CA1049564A - Process for the preparation of bis(hydroxyaryl) compounds - Google Patents
Process for the preparation of bis(hydroxyaryl) compoundsInfo
- Publication number
- CA1049564A CA1049564A CA200,733A CA200733A CA1049564A CA 1049564 A CA1049564 A CA 1049564A CA 200733 A CA200733 A CA 200733A CA 1049564 A CA1049564 A CA 1049564A
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- Prior art keywords
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- compound
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- bis
- phenol
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
- C07D317/12—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to ring carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/11—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms
- C07C37/115—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms using acetals
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Abstract The present process relates to the preparation of bis(hydroxy-aryl) compounds such as Bisphenol A (diphenylolpropane) and Bisphenol F by reacting phenol in the presence of an acidic condensation catalyst with an acetal and/or a ketal such as 2,2-dimethyl 1,3 -dioxolane. The process is advantageous in that the use of a sulphidic co-catalyst is no longer required. Also corrosion problem are substantially dimished since ethylene glycol is formed as a byproduct in stead of water.
The bis(hydroxyaryl)compounds are valuable starting materials for the production of resins, plastics, paints and varnishes.
The bis(hydroxyaryl)compounds are valuable starting materials for the production of resins, plastics, paints and varnishes.
Description
: `
- ~.0~95~;~
The invention relates to a process for the preparation of bis(hydroxyaryl) compounds, in particular to the preparation of bis(hydroxyaryl)alkanes such as 2,2~di(4-hydroxy-phenyl)propane3 often called diphenylolpropane or Bisphenol A and 2,2-di(4-hydroxyphenyl)methane, also called Bisphenol F.
The present invention mainly relates to the preparation of diphenylolpropane, however, without being restricted thereto. Bis(hydroxyaryl)alkenes and especially diphenylolpropane are important chemicals which can be used as starting compounds for various - :
resins, for instance epoxy resins.
The bis(hydroxyaryl) compounds according to , .. . .
~ the present invention may be represented by the following formula:
Rl ~ , HOAr - C - Ar'OH
:` ' ' R2 ., wherein R and R2 may each represent hydrogen or a saturated or unsaturated alkyl, cycloalkyl, aryl, alkaryl, aralkyl or heterocyclic group and Ar and Ar~ each represent a (substituted) aromatic nucleus.
If Rl and R2 are both methyl and Ar and Ar' both represent a phenylene radical the formula represents : - , ' ' ':
'': '' ',:
,~ ;, ~ - 3 -diphenylolpropane.
As bis(hydroxyaryl)compounds are in general very useful products it is not surprising that their preparatlon has been thoroughly investigated. By far the most extensively evaluated process for the preparation of diphenylolpropane is the reaction between phenol and acetone in the presence of an acid condensation agent, for instance, hydrogen chloride, preferably in the presence of a co-catalyst such as hydrogen sulphide, methylmercaptan, beta-mercaptopropionic acid and the like. Detailed descriptions of the prior art can be found, for instance, in British Patent ~ -Specifications Nos: 735,21~; 735,216 and 785,o79.
The reaction between phenol and acetone is normally . ,.
carried out in a continuous system using a large excess of phenol compared to the acetone to be reacted, for instance an excess up to 15 moles per mole of acetone. The reaction is generally effected at a tempe~ature in the range of from 20C to 85C, preferably in the range of from 45C to 65C, and at a pressure of from autogeneous up to about 10 bar. The use of suitable solvents has also been described.
The reaction as hereinbefore described is normally carried out in the presence of an acid condensation agent,~such as a hydrogen halide, e.g. hydrochloric ~` acid, preferably anhydrous hydrochloric acid, sulphuric acid, a Lewis acid or an acidic cation-exchange resin. ~ ;
;, . ~
~`, ~ . .
., ':,~
''.`,'' ~, :~.
04~S~
Sulphur compounds, sometimes bound to the appropriate acidic cation-exchange resin, are often used to accelerake the condensation reaction.
Many working-up procedures for the crude reaction product have been suggested in the literature and some of them are commercially applied. For instance, after flashing off most of the excess phenol, the product, sometimes in the form of its phenol or cresol adduct, is recovered from the reaction mixture by ~10 precipitation~ washing, recrystallization or any other suitable technique.
Although the process as described hereinbefore is advantageous in that rather simple and cheap starting materials may be used, many proposals have been presented in the literature in which compounds other than acetone are used. For instance, the use of propyne as well as propadiene has been described (British Patent - Specification 974,982). It is also possible to start with chloropropylene instead of acetone~ but all the proposals mentioned hereinbefore may be considered to be alternatives which are of little or no commercial `
importance -The classical process for the preparation of diphenylolpropane, which has proved to be of great economical interest has been e~tensively evaluated ~` over the years so that a highly advanced process ` has been commercialized, ~; .; -~'`. ', ' if,'`'` ' .",, ;''i' ": j :' i .'.'.,:`;
";;.'' .,.,', .
- 5 ~ ~ ~9 ~ ~
However, even the advanced process has a number of drawbacks which are inherent in the particular reaction system applied.
For instance, the use of a mercaptan or other sulphur-containing compound as a co-catalyst, which in itself is an attractive way to accelerate the reaction, automatically implies tha~ the product will contain a certain (limited) amount of sulphur, which is very difficult to remove. However, sulphur-free diphenylolpropane is required as a starting material in the production of polycarbonates. Pollution aspects, too, have to be taken into account when use is made of a volatile sulphldic co-catalyst, especially when the reaction is carried out in a large-scale plant. It is possible, of course, to circumvent the use of a sulphur compound, but the alternative process for the production of diphenylolpropane has to be carried out under super-atmos-pheric HCl-pressure which has many drawbacks in itself.
As water will invariably be formed when phenol -.
and acetone are reacted to diphenylolpropane, c.orrosion problems will arise as well, the more so as large amounts of hydrochloric acid ha~e necessarily to be ùsed, especially when the process is carried out ~`
in the absence of a sulphur compound. It should be noted that one of the biggest problems in a commercial diphenylolpropane plant always relates to the working-up .,....... ", :,'` ' `
'" I ,.
~ ;
i'~ '' ' ' ,` : :. ,~' ,` ' ~- . ,' , ,: .
.,'.. ` , ~,"' .
~" i :11' ~ ' ', .:
\ :
~49S64 - -of the aqueous hydrochloric acid obtained. An amount of equipment out of all proportion is necessary to ensure that the environment will not be contaminated by the plant effluents. The same can be said with respect to the use of a volatile sulphidic co-catalyst.
Another disadvantage of the classical process is the highly unfavourable phenol/acetone molar ratio to be used, which normally exceeds 10:1, and is sometimes as high as 15:1. Hence, up to 13 moles of phenol have to be separated from the product and are subsequently to be recycled to the reactor.
It has now surprisingly been found that bis(hydroxyaryl) com-pounds, and, in particular, diphenylolpropane can be prepared without almost any of the above-mentioned drawbacks by reacting a phenolic compound with an acetal and/or a ketal in the presence of an acidic catalyst. The expressions "acetal" and"Ketal" as used in the present description comprise the reaction products of compounds containing one or more hydroxylic groups with compounds ., , -containing a carbonyl function such as aldehydes (the condensation products may be mentioned acetals) and ketones (the condensation produ~ts may be mentioned ketals).
The invention provides a process for the preparation of bis ~hydroxyaryl) compounds by reacting a phenolic compound with an oxygen com-pound in the presence of an acidic condensation catalyst wherein the oxygen compound has the general formula:-,~,, ` ' 1 > / I R 4 ~) R'2 \ 0 - C - R'5 $~ 6 ~ wherein R'l and R'2 may each represent hydrogen or a saturated or unsaturated 3;''~ alkyl group and R'3 to R'6 may each represent hydrogen or a saturated or ~i, unsaturated alkyl, cycloalkyl, aryl, alkaryl or aralkyl group.,?l ,'' - :
., i':' ,, ~a~49S~4 The invention relates in particular to the preparation of Bisphenol A from phenol and the cyclic ketal 2,2-dimethyl-1,3-dioxolane and of Bisphenol F from phenol and the cyclic acetal 1,3-dioxolane in the presence of an acidic condensation catalyst.
The invention also relates to a preferred process for the preparation of (substituted) 1,3-dioxolanes, which can suitably be used as starting materials for the preparation of bis~hydroxyaryl) compounds according to the present invention.
The use of acetals and/or ketals and especially of the preferred class of (substituted~ 1,3-dioxolanes instead of acetone in the preparation of bis(hydroxyaryl) compounds has a number of advantages which are discussed hereinafter in an arbitrary sequence.
` In the first place, the process according to the present invention can be carried out in the absence of a volatile sulphur compound as a co-catalyst whilst maintaining an economically very acceptable reaction rate. This implies that the product ~oes not necessarily contain any sulphur impurities and can be suitably applied for sophisticated purposes, for ;
instance in the preparation of polycarbonates. It is also noted that -':
environmental problems connected with ; 20 ., ;
;..................................................................... :
.,, ' .
!j :,.,',.i'~ ' ' ' ,;.,~. i : .
~'" 1 ' .
- 8 - ~ 4~ S 6 the use of volatile sulphur compounds are no longer relevant. , , It has further been found that under the prevailing reaction conditions the amount of phenol required ' to maintain an economically acceptable recycle process can be lowered to some extent, for instance phenol/dioxolane ;
ratios not exceeding 10:1 or even as low as 8:1 can suitably be applied, which implies a considerable '' decrease of the amount of phenol to be ~lashed off -in the w,orking-up procedure and subsequently recycled ~, , to the reactor. It is without doubt that any reduction ,'' :
o~ the phenol/reactant ratio to be achieved offers ' , great economical advantages. , ~ -In the third place it should be noted that when ~ , use is'made of a (substituted) 1,3-dioxolane for ~ ' ` '-, the production of bis(hydroxyaryl) compounds, (substitutedj ~ ethylene glycol is obtained as a by-product, thus ; ~ diminishing the corrosion problems inherent in the ,~ water/hydrochloric acid system invariably present ~ , '20 to a considerable extent in the classical process. ~' .. . .. .
'' This also implies that a considerable amount of the -~
, hydrochloric acid may be recycled to the reactor.
- A small amount of the hydrochloric acid present will dissolve in water which may be present in the reaction ', system (e.g. as a contaminant of the phenolic compound ~ ~
~;J to be reacted) and the aqueous hydrochloric acid ', ;. ,::
,~; . .:
;. ,-,~, , .~:~ . ', ~;~. . ' ;
c :) ' .::
,,~." .
~ .
,;:
:~,..
,-i, . ;
-- - 9 - ~L(349564 solution obtained has consequently to be worked up but only a fraction of the equipment normally required to treat the effluent will be necessary.Moreover the presence of, for instance, ethylene glycol obtained in an amount substantially equal to the molar amount of DMDO converted has the advantage that it may act as a solvent for diphenylolpropane formed, thus facilitating the separation steps which have to be carried out after flashing off the major amount of excess phenol.
Thus, for the production of diphenylolpropane from phenol and DMDO according to the present invention the following reaction scheme can be given:
- ~.0~95~;~
The invention relates to a process for the preparation of bis(hydroxyaryl) compounds, in particular to the preparation of bis(hydroxyaryl)alkanes such as 2,2~di(4-hydroxy-phenyl)propane3 often called diphenylolpropane or Bisphenol A and 2,2-di(4-hydroxyphenyl)methane, also called Bisphenol F.
The present invention mainly relates to the preparation of diphenylolpropane, however, without being restricted thereto. Bis(hydroxyaryl)alkenes and especially diphenylolpropane are important chemicals which can be used as starting compounds for various - :
resins, for instance epoxy resins.
The bis(hydroxyaryl) compounds according to , .. . .
~ the present invention may be represented by the following formula:
Rl ~ , HOAr - C - Ar'OH
:` ' ' R2 ., wherein R and R2 may each represent hydrogen or a saturated or unsaturated alkyl, cycloalkyl, aryl, alkaryl, aralkyl or heterocyclic group and Ar and Ar~ each represent a (substituted) aromatic nucleus.
If Rl and R2 are both methyl and Ar and Ar' both represent a phenylene radical the formula represents : - , ' ' ':
'': '' ',:
,~ ;, ~ - 3 -diphenylolpropane.
As bis(hydroxyaryl)compounds are in general very useful products it is not surprising that their preparatlon has been thoroughly investigated. By far the most extensively evaluated process for the preparation of diphenylolpropane is the reaction between phenol and acetone in the presence of an acid condensation agent, for instance, hydrogen chloride, preferably in the presence of a co-catalyst such as hydrogen sulphide, methylmercaptan, beta-mercaptopropionic acid and the like. Detailed descriptions of the prior art can be found, for instance, in British Patent ~ -Specifications Nos: 735,21~; 735,216 and 785,o79.
The reaction between phenol and acetone is normally . ,.
carried out in a continuous system using a large excess of phenol compared to the acetone to be reacted, for instance an excess up to 15 moles per mole of acetone. The reaction is generally effected at a tempe~ature in the range of from 20C to 85C, preferably in the range of from 45C to 65C, and at a pressure of from autogeneous up to about 10 bar. The use of suitable solvents has also been described.
The reaction as hereinbefore described is normally carried out in the presence of an acid condensation agent,~such as a hydrogen halide, e.g. hydrochloric ~` acid, preferably anhydrous hydrochloric acid, sulphuric acid, a Lewis acid or an acidic cation-exchange resin. ~ ;
;, . ~
~`, ~ . .
., ':,~
''.`,'' ~, :~.
04~S~
Sulphur compounds, sometimes bound to the appropriate acidic cation-exchange resin, are often used to accelerake the condensation reaction.
Many working-up procedures for the crude reaction product have been suggested in the literature and some of them are commercially applied. For instance, after flashing off most of the excess phenol, the product, sometimes in the form of its phenol or cresol adduct, is recovered from the reaction mixture by ~10 precipitation~ washing, recrystallization or any other suitable technique.
Although the process as described hereinbefore is advantageous in that rather simple and cheap starting materials may be used, many proposals have been presented in the literature in which compounds other than acetone are used. For instance, the use of propyne as well as propadiene has been described (British Patent - Specification 974,982). It is also possible to start with chloropropylene instead of acetone~ but all the proposals mentioned hereinbefore may be considered to be alternatives which are of little or no commercial `
importance -The classical process for the preparation of diphenylolpropane, which has proved to be of great economical interest has been e~tensively evaluated ~` over the years so that a highly advanced process ` has been commercialized, ~; .; -~'`. ', ' if,'`'` ' .",, ;''i' ": j :' i .'.'.,:`;
";;.'' .,.,', .
- 5 ~ ~ ~9 ~ ~
However, even the advanced process has a number of drawbacks which are inherent in the particular reaction system applied.
For instance, the use of a mercaptan or other sulphur-containing compound as a co-catalyst, which in itself is an attractive way to accelerate the reaction, automatically implies tha~ the product will contain a certain (limited) amount of sulphur, which is very difficult to remove. However, sulphur-free diphenylolpropane is required as a starting material in the production of polycarbonates. Pollution aspects, too, have to be taken into account when use is made of a volatile sulphldic co-catalyst, especially when the reaction is carried out in a large-scale plant. It is possible, of course, to circumvent the use of a sulphur compound, but the alternative process for the production of diphenylolpropane has to be carried out under super-atmos-pheric HCl-pressure which has many drawbacks in itself.
As water will invariably be formed when phenol -.
and acetone are reacted to diphenylolpropane, c.orrosion problems will arise as well, the more so as large amounts of hydrochloric acid ha~e necessarily to be ùsed, especially when the process is carried out ~`
in the absence of a sulphur compound. It should be noted that one of the biggest problems in a commercial diphenylolpropane plant always relates to the working-up .,....... ", :,'` ' `
'" I ,.
~ ;
i'~ '' ' ' ,` : :. ,~' ,` ' ~- . ,' , ,: .
.,'.. ` , ~,"' .
~" i :11' ~ ' ', .:
\ :
~49S64 - -of the aqueous hydrochloric acid obtained. An amount of equipment out of all proportion is necessary to ensure that the environment will not be contaminated by the plant effluents. The same can be said with respect to the use of a volatile sulphidic co-catalyst.
Another disadvantage of the classical process is the highly unfavourable phenol/acetone molar ratio to be used, which normally exceeds 10:1, and is sometimes as high as 15:1. Hence, up to 13 moles of phenol have to be separated from the product and are subsequently to be recycled to the reactor.
It has now surprisingly been found that bis(hydroxyaryl) com-pounds, and, in particular, diphenylolpropane can be prepared without almost any of the above-mentioned drawbacks by reacting a phenolic compound with an acetal and/or a ketal in the presence of an acidic catalyst. The expressions "acetal" and"Ketal" as used in the present description comprise the reaction products of compounds containing one or more hydroxylic groups with compounds ., , -containing a carbonyl function such as aldehydes (the condensation products may be mentioned acetals) and ketones (the condensation produ~ts may be mentioned ketals).
The invention provides a process for the preparation of bis ~hydroxyaryl) compounds by reacting a phenolic compound with an oxygen com-pound in the presence of an acidic condensation catalyst wherein the oxygen compound has the general formula:-,~,, ` ' 1 > / I R 4 ~) R'2 \ 0 - C - R'5 $~ 6 ~ wherein R'l and R'2 may each represent hydrogen or a saturated or unsaturated 3;''~ alkyl group and R'3 to R'6 may each represent hydrogen or a saturated or ~i, unsaturated alkyl, cycloalkyl, aryl, alkaryl or aralkyl group.,?l ,'' - :
., i':' ,, ~a~49S~4 The invention relates in particular to the preparation of Bisphenol A from phenol and the cyclic ketal 2,2-dimethyl-1,3-dioxolane and of Bisphenol F from phenol and the cyclic acetal 1,3-dioxolane in the presence of an acidic condensation catalyst.
The invention also relates to a preferred process for the preparation of (substituted) 1,3-dioxolanes, which can suitably be used as starting materials for the preparation of bis~hydroxyaryl) compounds according to the present invention.
The use of acetals and/or ketals and especially of the preferred class of (substituted~ 1,3-dioxolanes instead of acetone in the preparation of bis(hydroxyaryl) compounds has a number of advantages which are discussed hereinafter in an arbitrary sequence.
` In the first place, the process according to the present invention can be carried out in the absence of a volatile sulphur compound as a co-catalyst whilst maintaining an economically very acceptable reaction rate. This implies that the product ~oes not necessarily contain any sulphur impurities and can be suitably applied for sophisticated purposes, for ;
instance in the preparation of polycarbonates. It is also noted that -':
environmental problems connected with ; 20 ., ;
;..................................................................... :
.,, ' .
!j :,.,',.i'~ ' ' ' ,;.,~. i : .
~'" 1 ' .
- 8 - ~ 4~ S 6 the use of volatile sulphur compounds are no longer relevant. , , It has further been found that under the prevailing reaction conditions the amount of phenol required ' to maintain an economically acceptable recycle process can be lowered to some extent, for instance phenol/dioxolane ;
ratios not exceeding 10:1 or even as low as 8:1 can suitably be applied, which implies a considerable '' decrease of the amount of phenol to be ~lashed off -in the w,orking-up procedure and subsequently recycled ~, , to the reactor. It is without doubt that any reduction ,'' :
o~ the phenol/reactant ratio to be achieved offers ' , great economical advantages. , ~ -In the third place it should be noted that when ~ , use is'made of a (substituted) 1,3-dioxolane for ~ ' ` '-, the production of bis(hydroxyaryl) compounds, (substitutedj ~ ethylene glycol is obtained as a by-product, thus ; ~ diminishing the corrosion problems inherent in the ,~ water/hydrochloric acid system invariably present ~ , '20 to a considerable extent in the classical process. ~' .. . .. .
'' This also implies that a considerable amount of the -~
, hydrochloric acid may be recycled to the reactor.
- A small amount of the hydrochloric acid present will dissolve in water which may be present in the reaction ', system (e.g. as a contaminant of the phenolic compound ~ ~
~;J to be reacted) and the aqueous hydrochloric acid ', ;. ,::
,~; . .:
;. ,-,~, , .~:~ . ', ~;~. . ' ;
c :) ' .::
,,~." .
~ .
,;:
:~,..
,-i, . ;
-- - 9 - ~L(349564 solution obtained has consequently to be worked up but only a fraction of the equipment normally required to treat the effluent will be necessary.Moreover the presence of, for instance, ethylene glycol obtained in an amount substantially equal to the molar amount of DMDO converted has the advantage that it may act as a solvent for diphenylolpropane formed, thus facilitating the separation steps which have to be carried out after flashing off the major amount of excess phenol.
Thus, for the production of diphenylolpropane from phenol and DMDO according to the present invention the following reaction scheme can be given:
2 ~ OH ~ C~c~ Cl acidic catalyst~
. (DMDO) , HO ~ - C ~ OH ~ H2C - OH
\ J C H2C - OH :~
~,.
. The phenolic compounds which may be reacted with an acetal and/or a ketal, for instance, with ~, 15 a (substituted) dioxolane, in accordance with the . , -;
.~ process of the present invention comprise the broad class of phenolic compounds having at least one replaceable : ~ hydrogen atom directly bound to a nuclear carbon ~ :
::" "
atom of the phenolic radical. By the term phenollc ~; 20 compoundsl' are meant those organic compounds which ~ . :
`! I ` :
':;:1 ` ` ' ' :
: :' , "~
.` :.' ' ~Y
~"' . ~ ' ~i' ` ::.
_ , '~. . ..
i''''l ' ; ' ~', '~,'', ' :
- lo - 1~4~S~4 contain an aromatic radical and at least one hydroxyl group, linked directly to a carbon atom contained in the nucleus of the aromatic radical. The phenolic compounds used as starting material comprise the simplest members o~ the class, phenol, and its homologues as well as substitution products containing at least one replaceable hydrogen atom directly attached to a nuclear carbon atom of the phenolic radical; they include those compounds wherein hydrogen atoms of the aromatic nucleus have been substituted by hydrocarbon radicals, such as alkyl, cycloalkyl, aryl, alkaryl and aralkyl groups. ~`
The following examples of phenolic compounds may be given: phenol, ortho-cresol, meta-cresol, ~ 15 para-cresol, the xylenols, thymol, carvacrol, cumenol, :
2,3-diethylphenol, 2-methyl-3-ethylphenol, 2,3-di-tert.butyl-phenol, 2,4-dimethyl-3-ethylphenolj 3,5-diethylphenol, 4-ethylphenol, 2-ethyl-4~methylphenol, 2,3,6-trimethyl-`, i' phenol, 2-methyl-4-tert.butylphenol, 2,4-di-tert.butyl-phenolg 2-tert.butyl-4-methylphenol, 2,3,5,6-tetra-methylphenol, o-phenylphenol, p-phenylphenol, alfa-naphthol, i~,. j . .
beta-naphthol, phenantrol and their homologues. The ~; phenolic compounds also comprise those compounds -; which contain more than one hydroxyl group in the nucleus as well as polynuclear compounds having one or more hydroxyl groups in each nucleus. Mixtures ' :
.'' If ~
. .; ', .'~ .
, ~:.~. . `. .
. ~ , . .
`'~'"" ": "
(1 91951E;~
of phenolic compounds may also serve as the phenolic starting material.
The acetals and/or ketals as defined hereinbefore which are reacted with the phenolic compounds according to the process of the present invention may be represented by the general formu.la R1\ - ~v ~ R43 C R5 (I~
R2 ~ C \ R6 wherein R1 to R8 may each represent hydrogen or a .`
saturated or unsaturated alkyl, cycloalkyl, aryl, ~ `~
alkaryl, aralkyl or heterocyclic group with the proviso that one of the groups R3, R4 or R5 together with i oné of the groups R6, R7 or R8 may be replaced by a carbon-carbon bond (thus giving a (substituted) ~-. ~ 1,3-dioxolane compound). It should be noted that ;. ~
compounds of the general formula (I) wherein at least ~ ..
~ 15 one of the groups R1 and R2 represents a hydrogen . :
`!, atom belong to the class of the acetals. .. :
. Preference is gi~en to compounds in which the . .
above-mentioned carbon-carbon bond is present, i.e.
. compounds of the (substituted) 1,3-dioxolane type ; .
.j 20 which are represented by the general formula :. :: . ..
'~ ' i' '.' ~ , ~'.''~ ,' :':
:,! ;
~'''' '' ,"' '" ' :
:A~
: ' , ' :,`` :
'.. -1. "";, ' 104~956~
~ \ / 5 (II) R'2 ~ C - R~6 wherein R'1 to R'6 ~ay each represent hydrogen or a saturated or unsaturated alkyl, cycloalkyl, aryl, alkaryl, ralkyl or heterocyclic group.
As suitable compounds of formula (I) may be `
mentioned 2,2-dimethoxypropane, 2,2-diethoxypropane, dimethoxymethane, diethoxymethane, 2-methoxy-2-ethoxypropane and methoxy ethoxymethane.
Preferred 1,3-dioxolane compounds according to formula (II) are those in which R'l and R'2 both ; 10 represent a methyl group, R'3 to R'6 being hydrogen and/or lower alkyl groups. Most preference is given to the use of 2,2-dimethyl-1,3-dioxolane (R'l and -~
~ R~2 each being methyl and R'3 to R'6 representing - hydrogen radicals) which leads to the formation of diphenylolpropane whe reacted with phenol in the ~ -presence of an acidic catalyst accordin~ to the process of the present invention.
It will be clear that the structure of the alkyl ,. . .
radical which links together the two hydroxyarl groups ~ 20 in the bis(hydroxyaryl) compounds depends on the ;;l groups (Rl) R'l and (R2) R'2 present in the acetal .~ :
"
~,:
.~: ,, .
. . . . . .
, -, . . .
:,.~.' ~ .
..... .
.,,., ,. .:
.,.;.. - : . ~. . : . ~
104~S~9~
and/or ketal compound according to formula (I) or ~II). In other words, a change in the groups (Rl) ~
R'l and ~R2) R'2 will cause the formation of a different ;`
type of bis(hydroxyaryl) compounds. When, for instance, (Rl)R7l and ~R2) R~2 are both hydrogen radicals the product of the condensation reaction, regardless the nature of (R3) R'3 to (R8) R'6, will be a bis(hydroxyalkyl) methane compound. When phenol is thus reacted with 1,3-dioxolane according to the process of the present invention the product will be 4,5'-bishydroxyphenyl-methane, also called Bisphenol Fo Starting with an asymmetrical dioxolane, (Rl) Rll being different from ~R2) R~2, the product will be an asymmetrical bis(hydroxy-aryl)alkane.
It is also possible to prepare mixtures of bis- ~
(hydroxyaryl) compounds, for instance, mixtures of ~ -Bisphenol A and Bisphenol F, by reacting a phenolic com- ~
". . .
;~ pound (e.g. phenol) with a mixture of (substituted) 1,3-dioxolanes (e.g. 2,2-dimethyl-1,3-dioxolane and 1,3-dioxol~ane). It should be noted that, for instance in the i-; preparation of a mixture of Bisphenol A and Bisphenol F, ;
instead of 1,3-dioxolane to be reacted, also its precursor -` formaldehyde, for instance in the form of trioxane, can ~
be used, in combination with 292-dimethyl-lj3-dioxolane ~ -Reference is made in this respect to United States Patent NoO 3,920,5730 ; ',` -:~ ' ' .,'~ ; .
.' ` .;
~,. :' ,, ,',"'`, ~ : , ' ~"."
",.. .
;. , ' .
:
... .
~ - 14 - 1~4~
in whicha preferred method ~or the preparation of a mixture of Bisphenol A and Bisphenol F has been described~nd claimed.
It is appreciated that in~tead of the acetal and/or ketal, and preferably o~ the (substituted) 1,3-dioxolane according to the present invention, bis(hydroxyaryl) compounds may also be prepared by reacting a phenolic compound with a (substituted) thioacetal and/or a (substituted) thioketal compound.
When applying a thioacetal and/or a thioketal compound, one should bear in mind, however, that the incentive of a sulphur-free process is no longer present. The use of rather large amounts of volatile sulphur compounds would impair the product quality and also cause environmental problems. The same arguments are true for the addition of a volatile mercapto compound as a co-catalyst to the phenol/DMDO system.
~ The acetals, and~or ketals, and especially the ;~-;i dioxolanes to be used in the process according to the present invention may be prepared by any suitablè
method. For instance, acetone and ethyleneglycol may be reacted in the presence of an acidic catalyst such as p-toluene-sulphonic acid (J. Chem.Eng.Data .. . .
;~ 7 (19629 p, 578~. The use of acidic cation-exchange resins has also been reported in condensation reactions between ketones and monovalent alcohols such as -~
", methanol or ethanol.
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It has been found that the ~substituted? dioxolanes to be used together with a phenolic compound according to the process of the present invention, can be suitably prepared by the following ~echnique, which is reported with respect to the preparation of 2,2-dimethyl-1,3-dioxolane but which is certainly not restricted to the preparation of this compound.
2,2-Dimethyl-1,3-dioxolane ~DMD0) may be produced ~ ~
by reacting acetone and ethyleneglycol at room temperature ~-in the presence of an acidic catalyst, in particular ;
an acidic cation exchange resin, for instance Amberlyst* -15 H . After neutralization, the reaction product ~
, . :;
is distilled, preferably in three steps: ~a) removal of acetone, ~b) removal of reaction water, using ;~
, for example, cyclohexane as an auxiliary distillation I agent and ~c) removal of DMD0 product; the acetone removed in the first step and the bottom product -~
of the third step being recycled to the reactor.
It will be appreciated that the above-mentioned process for the preparation of DMD0 can be suitably ~ j :
incorporated in an integrated diphenylolpropane ~`~
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,~, exists to use ethyleneglycol precursors, for instance ethylene oxide. The use of ethylene oxide would even substantially prevent the formation of reaction ~ ;
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However, this possibility is not attractive in that large amounts of reaction heat obtained would have to be dissipated.
The process for the preparation of DMD0, and in general of the (substituted) dioxolanes may be carried out at a temperature in the range of from 0C to 120~9preferably in the range of from 10~
to 90C and most preferably at 40C. The reagents are fed over an acidic cation exchange resin. The molar ratio of the reagents to be applied is by no means critical; for instance an acetone/ethyleneglycol .
moIar ratio of 10:1 can be suitably applied as well as a molar ratio of 1:10. Preference is given to i15 a molar ratio ethyleneglycol/acetone of from 2~
to 1:2. Excellent results were obtained using a molar ratio of 2:1.
;; ~ The crude reaction mixture is first neutralized with an appropriate base such as sodium bicarbonate or c~austic soda or an aqueous solution of said compound(s). -~
;i It has been found very suitable to carry out the 'i subsequent distillation in three steps. In the first :~ step acetone is substantially removed, which may be recycled to the reactor. In the second step water produced during the reaction is removed preferably with the aid of a water-immiscible hydrocarbon as ~! ~
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an auxiliary distillation agent such as cyclohexane, hexane or benzene. In the third step DMD0 may be distilled off and sent to storage or to a subsequent diphenylolpropane reactor when produced in an integrated ;~
process. The bottoms of the third distillation step, mainly consisting of ethylene glycol are recycled -to the DMD0-reactor.
In the process for the preparation of bis(hydroxyaryl)compounds according to the present invention the phenolic compound may be reacted with the acetal and/or the ketal, for instance with a (substituted) 1,3-dioxolane compound, in stoichiometric proportions. It is preferred, however, to use higher proportions of the phenolic compound, which may serve as a diluent, thus keeping the process in the liquid state~ The molar ratio of the phenolic compound to the acetal and/or the ketal, for instance to the (substituted) 1,3-dioxolane compound in the - reaot;on may range, for example from 20:1 to 2:1, preferably between 15:1 and 8:1 and most prererably between 12:1 and 10:1.
The reaction is carried out in the presence ` of an acidic catalyst-, preferably a strong mineral acid, which may be added continuously or incrementally ,'l during the course of the operation. All of the acid ` 25 employed may be introduced directly into the reaction `-` zone or it may be admixed, in part or entirely, with ; ' : ,' j ,, ~ . . .
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one or more of the components prior to their introduction into the reactor.
As acidic catalysts may be employed, for exampleJ hydrochloric acid, sulphuric acid, acetic acid, p-toluenesulphonic acid, alkane-sulphonic acids, hydrofluoric acid, boron trifluoride complexes and other acid-acting condensing agents, such as acidic cation-exchange resins, for example Amberlyst* 15 H~. The acidic cation-exchange resins may also contain additional fixed sulphur compounds. The use of hydrochloric acid and especially of anhydrous hydrochloric acid is ;~
preferred. Materials capable of liberating an acidic agent in situ ~ -under the reaction conditions may also be employed.
Relatively small amounts of the acidic agent generally ~ -suffice to speed up materially the reaction. The amount of acidic agent required to obtain optimum results will vary to some extent ~, in accordance with the specific acidic agent, reactants and operating conditions employed. The use of the acidic agent in an amount ~ between 0.1% and 30% by weight, and preferably between 0.2% and ;~~ 20% by weight, based on the phenolic reactant, is generally satis-factory. Excellent results have been obtained using hydrochloric acid in an amount of from 2.5% to 7.5% by weight based on the molar phenol intake. When employing a normally gaseous acidic agent such as hydrogen ~;
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chloride, attainment of the desired concentration thereof in the reaction mixture, particularly at higher temperatures, is facilitated by the use of superatmospheric pressures.
The process according to the present invention may be carried out in the absence but preferably in the presence of a solventO It should be noted that the excess of phenolic compound normally used (e.g. phenol exceeding a 2-3 molar ratio towards dioxolane reactant, depending on the way of precipitating the product) is considered to behave as a solvent. -A number of solvents which may each, or in combination, replace partially or even totally the excess of phenolic compound normally applied are for instance, primary -alcohols, such as methanol, ethanol and propanol;
glycols such as ethyleneglycol, the propylene glycols, ~-butyIene glycols, ethers, for instance di-isopropylether, tetrahydrofuran, dioxan, dichloroethane and the like.
~ . .
The use of ethyleneglycol in the production of diphenylolpropane is especially preferred in that this compound acts as a very good solvent for diphenylolpropane. Ethyleneglycol will also be ~ormed in situ when 2,2-dimethyl-1,3-di- -~
^ oxolane is used in the preparation of diphenylolpropane.
The use of ethylene~lycol in an amount of from 1 to 10 moles per mole of dioxolane compound to be ; reacted has proved to be satisfactory, amounts in ,`~, '. ' ~, ,'') ~., ' : ' :
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the range of from 2 to 3 moles per mole of dioxolane compound - in addition to an excess of phenol also applied - have given very satisfying results.
The process according to the present invention may be carried out at temperatures between 20C
and 150C, and preferably at temperatures between 40C and 85C. The process may be carried out under atmospheric, subatmospheric or superatmospheric pressure.
In general the use of pressures offrom atmospheric ~ -up to 10 bar is preferred.
The process according to the present invention ~
may be carried out batchwise, or in a semi-continuous -or a continuous manner. It is preferred to carry out the process of the present invention continuously which implies that the excess phenolic compound presènt as well as the amount of acidic catalyst can substantially be recycled to the reactor, which is very advantageous in that use can be made of rather simple equipment. ~ ~`
It is also possible to use more than one reactor and to recycle the excess phenolic compound to several~
reactors. For instance, when preparing diphenylolpropane from phenol and DMD0, excess phenol as well as hydrochloric acid may be recycled to the reactor(s) and also ethyleneglycol, ~; either formed from DMD0 or originally present as solvent, may be recycled to the reactor(s) or~ if ~ ~
~` desired, to the reactor used in the production of -.'''`'' . ~.
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DMD0 from acetone and ethylene glycol when employing an integrated diphenylolpropane process.
The reactants may be introduced into the reaction zone in separate streams, and such separated streams may be independently preheated. All or part of the individual components charged to the reaction zone may also be combined, and all or a part of the resulting mixture may be preheated before introduction into the reaction zone.
i 10The time of contact between the reagents may vary and depends to some degree on the specific operating conditions employed and the nature of the charge.
Contact times between 10 minutes and 10 hours, and preferably between 15 minutes and 2 hours are generally ~ -satisfactory~ although shorter or longer contact times may be employed, if desired.
The crude bis(hydroxyaryl) compounds obtained by the process according to the present invention may be purified by a number of methods depending on whether the bis(hydroxyaryl3 compound is obtained ....
as such or in the form of an adduct. .!.
`In general it has proved to be advantageous to remove the acidic catalyst, if employed in anhydrous form, as quickly as possible in order to prevent or to diminish corrosion problems. This can be effected, ~; for instance, by stripping with the aid of inert ~................................... ; :
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hydrocarbons such as cyclohexane.
One of the working-up procedures general'y applied involves the separation of the phenolic adduct of :
the bis(hydroxyaryl) compound formed by lowering ~-the temperature. After filtration of the adduct, the mother liquor containing - in the production of diphenylol-propane - phenol, ethyleneglycol and impurities is distilled in order to obtain phenol and/or ethylene glycol, which may be recycled to the appropriate reactor(s). If desired, the adduct crystals may be combined with heated phenol and water in amounts sufficient to produce a single-phase liquid mixture -~
~:, at approximately 60C. The mixture may be cooled with gentle stirring to ambient temperature in a ; 15 :~ew hours. The adduct crystals formed are separated ::
~; by centrifuging and may be rinsed with aqueous phenol to remove entrained liquid prior to the conversion . into product. The conversion can be carried out, for instance, by heating the adduct crystals under diminished pressure to a final temperature of approximately 200C to strip the phenol component, the purified .~,, . :
;.~ product remaining behind. Reference is made in this respect to ~ritish Patent Specification No. 1,274~798.
.,", ~ During the preparation of bis-hydroxyaryl compound .
. 25 via the classical process or via the process according ,:; , ... to the present invention certain amounts of isomers .~ o~ the desired compound(s) as well as higher condensation .,., ~ .
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products are invariably formed. Thus, during the production of 2,2-di(4-hydroxyphenol)propane, also called para,para-diphenylolpropane certain amounts of ortho30rtho - as well as ortho,para-diphenylolpropane are formed.
It may be advantageous - in order to increase the yield of the desired isomer - to subject a mixture relatively rich in unwanted isomers to an isomerization treatment. This isomerization treatment can be carried out at any suitable stage in the process for the ;
production of diphenylolpropane. For instance, the mother liquor obtained after filtration of the para,para-diphe-nylolpropane product, being predominantly rich in the unwanted ortho9para-isomer can be subjected to an isomerization treatment in the presence of an acidic isomerization catalyst, for instance in a separate isomerizer.
If desired, the product obtained may be subjected to physical treatments such as prilling in order ; 20 to increase the mechanical strength. ~ `
Bis(hydroxyaryl) compounds or reaction products comprising them, are o~ value as starting or intermediate materials in the production of, ~or instance, chemical derivatives, resins, plastics, paints, lacquers, varnishes, adhesives and textile printing compounds.
~` The bis(hydroxyaryl) compounds and in particular ;'',' , ":
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diphenylolpropane may easily be converted into bis(epoxyalkyl) ethers, for instance by reacting diphenylolpropane with an epoxy haloalkane such as epichlorohydrin at temperatures in the range of from 50C to 150C, preferably in the presence of a base.
The following examples are illustrative of the present invention.
EXAMPLE I
Pre~aration of 2l2-dimeth~ 3-dioxolane (DMD0) -~
DMD0 was prepared using a continuous flow reactor containing a bed of 100 ml (measured in dry condition) of hmberlyst 15 H~ wetted with acetone. At ambient temperature a mixture of acetone (DMK) and ethyleneglycol (EG) having a fixed molar ratio EG/DMK of 2 was pumped~
over the Amberlyst catalyst bed at liquid hourly space velocity (LHSV) of 10 l feed per l catalyst per hour. The water content of the feedstock was -below 0.2%w. The reaction was carried out at atmospheric pressure. Even after 400 hours of operation no catalyst activity decline was observed. An acetone conversion of 36 mole.~ was obtained.
The reactor effluent was made alkaline by the ~` addition of 0.02%w of sodium hydroxide (added as a 10%w aqueous solution), the resulting pH of the effluent being 8.8. After removal of unconverted acetone `
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by distillation, which was recycled to the reactor, DMD0 was recovered as the hetero-azeotrope DMD0/H20 boiling at 78.5C. The organic phase obtained, mainly consisting of DMD0 and also containing a small amount of water was dried by three additions of 1%w of potassium acetate and subsequently removing the aqueous layer thus formed. DMD0 obtained in a quantitative yield with respect to acetone converted contained only 0.3%w H20. The boiling point at atmospheric pressure ' 10 was 93C.
EXAMPLE II
Pre~aration of 2~_-dimeth~ 3-dioxolane (DMD0) in the ~resence_of di~hen~lol~ro~ane DMD0 was prepared using a continuous flow reactor containing a bed of 150 ml (measured in dry condition) of Amberlyst 15H wetted with acetone. At 40C a mixture of DMK and EG having a fixed molar ratio of 1035 was pumped over the catalyst bed at a liquid -~-~ hourly space velocity of 5 1 feed per 1 catalyst per `~ hour. The EG used contained 5 %w of diphenylolpropane. ~-~
The water content of the feedstock was well below -~
0,2 %w. The reaction was carried out at atmospheric -~ ;
: . , ,-, pressure. A steady EG conversion of 29 mole% was obtained during a 400 runhours life test. No catalyst activity decline was observed in this run time.
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~ 26 - ~0~5~5f~4 The reactor effluent was made alkaline by the addition of 0.01 %w of sodiumhydroxide (added as-a 10 %w aqueous solution), the resulting pH of the effluent beng 8.5.
The alkaline reaction product was distilled in a continuous distillation column. Unconverted DMK
was taken overhead for recycle to the DMD0-producing;
reactor. Via a side-stream the DMD0/water hetero-azeotrope was collected, the two phase system obtained was separated into an organic layer which was returned to the continuous distillation column, and an aqueous phase which was distilled separately for recovery :. . of DMD0-dissolved in the water - in the form of the DMD0/water hetero~azeotrope which was returned to the continuous distillation column.
The bottom stream of the continuous distillation ~-:
. column.consisting of dry DMD0 in EG and also containing the initial diphenylolpropane was sent to the diphenylolpropane , manufacturing section.
; 20 This example clearly demonstrates that DMD0 can be suitably prepared in the presence of diphenylolpropane : which ls highly advantageous for the production of . diphenylolpropane in an ntegrated process starting .~ with the production o~ DMD0.
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~4~S1691 EXAMPLE III
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_rep_r t_on _f diphenylolpropane_fro_ ~h_n_l_a_d D D0 Into a 300 ml stirred-tank reactor made of Hastelloy* B
were introduced at room temperature 600 grams per hour of a liquid feedstock containing phenol, DMD0 and ethyleneglycol in a molar `
ratio of 10:1:2.4. Separately, gaseous anhydrous HCl was introduced into the reactor via a dip-pipe at an amount of 30 grams per hour. The reaction was carried out at substantially atmospheric pressure, the reactor being operated liquid full.
The reactor contents were stirred with a flat turbine stirrer C650 rpm). The reactor was electrically heated to mamtain a reaction temperature of 60C.
After three hours running-in, stable operation was ~ -reached and samples of the reactor contents were analysed. The -~ ~
conversion of DMD0 proved to be 90%. The diphenylolpropane ~;
produced contained 10%w of the ortho-para isomer.
EXAMPLE IV :
., , :, The experiment of Example III was repeated, except that ; the hourly throughput of the feed was 300 grams and that of gaseous 20 HCl 15 grams respectively.
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The Dl~0 conversion proved to be 95.4~ and the diphenylpropane product contained 1 o.8~ of ortho-para isomer.
EXAMPL~ V
The experiment of Example III was repeated, except that the hourly throughput of the feed was 1200 grams and that Or gaseous HCl 60 grams. The DMD0 conversion proved to be 76.7% and the diphenylol-propane product contained 11.4% of ortho-para isomer.
EXAMPL~ VI
Pre~aration o~ di~hen lolmethane from ~henol and ~- .
The experiment of Example III was repeated, except that a liquid feedstook containing phenol, dioxolane-1,3 (formaldehyde-glycol) and ethylene glycol in a molar ratio o~ 10:1:2,4 was processed. The dioxolane-1,~
conversion proved to be >99%. The selectivity to ` - diphenylolmethane isomers was 84~ and the isomer . . .
distribution towards para, para-~ orthoJ para- and ortho, ~
f ortho-diphenylolmethane, respectively was close to 1:2 1.
~XAMPL~ VII ~ ~
In a 100 ml all glass reactor a catalyst bed o~ 90 ml Amberlyst 15 H was installed. The reactor heating mantle ~i was set at 60C. A liquid feedstock containing phenol, '~ dioxolane~ and ethylene glycol in a molar ratio o~
10-1:1,6 was pumped through the catalyst bed at a liquid~
hourly space velocity (LHSV) of 1 l (l cat hr 1)~
~l The reactor effluent obtained showed a dioxolane-1,3 conversion rl o~ 97$ for the first 24 hours. The isomer distribution ~'' " ' .
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1al 49S69 towards para~ para~ h~, para- and ortho) ortho- -~
diphenylol methane~ respectively, was 36:42:22.
EXAMPLE VIII
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Isomerization of ortho, para-diphen~lol~ro~ane into ~
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Into a ~00 ml stirred tank made o~ Hastelloy B
were introduced at room temperature ~00 grams o~ a liquid feedstock containing phenol (77%w),ethyleneglycol ~ -~
(15~) and diphenylolpropane (8~ow)~ The weight ratio ortho, para- to para, para-diphenylolpropane was ~ -2 6/7 4 ~ r Separately, gaseous HCl was introduced into the reactor via a dip-pipe just above the stirrer at an amount of 15 grams per hour. The isomerization reaction was carried out at 60C under atmospheric pressure.
The reactor contents were stirred with a flat turbine stirrer at 650 rpm, the reactor being operated liquid full.
After three hours running-in the e~luent of the :
reactor was anaLyzed to determine the ortho, para-/para para-diphenylolpropane ratio. A constant value of 12/88 w/w was ~ound ~or several hours indicating that thermo-dynamic equilibrlum at 60C (ratio 9/91) was nearly reached.
A similar experiment ~ras carried out, except that a residence time of thirty mlnutes was used. The ortho, ~para-/
para, para-diphenylolpropane ~reight ratio was 16.5/83.5 w/w. `;~
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. The phenolic compounds which may be reacted with an acetal and/or a ketal, for instance, with ~, 15 a (substituted) dioxolane, in accordance with the . , -;
.~ process of the present invention comprise the broad class of phenolic compounds having at least one replaceable : ~ hydrogen atom directly bound to a nuclear carbon ~ :
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atom of the phenolic radical. By the term phenollc ~; 20 compoundsl' are meant those organic compounds which ~ . :
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- lo - 1~4~S~4 contain an aromatic radical and at least one hydroxyl group, linked directly to a carbon atom contained in the nucleus of the aromatic radical. The phenolic compounds used as starting material comprise the simplest members o~ the class, phenol, and its homologues as well as substitution products containing at least one replaceable hydrogen atom directly attached to a nuclear carbon atom of the phenolic radical; they include those compounds wherein hydrogen atoms of the aromatic nucleus have been substituted by hydrocarbon radicals, such as alkyl, cycloalkyl, aryl, alkaryl and aralkyl groups. ~`
The following examples of phenolic compounds may be given: phenol, ortho-cresol, meta-cresol, ~ 15 para-cresol, the xylenols, thymol, carvacrol, cumenol, :
2,3-diethylphenol, 2-methyl-3-ethylphenol, 2,3-di-tert.butyl-phenol, 2,4-dimethyl-3-ethylphenolj 3,5-diethylphenol, 4-ethylphenol, 2-ethyl-4~methylphenol, 2,3,6-trimethyl-`, i' phenol, 2-methyl-4-tert.butylphenol, 2,4-di-tert.butyl-phenolg 2-tert.butyl-4-methylphenol, 2,3,5,6-tetra-methylphenol, o-phenylphenol, p-phenylphenol, alfa-naphthol, i~,. j . .
beta-naphthol, phenantrol and their homologues. The ~; phenolic compounds also comprise those compounds -; which contain more than one hydroxyl group in the nucleus as well as polynuclear compounds having one or more hydroxyl groups in each nucleus. Mixtures ' :
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of phenolic compounds may also serve as the phenolic starting material.
The acetals and/or ketals as defined hereinbefore which are reacted with the phenolic compounds according to the process of the present invention may be represented by the general formu.la R1\ - ~v ~ R43 C R5 (I~
R2 ~ C \ R6 wherein R1 to R8 may each represent hydrogen or a .`
saturated or unsaturated alkyl, cycloalkyl, aryl, ~ `~
alkaryl, aralkyl or heterocyclic group with the proviso that one of the groups R3, R4 or R5 together with i oné of the groups R6, R7 or R8 may be replaced by a carbon-carbon bond (thus giving a (substituted) ~-. ~ 1,3-dioxolane compound). It should be noted that ;. ~
compounds of the general formula (I) wherein at least ~ ..
~ 15 one of the groups R1 and R2 represents a hydrogen . :
`!, atom belong to the class of the acetals. .. :
. Preference is gi~en to compounds in which the . .
above-mentioned carbon-carbon bond is present, i.e.
. compounds of the (substituted) 1,3-dioxolane type ; .
.j 20 which are represented by the general formula :. :: . ..
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~ \ / 5 (II) R'2 ~ C - R~6 wherein R'1 to R'6 ~ay each represent hydrogen or a saturated or unsaturated alkyl, cycloalkyl, aryl, alkaryl, ralkyl or heterocyclic group.
As suitable compounds of formula (I) may be `
mentioned 2,2-dimethoxypropane, 2,2-diethoxypropane, dimethoxymethane, diethoxymethane, 2-methoxy-2-ethoxypropane and methoxy ethoxymethane.
Preferred 1,3-dioxolane compounds according to formula (II) are those in which R'l and R'2 both ; 10 represent a methyl group, R'3 to R'6 being hydrogen and/or lower alkyl groups. Most preference is given to the use of 2,2-dimethyl-1,3-dioxolane (R'l and -~
~ R~2 each being methyl and R'3 to R'6 representing - hydrogen radicals) which leads to the formation of diphenylolpropane whe reacted with phenol in the ~ -presence of an acidic catalyst accordin~ to the process of the present invention.
It will be clear that the structure of the alkyl ,. . .
radical which links together the two hydroxyarl groups ~ 20 in the bis(hydroxyaryl) compounds depends on the ;;l groups (Rl) R'l and (R2) R'2 present in the acetal .~ :
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and/or ketal compound according to formula (I) or ~II). In other words, a change in the groups (Rl) ~
R'l and ~R2) R'2 will cause the formation of a different ;`
type of bis(hydroxyaryl) compounds. When, for instance, (Rl)R7l and ~R2) R~2 are both hydrogen radicals the product of the condensation reaction, regardless the nature of (R3) R'3 to (R8) R'6, will be a bis(hydroxyalkyl) methane compound. When phenol is thus reacted with 1,3-dioxolane according to the process of the present invention the product will be 4,5'-bishydroxyphenyl-methane, also called Bisphenol Fo Starting with an asymmetrical dioxolane, (Rl) Rll being different from ~R2) R~2, the product will be an asymmetrical bis(hydroxy-aryl)alkane.
It is also possible to prepare mixtures of bis- ~
(hydroxyaryl) compounds, for instance, mixtures of ~ -Bisphenol A and Bisphenol F, by reacting a phenolic com- ~
". . .
;~ pound (e.g. phenol) with a mixture of (substituted) 1,3-dioxolanes (e.g. 2,2-dimethyl-1,3-dioxolane and 1,3-dioxol~ane). It should be noted that, for instance in the i-; preparation of a mixture of Bisphenol A and Bisphenol F, ;
instead of 1,3-dioxolane to be reacted, also its precursor -` formaldehyde, for instance in the form of trioxane, can ~
be used, in combination with 292-dimethyl-lj3-dioxolane ~ -Reference is made in this respect to United States Patent NoO 3,920,5730 ; ',` -:~ ' ' .,'~ ; .
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in whicha preferred method ~or the preparation of a mixture of Bisphenol A and Bisphenol F has been described~nd claimed.
It is appreciated that in~tead of the acetal and/or ketal, and preferably o~ the (substituted) 1,3-dioxolane according to the present invention, bis(hydroxyaryl) compounds may also be prepared by reacting a phenolic compound with a (substituted) thioacetal and/or a (substituted) thioketal compound.
When applying a thioacetal and/or a thioketal compound, one should bear in mind, however, that the incentive of a sulphur-free process is no longer present. The use of rather large amounts of volatile sulphur compounds would impair the product quality and also cause environmental problems. The same arguments are true for the addition of a volatile mercapto compound as a co-catalyst to the phenol/DMDO system.
~ The acetals, and~or ketals, and especially the ;~-;i dioxolanes to be used in the process according to the present invention may be prepared by any suitablè
method. For instance, acetone and ethyleneglycol may be reacted in the presence of an acidic catalyst such as p-toluene-sulphonic acid (J. Chem.Eng.Data .. . .
;~ 7 (19629 p, 578~. The use of acidic cation-exchange resins has also been reported in condensation reactions between ketones and monovalent alcohols such as -~
", methanol or ethanol.
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It has been found that the ~substituted? dioxolanes to be used together with a phenolic compound according to the process of the present invention, can be suitably prepared by the following ~echnique, which is reported with respect to the preparation of 2,2-dimethyl-1,3-dioxolane but which is certainly not restricted to the preparation of this compound.
2,2-Dimethyl-1,3-dioxolane ~DMD0) may be produced ~ ~
by reacting acetone and ethyleneglycol at room temperature ~-in the presence of an acidic catalyst, in particular ;
an acidic cation exchange resin, for instance Amberlyst* -15 H . After neutralization, the reaction product ~
, . :;
is distilled, preferably in three steps: ~a) removal of acetone, ~b) removal of reaction water, using ;~
, for example, cyclohexane as an auxiliary distillation I agent and ~c) removal of DMD0 product; the acetone removed in the first step and the bottom product -~
of the third step being recycled to the reactor.
It will be appreciated that the above-mentioned process for the preparation of DMD0 can be suitably ~ j :
incorporated in an integrated diphenylolpropane ~`~
;. , :
plant.
.. ~ , .
~ It should further be noted that the possibility -;
,~, exists to use ethyleneglycol precursors, for instance ethylene oxide. The use of ethylene oxide would even substantially prevent the formation of reaction ~ ;
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However, this possibility is not attractive in that large amounts of reaction heat obtained would have to be dissipated.
The process for the preparation of DMD0, and in general of the (substituted) dioxolanes may be carried out at a temperature in the range of from 0C to 120~9preferably in the range of from 10~
to 90C and most preferably at 40C. The reagents are fed over an acidic cation exchange resin. The molar ratio of the reagents to be applied is by no means critical; for instance an acetone/ethyleneglycol .
moIar ratio of 10:1 can be suitably applied as well as a molar ratio of 1:10. Preference is given to i15 a molar ratio ethyleneglycol/acetone of from 2~
to 1:2. Excellent results were obtained using a molar ratio of 2:1.
;; ~ The crude reaction mixture is first neutralized with an appropriate base such as sodium bicarbonate or c~austic soda or an aqueous solution of said compound(s). -~
;i It has been found very suitable to carry out the 'i subsequent distillation in three steps. In the first :~ step acetone is substantially removed, which may be recycled to the reactor. In the second step water produced during the reaction is removed preferably with the aid of a water-immiscible hydrocarbon as ~! ~
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an auxiliary distillation agent such as cyclohexane, hexane or benzene. In the third step DMD0 may be distilled off and sent to storage or to a subsequent diphenylolpropane reactor when produced in an integrated ;~
process. The bottoms of the third distillation step, mainly consisting of ethylene glycol are recycled -to the DMD0-reactor.
In the process for the preparation of bis(hydroxyaryl)compounds according to the present invention the phenolic compound may be reacted with the acetal and/or the ketal, for instance with a (substituted) 1,3-dioxolane compound, in stoichiometric proportions. It is preferred, however, to use higher proportions of the phenolic compound, which may serve as a diluent, thus keeping the process in the liquid state~ The molar ratio of the phenolic compound to the acetal and/or the ketal, for instance to the (substituted) 1,3-dioxolane compound in the - reaot;on may range, for example from 20:1 to 2:1, preferably between 15:1 and 8:1 and most prererably between 12:1 and 10:1.
The reaction is carried out in the presence ` of an acidic catalyst-, preferably a strong mineral acid, which may be added continuously or incrementally ,'l during the course of the operation. All of the acid ` 25 employed may be introduced directly into the reaction `-` zone or it may be admixed, in part or entirely, with ; ' : ,' j ,, ~ . . .
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one or more of the components prior to their introduction into the reactor.
As acidic catalysts may be employed, for exampleJ hydrochloric acid, sulphuric acid, acetic acid, p-toluenesulphonic acid, alkane-sulphonic acids, hydrofluoric acid, boron trifluoride complexes and other acid-acting condensing agents, such as acidic cation-exchange resins, for example Amberlyst* 15 H~. The acidic cation-exchange resins may also contain additional fixed sulphur compounds. The use of hydrochloric acid and especially of anhydrous hydrochloric acid is ;~
preferred. Materials capable of liberating an acidic agent in situ ~ -under the reaction conditions may also be employed.
Relatively small amounts of the acidic agent generally ~ -suffice to speed up materially the reaction. The amount of acidic agent required to obtain optimum results will vary to some extent ~, in accordance with the specific acidic agent, reactants and operating conditions employed. The use of the acidic agent in an amount ~ between 0.1% and 30% by weight, and preferably between 0.2% and ;~~ 20% by weight, based on the phenolic reactant, is generally satis-factory. Excellent results have been obtained using hydrochloric acid in an amount of from 2.5% to 7.5% by weight based on the molar phenol intake. When employing a normally gaseous acidic agent such as hydrogen ~;
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chloride, attainment of the desired concentration thereof in the reaction mixture, particularly at higher temperatures, is facilitated by the use of superatmospheric pressures.
The process according to the present invention may be carried out in the absence but preferably in the presence of a solventO It should be noted that the excess of phenolic compound normally used (e.g. phenol exceeding a 2-3 molar ratio towards dioxolane reactant, depending on the way of precipitating the product) is considered to behave as a solvent. -A number of solvents which may each, or in combination, replace partially or even totally the excess of phenolic compound normally applied are for instance, primary -alcohols, such as methanol, ethanol and propanol;
glycols such as ethyleneglycol, the propylene glycols, ~-butyIene glycols, ethers, for instance di-isopropylether, tetrahydrofuran, dioxan, dichloroethane and the like.
~ . .
The use of ethyleneglycol in the production of diphenylolpropane is especially preferred in that this compound acts as a very good solvent for diphenylolpropane. Ethyleneglycol will also be ~ormed in situ when 2,2-dimethyl-1,3-di- -~
^ oxolane is used in the preparation of diphenylolpropane.
The use of ethylene~lycol in an amount of from 1 to 10 moles per mole of dioxolane compound to be ; reacted has proved to be satisfactory, amounts in ,`~, '. ' ~, ,'') ~., ' : ' :
: .
, .. , ~ ,, ~04~
the range of from 2 to 3 moles per mole of dioxolane compound - in addition to an excess of phenol also applied - have given very satisfying results.
The process according to the present invention may be carried out at temperatures between 20C
and 150C, and preferably at temperatures between 40C and 85C. The process may be carried out under atmospheric, subatmospheric or superatmospheric pressure.
In general the use of pressures offrom atmospheric ~ -up to 10 bar is preferred.
The process according to the present invention ~
may be carried out batchwise, or in a semi-continuous -or a continuous manner. It is preferred to carry out the process of the present invention continuously which implies that the excess phenolic compound presènt as well as the amount of acidic catalyst can substantially be recycled to the reactor, which is very advantageous in that use can be made of rather simple equipment. ~ ~`
It is also possible to use more than one reactor and to recycle the excess phenolic compound to several~
reactors. For instance, when preparing diphenylolpropane from phenol and DMD0, excess phenol as well as hydrochloric acid may be recycled to the reactor(s) and also ethyleneglycol, ~; either formed from DMD0 or originally present as solvent, may be recycled to the reactor(s) or~ if ~ ~
~` desired, to the reactor used in the production of -.'''`'' . ~.
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DMD0 from acetone and ethylene glycol when employing an integrated diphenylolpropane process.
The reactants may be introduced into the reaction zone in separate streams, and such separated streams may be independently preheated. All or part of the individual components charged to the reaction zone may also be combined, and all or a part of the resulting mixture may be preheated before introduction into the reaction zone.
i 10The time of contact between the reagents may vary and depends to some degree on the specific operating conditions employed and the nature of the charge.
Contact times between 10 minutes and 10 hours, and preferably between 15 minutes and 2 hours are generally ~ -satisfactory~ although shorter or longer contact times may be employed, if desired.
The crude bis(hydroxyaryl) compounds obtained by the process according to the present invention may be purified by a number of methods depending on whether the bis(hydroxyaryl3 compound is obtained ....
as such or in the form of an adduct. .!.
`In general it has proved to be advantageous to remove the acidic catalyst, if employed in anhydrous form, as quickly as possible in order to prevent or to diminish corrosion problems. This can be effected, ~; for instance, by stripping with the aid of inert ~................................... ; :
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hydrocarbons such as cyclohexane.
One of the working-up procedures general'y applied involves the separation of the phenolic adduct of :
the bis(hydroxyaryl) compound formed by lowering ~-the temperature. After filtration of the adduct, the mother liquor containing - in the production of diphenylol-propane - phenol, ethyleneglycol and impurities is distilled in order to obtain phenol and/or ethylene glycol, which may be recycled to the appropriate reactor(s). If desired, the adduct crystals may be combined with heated phenol and water in amounts sufficient to produce a single-phase liquid mixture -~
~:, at approximately 60C. The mixture may be cooled with gentle stirring to ambient temperature in a ; 15 :~ew hours. The adduct crystals formed are separated ::
~; by centrifuging and may be rinsed with aqueous phenol to remove entrained liquid prior to the conversion . into product. The conversion can be carried out, for instance, by heating the adduct crystals under diminished pressure to a final temperature of approximately 200C to strip the phenol component, the purified .~,, . :
;.~ product remaining behind. Reference is made in this respect to ~ritish Patent Specification No. 1,274~798.
.,", ~ During the preparation of bis-hydroxyaryl compound .
. 25 via the classical process or via the process according ,:; , ... to the present invention certain amounts of isomers .~ o~ the desired compound(s) as well as higher condensation .,., ~ .
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products are invariably formed. Thus, during the production of 2,2-di(4-hydroxyphenol)propane, also called para,para-diphenylolpropane certain amounts of ortho30rtho - as well as ortho,para-diphenylolpropane are formed.
It may be advantageous - in order to increase the yield of the desired isomer - to subject a mixture relatively rich in unwanted isomers to an isomerization treatment. This isomerization treatment can be carried out at any suitable stage in the process for the ;
production of diphenylolpropane. For instance, the mother liquor obtained after filtration of the para,para-diphe-nylolpropane product, being predominantly rich in the unwanted ortho9para-isomer can be subjected to an isomerization treatment in the presence of an acidic isomerization catalyst, for instance in a separate isomerizer.
If desired, the product obtained may be subjected to physical treatments such as prilling in order ; 20 to increase the mechanical strength. ~ `
Bis(hydroxyaryl) compounds or reaction products comprising them, are o~ value as starting or intermediate materials in the production of, ~or instance, chemical derivatives, resins, plastics, paints, lacquers, varnishes, adhesives and textile printing compounds.
~` The bis(hydroxyaryl) compounds and in particular ;'',' , ":
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.
.
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diphenylolpropane may easily be converted into bis(epoxyalkyl) ethers, for instance by reacting diphenylolpropane with an epoxy haloalkane such as epichlorohydrin at temperatures in the range of from 50C to 150C, preferably in the presence of a base.
The following examples are illustrative of the present invention.
EXAMPLE I
Pre~aration of 2l2-dimeth~ 3-dioxolane (DMD0) -~
DMD0 was prepared using a continuous flow reactor containing a bed of 100 ml (measured in dry condition) of hmberlyst 15 H~ wetted with acetone. At ambient temperature a mixture of acetone (DMK) and ethyleneglycol (EG) having a fixed molar ratio EG/DMK of 2 was pumped~
over the Amberlyst catalyst bed at liquid hourly space velocity (LHSV) of 10 l feed per l catalyst per hour. The water content of the feedstock was -below 0.2%w. The reaction was carried out at atmospheric pressure. Even after 400 hours of operation no catalyst activity decline was observed. An acetone conversion of 36 mole.~ was obtained.
The reactor effluent was made alkaline by the ~` addition of 0.02%w of sodium hydroxide (added as a 10%w aqueous solution), the resulting pH of the effluent being 8.8. After removal of unconverted acetone `
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~ - 25 -~O'q~
by distillation, which was recycled to the reactor, DMD0 was recovered as the hetero-azeotrope DMD0/H20 boiling at 78.5C. The organic phase obtained, mainly consisting of DMD0 and also containing a small amount of water was dried by three additions of 1%w of potassium acetate and subsequently removing the aqueous layer thus formed. DMD0 obtained in a quantitative yield with respect to acetone converted contained only 0.3%w H20. The boiling point at atmospheric pressure ' 10 was 93C.
EXAMPLE II
Pre~aration of 2~_-dimeth~ 3-dioxolane (DMD0) in the ~resence_of di~hen~lol~ro~ane DMD0 was prepared using a continuous flow reactor containing a bed of 150 ml (measured in dry condition) of Amberlyst 15H wetted with acetone. At 40C a mixture of DMK and EG having a fixed molar ratio of 1035 was pumped over the catalyst bed at a liquid -~-~ hourly space velocity of 5 1 feed per 1 catalyst per `~ hour. The EG used contained 5 %w of diphenylolpropane. ~-~
The water content of the feedstock was well below -~
0,2 %w. The reaction was carried out at atmospheric -~ ;
: . , ,-, pressure. A steady EG conversion of 29 mole% was obtained during a 400 runhours life test. No catalyst activity decline was observed in this run time.
!, I
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~ 26 - ~0~5~5f~4 The reactor effluent was made alkaline by the addition of 0.01 %w of sodiumhydroxide (added as-a 10 %w aqueous solution), the resulting pH of the effluent beng 8.5.
The alkaline reaction product was distilled in a continuous distillation column. Unconverted DMK
was taken overhead for recycle to the DMD0-producing;
reactor. Via a side-stream the DMD0/water hetero-azeotrope was collected, the two phase system obtained was separated into an organic layer which was returned to the continuous distillation column, and an aqueous phase which was distilled separately for recovery :. . of DMD0-dissolved in the water - in the form of the DMD0/water hetero~azeotrope which was returned to the continuous distillation column.
The bottom stream of the continuous distillation ~-:
. column.consisting of dry DMD0 in EG and also containing the initial diphenylolpropane was sent to the diphenylolpropane , manufacturing section.
; 20 This example clearly demonstrates that DMD0 can be suitably prepared in the presence of diphenylolpropane : which ls highly advantageous for the production of . diphenylolpropane in an ntegrated process starting .~ with the production o~ DMD0.
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~4~S1691 EXAMPLE III
:
_rep_r t_on _f diphenylolpropane_fro_ ~h_n_l_a_d D D0 Into a 300 ml stirred-tank reactor made of Hastelloy* B
were introduced at room temperature 600 grams per hour of a liquid feedstock containing phenol, DMD0 and ethyleneglycol in a molar `
ratio of 10:1:2.4. Separately, gaseous anhydrous HCl was introduced into the reactor via a dip-pipe at an amount of 30 grams per hour. The reaction was carried out at substantially atmospheric pressure, the reactor being operated liquid full.
The reactor contents were stirred with a flat turbine stirrer C650 rpm). The reactor was electrically heated to mamtain a reaction temperature of 60C.
After three hours running-in, stable operation was ~ -reached and samples of the reactor contents were analysed. The -~ ~
conversion of DMD0 proved to be 90%. The diphenylolpropane ~;
produced contained 10%w of the ortho-para isomer.
EXAMPLE IV :
., , :, The experiment of Example III was repeated, except that ; the hourly throughput of the feed was 300 grams and that of gaseous 20 HCl 15 grams respectively.
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The Dl~0 conversion proved to be 95.4~ and the diphenylpropane product contained 1 o.8~ of ortho-para isomer.
EXAMPL~ V
The experiment of Example III was repeated, except that the hourly throughput of the feed was 1200 grams and that Or gaseous HCl 60 grams. The DMD0 conversion proved to be 76.7% and the diphenylol-propane product contained 11.4% of ortho-para isomer.
EXAMPL~ VI
Pre~aration o~ di~hen lolmethane from ~henol and ~- .
The experiment of Example III was repeated, except that a liquid feedstook containing phenol, dioxolane-1,3 (formaldehyde-glycol) and ethylene glycol in a molar ratio o~ 10:1:2,4 was processed. The dioxolane-1,~
conversion proved to be >99%. The selectivity to ` - diphenylolmethane isomers was 84~ and the isomer . . .
distribution towards para, para-~ orthoJ para- and ortho, ~
f ortho-diphenylolmethane, respectively was close to 1:2 1.
~XAMPL~ VII ~ ~
In a 100 ml all glass reactor a catalyst bed o~ 90 ml Amberlyst 15 H was installed. The reactor heating mantle ~i was set at 60C. A liquid feedstock containing phenol, '~ dioxolane~ and ethylene glycol in a molar ratio o~
10-1:1,6 was pumped through the catalyst bed at a liquid~
hourly space velocity (LHSV) of 1 l (l cat hr 1)~
~l The reactor effluent obtained showed a dioxolane-1,3 conversion rl o~ 97$ for the first 24 hours. The isomer distribution ~'' " ' .
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, , . .: .:
.
1al 49S69 towards para~ para~ h~, para- and ortho) ortho- -~
diphenylol methane~ respectively, was 36:42:22.
EXAMPLE VIII
__ .
Isomerization of ortho, para-diphen~lol~ro~ane into ~
~1 " .
Into a ~00 ml stirred tank made o~ Hastelloy B
were introduced at room temperature ~00 grams o~ a liquid feedstock containing phenol (77%w),ethyleneglycol ~ -~
(15~) and diphenylolpropane (8~ow)~ The weight ratio ortho, para- to para, para-diphenylolpropane was ~ -2 6/7 4 ~ r Separately, gaseous HCl was introduced into the reactor via a dip-pipe just above the stirrer at an amount of 15 grams per hour. The isomerization reaction was carried out at 60C under atmospheric pressure.
The reactor contents were stirred with a flat turbine stirrer at 650 rpm, the reactor being operated liquid full.
After three hours running-in the e~luent of the :
reactor was anaLyzed to determine the ortho, para-/para para-diphenylolpropane ratio. A constant value of 12/88 w/w was ~ound ~or several hours indicating that thermo-dynamic equilibrlum at 60C (ratio 9/91) was nearly reached.
A similar experiment ~ras carried out, except that a residence time of thirty mlnutes was used. The ortho, ~para-/
para, para-diphenylolpropane ~reight ratio was 16.5/83.5 w/w. `;~
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Claims (14)
PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for the preparation of bis(hydroxyaryl) compounds by reacting a phenolic compound with an oxygen compound in the presence of an acidic condensation catalyst wherein the oxygen compound has the general formula:- (II) wherein R'1 and R'2 may each represent hydrogen or a saturated or unsaturated alkyl group and R'3 to R'6 may each represent hydrogen or a saturated or unsaturated alkyl, cycloalkyl, aryl, alkaryl or aralkyl group.
2. A process as claimed in claim 1, wherein the compound II is 1,3-dioxolane.
3. A process as claimed in claim 1, wherein the compound (II) is 2,2-dimethyldioxolane.
4. A process as claimed in claim 1, wherein as phenolic reactant phenol, a cresol or a xylenol is used.
5. A process as claimed in claim 1, wherein the phenolic reactant and the acetal and/or ketal are used in a molar ratio of from 20:1 to 2:1.
6. A process as claimed in claim 1, wherein the phenolic reactant and the acetal and/or ketal are reacted in the presence of an acidic condensation catalyst in an amount in the range of from 0.1% to 30%w calculated on total mixture.
7. A process as claimed in claim 6, wherein hydrochloric acid or an acidic cation-exchange resin is used as the acidic condensation catalyst.
8. A process as claimed in claim 1, wherein ethylene glycol is used as an additional solvent.
9. A process as claimed in claim 8, wherein the process is carried out using 1 to 10 moles of ethylene glycol per mole of acetal and/or ketal.
10. A process as claimed in claim 1, wherein the reaction is carried out at a temperature in the range of from 20°C to 150°C.
11. A process as claimed in claim 1, wherein the reaction is carried out at a pressure of from atmospheric up to 10 bar.
12. A process as claimed in claim 1, wherein the time of contact between the reactants is between 10 minutes and 10 hours.
13. A process as claimed in claim 1, wherein the process is carried out in a continuous manner.
14. A process as claimed in claim 1, wherein the process is integra-ted with a process for the production of the acetal and/or ketal to be used as a starting material.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB2783673A GB1470759A (en) | 1973-06-12 | 1973-06-12 | Process for the preparation of bis-hydroxyaryl-compounds |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1049564A true CA1049564A (en) | 1979-02-27 |
Family
ID=10266096
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA200,733A Expired CA1049564A (en) | 1973-06-12 | 1974-05-24 | Process for the preparation of bis(hydroxyaryl) compounds |
Country Status (14)
| Country | Link |
|---|---|
| JP (1) | JPS5014662A (en) |
| BE (1) | BE816134A (en) |
| CA (1) | CA1049564A (en) |
| CS (1) | CS181761B2 (en) |
| DD (1) | DD111893A5 (en) |
| DE (1) | DE2427881A1 (en) |
| ES (1) | ES427137A1 (en) |
| FR (1) | FR2233305B1 (en) |
| GB (1) | GB1470759A (en) |
| IT (1) | IT1014874B (en) |
| NL (1) | NL7407722A (en) |
| PL (1) | PL97499B1 (en) |
| RO (1) | RO68407A (en) |
| ZA (1) | ZA743671B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2457272A1 (en) * | 1979-05-23 | 1980-12-19 | Gen Electric | High purity bisphenol prodn. in high yield - by reaction of phenol and cpd. contg. ether linkage in presence of acid condensing agent |
| JPH07115542B2 (en) * | 1985-12-20 | 1995-12-13 | 富士写真フイルム株式会社 | Recording material using bisphenol compound |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1329787A (en) * | 1961-06-12 | 1963-06-14 | Ici Ltd | Production and application of tetraphenols |
-
1973
- 1973-06-12 GB GB2783673A patent/GB1470759A/en not_active Expired
-
1974
- 1974-05-24 CA CA200,733A patent/CA1049564A/en not_active Expired
- 1974-06-07 IT IT23746/74A patent/IT1014874B/en active
- 1974-06-10 ES ES427137A patent/ES427137A1/en not_active Expired
- 1974-06-10 DE DE19742427881 patent/DE2427881A1/en not_active Withdrawn
- 1974-06-10 RO RO7479103A patent/RO68407A/en unknown
- 1974-06-10 CS CS7400004102A patent/CS181761B2/en unknown
- 1974-06-10 JP JP49065116A patent/JPS5014662A/ja active Pending
- 1974-06-10 ZA ZA00743671A patent/ZA743671B/en unknown
- 1974-06-10 NL NL7407722A patent/NL7407722A/xx not_active Application Discontinuation
- 1974-06-10 BE BE145256A patent/BE816134A/en unknown
- 1974-06-10 PL PL1974171805A patent/PL97499B1/en unknown
- 1974-06-10 FR FR7420010A patent/FR2233305B1/fr not_active Expired
- 1974-06-11 DD DD179087A patent/DD111893A5/xx unknown
Also Published As
| Publication number | Publication date |
|---|---|
| FR2233305A1 (en) | 1975-01-10 |
| DD111893A5 (en) | 1975-03-12 |
| PL97499B1 (en) | 1978-02-28 |
| ES427137A1 (en) | 1976-07-16 |
| AU6994374A (en) | 1975-12-11 |
| RO68407A (en) | 1980-06-15 |
| NL7407722A (en) | 1974-12-16 |
| FR2233305B1 (en) | 1978-01-13 |
| GB1470759A (en) | 1977-04-21 |
| BE816134A (en) | 1974-12-10 |
| CS181761B2 (en) | 1978-03-31 |
| ZA743671B (en) | 1975-08-27 |
| DE2427881A1 (en) | 1975-01-09 |
| IT1014874B (en) | 1977-04-30 |
| JPS5014662A (en) | 1975-02-15 |
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