yield of the product is 92% of theory.
Example 7 82 g of 4-methyl-2-tert.butylphenol, 250 ml of dimethyl-:
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acetal and 2.5 g of concentrated sulphuric acid are put into the reactor described in Example 1. The contents of the reactor are stirred for 2.5 hrs at 64-70~C. Subsequent treatment of the obtained reaction mixture and separation of the desired product are carried out following the procedure described in Example 1.
2,2'-ethylidenebis(4-methyl-6-tert.butylphenol) is produced, m.p. 104-105~C. The yield of the product is 800/o of theory.
Example 8 103 g of 2,4-ditert.butylphenol, 300 ml of diethyl-formal and 3 g of concentrated sulphuric acid are put into the reactor described in Example 1. The contents of the reactor are stirred for 2.5 hrs at 85-95~C. Subsequent treatment of the obtained reaction mixture and separation of the desired product are performed following the procedure described in ~ Example 1.
`'A~ 2,2'-methylenebis(4,6-ditert.butylphenol), m.p. ~ -141-142~C, is obtained in 75% yield of theory. ~ -' ~: -, 1 , , ., .
~j .
~' , , Example 9 82 g of 4-methyl-2-tert.butylphenol, 400 ml of diethyl-acetal, and 2.5 g of concentrated sulphuric acid are put into the reactor described in Example 1. The contents of the reactor are stirred for 3 hrs at 103-llO~C. Subsequent treatment of the obtained reaction mixture and separation of the desired product are performed following the p~ocedure described in Example 1.
2,2'-ethylidenebis(4-methyl-6-tert.butylphenol) is obtained, m.p. 104-105~C. The yield of the product is 70%
of theory.
Example 10 61 g of 2,4-xylenol, 400 ml of diisopropylacetal, and 2.5 g of concentrated sulphuric acid are put into the reactor described in Example 1. The contents of the reactor are stirred -for 3 hrs at 82-90~C. Subsequent treatment of the obtained reaction mixture and separation of the desired product are performed following the procedure described in Example 1.
2,2~-methylenebis(4,6-dimethylphenol) is produced, m.p. 125-126~C, in 85% yield of theory.
_ g _ '', ~-~ ~ ',. -.
Example 11 61 g of 2,4-xylenol, 220 ml of methylal, and 2.5 g of phosphoric acid are put into the reactor described in Example 1. The contents of the reactor are stirred for 3 hrs at 95-110UC.
Subsequent treatment of the obtained reaction mixture and separation of the desired product are performed following the procedure described in Example 1.
2,2'-methylenebis(4,6-dimethylphenol) is produced, m.p. 125-126UC, in 83% yield of theory.
Example 12 82 g of 4-methyl-2-tert.butylphenol, 250 ml of di-methylacetal, and 3 g of toluene sulphonic acid are put into the reactor described in Example 1. The contents of the reactor ;-are stirred for 2.5 hrs at 75-80C. Subsequent treatment of the reaction mixture and separation of the desired product are performed follcwing the procedure described in Example 1.
butylphenol), the most important stabilizer of this class, is widely used to protect rubbers, resins, polyolefins, chloro- and nitrogen-containing polymers, polyoxymethylene, polystyrene and other polymers against thermal oxidation.
Known in the art are batch processes of producing 2,2'-methylene-bis(4,6-dialkylphenols) based on emulsion condensation of 2,4-dialkylphenols with a condensing agent. For example, formaldehyde is used as a condensing agent. Condensation is run in the presence of an acid catalyst, for example, sulphuric acid. The process is carried out in a water emulsion of 2,4-dial-kylphenol containing a surfactant and an organic solvent at a temperature from 75C to 90C. The main disadvantage of this process is the formation of waste water in large amounts, con-taminated with the surfactant and organic solvents.
In other sources, a method of producing 2,2'-methylene-bis(4,6-dialkylphenols) is described consisting in condensation :
e .
, ~ 1 ~
' ' .
of 2,4-dialkylphenols with formaldehyde in an organic solvent at a temperature from 90~C to llO~C. The method fails to ensure the high yield of pure product. The formation of waste water is not excluded either since formaldehyde is used as a 37% aqueous solution.
;; In some methods, paraform is used as the condensing agent, but the desired product obtained in low yield and of poor quality. Condensation with trioxymethylene is performed in an aqueous solution of formic acid. Therefore, the formation of waste water is also possible.
Likewise known in the art is a method of producing 2,2'-methylenebis(4,6-dialkylphenols) by water-emulsion condensation of 2,4-dialkylphenols with a 36% aqueous solution of formaldehyde as the condensing agent.
As 2,4-dialkylphenols use is made, for example, of 4-; methyl-2-tert.butylphenol,4-ethyl-2-tert.butylphenyl, 4-ethyl-2-tert.octylphenol.
The reaction is carried out in the presence of an organic solvent, for example, heptane, chlorobenzene, a surfact-ant, and sulphuric acid as a catalyst.
The reaction temperature is maintained within a range from 30~C to 140~C, for example, 75U-9OuC.
As a result, a mixture is obtained containing the de-sired product. The mixture is neutralized with sodium hydroxide solu-:
, ,''' ' .~ ' .
, . .
tion and the desired product is i~olated by known methods, suchas filtration or centrifugation. The yield of the de~ired pro-duct is 96-9~/o.
The method is disadvantageous in that waste water is used in large amount3 containing impurities of the organic solvent and the surfactant: 12,000-15,000 litres of waste water are formed per 1 ton of the desired product.
The same disadvantage is inherent in a known continuous method of producing 2,2'-methylenebis(4-methyl_6_tert~butylphenol), based on water-emul~ion condensation of 4-methyl-2-tert.butyl-phenol with formaldehyde.
It is an object of the invention to provide a method of producing a 2,2-alkylidenebis(4,6-dialkylphenol) which will pre-clude waste water formation, ensuring high yield of a high quality end product.
The present invention provides a method of producing a 2,2'-lower alkylidenebis(4,6-dialkylphenol), comprising react-ing a 2,4-dialkylphenol with an acetal in the presence of an acid catalyst at a temperature of from 30C to 140C, in a molar ratio of 1 mole of 2,4-dialkylphenol per 1 to 10 moles of acetal, with the formation of a reaction mixture containing the desired product and subsequently separating the desired product from said mixture.
The 2,2'-lower alkylidenebis(4,6-dialkylphenols) pro-duced include, by way of example, 2,2'-methylenebis(4,6-dialkyl-phenol and 2,2'-ethylidenebis(4,6-dialkylphenol).
:.
. "
~ i - 3 -As a catalyst, use can be made of sulphuric, phos-phoric, perchlori~, to~uene sulphonic and other m~neral or organic acids, as well as cation exchange resins, for example, sulphated copolymer of styrene with divinylbenzene.
The reaction can be carried out in a wide temperature range from 30 to 140C.
The reaction proceeds in an acetal medium which is both a condensing agent and a solvent. Therefore, it is taken in amounts of 1-10 moles acetal per 1 mole of 2,4-dialkylphenol (preferably 4-5 moles); stoichiometric relationship is 0.5 mole of acetal per 1 le of 2,4-dialkylphenol. Excess acetal not participating in the reaction is removed and used in sub-sequent syntheses.
As acetals it is recommended to use, for example, dimethylformal (i.e. methylal), diethylformal, dimethylacetal, diethylacetal diisopropylàcetal~ànd the likè. ~-; Condensation of 2,4-dialkylphenols with acetals allows the production of 2,2'-methylenebis(4,6-dialkylphenols) not only in a batch process, but also continuously, without the formation of waste water and waste products. The yield of 2,2'-methylenebis(4,6-dialkylphenols) obtained by this method is as high as 98%. The products are of high quality.
Thus, for-example, 2,2'-methylenebis(4-methyl-6-tert.butyl-phenol) has a melting point of no less than 128-129C.
The method is technologically simple. No new equip-ment is ~' ~
. .
~ - 4 -., ~ .
, :, . - - . ~ ' ~06228Z
required for its implementation.
Due to the use of acetals, the reaction proceeds in a solution. Thus, there is no need to introduce surfactants into the reaction mixture.
The proposed method is realized as follows.
2,4-dialkylphenol is dissolved in acetal and the solu-tion is stirred in the presence of catalytic amounts of an acid catalyst, for example, sulphuric, phosphoric acids, sulphates co-polymer of styrene with divinylbenzene, and the like.
The reaction may be carried out over a wide temperature range from 30 to 140C. As a result, a reaction mixture is ob-tained containing the desired product. The mixture is then cooled, the catalyst is neutralized and removed. When sulphated copolymer of styrene with divinylbenzene is used as the catalyst, it is removed from the reaction mixture just after cooling this mixture. ~ext, the unreacted acetal is distilled off from said mixture and the desired product is delivered, in the form of a melt, for flaking.
For a better understanding of the present invention specific examples are given hereinbelow by way of illustration.
Example 1 82 g of 4-methyl-2-tert.butylphenol, 200 ml of methylal, and 2.5g of concentrated sulphuric acid are put into a reactor fitted with a thermometer, a condenser, and a stirrer.
The contents of the reactor are stirred for 2 hrs at 60-70UC. Then the obtained reaction mixture is cooled to 20~C, calcium oxide is added for neutralization of sulphuric acid, and after stirring for another 20 min, the mixture is filtrated.
. ~ .
~ - 5 -.:
:
~ ~ ' ' ' ' The unreacted methylal is distilled off from the filtrate. The residue is 2~2 I-methylenebis(4-methyl-6-tert.butylphenol), m.p.
128-129~C. The yield of the product is 98% of theory.
Example 2 60 g of cation-exchange resin (sulphated copolymer of styrene with divinylbenzene) and a solution of 82 g of 4-methyl-2-tert.butylphenol in 180 ml of methylal are put into the reacto.
described in Example 1. The contents of the reactor is stirred for 3 hrs at 30-70C. The obtained reaction mixture is cooled to 20UC, the catalyst is separated by filtration, and the unre-acted methylal is distilled off from the filtrate.
The product obtained is analogous to that in Example 1.
The yield is 97% of theory.
Example 3 103 g of 2,4-ditert.butylphenol, 220 ml of methylal, and 3 g of concentrated sulphuric acid are put into the reactor ~r described in Example 1. The contents of the reactor are stirred ~ for 1.5 hrs at 80-lOO~C.
Subsequent treatment of the obtained reaction mixture and isolation of the desired product are performed as specified in Example 1.
2,2'-methylenebis(4,6-ditert.butylphenol) is obtained, :-.
~ m.p. 141-142~C. The yield of the product is 98% of theory. ~ ;
c Example 4 A 30/O solution of 4-methyl-2-tert.butylphenol in methyl-al is passed through two tubular reactors in series filled with ~ -, a cation-exchange resin similar to that described in Example 2.
. 1 . ~ .
` , ':
. - - : ,:, , The temperature in the first reactor is 50-60UC, and in the second, 70-80~C. The solution is passed at a rate of 50-60 ml per hr. After the second reactor, the unreacted methylal is removed from the obtained reaction mixture. The residue is 2,2'-methylenebis(4-methyl-6-tert.butylphenol), m.p. 129-130UC.
The yield of the product is 99~/O of theory. The distilled methylal is recycled for the preparation of a solution of 4-methyl-2-tert.butylphenol.
Example 5 82 g of 4-methyl-2-tert.butylphenol, 300 ml of diethyl-formal and 2.5 g of concentrated sulphuric acid are put into the reactor described in Example 1. The contents of the reactor are stirred for 2.5 hrs at 85-95UC. Subsequent treatment of the obtained reaction mixture and separation of the desired pro-ductare performed following the procedure described in Example 1.
2,2'-methylenebis(4-methyl-6-tert.butylphenol) is , produced, m.p. 128-129C, in yield 86% of theory.
Example 6 60 g of a cation-exchange resin of the kind described in Example 2 and a solution of 82 g of 4-methyl-2-tert.butyl-phenol in 250 ml of diethylformal are put into the reactor de-scribed in Example 1. The contents of the reactor are stirred for 4 hrs at 85-95~C. Subsequent treatment of the obtained re-action mixture and isolation of the desired product are per-formed following the procedure described in Example 2.
; ~,2'-methylenebis(4-methyl-6-tert.butylphenol) is pro-duced, m.p. 128-129~C. The yield of the product is 92% of theory.
Example 7 82 g of 4-methyl-2-tert.butylphenol, 250 ml of dimethyl-:
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acetal and 2.5 g of concentrated sulphuric acid are put into the reactor described in Example 1. The contents of the reactor are stirred for 2.5 hrs at 64-70~C. Subsequent treatment of the obtained reaction mixture and separation of the desired product are carried out following the procedure described in Example 1.
2,2'-ethylidenebis(4-methyl-6-tert.butylphenol) is produced, m.p. 104-105~C. The yield of the product is 800/o of theory.
Example 8 103 g of 2,4-ditert.butylphenol, 300 ml of diethyl-formal and 3 g of concentrated sulphuric acid are put into the reactor described in Example 1. The contents of the reactor are stirred for 2.5 hrs at 85-95~C. Subsequent treatment of the obtained reaction mixture and separation of the desired product are performed following the procedure described in ~ Example 1.
`'A~ 2,2'-methylenebis(4,6-ditert.butylphenol), m.p. ~ -141-142~C, is obtained in 75% yield of theory. ~ -' ~: -, 1 , , ., .
~j .
~' , , Example 9 82 g of 4-methyl-2-tert.butylphenol, 400 ml of diethyl-acetal, and 2.5 g of concentrated sulphuric acid are put into the reactor described in Example 1. The contents of the reactor are stirred for 3 hrs at 103-llO~C. Subsequent treatment of the obtained reaction mixture and separation of the desired product are performed following the p~ocedure described in Example 1.
2,2'-ethylidenebis(4-methyl-6-tert.butylphenol) is obtained, m.p. 104-105~C. The yield of the product is 70%
of theory.
Example 10 61 g of 2,4-xylenol, 400 ml of diisopropylacetal, and 2.5 g of concentrated sulphuric acid are put into the reactor described in Example 1. The contents of the reactor are stirred -for 3 hrs at 82-90~C. Subsequent treatment of the obtained reaction mixture and separation of the desired product are performed following the procedure described in Example 1.
2,2~-methylenebis(4,6-dimethylphenol) is produced, m.p. 125-126~C, in 85% yield of theory.
_ g _ '', ~-~ ~ ',. -.
Example 11 61 g of 2,4-xylenol, 220 ml of methylal, and 2.5 g of phosphoric acid are put into the reactor described in Example 1. The contents of the reactor are stirred for 3 hrs at 95-110UC.
Subsequent treatment of the obtained reaction mixture and separation of the desired product are performed following the procedure described in Example 1.
2,2'-methylenebis(4,6-dimethylphenol) is produced, m.p. 125-126UC, in 83% yield of theory.
Example 12 82 g of 4-methyl-2-tert.butylphenol, 250 ml of di-methylacetal, and 3 g of toluene sulphonic acid are put into the reactor described in Example 1. The contents of the reactor ;-are stirred for 2.5 hrs at 75-80C. Subsequent treatment of the reaction mixture and separation of the desired product are performed follcwing the procedure described in Example 1.
3 2,2'-ethylidenebis(4-methyl-6-tert.butylphenol) is produced, m.p. 104-105UC, in 82% yield of theory.
Example 13 ~ .
82 g of 4-methyl-2-tert.butylphenol, 200 ml of methylal, and 3.5 g of perchloric acid are put into the reactor described in Example 1. The contents of the reactor are stirred for 3 hrs l at 30-40UC. Subsequent treatment of the obtained reaction ;l mixture and separation of the desired product are carried out following the procedure described in Example 1.
' 2,2'-methylenebis(4-methyl-6-tert.butylphenol) is `'3 produced, m.p. 128-129UC, in 85% yield of theory.
, ~06Z28Z
Example 14 60 g of a cation-exchange resin similar to that de-scribed in Example 2 and a solution of 87 g of 4-ethyl-2-tert.-butylphenol in 200 ml methylal are put into the reactor described in Example 1. The contents of the reactor are stirred for 3 hrs at 80-85~C. Subsequent treatment of the obtained reaction mix-ture and separation of the desired product are performed follow-ing the procedure described in Example 2.
2,2'-methylenebis(4-ethyl-6-tert.butylphenol) is pro-duced, m.p. 123-125UC, in 81% yield of theory.
Example 15 93 g of 4-methyl-2-cyclohexylphenol, 220 ml of methylal, and 3 g of concentrated sulphuric acid are put into the reactor described in Example 1. The contents of the reactor are stirred for 2 hrs at 85-95UC. Subsequent treatment of the obtained re-action mixture and separation of the desired product are per-formed by following the procedure described in Example 1.
2,2-methylenebis(4-methyl-6-cyclohexylphenol) is produced m.p. 118-119C, in 90% yield of theory.
Example 16 60 g of a cation-exchange resin similar to that used in Example 2 and a solution of 82 g of 4-methyl-2-tert.butyl-:
phenol in 75 ml of methylal are put into an air-tight steel reactor fitted with a stirrer. The contents of the reactor are stirred for 1 hr at 135-140~C. Then, the reactor is opened.
Subsequent treatment of the obtained reaction mixture and ; separation of the desired product are carried out following the procedure described in Example 2. 2,21-methylenebis(4-methyl-6-tert.butylphenol) is produced, m.p. 129-130~C, in 99~/O yield of theory.
'' ' .
Example 13 ~ .
82 g of 4-methyl-2-tert.butylphenol, 200 ml of methylal, and 3.5 g of perchloric acid are put into the reactor described in Example 1. The contents of the reactor are stirred for 3 hrs l at 30-40UC. Subsequent treatment of the obtained reaction ;l mixture and separation of the desired product are carried out following the procedure described in Example 1.
' 2,2'-methylenebis(4-methyl-6-tert.butylphenol) is `'3 produced, m.p. 128-129UC, in 85% yield of theory.
, ~06Z28Z
Example 14 60 g of a cation-exchange resin similar to that de-scribed in Example 2 and a solution of 87 g of 4-ethyl-2-tert.-butylphenol in 200 ml methylal are put into the reactor described in Example 1. The contents of the reactor are stirred for 3 hrs at 80-85~C. Subsequent treatment of the obtained reaction mix-ture and separation of the desired product are performed follow-ing the procedure described in Example 2.
2,2'-methylenebis(4-ethyl-6-tert.butylphenol) is pro-duced, m.p. 123-125UC, in 81% yield of theory.
Example 15 93 g of 4-methyl-2-cyclohexylphenol, 220 ml of methylal, and 3 g of concentrated sulphuric acid are put into the reactor described in Example 1. The contents of the reactor are stirred for 2 hrs at 85-95UC. Subsequent treatment of the obtained re-action mixture and separation of the desired product are per-formed by following the procedure described in Example 1.
2,2-methylenebis(4-methyl-6-cyclohexylphenol) is produced m.p. 118-119C, in 90% yield of theory.
Example 16 60 g of a cation-exchange resin similar to that used in Example 2 and a solution of 82 g of 4-methyl-2-tert.butyl-:
phenol in 75 ml of methylal are put into an air-tight steel reactor fitted with a stirrer. The contents of the reactor are stirred for 1 hr at 135-140~C. Then, the reactor is opened.
Subsequent treatment of the obtained reaction mixture and ; separation of the desired product are carried out following the procedure described in Example 2. 2,21-methylenebis(4-methyl-6-tert.butylphenol) is produced, m.p. 129-130~C, in 99~/O yield of theory.
'' ' .
Claims (7)
1. A method of producing a 2,2'-lower alkylidenebis (4,6-dialkylphenol), comprising reacting a 2,4-dialkylphenol with an acetal in the presence of an acid catalyst at a temperature of from 30°C to 140°C, in a molar ratio of 1 mole of 2,4-dialkylphenol per 1 to 10 moles of acetal, with the formation of a reaction mixture containing the desired product and subsequently separating the desired product from said mixture.
2. A method according to claim 1, wherein 4 to 5 moles of acetal per 1 mole of 2,4-dialkylphenol are used.
3. A method according to claim 1, wherein said acetal is selected from the group consisting of dimethylformal, diethylformal, dimethylacetal, diethylacetal and diisopropyl-acetal.
4. A method according to claim 1, 2 or 3, wherein said 2,2'-lower alkylidenebis(4,6-dialkylphenol) is a 2,2'-methylene-bis (4,6-dialkylphenol).
5. A method according to claim 1, 2 or 3, wherein said 2,2'-lower alkylidenebis(4,6-dialkylphenol) is a 2,2'-ethylidene-bis (4,6-dialkylphenol).
6. A method according to claim 1, 2 or 3, wherein said alkyl groups in said dialkylphenol, may be the same or different and are selected from lower alkyl groups of 1 to 4 carbon atoms and cyclohexyl.
7. A method according to claim 1, 2 or 3, wherein said 2,4-dialkylphenol is 2,4-xylenol, 4-methyl-2-tert.butylphenol 4-ethyl-2-tert.butylphenol, 2,4-ditert.butylphenol, or 4-methyl-2-cyclohexylphenol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA242,524A CA1062282A (en) | 1975-12-22 | 1975-12-22 | Method of producing 2,2'-lower alkylidene-bis(4,6-dialkylphenols) |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA242,524A CA1062282A (en) | 1975-12-22 | 1975-12-22 | Method of producing 2,2'-lower alkylidene-bis(4,6-dialkylphenols) |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1062282A true CA1062282A (en) | 1979-09-11 |
Family
ID=4104834
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA242,524A Expired CA1062282A (en) | 1975-12-22 | 1975-12-22 | Method of producing 2,2'-lower alkylidene-bis(4,6-dialkylphenols) |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1062282A (en) |
-
1975
- 1975-12-22 CA CA242,524A patent/CA1062282A/en not_active Expired
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