CA1118433A - Preparation of polyglycidyl ethers of polyhydric phenols - Google Patents
Preparation of polyglycidyl ethers of polyhydric phenolsInfo
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- CA1118433A CA1118433A CA000304960A CA304960A CA1118433A CA 1118433 A CA1118433 A CA 1118433A CA 000304960 A CA000304960 A CA 000304960A CA 304960 A CA304960 A CA 304960A CA 1118433 A CA1118433 A CA 1118433A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
- C07D303/18—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by etherified hydroxyl radicals
- C07D303/20—Ethers with hydroxy compounds containing no oxirane rings
- C07D303/24—Ethers with hydroxy compounds containing no oxirane rings with polyhydroxy compounds
Abstract
ABSTRACT
Process for the preparation of a polyglycidyl ether of a polyhydric phenol, comprising the steps of reacting the polyhydric phenol with from 2.5 to 10 moles an epihalohydrin per hydroxy equivalent in the presence of a condensation catalyst, water, and an oxygen-containing volatile organic solvent, and de-hydrohalogenating with aqueous alkali metal hydroxide, with separation of aqueous phase and organic phase in one or more stages and recovery of the polyglycidyl ether from the last organic phase, wherein at least part of at least one separated aqueous is recycled to an earlier stage of the process.
Process for the preparation of a polyglycidyl ether of a polyhydric phenol, comprising the steps of reacting the polyhydric phenol with from 2.5 to 10 moles an epihalohydrin per hydroxy equivalent in the presence of a condensation catalyst, water, and an oxygen-containing volatile organic solvent, and de-hydrohalogenating with aqueous alkali metal hydroxide, with separation of aqueous phase and organic phase in one or more stages and recovery of the polyglycidyl ether from the last organic phase, wherein at least part of at least one separated aqueous is recycled to an earlier stage of the process.
Description
~1~8~33 PREPARATION OF POLYGLYCIDYI. ETHERS OF
POLYHYDRIC PHENOLS
The invention is concerned with a process for the preparation of polyglycidyl ethers of polyhydric phenols and with the polyglycidyl ethers so prepared.
It is known that polyglycidyl ethers can be prepared by reaction of an epihalohydrin with a polyhydric phenol~ for example, diphenylol methane, novola~$,tetraphenylol ethane, and in particular diphenylo propane~ which is also known as bisphenol A, or 2,2-bis(4-hydroxyphenyl~propane. Diglycidyl ethers of the latter can be represented by the formula:-CH2_CH_CH2-O-R-O~CH2-,CH-CH2-O R ~n 2 \ / 2 wherein n is a number having an average value of from 0 to 15, and R is the hydrocarbon residue of the dihydric phenol, that is the group of formula:-Q ~ ( II~
' An important class of such diglycidyl ethers arethe liquid grades - the technical products of formula I which are liquid at room temperature; therein the average value of n is low, preferably below 0.25, and ideally is 0. In theory such liquid diglycidyl ethers should have epoxide equivalent weights equal to half of their molecular weights but in practice they tend to be higher, for example due to the formation of poly-meric by-products, or hydrolysis of glycidyl end groups.
It is well known that such diglycidyl ethers may be prepared by reacting the dihydric phenol with an epihalohydrin such as epichlorohydrin, in the presence of an aqueous solution of an ionizable hydroxide, for example an alkali-metal hydroxide such as sodium hydroxide; it is also known that such reactions can be carried out in the presence of an oxygen-containing volatile organic solvent such as a ketone (acetone) or an alcohol (isopropanol) (U.S. 2,848,435; U.S. 2,986,551/2 and U.S. 3,069,434. It is also well known that the use of a molar excess of epihalohydrin such as from 5 to 20 moles for each mole of dihydric phenol, reduces the formation of products of formula I wherein n is higher then zero.
The reaction, wherein an excess of epichlorohydrin and sodium hydroxide are used, may be represented by the equation:-
POLYHYDRIC PHENOLS
The invention is concerned with a process for the preparation of polyglycidyl ethers of polyhydric phenols and with the polyglycidyl ethers so prepared.
It is known that polyglycidyl ethers can be prepared by reaction of an epihalohydrin with a polyhydric phenol~ for example, diphenylol methane, novola~$,tetraphenylol ethane, and in particular diphenylo propane~ which is also known as bisphenol A, or 2,2-bis(4-hydroxyphenyl~propane. Diglycidyl ethers of the latter can be represented by the formula:-CH2_CH_CH2-O-R-O~CH2-,CH-CH2-O R ~n 2 \ / 2 wherein n is a number having an average value of from 0 to 15, and R is the hydrocarbon residue of the dihydric phenol, that is the group of formula:-Q ~ ( II~
' An important class of such diglycidyl ethers arethe liquid grades - the technical products of formula I which are liquid at room temperature; therein the average value of n is low, preferably below 0.25, and ideally is 0. In theory such liquid diglycidyl ethers should have epoxide equivalent weights equal to half of their molecular weights but in practice they tend to be higher, for example due to the formation of poly-meric by-products, or hydrolysis of glycidyl end groups.
It is well known that such diglycidyl ethers may be prepared by reacting the dihydric phenol with an epihalohydrin such as epichlorohydrin, in the presence of an aqueous solution of an ionizable hydroxide, for example an alkali-metal hydroxide such as sodium hydroxide; it is also known that such reactions can be carried out in the presence of an oxygen-containing volatile organic solvent such as a ketone (acetone) or an alcohol (isopropanol) (U.S. 2,848,435; U.S. 2,986,551/2 and U.S. 3,069,434. It is also well known that the use of a molar excess of epihalohydrin such as from 5 to 20 moles for each mole of dihydric phenol, reduces the formation of products of formula I wherein n is higher then zero.
The reaction, wherein an excess of epichlorohydrin and sodium hydroxide are used, may be represented by the equation:-
2 C~ -~H-CH2-Cl + HO-R-OH + 2 NaOH >
o CH\2 /CH C~12-O-R-O-CH2-C~I-CH2 1 2H20 1 2NaCl (III) wherein R is as defined above.
It is generally accepted that the above reaction pro-ceeds via two steps. The first step, sometimes referred to as the condensation reaction, results mainly in the formation of dichlorohydrins and may be represented by the equation:-2 CH2-CH-CH2-Cl ~ HO-R-OH _aO~ CH2-CH-CH2-O-R-o-CH2-CH-CH2 O Cl OH OH Cl (IV) and the second step, sometimes referred to as the dehydrochlo-rination reaction, results mainly in the removal of hydrogen chloride from the dichlorohydrins and may be represented by the equation:-CH2-CH-CH2-O-R-O-CH2-,cH-c,H2 ~ 2 NaOH
Cl OH OH Cl 2/CH CH2 R CH2 C\H /H2 + 2 NaCl ~ 2H2 (V) O O
In the reaction, sodium hydroxide functions both as the condensation catalyst and as the dehydrohalogenating agent as do ionizable hydroxides in general. It can be seen that, if no products of formula I wherein n is 1 or higher are formed, the reaction requires 2 moles of sodium hydroxide for each mole of dihydric phenol although in practice a stoichiometric ~ i excess is mostly used.
It is known to carry out reaction III in such a way that these two steps occur concomittently but it has also been proposed to carry out the reaction in 5 stages in which the condensation reaction takes place to a large extent before the dehydrohalogenation reaction takes place. In such multistage processes it has been proposed to stage the addition of the ionizable hydroxide or to use in the first stage a different condensation catalyst, such as an ionizable chloride, bromide, iodide, sulphide or cyanide, which is not capable of acting, to any appreciable extent, as a dehydrohalogenating agent (U.K. 897,744; U.S.
2,943,095/6; U.S. 3,023,225; U.S. 3,069,434; U.S.
o CH\2 /CH C~12-O-R-O-CH2-C~I-CH2 1 2H20 1 2NaCl (III) wherein R is as defined above.
It is generally accepted that the above reaction pro-ceeds via two steps. The first step, sometimes referred to as the condensation reaction, results mainly in the formation of dichlorohydrins and may be represented by the equation:-2 CH2-CH-CH2-Cl ~ HO-R-OH _aO~ CH2-CH-CH2-O-R-o-CH2-CH-CH2 O Cl OH OH Cl (IV) and the second step, sometimes referred to as the dehydrochlo-rination reaction, results mainly in the removal of hydrogen chloride from the dichlorohydrins and may be represented by the equation:-CH2-CH-CH2-O-R-O-CH2-,cH-c,H2 ~ 2 NaOH
Cl OH OH Cl 2/CH CH2 R CH2 C\H /H2 + 2 NaCl ~ 2H2 (V) O O
In the reaction, sodium hydroxide functions both as the condensation catalyst and as the dehydrohalogenating agent as do ionizable hydroxides in general. It can be seen that, if no products of formula I wherein n is 1 or higher are formed, the reaction requires 2 moles of sodium hydroxide for each mole of dihydric phenol although in practice a stoichiometric ~ i excess is mostly used.
It is known to carry out reaction III in such a way that these two steps occur concomittently but it has also been proposed to carry out the reaction in 5 stages in which the condensation reaction takes place to a large extent before the dehydrohalogenation reaction takes place. In such multistage processes it has been proposed to stage the addition of the ionizable hydroxide or to use in the first stage a different condensation catalyst, such as an ionizable chloride, bromide, iodide, sulphide or cyanide, which is not capable of acting, to any appreciable extent, as a dehydrohalogenating agent (U.K. 897,744; U.S.
2,943,095/6; U.S. 3,023,225; U.S. 3,069,434; U.S.
3,309,384; U.S. 3,221,032 and U.S. 3,352,825).
It should also be noted that the above reaction produces water and sodium chloride, and processes are known wherein the sodium chloride is allowed to dis-solve in water and the brine is separated from the organic phase. The brine, after the removal of any unreacted epichlorohydrin and any oxygen-containing volatile organic solvent therefrom, is usually dis-carded although it has been proposed to use some of it as a wàshing medium for the final reaction mixture (U.S. 2,986,551). It has also been proposed to carry out the dehydrochlorination reaction in two stages with an intermediate brine removal stage (U.S.
3,023,225; U.S. 3,069,434 and U.S. 4,017,523) or an intermediate epihalohydrin recovery stage (U.S.
2,841,595; U.K. 1,173,191~. It has also been proposed to remove unreacted epichlorohydrin after the conden-sation reaction but before the dehydrohalogenationreackion (U.K. 897,744).
The known processes for the production of poly-glycidyl ethers usually suffer from one or more dis-advantages such as the formation of an undesirable amount of by-products e.g. polymeric compounds, epihalohydrin hydrolysis products, solvent-derived products etc.; the formation of polyglycidyl ethers having an unacceptably high saponifiable chlorine content; the loss of reactants and products in the discarded brine, and the difficulty in operating the process continually. The brine or brines contain usually, apart from some epichlorohydrin and solvent, resinous contaminants, which on an attempt to recover the valuable volatile components by stripping di~tillation, tend to contaminate the stripper column.
The reactions are sometimes extremely slow, and, in an effort to improve the speed by raising the temperature, side reactions can greatly afflict economic recovery of epichlorohydrin, or the quality of the final resin.
We have now found a new process for the preparation of polyglycidyl ethers which is substantial-ly free of the above disadvantages. The new process allows easy operation, high recovery of solvent and epihalohydrin, production of polyglycldyl ethers of high quality, and of effluent low in alkalinity and in organic contaminants.
The new process is a multi-stage process in which at some stages a brine is separated and one or more of these brines are recycled to an earlier stage in the process; the new process may be carried out as a continuous process or as a multi-stage batch process.
The invention can be defined as a process for the preparation of a polyglycidyl ether of a polyhydric phenol wherein the polyhydric phenol is reacted with from 2.5 to 10 moles of an epihalohydrin per phenolic hydroxy equivalent in the presence of a condensation catalyst, water and a volatile organic solvent, and the reaction product is reacted with aqueous alkali metal hydroxide, with separation of aqueous phase and organic phase in one or more stages and recovery of the polyglycidyl ether from the last organic phase, wherein at least part of at least one separated aqueous phaBe iB recycled to an earlier stage of the process.
In a further definition the invention provides a process for the preparation of polyglycidyl ethers of polyhydric phenols comprising the steps of:-(A) reacting in one or more stages(i) a polyhydric phenol;
(ii) an epihalohydrin in an amount of from 2.5 to 10 moles for each phenolic hydroxy equivalent of (i); and (iii) a condensation catalyst, with the proviso that if the condensation catalyst contains an ionizable hydroxide then the amount thereof is at most 0.75 moles for each phenolic hydroxy equivalent of (i);
(C) reacting in one or more stages the reaction product obtained in step A with an aqueous solution of an alkalimetal hydroxide, wherein the total amount of alkali-metal hydroxide reacted, together with the amount of ionizable hydroxide, if any, added in step A, is at least 1.0 moles for each phenolic hydroxy equivalent of (i) added in step A, separating the reaction product, or each reaction product of each stage, into an aqueous phase and an organic phase and, if two or more reaction stages are used, reacting each separated organic phase, with the exception of the last organic phase, in the next reaction stage ? of this step C, (D) recycling at least part of an aqueous phase obtained in step C to step A or to one or more stages thereof and/or to an earlier stage, if any, of step C, and (E) recovering the polyglycidyl ether of the poly-hydric phenol from the organic phase or the last organic phase obtained in step C.
A preferred embodiment of the present invention is a process for the preparation of polyglycidyl ethers of polyhydric phenols comprising the steps of:
(A) reacting in one or more stages, at a temperature of below 75C, (i) a polyhydric phenol;
(ii) an epihalohydrin in an amount of from 2.5 to 10 moles for each phenolic eqùivalent of (i);
; 10 in the presence of (iii) an oxygen-containing volatile organic solvent in such an amount that it represents from 20 to 200 %w based on the weight of (ii) and - from 2 to 15 moles for each phenolic ; 15 equivalent of (i);
(iv) water in an amount of at least 15 %w based on the weight of (ii), and (v) a condensation catalyst, with the proviso that if the condensation catalyst is an ionizable hydroxide the amount thereof is at most 0.75 moles for each phenolic equivalent of (i);
(B) separating the reaction product obtained in step A into an aqueous phase and an organic phase;
(C) reacting, in two or more stages, the organic phase obtained in step B, at a temperature of below 75C, with an aqueous solution of an alkali-mekal hydroxide, wherein the amount of alkali-metal hydroxide added in the first stage, together with the amount of ionizable hydroxide, if any, added in step A, is less than 1.0 moles for each phenolic equivalent of (i) added in step A and wherein the total amount of alkali-metal hydroxide added, together with the amount of ionizable hydroxide, if any, added in step A is at least 1.0 moles for each phenolic equivalent of (i) added in step A, separating the reaction product of each stage into an aqueous phase and an organic phase and reacting each separated organic phase with the exception of the last separated organic phase, in the next reaction stage of this step C;
(D) recycling at least a part of a separated aqueous phase obtained in step C to step A or to one of the stages thereof, and (E) recovering the polyglycidyl ether of the poly-hydric phenol from the last organic phase obtained in step C.
The reaction step A may be carried out in several stages. A single multi-stage reactor may be used, for example of the type described in U.S.
3,129,232, or several separate reactors in series or a combination of at least one single multi-stage reactor and at least one separate reactor in series may be used.
The polyhydric phenol for use in step A is preferably a dihydric phenol, and more preferably a di(hydroxyphenyl~-alkane of the general formula:-HO ~ R2 OH (VI) wherein R1 and R2 are H atoms or the same ordifferent C1 to C6 alkyl groups. Preferably the hydroxyl groups are in both para-positions with respect to the alkylene group. Examples include diphenylol-methane (Bisphenol F), diphenylolethane, and diphenylol-propane (Bisphenol A), the latter being preferred, andmixtures thereof, such as mixtures of the bisphenols A and F, preferably in a 7O:3O weight ratio. Poly-hydric phenols with more than 2, for example 3, 4, or 5, hydroxy aromatic groups per molecule, may also be used in step A; examples are technical 1,1,2,2-tetra-(4-hydroxyphenyl)ethane and novolacs.
The epihalohydrin for use in step A is suitably epichlorohydrin or epibromohydrin with the former being preferred. Preferred amounts of epihalohydrin are from 3~5 to 8 moles for each phenolic equivalent of polyhydric phenol.
If step A is carried out in two or more stages both the epihalohydrin and the polyhydric phenol are added to the first stage.
Suitable condensation catalysts for use in step A are ionizable hydroxides, chlorides, bromides, io-dides, sulphides and cyanides.
1~18433 The amount of condensation catalyst may vary considerably, for example from 0.005 to 1.5 moles for each phenolic equivalent of polyhydric phenol, with the proviso that if an ionizable hydroxide is used then the amounts thereof should not be more than 0.75 moles for each phenolic equivalent of polyhydric phenol; in this case the amount of ionizable hydroxide added in the first stage of step A is preferably from 0.025 to 0.425 moles, more preferably from 0.05 to 0.25 moles per phenolic equivalent of polyhydric phenol, and the total amount of ionizable hydroxide added in step A is pre~erably from 0.05 to 0.75 moles more preferably from 0.25 to o.6 moles per phenolic equi-valent of polyhydric phenol. It is preferred that if substantially no ionizable hydroxide is added in step A then the amount of the condensation catalyst is at least 0.075 mole for each phenolic equivalent of poly-hydric phenol. Preferred condensation catalysts are in the ammonium or alkali-metal form. The more pre-ferred condensation catalyst are the ammonium andalkali-metal hydroxides and halides. The preferred halides are the chlorides and bromides with the former being particularly preferred. Preferred ammonium compounds are quarternary ammonium compounds such as tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide, tetramethyl ammonium chloride, methyl triethyl ammonium chloride and benzyl trimethyl ammonium chloride. Preferred alkali-metal compounds are the hydroxides and chlorides of lithium, sodium and potassium. The most preferred condensation catalysts for use in step A are sodium hydroxide and/or sodium chloride; a highly preferred condensation catalyst in step A is a mixture of sodium hydroxide and sodium chloride. Such a mixture is that present in the first and optionally further aqueous phases obtained in step C. Suitably the condensation catalysts are fed to step A as aqueous solutions. If step A is carried out in two or more stages the condensation catalyst, or a part thereof, is added to the first stage, and preferably condensation catalyst is added to each stage.
An oxygen-containing volatile organic solvent and/or waker may also be added in step A. In the preferred embodiment of the present invention both an oxygen-containing volatile organic solvent and water are added in step A. Suitably the amount of oxygen-containing organic solvent added is from 20 to 200 %w ba~ed on the weight of the epihalohydrin with the proviso that this amount should not be below 2 moles or above 15 moles for each phenolic equivalent of polydihydric phenol and suitably the amount of water i8 at least 15 %w based on the weight of epihalohy-drin. In this preferred embodiment the amount of water is such that the reaction product mixture of step A
separates into two liquid phases, an organic phase and an aqueous phase. Preferably the amount of water is such that any ionizable halides added or formed in step A are dissolved to produce a step A reaction product mixture which is substantially free of solid particles. Consequently the optimal amount of water will depend upon the specific ionizable halide added or formed. in general the amount of water should be from 400 to 600 %w, based on the weight of ionizable halide. In general there is no upper limit to the amount of water added in step A although in practice it will be restricted by such factors as optimal reactor volume, solvent recovery costs, epihalohydrin hydrolysis, etc. In practice the amount of added water present may be from 30 to 60 %w based on the weight of oxygen-containing volatile organic solvent.
In this preferred embodiment the water may be added to step A in several ways e.g. it may be included in a polyhydric phenol/oxygen-containing volatile organic solvent, if any, feed stream and/or added as an aqueous solution of condensation catalyst and/or added as a recycled aqueous phase, obtained in step C, and/or added as a recycled aqueous phase obtained in the recovery step e.g. a recycled washwater and/or added as a separate water stream. In this preferred em-bodiment the use of too low an amount of oxygen-containing volatile organic solvent will result in an 111~433 unacceptably low reaction rate in step A and the use of too high an amount will result in highly viscous products and unacceptably high solvent recovery costs.
The oxygen-containing volatile organic solvent should be halogen-free and volatile, that is have a boiling point at atmospheric pressure of preferably not above 120C and not below 50C; it should have one oxygen atom per molecule; it should be an alcohol or a ketone, and have preferably 3 to 6, more preferably 3 or 4, carbon atoms per molecule; examples are the ketones acetone and methyl ethyl ketone, and the alcohols propanol, isopropanol, butanol, and isobutanol. Suita-ble alcohols are in general the Cl to C6 alkanols, such as methanol, ethanol; preferred is isopropanol.
Preferred amounts of oxygen-containing volatile organic solvent are from 30 to 100 %w based on the weight of the epihalohydrin. If step A is carried out in two or more stages the oxygen-containing solvent and at least the above minimum amount of water, that is at lea8t 15 %w based on the weight of epihalohydrin, are added in the first stage.
The reaction temperature of step A depends on whether or not an oxygen-containing organic solvent and/or water are added in step A, and the amounts thereof, and on the type of condensation catalyst used but in general will be at least 25C and preferably from 35 to 120C. In the preferred embodiment of the present invention, using an oxygen-containing volatile organic solvent and water in step A, the reaction temperature is preferably below 75C, more preferably from 35 to 65C. One o~ the attractive features of the present process is that residence times in step A below 6 hours are sufficient for an acceptable conversion, and that generally the residence time can be from 0.15 to 4.0 hours.
The total residence time in step A will depend upon the reaction temperature. In the preferred em-bodiment as defined above total residence times of for example below 4.0 hours are sufficient. Residence times as low as 0.05 hours (at 65C or higher) have been found suitable, residence times of from 0.25 to 2.0 hours (at lower temperatures) are generally suita-ble. If step A in the preferred embodiment is carried out in two or more stages (as is preferred) the residence time in the last stage of step A is prefer-ably below 1.0 hour.
The reaction product mixture obtained in step A
may be reacted, without additional treatment, in step C or the unreacted epichlorohydrin may be removed therefrom before it is reacted in step C. In the preferred embodiment of the invention, in which an oY.ygen-containing organic solvent and water is added in step A, the aqueous phase and the organic phase are separated (by settling and decantation, or by ~1~8433 centrifugation) (step B) and the organic phase is further reacted in step C. The settling is very fast, and settling times can be as low as one minute in a continuous process; in a batch process a longer settling time can be accepted; settling is generally completed within 0.5 hours. It is not necessary to heat or cool the reaction product before or during separation. The aqeuous phase thus obtained is a substantially neutral aqueous solution comprising ionizable halide; the small amounts of unreacted epihalohydrin and oxygen-containing organic solvent which it also contains can easily be removed by conventional techniques such as stripping and may be used, as appropriate, in reaction step A or reaction step C. The stripped effluent may be dis-carded.
In the preferred embodiment the organic phaseobtained in step B is reacted in step C, in one or more stages, preferably two stages, with an aqueous solution, such as a from 20 to 50 %w aqueous solution, of an alkali-metal hydroxide, preferably sodium hydroxide.
In the first stage of step C the amount of alkali-metal hydroxide added, together with the amount of ionizable hydroxide, if any, added in step A, is less than 1.0 mole, preferably from 0.85 to 0.99 moles, for each phenolic equivalent of polyhydric phenol.
added in step A. The components of the aqueous solution may be added separately to the organic phase and may be at least partly provided by recycling the second and any subsequent aqueous phases obtained in step C. The total residence time needed for step C is below 2.0 hours with the residence time for the first stage of step C being preferably from 0.16 to 1.0 hours.
The reaction temperature for the first stage of step C
is preferably above 25C, more preferably from 35 to 65C. The unreacted epihalohydrin and oxygen-containing volatile organic solvent recovered from the aqueous phase obtained in step B may be added to this first stage of step C.
The reaction product obtained in the first stage of step C readily forms, upon settling, an organic phase and an aqueous phase which may easily be separated in the manner described above for step B.
The aqueous phase thus separated, which is a slightly alkaline aqueous solution comprising alkali-metal halide, a small amount of alkali-metal hydroxide and some phenolic compounds, for example phenolic chlorohydrin ethers, phenolic glycidyl ethers, and polyhydric phenols, is then recycled to step A. The aqueous phase may first be neutralized, especially if, as in the case of a batch process, it is stored before being added to step A. The aqueous phase may be re-cycled to any stage of step A and in the case of amulti-stage step A may be recycled to the first or a subsequent stage thereof, in the latter case the 1~8433 .
catalytic effect of the components of this aqueous phase may not be significant.
The organic phase obtained after the first stage of step C is then reacted with further amounts of an aqueous solution, such as a from 20 to 50 %w aqueous solution, of an alkali-metal hydroxide, preferably sodium hydroxide, wherein the amount thereof is such that the total amount of alkali-metal hydroxide added in step C, together with the amount of ionizable hydroxide, if any, added in step A, is at least 1.0 moles, preferably from 1.05 to 1.5 moles, for each phenolic equivalent of polyhydric phenol used in step A. Suitably step C comprises only two stages and preferably the residence time for the second stage thereof is 0.016 to 0.4 hours and preferably the reaction temperature is from 25 to 65C.
After the second and subsequent stages, if any, of step C, the reaction product readily forms, upon settling, an organic phase and an aqueous phase which may be separated in the manner described above for step B.
The aqueous phase thus separated which is an alkaline aqueous solution comprising alkali-metal hydroxide and small amounts of alkali-metal chloride, in one preferred embodiment of the invention, is recycled to step A or to one of the stages thereof, preferably to the first stage thereof, and therefore ~1~8433 provides, at least in park, the water and condensation catalyst required in step A. In this preferred embodiment of the invention, the aqueous phase may also be recycled to the first stage of step C or to a first stage of a further step C and therefore provides, at least in part, the aqueous solution of alkali-metal hydroxide required.
The organic phase obtained after the last stage of step C is then worked up to recover the polyglycidyl ether therefrom. The manner or working up is not critical and usually comprises one or more washing steps and the removal of the unreacted epihalohydrin, oxygen-containing organic solvent and water therefrom.
The recovered epihalohydrin, oxygen-containing organic solvent, water and washwater may be recycled, where appropriate to one or both of steps A and C or to one or both of further steps A and C. The recovered poly-glycidyl ether may be further treated, if desired, with small amounts of alkali-metal hydroxide in solvents, such as hydrocarbon solventse.g. toluene.
This preferred embodiment will now be illustrated by reference to the accompanying drawings in which Figures 1 to 4 are schematic diagrams of this preferred embodiment.
In Figure 1, the feedstock stream 1 comprising a polyhydric phenol, epihalohydrin, oxygen-containing volatile organic solvent and water, together with the ~8433 aqueous phase recycle stream 13, are continuously fed to reactor Al. Suitably the feedstock stream 1 is pre-heated to the desired reaction temperature by means of heaters, not shown. The reaction product stream 2 is continuously withdraun and fed to reactor A2, together with the aqueous phase recycle stream 9. The reaction product stream 3 is continuously withdrawn and fed to separator B and the lower aqueous phase is continuously withdrawn as stream 5. The upper organic phase is also continuously withdrawn, as stream 4, and fed, together with an aqueous solution of alkali-metal hydroxide, stream 6, to reactor Cl, after which the reaction product stream 7 is continuously withdrawn and fed to separator Sl. The lower aqueous phase is continuously withdrawn, as stream 9, and fed to reactor A2. The upper organic phase is also con-tinuously withdrawn, as stream 8, and fed, together with an aqueous solution of alkali-metal hydroxide, stream 10, to reactor C2 after which the reaction product stream 11 is continuously withdrawn and fed to separator S2. The lower aqueous phase is con-tinuously withdrawn, as stream 13, and recycled to reactor Al. The upper organic phase is also continuously withdrawn, as stream 12, and the poly-Klycidyl ether recovered therefrom.
In Figure 2, the scheme is substantially thesame as for figure 1 with the differences that the lower aqueous phase which is continuously withdrawn as stream 13 is fed to reactor C1, and that an aqueous solution of alkali-metal hydroxide, stream 14, is continuously fed to reactor A1.
In Figure 3, the scheme is substantially the same as for figure 1 with the difference that the lower aqueous phase which is continuously withdrawn as stream 9 is fed to the reactor A1. Moreover A1 is the single reactor in step A and the reaction product stream 2 is fed directly to separator B.
In Figure 4, the scheme is substantially the same as for figure 3 with the difference that the lower aqueous phase which is continuously withdrawn as stream 13 is fed to reactor C1.
Other embodiments of the invention are given below in a generalized form. The product of step A, or the organic phase obtained in step B, is reacted in step C, in one or more stages, with an aqueous ~olution, such as a from 20 to 50 %w aqueous solution, of an alkali-metal hydroxide, preferably sodium hydroxide. The amount of alkali-metal hydroxide added, together with the amount of ionizable hydroxide, if any, added in step A, is more than 1.0 moles, preferably from 1.05 to 1.5 moles for each phenolic equivalent of polyhydric phenol used in step A. If the unreacted epihalohydrin is removed before step C it may be de-sirable to add to the reaction product a solvent such ~J ~8~33 as toluene, benzene or methyl isobutyl ketone.
Suitable amounts of such solvents are from 50 to 300 %w based on the reaction product to be used in step C.
In one embodiment of the present invention step C
is carried out in one stage and the reaction product allowed to settle upon which an aqueous phase and an organic phase are formed and the aqueous phase is separated as described above. The separated aqueous phase which is an alkaline aqueous solution of alkali-metal halide and alkali-metal hydroxide is then used, at least in part, as a condensation catalyst in step A or one of the stages thereof. In this embodiment the organic phase obtained is worked up to recover the polyglycidyl ether therefrom. The manner of working up is not critical and usually comprises one or more waæhing steps and the removal of water and, if present, unreacted epihalohydrin, and solvents therefrom de-pending upon the particular conditions used. The re-covered polyglycidyl ether may be further treated with Bmall amounts of sodium hydroxide in solvents, such as hydrocarbon solvents e.g. toluene or oxygen-containing solvents such as ketones e.g. MEK, MIBK.
In another embodiment of the present invention step C is carried out in at least two stages. The reaction product is allowed to settle after each stage, the aqueous phases separated as described above and the final organic phase worked up as described ~18433 above. Preferably from 1.0 to 1.15 moles and from 0.05 to 0.35 moles of alkali-metal hydroxide (for each phenolic equivalent of polyhydric phenol added in stage A) are added in the first stage and subsequent stages of step G respectively. Suitably each separated aqueous phase, or a part thereof, is used as a conden-sation catalyst in step A or a further step A or the first separated aqueous phase is used as a condensation catalyst in step A or one of the stages thereof and the second and any subsequent separated aqueous phases are used as a source of aqueous alkali-metal hydroxide solution in step C or one of the stages thereof. If the first separated aqueous phase is not used as a conden-sation catalyst then it may be discarded.
The reaction temperature of step C depends upon the reaction conditions used but is preferably above 25C, more preferably from 35 to 100C. In the pre-ferred embodiment of the invention, in which an oxygen-containing organic solvent and water are added in step A the reaction temperature is suitably below 75C. The total residence time in step C is suitably below 4.0 hours.
The invention is illustrated by the following example8. In Examples 1 to 6 and 10 the figures given are those obtained under steady-state conditions (approximately 15 hours~. Before these conditions were achieved artificial streams were used instead of the recycle streams. In the other examples the first batch was made using an artificial stream, which in subsequent batches was replaced by the appropriate effluent from a foregoing batch.
Example 1 The process scheme described in ~igure 1 was used.
The reactor Al (2 litres) was continuously fed by (a) a feedstock stream 1, (1145.6 g/h), preheated to a temperature of 43C, comprising g/h diphenylol propane 119.7 epichlorohydrin 582.8 isopropanol 340.2 water 102.9 and (b) the recycle stream 13, (57.5 g/h), from separator S2 comprising g/h sodium hydroxide 7 sodium chloride 5 i~opropanol 2 epichlorohydrin 0.5 water 43 This recycle stream also contained about 4 g/l of non-volatile carbon compounds of which about 10 %w was aromatic compounds.
Reactor Al was maintained at a temperature of 43C
and the residence time was 45 minutes.
The reaction product stream 2 was continuously withdrawn and fed (1203.1 g/h) to reactor A2 ( 4 litres) together with the recycle stream 9, (198.9 g/h), from separator S1, comprising g/h sodium hydroxide 2 sodium chloride 43 isopropanol 7 epichlorohydrin 2 water 144.9 This recycle stream also contained about 3 g/l of non-Yolatile carbon compounds of which about 90 %w was `
aromatic compounds.
~eactor A2 was maintained at a temperature of 43C
and the residence time was 5 minutes.
The reaction product stream 3 was continuously withdrawn and fed (1402 g/h) to separator B in which two phases formed. The lower aqueous phase was with-drawn, (295.3 g/h), as stream 5, and worked up as des-cribed below. The residence time in separator B was 10 minutes.
The upper organic phase was continuously withdrawn, as stream 4, and fed (1106.7 g/h) to reactor C1, (2.0 litres) together with a 20 ~w aqueous solution of sodium hydroxide (157.6 g/h~, stream 6.
Reactor C1 was maintained at a temperature of 43C
~118433 and the residence time was 30 minutes.
The reaction product stream 7 was continuously withdrawn and fed (1264.2 g/h) to separator S1 in which two phases formed. The lower aqueous phase was with-drawn, as stream 9, and continuously fed (198.9 g/h) to reactor A2. The residence time in separator S1 was 10 minutes.
The upper organic phase was continuously with-drawn, as stream 8, and fed (1065.1 g/h~, after cooling, 10 to reactor C2 (0.4 litres) together with a 20 %w aqueous solution of sodium hydroxide (52.5 g/h).
Reactor C2 was maintained at a temperature of 33C
and the residence time was 5 minutes.
The reaction product stream 11 was continuously 15 withdrawn and fed (117.6 g/h) to separator S2 in which two phases formed. The lower a~ueous phase was withdrawn, as stream 13, and continuously fed (57.5 g/h) to reactor A1. The residence time in separator S2 was 10 minutes.
The upper organic phase was withdrawn (1060.1 g/h), washed with water to remove any sodium chloride there-from, flashed and steam-stripped to remove isopropanol, water and epichlorohydrin therefrom which were recycled to the various reactors where appropriate. The recovered liquid diglycidyl ether of diphenylol propane had the following properties:-epoxide equivalent weight 175 ~118433 saponifiable chlorine (%w) 0.03 viscosity (Poise; 25C) 120 The lower aqueous phase, withdrawn as stream 5, was stripped to remove any isopropanol and unreacted epichlorohydrin therefrom which was recycled, where appropriate, to reactor A2. The stripped effluent had the following composition:-%w sodium chloride 23 sodium hydroxide ~ o.o8 carbon-containing compounds 0.10 water balance Example 2 Example 1 was repeated with the differences that separation step B was omitted and that a portion of the lower aqueous stream 9, was bled (295.3 g/h) and worked up as described for the lower aqueous phase withdrawn as stream 5. The recovered liquid digly-cidyl ether of diphenylol propane had the following properties:-epoxide equivalent weight 179 saponifiable chlorine (%w) 0.05 viscosity (25C, Poise) 122 and the stripped effluent, derived from the bleed stream, had the following composition:-%wsodium chloride 22 sodium hydroxide ~118433 carbon-containing compounds 0.3 water balance.
Example 3 The process scheme described in Figure 2 was used, in which the same temperatures and residence times as described in Example 1 were used.
The reactor A2 (2 litres) was continuously fed by (a) a feedstock stream as described in Example 1, and (b) a 20 %w aqueous solution of alkali-metal hydroxide, stream 14, (57.5 g/h).
The reaction product stream 2 was continuously withdrawn and fed (1203.1 g/h) to reactor A2 toge~her with the recycle stream 9, (200.6 g/h), from separator Sl, comprising g/h sodium hydroxide 2 sodium chloride 43 isopropyl alcohol 7 epichlorohydrin 2 water 146 This recycle stream also contained about 5 g/l of non-volatile carbon compoundsof which about 90 %w was aromatic compounds.
The reaction product stream 3 was continuously withdrawn and fed (1398.7 g/h) to separator B in which two phases formed. The lower aqueous phase was with-drawn (294.7 g/h~, as stream 5, and worked up as des-cribed in Example 1.
The upper organic phase was withdrawn, as stream4, and continuously fed (1104.0 g/h) to reactor C
together with a 20 %w aqueous solution of sodium hydroxide (100 g/h)~ stream 6, and the recycle stream 13 (57.7 g/h) 7 from separator S2, comprising g/h sodium hydroxide 7 sodium chloride 5 volatile carbon compounds 2.5 water 43.2 This recycle stream also contained about 5 g/l of non-volatile carbon compounds of which about 10 %w was aromatic compounds.
The reaction product stream 7 was continuously withdrawn and fed (1266.7 g/h) to separator S1 in which two phases formed. The lower aqueous stream was with-drawn, as stream 9, and fed (200.6 g/h~ to reactor A2.
The upper organic phase was withdrawn, as stream 8, and continuously fed (1066.1 g/h), after cooling, to reactor C2 together with a 20 %w aqueous solution of sodium hydroxide (52.2 g/h), stream 10.
The reaction product stream 11 was continuously withdrawn and fed (1118.6 g/h) to separator S2 in which two phases formed. The lower aqueous phase was with-drawn, as stream 13, and continuously fed (37.7 g/h) to reactor C1.
` 111~433 3o The upper organic phase was withdrawn (1060.9 g/h) and worked up as described in Example 1. The recovered liquid diglycidyl ether of diphenylol propane had the following properties:-epoxide equivalent weight 181 saponifiable chlorine (%w) 0.08 viscosity (25C, Poise) 125 The lower aqueous phase, withdrawn as stream 5, after stripping had the following composition %w sodium chloride 23 sodium hydroxide 0.08 carbon-containing compounds 0.14 water balance Example 4 Example 3 was repeated with the differences that the separation step B was omitted and that a portion of the lower aqueous stream 9, was bled (294.7 g/h) and worked up as described for the lower aqueous phase withdrawn as stream 5. The recovered liquid diglycidyl ether of diphenylol propane had the following proper-ties:-epoxide equivalent weight 180 saponifiable chlorine (%w) 0.07 viscosity t25C, Poise) 120 and the stripped effluent, derived from the bleed stream, had the following composition:-11~8433 %w sodium chloride 23 sodium hydroxide carbon-containing compounds o.6 water balance Exa`mple 5 Example 1 was repeated using the process scheme described in Figure 3. Substantially the same results were obtained.
10` Examp'le 6 Example 2 was repeated using the process scheme described in Figure 4. The results obtained were substantially the same as for example 2 except that the stripped effluent obtained from stream 5 contained less than 0.05 %w of sodium hydroxide and that the recovered diglycidyl ether had a viscosity (25C, Poise) of 133.
Exa`mp'le 7 ' In this example t.he process of the present invention was carried out in a batch manner.
` P'art' A
A mixture of diphenylol propane (114 g), epichlorohydrin (555 g), isopropanol (324 g) and water (80 g) was charged to a reactor (2 litres) and reacted with an artificial stream - a solution of sodium hydroxide (9.5 g) and sodium chloride (o.8 g) in water (40 g) - for 1 hour at 45C. The reaction ~lBD~33 pro,duct was allowed to settle and the lower aqueous phase (first) was separated.
The remaining organic phase was reacted with a solution of sodium hydroxide (30 g) in water (121 g) for 20 minutes at 45C after which the lower aqueous phase (second) was separated.
The remaining organic phase was reacted with a solution of sodium hydroxide (10 g~ in water (40 g~
for 5 minutes at 30C and the lower aqueous phase (third) separated and stored.
The remaining organic phase was worked up as described above. The liquid diglycidyl ether of di-phenylol propane had the following properties:-epoxide equivalent weight 179 saponifiable chlorine (%w) 0.07 viscosity (25C, Poise) 83 The first aqueous phase was stripped to removeisopropanol and unreacted epichlorohydrin therefrom.
The stripped effluent, which was discarded, had the following composition:-%w sodium chloride 22 sodium hydroxide ~ 0.05 carbon-containing compounds 0.1 water balance The second aqueous phase was also stripped to remove any isopropanol and unreacted epichlorohydrin therefrom, to enable analysis for other carbon compounds. The stripped effluent (198 g), which was stored, had the following composition:-%w sodium chloride 21.5 sodium hydroxide 0.9 carbon-containing compounds 0.4 water balance.
Par't B
10 The above experiment was repeated 5 times, but with the difference that in each experiment the aqueous solution of sodium hydroxide and sodium chloride used in the first step in the above experiment was replaced by the stored second and third aqueous effluents of the foregoing experiment; the second effluent was not stripped anymore, but used as such.
The first aqueous phases (stripped) contained 0.1-0.2 %w of carbon-containing compounds, 22 %w NaCl, and ~0.05 %w NaOH, and the liquid diglycidyl ether had epoxide equivalent weights 178-182, saponifiable Cl 0.05-o.o8 %w and viscosity 80-84 Poise (25C).
' Examp'le' 8 Example 7 was repeated with the difference that the solution of sodium hydroxide and sodium chloride used in the first step of Part A to initiate the series was replaced by solutions in water (40 g), of sodium chloride (10 g~, lithium chloride (8 g~, potassium 1~18433 chloride (12 g) and tetramethylammonium chloride (20 g), and the amount of sodium hydroxide used after the first separation was increased to 39 g. In Part B this amount was again reduced to 30 g. The results obtained were substantially the same as for Example 7; the resin analysis was the same, and the first aqueous (stripped) contained also 0.1-0.2 %w carbon-containing compound.
Example 9 10 Example 7 was repeated, with the difference that the diphenylol propane was replaced by an equivalent amount of diphenylol methane (100 g~.
The liquid diglycidyl ether of diphenylol methane had the following properties:
epoxide equivalent weight 170 saponifiable chlorine (%w) 0.05 viscosity (25C, Poise) 33 phenolic hydroxy (meq/100 g) 1.2 The aqueous phases of Part A were stripped to remove isopropanol and epichlorohydrin; the stripped effluents had essentially the same compositions as in Examples 7.
Example 10 Continuous experiment, as in Example 1, but with a different process scheme, and higher reaction tem-peratures (60C~.
The process scheme consisted of 4 reactors in ~118~33 series, each 0.25 l, numbered A, C1, C2, and C3 res-pectively, with a phase separator (numbered B, S1,S2, and S3, respectively) after each reactor.
The aqueous phase from separator S3 was recycled to reactor A (42.6 g/h, contained NaOH 4.7 %w, NaC1 14.7 %w, and 1000-3000 ppm resinous compounds).The aqueous phases from separators B, S1 and S2 were not recycled, but stripped to recover isopropanol (4 %w) and epichlorohydrin (1 %w) and discarded: they con-tained less than 200 ppm resinous compounds whichdoes not contaminate the stripper in continuous operation.
The continuous feed for reactor A consisted of the streams (a), (b) and (c):
15 (a) feedstock stream (1145.6 ~/h~, preheated to 55C, comprising g/h diphenylol propane 119.7 epichlorohydrin 582.8 isopropanol 340.2 water 102.9 (b) 20 %w aqueous solution of sodium hydroxide (106 g/h) (c) aqueous phase from separator S3 as indicated above.
The temperature of reactor A was kept at 60~C. The reaction stream was continuously withdrawn from reactor A, and fed to separator B in which two phases formed.
The lower aqueous phase (149 g/h~ and the upper organic 11~8433 phase were withdrawn, and the latter continuously fed to reactor Cl, together with a 20 %w aqueous solution of sodium hydroxide (64 g/h). The temperature in reactor Cl was kept at 60C.
The reactor stream from Cl was continuously fed to separator Sl, where two layers formed which were withdrawn (lower aqueous layer: 101 g/h). The upper organic phase was continuously fed to reactor C2, to-gether with a 20 %w aqueous solution of sodium hydroxide (32 g/h).
The temperature in C2 was kept at 60C.
The reactor stream from C2 was fed to separator S2; the two layers formed were separated and withdrawn (lower aqueous layer: 38 g/h) and the upper organic layer continuously fed to reactor C3, together with a 20 %w aqueous solution of sodium hydroxide (32 g/h).
The temperature in C3 was kept at 60C.
The reactor stream from C3 was fed to separator S3, the layers formed were withdrawn; the lower aqueou5 layer was continuously fed to reactor A.
The upper organic layer (1036 g/h) was con-tinuously washed with water to remove any sodium chloride and sodium hydroxide therefrom, and then flashed and steam-stripped to remove isopropanol, epichlorohydrin and water (this mixture of volatiles can be recycled to reactor A, with fresh components to make up for the right feed composition).
11~. B~33 .
The recovered liquid diglycidyl ether of diphenylol propane had the following properties:
epoxide equivalent weight 183 saponifiable chlorine ~%w) 0.01 phenolic hydroxy (meq./100 g) 1.1 viscosity ~Poise; 25C) 105 Example 11 A mixture of diphenylol propane (109 g), epichlorohydrin (886 g), isopropanol (346 g) and water (87 g) was charged to a reactor ~2 litres) and 0 reacted with a solution (added over 5 minutes) of sodium chloride (50.6 g) and sodium hydroxide (1.9 g) in water ~117.5 g) for a total of 20 minutes at 45C.
The reaction product was allowed to settle and the lower aqueous phase ~first) was separated. The remaining organic phase was reacted with a 19.4% aqueous solution of sodium hydroxide (204 g) for 15 minutes at 45 after which the lower aqueous phase ~second) was separated.
The remaining organic phase was reacted with water to remove any sodium chloride therefrom, flashed and steam-stripped to remove isopropanol, water and epichlorohydrin therefrom. The product was dissolved in toluene and treated with a 2.5 %w solution of sodium hydroxide.
The final product had the following properties.
epoxide equivalent weight 178 saponifiable chlorine ~%w) 0.03 viscosity (25C, Poise) 76 The first aqueous phase was stripped to remove isopropanol and un-reacted epihalohydrin therefrom.
P~
The stripped effluent, which was discarded, had the following composition:-%w sodium chloride 23 sodium hydroxide 0.04 water 77 The second aqueous phase was also stripped to remove isopropanol and epichlorohydrin therefrom. ~he stripped effluent (231 g), which was stored, had the following composition:-%w sodium chloride 22 sodium hydroxide 1.0 water 77 15 The above experiment was repeated with the differ-ence that in the first step the aqueous solution of sodium chloride and sodium hydroxide was replaced by the stored stripped effluent obtained from the second aqueous phase.
Substantially the same results were obtained.
EXample 12 The procedures of example 11 were repeated with the differences that the first reaction product was not allowed to settle, but reacted immediately with the 19.4 % w aqueous solution of sodium hydroxide and that only a part (231 g~ of the subsequently obtained lower aqueous phase, after stripping, was used in place ~18433 of the aqueous solution of sodium chloride and sodium hydroxide in the repeat experiment. The recovered diglycidyl ether had substantially the same properties as that obtained in example 11.
Example 13 The first experiment of example 11 was repeated with the differences that both of the aqueous phases, after stripping, were discarded and that the second organic phase was not worked-up but reacted with a 20.1 %w aqueous solution of sodium hydroxide (58 g) for 5 minutes at 42C after which the reaction product was allowed to settle and the aqueous phase (third) was separated. The organic phase thus ob-tained was washed and steam-stripped to remove iso-propanol, water and epichlorohydrin therefrom to produce a final product having the following properties:-epoxide equivalent weight 178 saponifiable chlorine (%w) 0.11 viscosity (25C, Poise) 75 The third separated aqueous phase was stripped to remove -,sopropanol and epihalohydrin therefrom. The stripped effluent (65 g), which was stored, had the following composition:-%w 25 sodium chloride 10 sodium hydroxide ` 8 water 82 ~8433 In the repeat experiment the 19.4 %w aqueous solution of sodium hydroxide reacted with the first organic phase was partly made-up from the above stored stripped effluent. The final product has substantially the same properties as described above.
Example 14 A mixture of diphenylol propane (109 g), epi-chlorohydrin (886 g) and 1 molé % of tetramethyl-ammonium chloride (based on diphenylol propane) and reacted for 2 hours at 100C after which the unreacted epichlorohydrin was removed by vacuum distillation.
The reaction product was dissolved in methyl isobutyl -~;
ketone to produce a 35 %w solution which was reacted with a 5 %w aqueous solution of sodium hydroxide containing 1.01 moles of sodium hydroxide for 1 hour at 85C after which the reaction product was allowed to settle and the lower aqueous phase was withdrawn and discarded.
The remaining organic phase was reacted with a further 20.1 %w aqueous solution of sodium hydroxide in an amount corresponding to 0.25 moles of sodium hydroxide for each mole of diphenylol propane after which the lower aqueous phase was withdrawn and stored.
The remaining organic phase was washed and steam-~tripped to remoYe the methyl isohutyl ketone and watertherefrom to produce a finaI product ha~ing the following properties.-~118433 epoxide equivalent weight 185 saponifiable chlorine (%w) 0.1 viscosity (25c, Poise) 80 The above experiment was repeated with the 5 difference that the 5 %w aqueous solution of sodiumhydroxide reacted with the first organic phase was partly made-up from the above stored aqueous phase.
The final product had substantially the same properties as described above.
Example 15 The novolac used in this example had molecular weight 500-600 and contained 0. 96 phenolic equivalents per 100g.
Part A. (Initiating the series of experiments) Novolac 15 (0.54 kg), epichlorohydrin ( 2.42 kg)~ isopropanol (1.42 kg) and water (o.78 kg) were heated to 35 c in a 6 l-reactor with stirrer, and reacted with a solution of sodium hydroxide ( 52 g) in water ( 52 g) during 20 minutes at 45C.
A solution of sodium hydroxide ( 151 g) in water (151 g) was added in 4 equal parts at 5 minutes inter-vals.
~he temperature rose to 50c, and was reduced to 45C
by cooling. After 30 minutes the phases were separated 25 ( settling time 15 minutes), the aqueous phase (first) was stripped to recover isopropanol and epichlorohydrin and discarded (NaOH content; 0.1 %w~.
~i~8433 The organic phase was cooled to 30C, and reacted with a solution of sodium hydroxide (52 g2 in water (208 g) for 5 minutes. The phases were separated (settling time 15 minutes~, and the aqueous phase was (second2 stored.
The resin was recovered from the organic phase by vacuum stripping distillation; the crude resin was dissolved in methyl ethyl ketone (2 12, and the so-lution washed twice with a dilute aqueous sodium dihydro phosphate solution (o.6 l; 0.3 %w NaH2PO4).
Volatiles were distilled off, last traces in vacuum at 120C.
The resin had the following properties:-epoxide equivalent weight 186 saponifiable chlorine (%w) 0.15 phenolic hydroxy (meq./100 g) 3.5Par't B (according to the invention2. The experiment was repeated four times, with the exception that now aqueous sodium hydroxide in the first step was re-placed by the s,tored aqueous phase of the foregoingexperiment.
Here also settling timesof 15 minutes were sufficient, the first aqueous phase was low in alkalinity, and the resin properties were the same (within 1% accuracy).
Exampl'e' 16 Example 15 was repeated, with the difference that 11~8433 the novolac was replaced by the equivalent amount of a technical tetraphenylol ethane (520 g; 10 phenolic equivalents per kg). The resin properties were (1% accuracy):-epoxy equivalent weight 172 saponifiable chlorine (%w) 0.05 phenolic hydroxy (meq/100 g) 2 Here also settling times of 15 minutes were sufficient, and the first aqueous phases of the series were low in alkalinity.
It should also be noted that the above reaction produces water and sodium chloride, and processes are known wherein the sodium chloride is allowed to dis-solve in water and the brine is separated from the organic phase. The brine, after the removal of any unreacted epichlorohydrin and any oxygen-containing volatile organic solvent therefrom, is usually dis-carded although it has been proposed to use some of it as a wàshing medium for the final reaction mixture (U.S. 2,986,551). It has also been proposed to carry out the dehydrochlorination reaction in two stages with an intermediate brine removal stage (U.S.
3,023,225; U.S. 3,069,434 and U.S. 4,017,523) or an intermediate epihalohydrin recovery stage (U.S.
2,841,595; U.K. 1,173,191~. It has also been proposed to remove unreacted epichlorohydrin after the conden-sation reaction but before the dehydrohalogenationreackion (U.K. 897,744).
The known processes for the production of poly-glycidyl ethers usually suffer from one or more dis-advantages such as the formation of an undesirable amount of by-products e.g. polymeric compounds, epihalohydrin hydrolysis products, solvent-derived products etc.; the formation of polyglycidyl ethers having an unacceptably high saponifiable chlorine content; the loss of reactants and products in the discarded brine, and the difficulty in operating the process continually. The brine or brines contain usually, apart from some epichlorohydrin and solvent, resinous contaminants, which on an attempt to recover the valuable volatile components by stripping di~tillation, tend to contaminate the stripper column.
The reactions are sometimes extremely slow, and, in an effort to improve the speed by raising the temperature, side reactions can greatly afflict economic recovery of epichlorohydrin, or the quality of the final resin.
We have now found a new process for the preparation of polyglycidyl ethers which is substantial-ly free of the above disadvantages. The new process allows easy operation, high recovery of solvent and epihalohydrin, production of polyglycldyl ethers of high quality, and of effluent low in alkalinity and in organic contaminants.
The new process is a multi-stage process in which at some stages a brine is separated and one or more of these brines are recycled to an earlier stage in the process; the new process may be carried out as a continuous process or as a multi-stage batch process.
The invention can be defined as a process for the preparation of a polyglycidyl ether of a polyhydric phenol wherein the polyhydric phenol is reacted with from 2.5 to 10 moles of an epihalohydrin per phenolic hydroxy equivalent in the presence of a condensation catalyst, water and a volatile organic solvent, and the reaction product is reacted with aqueous alkali metal hydroxide, with separation of aqueous phase and organic phase in one or more stages and recovery of the polyglycidyl ether from the last organic phase, wherein at least part of at least one separated aqueous phaBe iB recycled to an earlier stage of the process.
In a further definition the invention provides a process for the preparation of polyglycidyl ethers of polyhydric phenols comprising the steps of:-(A) reacting in one or more stages(i) a polyhydric phenol;
(ii) an epihalohydrin in an amount of from 2.5 to 10 moles for each phenolic hydroxy equivalent of (i); and (iii) a condensation catalyst, with the proviso that if the condensation catalyst contains an ionizable hydroxide then the amount thereof is at most 0.75 moles for each phenolic hydroxy equivalent of (i);
(C) reacting in one or more stages the reaction product obtained in step A with an aqueous solution of an alkalimetal hydroxide, wherein the total amount of alkali-metal hydroxide reacted, together with the amount of ionizable hydroxide, if any, added in step A, is at least 1.0 moles for each phenolic hydroxy equivalent of (i) added in step A, separating the reaction product, or each reaction product of each stage, into an aqueous phase and an organic phase and, if two or more reaction stages are used, reacting each separated organic phase, with the exception of the last organic phase, in the next reaction stage ? of this step C, (D) recycling at least part of an aqueous phase obtained in step C to step A or to one or more stages thereof and/or to an earlier stage, if any, of step C, and (E) recovering the polyglycidyl ether of the poly-hydric phenol from the organic phase or the last organic phase obtained in step C.
A preferred embodiment of the present invention is a process for the preparation of polyglycidyl ethers of polyhydric phenols comprising the steps of:
(A) reacting in one or more stages, at a temperature of below 75C, (i) a polyhydric phenol;
(ii) an epihalohydrin in an amount of from 2.5 to 10 moles for each phenolic eqùivalent of (i);
; 10 in the presence of (iii) an oxygen-containing volatile organic solvent in such an amount that it represents from 20 to 200 %w based on the weight of (ii) and - from 2 to 15 moles for each phenolic ; 15 equivalent of (i);
(iv) water in an amount of at least 15 %w based on the weight of (ii), and (v) a condensation catalyst, with the proviso that if the condensation catalyst is an ionizable hydroxide the amount thereof is at most 0.75 moles for each phenolic equivalent of (i);
(B) separating the reaction product obtained in step A into an aqueous phase and an organic phase;
(C) reacting, in two or more stages, the organic phase obtained in step B, at a temperature of below 75C, with an aqueous solution of an alkali-mekal hydroxide, wherein the amount of alkali-metal hydroxide added in the first stage, together with the amount of ionizable hydroxide, if any, added in step A, is less than 1.0 moles for each phenolic equivalent of (i) added in step A and wherein the total amount of alkali-metal hydroxide added, together with the amount of ionizable hydroxide, if any, added in step A is at least 1.0 moles for each phenolic equivalent of (i) added in step A, separating the reaction product of each stage into an aqueous phase and an organic phase and reacting each separated organic phase with the exception of the last separated organic phase, in the next reaction stage of this step C;
(D) recycling at least a part of a separated aqueous phase obtained in step C to step A or to one of the stages thereof, and (E) recovering the polyglycidyl ether of the poly-hydric phenol from the last organic phase obtained in step C.
The reaction step A may be carried out in several stages. A single multi-stage reactor may be used, for example of the type described in U.S.
3,129,232, or several separate reactors in series or a combination of at least one single multi-stage reactor and at least one separate reactor in series may be used.
The polyhydric phenol for use in step A is preferably a dihydric phenol, and more preferably a di(hydroxyphenyl~-alkane of the general formula:-HO ~ R2 OH (VI) wherein R1 and R2 are H atoms or the same ordifferent C1 to C6 alkyl groups. Preferably the hydroxyl groups are in both para-positions with respect to the alkylene group. Examples include diphenylol-methane (Bisphenol F), diphenylolethane, and diphenylol-propane (Bisphenol A), the latter being preferred, andmixtures thereof, such as mixtures of the bisphenols A and F, preferably in a 7O:3O weight ratio. Poly-hydric phenols with more than 2, for example 3, 4, or 5, hydroxy aromatic groups per molecule, may also be used in step A; examples are technical 1,1,2,2-tetra-(4-hydroxyphenyl)ethane and novolacs.
The epihalohydrin for use in step A is suitably epichlorohydrin or epibromohydrin with the former being preferred. Preferred amounts of epihalohydrin are from 3~5 to 8 moles for each phenolic equivalent of polyhydric phenol.
If step A is carried out in two or more stages both the epihalohydrin and the polyhydric phenol are added to the first stage.
Suitable condensation catalysts for use in step A are ionizable hydroxides, chlorides, bromides, io-dides, sulphides and cyanides.
1~18433 The amount of condensation catalyst may vary considerably, for example from 0.005 to 1.5 moles for each phenolic equivalent of polyhydric phenol, with the proviso that if an ionizable hydroxide is used then the amounts thereof should not be more than 0.75 moles for each phenolic equivalent of polyhydric phenol; in this case the amount of ionizable hydroxide added in the first stage of step A is preferably from 0.025 to 0.425 moles, more preferably from 0.05 to 0.25 moles per phenolic equivalent of polyhydric phenol, and the total amount of ionizable hydroxide added in step A is pre~erably from 0.05 to 0.75 moles more preferably from 0.25 to o.6 moles per phenolic equi-valent of polyhydric phenol. It is preferred that if substantially no ionizable hydroxide is added in step A then the amount of the condensation catalyst is at least 0.075 mole for each phenolic equivalent of poly-hydric phenol. Preferred condensation catalysts are in the ammonium or alkali-metal form. The more pre-ferred condensation catalyst are the ammonium andalkali-metal hydroxides and halides. The preferred halides are the chlorides and bromides with the former being particularly preferred. Preferred ammonium compounds are quarternary ammonium compounds such as tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide, tetramethyl ammonium chloride, methyl triethyl ammonium chloride and benzyl trimethyl ammonium chloride. Preferred alkali-metal compounds are the hydroxides and chlorides of lithium, sodium and potassium. The most preferred condensation catalysts for use in step A are sodium hydroxide and/or sodium chloride; a highly preferred condensation catalyst in step A is a mixture of sodium hydroxide and sodium chloride. Such a mixture is that present in the first and optionally further aqueous phases obtained in step C. Suitably the condensation catalysts are fed to step A as aqueous solutions. If step A is carried out in two or more stages the condensation catalyst, or a part thereof, is added to the first stage, and preferably condensation catalyst is added to each stage.
An oxygen-containing volatile organic solvent and/or waker may also be added in step A. In the preferred embodiment of the present invention both an oxygen-containing volatile organic solvent and water are added in step A. Suitably the amount of oxygen-containing organic solvent added is from 20 to 200 %w ba~ed on the weight of the epihalohydrin with the proviso that this amount should not be below 2 moles or above 15 moles for each phenolic equivalent of polydihydric phenol and suitably the amount of water i8 at least 15 %w based on the weight of epihalohy-drin. In this preferred embodiment the amount of water is such that the reaction product mixture of step A
separates into two liquid phases, an organic phase and an aqueous phase. Preferably the amount of water is such that any ionizable halides added or formed in step A are dissolved to produce a step A reaction product mixture which is substantially free of solid particles. Consequently the optimal amount of water will depend upon the specific ionizable halide added or formed. in general the amount of water should be from 400 to 600 %w, based on the weight of ionizable halide. In general there is no upper limit to the amount of water added in step A although in practice it will be restricted by such factors as optimal reactor volume, solvent recovery costs, epihalohydrin hydrolysis, etc. In practice the amount of added water present may be from 30 to 60 %w based on the weight of oxygen-containing volatile organic solvent.
In this preferred embodiment the water may be added to step A in several ways e.g. it may be included in a polyhydric phenol/oxygen-containing volatile organic solvent, if any, feed stream and/or added as an aqueous solution of condensation catalyst and/or added as a recycled aqueous phase, obtained in step C, and/or added as a recycled aqueous phase obtained in the recovery step e.g. a recycled washwater and/or added as a separate water stream. In this preferred em-bodiment the use of too low an amount of oxygen-containing volatile organic solvent will result in an 111~433 unacceptably low reaction rate in step A and the use of too high an amount will result in highly viscous products and unacceptably high solvent recovery costs.
The oxygen-containing volatile organic solvent should be halogen-free and volatile, that is have a boiling point at atmospheric pressure of preferably not above 120C and not below 50C; it should have one oxygen atom per molecule; it should be an alcohol or a ketone, and have preferably 3 to 6, more preferably 3 or 4, carbon atoms per molecule; examples are the ketones acetone and methyl ethyl ketone, and the alcohols propanol, isopropanol, butanol, and isobutanol. Suita-ble alcohols are in general the Cl to C6 alkanols, such as methanol, ethanol; preferred is isopropanol.
Preferred amounts of oxygen-containing volatile organic solvent are from 30 to 100 %w based on the weight of the epihalohydrin. If step A is carried out in two or more stages the oxygen-containing solvent and at least the above minimum amount of water, that is at lea8t 15 %w based on the weight of epihalohydrin, are added in the first stage.
The reaction temperature of step A depends on whether or not an oxygen-containing organic solvent and/or water are added in step A, and the amounts thereof, and on the type of condensation catalyst used but in general will be at least 25C and preferably from 35 to 120C. In the preferred embodiment of the present invention, using an oxygen-containing volatile organic solvent and water in step A, the reaction temperature is preferably below 75C, more preferably from 35 to 65C. One o~ the attractive features of the present process is that residence times in step A below 6 hours are sufficient for an acceptable conversion, and that generally the residence time can be from 0.15 to 4.0 hours.
The total residence time in step A will depend upon the reaction temperature. In the preferred em-bodiment as defined above total residence times of for example below 4.0 hours are sufficient. Residence times as low as 0.05 hours (at 65C or higher) have been found suitable, residence times of from 0.25 to 2.0 hours (at lower temperatures) are generally suita-ble. If step A in the preferred embodiment is carried out in two or more stages (as is preferred) the residence time in the last stage of step A is prefer-ably below 1.0 hour.
The reaction product mixture obtained in step A
may be reacted, without additional treatment, in step C or the unreacted epichlorohydrin may be removed therefrom before it is reacted in step C. In the preferred embodiment of the invention, in which an oY.ygen-containing organic solvent and water is added in step A, the aqueous phase and the organic phase are separated (by settling and decantation, or by ~1~8433 centrifugation) (step B) and the organic phase is further reacted in step C. The settling is very fast, and settling times can be as low as one minute in a continuous process; in a batch process a longer settling time can be accepted; settling is generally completed within 0.5 hours. It is not necessary to heat or cool the reaction product before or during separation. The aqeuous phase thus obtained is a substantially neutral aqueous solution comprising ionizable halide; the small amounts of unreacted epihalohydrin and oxygen-containing organic solvent which it also contains can easily be removed by conventional techniques such as stripping and may be used, as appropriate, in reaction step A or reaction step C. The stripped effluent may be dis-carded.
In the preferred embodiment the organic phaseobtained in step B is reacted in step C, in one or more stages, preferably two stages, with an aqueous solution, such as a from 20 to 50 %w aqueous solution, of an alkali-metal hydroxide, preferably sodium hydroxide.
In the first stage of step C the amount of alkali-metal hydroxide added, together with the amount of ionizable hydroxide, if any, added in step A, is less than 1.0 mole, preferably from 0.85 to 0.99 moles, for each phenolic equivalent of polyhydric phenol.
added in step A. The components of the aqueous solution may be added separately to the organic phase and may be at least partly provided by recycling the second and any subsequent aqueous phases obtained in step C. The total residence time needed for step C is below 2.0 hours with the residence time for the first stage of step C being preferably from 0.16 to 1.0 hours.
The reaction temperature for the first stage of step C
is preferably above 25C, more preferably from 35 to 65C. The unreacted epihalohydrin and oxygen-containing volatile organic solvent recovered from the aqueous phase obtained in step B may be added to this first stage of step C.
The reaction product obtained in the first stage of step C readily forms, upon settling, an organic phase and an aqueous phase which may easily be separated in the manner described above for step B.
The aqueous phase thus separated, which is a slightly alkaline aqueous solution comprising alkali-metal halide, a small amount of alkali-metal hydroxide and some phenolic compounds, for example phenolic chlorohydrin ethers, phenolic glycidyl ethers, and polyhydric phenols, is then recycled to step A. The aqueous phase may first be neutralized, especially if, as in the case of a batch process, it is stored before being added to step A. The aqueous phase may be re-cycled to any stage of step A and in the case of amulti-stage step A may be recycled to the first or a subsequent stage thereof, in the latter case the 1~8433 .
catalytic effect of the components of this aqueous phase may not be significant.
The organic phase obtained after the first stage of step C is then reacted with further amounts of an aqueous solution, such as a from 20 to 50 %w aqueous solution, of an alkali-metal hydroxide, preferably sodium hydroxide, wherein the amount thereof is such that the total amount of alkali-metal hydroxide added in step C, together with the amount of ionizable hydroxide, if any, added in step A, is at least 1.0 moles, preferably from 1.05 to 1.5 moles, for each phenolic equivalent of polyhydric phenol used in step A. Suitably step C comprises only two stages and preferably the residence time for the second stage thereof is 0.016 to 0.4 hours and preferably the reaction temperature is from 25 to 65C.
After the second and subsequent stages, if any, of step C, the reaction product readily forms, upon settling, an organic phase and an aqueous phase which may be separated in the manner described above for step B.
The aqueous phase thus separated which is an alkaline aqueous solution comprising alkali-metal hydroxide and small amounts of alkali-metal chloride, in one preferred embodiment of the invention, is recycled to step A or to one of the stages thereof, preferably to the first stage thereof, and therefore ~1~8433 provides, at least in park, the water and condensation catalyst required in step A. In this preferred embodiment of the invention, the aqueous phase may also be recycled to the first stage of step C or to a first stage of a further step C and therefore provides, at least in part, the aqueous solution of alkali-metal hydroxide required.
The organic phase obtained after the last stage of step C is then worked up to recover the polyglycidyl ether therefrom. The manner or working up is not critical and usually comprises one or more washing steps and the removal of the unreacted epihalohydrin, oxygen-containing organic solvent and water therefrom.
The recovered epihalohydrin, oxygen-containing organic solvent, water and washwater may be recycled, where appropriate to one or both of steps A and C or to one or both of further steps A and C. The recovered poly-glycidyl ether may be further treated, if desired, with small amounts of alkali-metal hydroxide in solvents, such as hydrocarbon solventse.g. toluene.
This preferred embodiment will now be illustrated by reference to the accompanying drawings in which Figures 1 to 4 are schematic diagrams of this preferred embodiment.
In Figure 1, the feedstock stream 1 comprising a polyhydric phenol, epihalohydrin, oxygen-containing volatile organic solvent and water, together with the ~8433 aqueous phase recycle stream 13, are continuously fed to reactor Al. Suitably the feedstock stream 1 is pre-heated to the desired reaction temperature by means of heaters, not shown. The reaction product stream 2 is continuously withdraun and fed to reactor A2, together with the aqueous phase recycle stream 9. The reaction product stream 3 is continuously withdrawn and fed to separator B and the lower aqueous phase is continuously withdrawn as stream 5. The upper organic phase is also continuously withdrawn, as stream 4, and fed, together with an aqueous solution of alkali-metal hydroxide, stream 6, to reactor Cl, after which the reaction product stream 7 is continuously withdrawn and fed to separator Sl. The lower aqueous phase is continuously withdrawn, as stream 9, and fed to reactor A2. The upper organic phase is also con-tinuously withdrawn, as stream 8, and fed, together with an aqueous solution of alkali-metal hydroxide, stream 10, to reactor C2 after which the reaction product stream 11 is continuously withdrawn and fed to separator S2. The lower aqueous phase is con-tinuously withdrawn, as stream 13, and recycled to reactor Al. The upper organic phase is also continuously withdrawn, as stream 12, and the poly-Klycidyl ether recovered therefrom.
In Figure 2, the scheme is substantially thesame as for figure 1 with the differences that the lower aqueous phase which is continuously withdrawn as stream 13 is fed to reactor C1, and that an aqueous solution of alkali-metal hydroxide, stream 14, is continuously fed to reactor A1.
In Figure 3, the scheme is substantially the same as for figure 1 with the difference that the lower aqueous phase which is continuously withdrawn as stream 9 is fed to the reactor A1. Moreover A1 is the single reactor in step A and the reaction product stream 2 is fed directly to separator B.
In Figure 4, the scheme is substantially the same as for figure 3 with the difference that the lower aqueous phase which is continuously withdrawn as stream 13 is fed to reactor C1.
Other embodiments of the invention are given below in a generalized form. The product of step A, or the organic phase obtained in step B, is reacted in step C, in one or more stages, with an aqueous ~olution, such as a from 20 to 50 %w aqueous solution, of an alkali-metal hydroxide, preferably sodium hydroxide. The amount of alkali-metal hydroxide added, together with the amount of ionizable hydroxide, if any, added in step A, is more than 1.0 moles, preferably from 1.05 to 1.5 moles for each phenolic equivalent of polyhydric phenol used in step A. If the unreacted epihalohydrin is removed before step C it may be de-sirable to add to the reaction product a solvent such ~J ~8~33 as toluene, benzene or methyl isobutyl ketone.
Suitable amounts of such solvents are from 50 to 300 %w based on the reaction product to be used in step C.
In one embodiment of the present invention step C
is carried out in one stage and the reaction product allowed to settle upon which an aqueous phase and an organic phase are formed and the aqueous phase is separated as described above. The separated aqueous phase which is an alkaline aqueous solution of alkali-metal halide and alkali-metal hydroxide is then used, at least in part, as a condensation catalyst in step A or one of the stages thereof. In this embodiment the organic phase obtained is worked up to recover the polyglycidyl ether therefrom. The manner of working up is not critical and usually comprises one or more waæhing steps and the removal of water and, if present, unreacted epihalohydrin, and solvents therefrom de-pending upon the particular conditions used. The re-covered polyglycidyl ether may be further treated with Bmall amounts of sodium hydroxide in solvents, such as hydrocarbon solvents e.g. toluene or oxygen-containing solvents such as ketones e.g. MEK, MIBK.
In another embodiment of the present invention step C is carried out in at least two stages. The reaction product is allowed to settle after each stage, the aqueous phases separated as described above and the final organic phase worked up as described ~18433 above. Preferably from 1.0 to 1.15 moles and from 0.05 to 0.35 moles of alkali-metal hydroxide (for each phenolic equivalent of polyhydric phenol added in stage A) are added in the first stage and subsequent stages of step G respectively. Suitably each separated aqueous phase, or a part thereof, is used as a conden-sation catalyst in step A or a further step A or the first separated aqueous phase is used as a condensation catalyst in step A or one of the stages thereof and the second and any subsequent separated aqueous phases are used as a source of aqueous alkali-metal hydroxide solution in step C or one of the stages thereof. If the first separated aqueous phase is not used as a conden-sation catalyst then it may be discarded.
The reaction temperature of step C depends upon the reaction conditions used but is preferably above 25C, more preferably from 35 to 100C. In the pre-ferred embodiment of the invention, in which an oxygen-containing organic solvent and water are added in step A the reaction temperature is suitably below 75C. The total residence time in step C is suitably below 4.0 hours.
The invention is illustrated by the following example8. In Examples 1 to 6 and 10 the figures given are those obtained under steady-state conditions (approximately 15 hours~. Before these conditions were achieved artificial streams were used instead of the recycle streams. In the other examples the first batch was made using an artificial stream, which in subsequent batches was replaced by the appropriate effluent from a foregoing batch.
Example 1 The process scheme described in ~igure 1 was used.
The reactor Al (2 litres) was continuously fed by (a) a feedstock stream 1, (1145.6 g/h), preheated to a temperature of 43C, comprising g/h diphenylol propane 119.7 epichlorohydrin 582.8 isopropanol 340.2 water 102.9 and (b) the recycle stream 13, (57.5 g/h), from separator S2 comprising g/h sodium hydroxide 7 sodium chloride 5 i~opropanol 2 epichlorohydrin 0.5 water 43 This recycle stream also contained about 4 g/l of non-volatile carbon compounds of which about 10 %w was aromatic compounds.
Reactor Al was maintained at a temperature of 43C
and the residence time was 45 minutes.
The reaction product stream 2 was continuously withdrawn and fed (1203.1 g/h) to reactor A2 ( 4 litres) together with the recycle stream 9, (198.9 g/h), from separator S1, comprising g/h sodium hydroxide 2 sodium chloride 43 isopropanol 7 epichlorohydrin 2 water 144.9 This recycle stream also contained about 3 g/l of non-Yolatile carbon compounds of which about 90 %w was `
aromatic compounds.
~eactor A2 was maintained at a temperature of 43C
and the residence time was 5 minutes.
The reaction product stream 3 was continuously withdrawn and fed (1402 g/h) to separator B in which two phases formed. The lower aqueous phase was with-drawn, (295.3 g/h), as stream 5, and worked up as des-cribed below. The residence time in separator B was 10 minutes.
The upper organic phase was continuously withdrawn, as stream 4, and fed (1106.7 g/h) to reactor C1, (2.0 litres) together with a 20 ~w aqueous solution of sodium hydroxide (157.6 g/h~, stream 6.
Reactor C1 was maintained at a temperature of 43C
~118433 and the residence time was 30 minutes.
The reaction product stream 7 was continuously withdrawn and fed (1264.2 g/h) to separator S1 in which two phases formed. The lower aqueous phase was with-drawn, as stream 9, and continuously fed (198.9 g/h) to reactor A2. The residence time in separator S1 was 10 minutes.
The upper organic phase was continuously with-drawn, as stream 8, and fed (1065.1 g/h~, after cooling, 10 to reactor C2 (0.4 litres) together with a 20 %w aqueous solution of sodium hydroxide (52.5 g/h).
Reactor C2 was maintained at a temperature of 33C
and the residence time was 5 minutes.
The reaction product stream 11 was continuously 15 withdrawn and fed (117.6 g/h) to separator S2 in which two phases formed. The lower a~ueous phase was withdrawn, as stream 13, and continuously fed (57.5 g/h) to reactor A1. The residence time in separator S2 was 10 minutes.
The upper organic phase was withdrawn (1060.1 g/h), washed with water to remove any sodium chloride there-from, flashed and steam-stripped to remove isopropanol, water and epichlorohydrin therefrom which were recycled to the various reactors where appropriate. The recovered liquid diglycidyl ether of diphenylol propane had the following properties:-epoxide equivalent weight 175 ~118433 saponifiable chlorine (%w) 0.03 viscosity (Poise; 25C) 120 The lower aqueous phase, withdrawn as stream 5, was stripped to remove any isopropanol and unreacted epichlorohydrin therefrom which was recycled, where appropriate, to reactor A2. The stripped effluent had the following composition:-%w sodium chloride 23 sodium hydroxide ~ o.o8 carbon-containing compounds 0.10 water balance Example 2 Example 1 was repeated with the differences that separation step B was omitted and that a portion of the lower aqueous stream 9, was bled (295.3 g/h) and worked up as described for the lower aqueous phase withdrawn as stream 5. The recovered liquid digly-cidyl ether of diphenylol propane had the following properties:-epoxide equivalent weight 179 saponifiable chlorine (%w) 0.05 viscosity (25C, Poise) 122 and the stripped effluent, derived from the bleed stream, had the following composition:-%wsodium chloride 22 sodium hydroxide ~118433 carbon-containing compounds 0.3 water balance.
Example 3 The process scheme described in Figure 2 was used, in which the same temperatures and residence times as described in Example 1 were used.
The reactor A2 (2 litres) was continuously fed by (a) a feedstock stream as described in Example 1, and (b) a 20 %w aqueous solution of alkali-metal hydroxide, stream 14, (57.5 g/h).
The reaction product stream 2 was continuously withdrawn and fed (1203.1 g/h) to reactor A2 toge~her with the recycle stream 9, (200.6 g/h), from separator Sl, comprising g/h sodium hydroxide 2 sodium chloride 43 isopropyl alcohol 7 epichlorohydrin 2 water 146 This recycle stream also contained about 5 g/l of non-volatile carbon compoundsof which about 90 %w was aromatic compounds.
The reaction product stream 3 was continuously withdrawn and fed (1398.7 g/h) to separator B in which two phases formed. The lower aqueous phase was with-drawn (294.7 g/h~, as stream 5, and worked up as des-cribed in Example 1.
The upper organic phase was withdrawn, as stream4, and continuously fed (1104.0 g/h) to reactor C
together with a 20 %w aqueous solution of sodium hydroxide (100 g/h)~ stream 6, and the recycle stream 13 (57.7 g/h) 7 from separator S2, comprising g/h sodium hydroxide 7 sodium chloride 5 volatile carbon compounds 2.5 water 43.2 This recycle stream also contained about 5 g/l of non-volatile carbon compounds of which about 10 %w was aromatic compounds.
The reaction product stream 7 was continuously withdrawn and fed (1266.7 g/h) to separator S1 in which two phases formed. The lower aqueous stream was with-drawn, as stream 9, and fed (200.6 g/h~ to reactor A2.
The upper organic phase was withdrawn, as stream 8, and continuously fed (1066.1 g/h), after cooling, to reactor C2 together with a 20 %w aqueous solution of sodium hydroxide (52.2 g/h), stream 10.
The reaction product stream 11 was continuously withdrawn and fed (1118.6 g/h) to separator S2 in which two phases formed. The lower aqueous phase was with-drawn, as stream 13, and continuously fed (37.7 g/h) to reactor C1.
` 111~433 3o The upper organic phase was withdrawn (1060.9 g/h) and worked up as described in Example 1. The recovered liquid diglycidyl ether of diphenylol propane had the following properties:-epoxide equivalent weight 181 saponifiable chlorine (%w) 0.08 viscosity (25C, Poise) 125 The lower aqueous phase, withdrawn as stream 5, after stripping had the following composition %w sodium chloride 23 sodium hydroxide 0.08 carbon-containing compounds 0.14 water balance Example 4 Example 3 was repeated with the differences that the separation step B was omitted and that a portion of the lower aqueous stream 9, was bled (294.7 g/h) and worked up as described for the lower aqueous phase withdrawn as stream 5. The recovered liquid diglycidyl ether of diphenylol propane had the following proper-ties:-epoxide equivalent weight 180 saponifiable chlorine (%w) 0.07 viscosity t25C, Poise) 120 and the stripped effluent, derived from the bleed stream, had the following composition:-11~8433 %w sodium chloride 23 sodium hydroxide carbon-containing compounds o.6 water balance Exa`mple 5 Example 1 was repeated using the process scheme described in Figure 3. Substantially the same results were obtained.
10` Examp'le 6 Example 2 was repeated using the process scheme described in Figure 4. The results obtained were substantially the same as for example 2 except that the stripped effluent obtained from stream 5 contained less than 0.05 %w of sodium hydroxide and that the recovered diglycidyl ether had a viscosity (25C, Poise) of 133.
Exa`mp'le 7 ' In this example t.he process of the present invention was carried out in a batch manner.
` P'art' A
A mixture of diphenylol propane (114 g), epichlorohydrin (555 g), isopropanol (324 g) and water (80 g) was charged to a reactor (2 litres) and reacted with an artificial stream - a solution of sodium hydroxide (9.5 g) and sodium chloride (o.8 g) in water (40 g) - for 1 hour at 45C. The reaction ~lBD~33 pro,duct was allowed to settle and the lower aqueous phase (first) was separated.
The remaining organic phase was reacted with a solution of sodium hydroxide (30 g) in water (121 g) for 20 minutes at 45C after which the lower aqueous phase (second) was separated.
The remaining organic phase was reacted with a solution of sodium hydroxide (10 g~ in water (40 g~
for 5 minutes at 30C and the lower aqueous phase (third) separated and stored.
The remaining organic phase was worked up as described above. The liquid diglycidyl ether of di-phenylol propane had the following properties:-epoxide equivalent weight 179 saponifiable chlorine (%w) 0.07 viscosity (25C, Poise) 83 The first aqueous phase was stripped to removeisopropanol and unreacted epichlorohydrin therefrom.
The stripped effluent, which was discarded, had the following composition:-%w sodium chloride 22 sodium hydroxide ~ 0.05 carbon-containing compounds 0.1 water balance The second aqueous phase was also stripped to remove any isopropanol and unreacted epichlorohydrin therefrom, to enable analysis for other carbon compounds. The stripped effluent (198 g), which was stored, had the following composition:-%w sodium chloride 21.5 sodium hydroxide 0.9 carbon-containing compounds 0.4 water balance.
Par't B
10 The above experiment was repeated 5 times, but with the difference that in each experiment the aqueous solution of sodium hydroxide and sodium chloride used in the first step in the above experiment was replaced by the stored second and third aqueous effluents of the foregoing experiment; the second effluent was not stripped anymore, but used as such.
The first aqueous phases (stripped) contained 0.1-0.2 %w of carbon-containing compounds, 22 %w NaCl, and ~0.05 %w NaOH, and the liquid diglycidyl ether had epoxide equivalent weights 178-182, saponifiable Cl 0.05-o.o8 %w and viscosity 80-84 Poise (25C).
' Examp'le' 8 Example 7 was repeated with the difference that the solution of sodium hydroxide and sodium chloride used in the first step of Part A to initiate the series was replaced by solutions in water (40 g), of sodium chloride (10 g~, lithium chloride (8 g~, potassium 1~18433 chloride (12 g) and tetramethylammonium chloride (20 g), and the amount of sodium hydroxide used after the first separation was increased to 39 g. In Part B this amount was again reduced to 30 g. The results obtained were substantially the same as for Example 7; the resin analysis was the same, and the first aqueous (stripped) contained also 0.1-0.2 %w carbon-containing compound.
Example 9 10 Example 7 was repeated, with the difference that the diphenylol propane was replaced by an equivalent amount of diphenylol methane (100 g~.
The liquid diglycidyl ether of diphenylol methane had the following properties:
epoxide equivalent weight 170 saponifiable chlorine (%w) 0.05 viscosity (25C, Poise) 33 phenolic hydroxy (meq/100 g) 1.2 The aqueous phases of Part A were stripped to remove isopropanol and epichlorohydrin; the stripped effluents had essentially the same compositions as in Examples 7.
Example 10 Continuous experiment, as in Example 1, but with a different process scheme, and higher reaction tem-peratures (60C~.
The process scheme consisted of 4 reactors in ~118~33 series, each 0.25 l, numbered A, C1, C2, and C3 res-pectively, with a phase separator (numbered B, S1,S2, and S3, respectively) after each reactor.
The aqueous phase from separator S3 was recycled to reactor A (42.6 g/h, contained NaOH 4.7 %w, NaC1 14.7 %w, and 1000-3000 ppm resinous compounds).The aqueous phases from separators B, S1 and S2 were not recycled, but stripped to recover isopropanol (4 %w) and epichlorohydrin (1 %w) and discarded: they con-tained less than 200 ppm resinous compounds whichdoes not contaminate the stripper in continuous operation.
The continuous feed for reactor A consisted of the streams (a), (b) and (c):
15 (a) feedstock stream (1145.6 ~/h~, preheated to 55C, comprising g/h diphenylol propane 119.7 epichlorohydrin 582.8 isopropanol 340.2 water 102.9 (b) 20 %w aqueous solution of sodium hydroxide (106 g/h) (c) aqueous phase from separator S3 as indicated above.
The temperature of reactor A was kept at 60~C. The reaction stream was continuously withdrawn from reactor A, and fed to separator B in which two phases formed.
The lower aqueous phase (149 g/h~ and the upper organic 11~8433 phase were withdrawn, and the latter continuously fed to reactor Cl, together with a 20 %w aqueous solution of sodium hydroxide (64 g/h). The temperature in reactor Cl was kept at 60C.
The reactor stream from Cl was continuously fed to separator Sl, where two layers formed which were withdrawn (lower aqueous layer: 101 g/h). The upper organic phase was continuously fed to reactor C2, to-gether with a 20 %w aqueous solution of sodium hydroxide (32 g/h).
The temperature in C2 was kept at 60C.
The reactor stream from C2 was fed to separator S2; the two layers formed were separated and withdrawn (lower aqueous layer: 38 g/h) and the upper organic layer continuously fed to reactor C3, together with a 20 %w aqueous solution of sodium hydroxide (32 g/h).
The temperature in C3 was kept at 60C.
The reactor stream from C3 was fed to separator S3, the layers formed were withdrawn; the lower aqueou5 layer was continuously fed to reactor A.
The upper organic layer (1036 g/h) was con-tinuously washed with water to remove any sodium chloride and sodium hydroxide therefrom, and then flashed and steam-stripped to remove isopropanol, epichlorohydrin and water (this mixture of volatiles can be recycled to reactor A, with fresh components to make up for the right feed composition).
11~. B~33 .
The recovered liquid diglycidyl ether of diphenylol propane had the following properties:
epoxide equivalent weight 183 saponifiable chlorine ~%w) 0.01 phenolic hydroxy (meq./100 g) 1.1 viscosity ~Poise; 25C) 105 Example 11 A mixture of diphenylol propane (109 g), epichlorohydrin (886 g), isopropanol (346 g) and water (87 g) was charged to a reactor ~2 litres) and 0 reacted with a solution (added over 5 minutes) of sodium chloride (50.6 g) and sodium hydroxide (1.9 g) in water ~117.5 g) for a total of 20 minutes at 45C.
The reaction product was allowed to settle and the lower aqueous phase ~first) was separated. The remaining organic phase was reacted with a 19.4% aqueous solution of sodium hydroxide (204 g) for 15 minutes at 45 after which the lower aqueous phase ~second) was separated.
The remaining organic phase was reacted with water to remove any sodium chloride therefrom, flashed and steam-stripped to remove isopropanol, water and epichlorohydrin therefrom. The product was dissolved in toluene and treated with a 2.5 %w solution of sodium hydroxide.
The final product had the following properties.
epoxide equivalent weight 178 saponifiable chlorine ~%w) 0.03 viscosity (25C, Poise) 76 The first aqueous phase was stripped to remove isopropanol and un-reacted epihalohydrin therefrom.
P~
The stripped effluent, which was discarded, had the following composition:-%w sodium chloride 23 sodium hydroxide 0.04 water 77 The second aqueous phase was also stripped to remove isopropanol and epichlorohydrin therefrom. ~he stripped effluent (231 g), which was stored, had the following composition:-%w sodium chloride 22 sodium hydroxide 1.0 water 77 15 The above experiment was repeated with the differ-ence that in the first step the aqueous solution of sodium chloride and sodium hydroxide was replaced by the stored stripped effluent obtained from the second aqueous phase.
Substantially the same results were obtained.
EXample 12 The procedures of example 11 were repeated with the differences that the first reaction product was not allowed to settle, but reacted immediately with the 19.4 % w aqueous solution of sodium hydroxide and that only a part (231 g~ of the subsequently obtained lower aqueous phase, after stripping, was used in place ~18433 of the aqueous solution of sodium chloride and sodium hydroxide in the repeat experiment. The recovered diglycidyl ether had substantially the same properties as that obtained in example 11.
Example 13 The first experiment of example 11 was repeated with the differences that both of the aqueous phases, after stripping, were discarded and that the second organic phase was not worked-up but reacted with a 20.1 %w aqueous solution of sodium hydroxide (58 g) for 5 minutes at 42C after which the reaction product was allowed to settle and the aqueous phase (third) was separated. The organic phase thus ob-tained was washed and steam-stripped to remove iso-propanol, water and epichlorohydrin therefrom to produce a final product having the following properties:-epoxide equivalent weight 178 saponifiable chlorine (%w) 0.11 viscosity (25C, Poise) 75 The third separated aqueous phase was stripped to remove -,sopropanol and epihalohydrin therefrom. The stripped effluent (65 g), which was stored, had the following composition:-%w 25 sodium chloride 10 sodium hydroxide ` 8 water 82 ~8433 In the repeat experiment the 19.4 %w aqueous solution of sodium hydroxide reacted with the first organic phase was partly made-up from the above stored stripped effluent. The final product has substantially the same properties as described above.
Example 14 A mixture of diphenylol propane (109 g), epi-chlorohydrin (886 g) and 1 molé % of tetramethyl-ammonium chloride (based on diphenylol propane) and reacted for 2 hours at 100C after which the unreacted epichlorohydrin was removed by vacuum distillation.
The reaction product was dissolved in methyl isobutyl -~;
ketone to produce a 35 %w solution which was reacted with a 5 %w aqueous solution of sodium hydroxide containing 1.01 moles of sodium hydroxide for 1 hour at 85C after which the reaction product was allowed to settle and the lower aqueous phase was withdrawn and discarded.
The remaining organic phase was reacted with a further 20.1 %w aqueous solution of sodium hydroxide in an amount corresponding to 0.25 moles of sodium hydroxide for each mole of diphenylol propane after which the lower aqueous phase was withdrawn and stored.
The remaining organic phase was washed and steam-~tripped to remoYe the methyl isohutyl ketone and watertherefrom to produce a finaI product ha~ing the following properties.-~118433 epoxide equivalent weight 185 saponifiable chlorine (%w) 0.1 viscosity (25c, Poise) 80 The above experiment was repeated with the 5 difference that the 5 %w aqueous solution of sodiumhydroxide reacted with the first organic phase was partly made-up from the above stored aqueous phase.
The final product had substantially the same properties as described above.
Example 15 The novolac used in this example had molecular weight 500-600 and contained 0. 96 phenolic equivalents per 100g.
Part A. (Initiating the series of experiments) Novolac 15 (0.54 kg), epichlorohydrin ( 2.42 kg)~ isopropanol (1.42 kg) and water (o.78 kg) were heated to 35 c in a 6 l-reactor with stirrer, and reacted with a solution of sodium hydroxide ( 52 g) in water ( 52 g) during 20 minutes at 45C.
A solution of sodium hydroxide ( 151 g) in water (151 g) was added in 4 equal parts at 5 minutes inter-vals.
~he temperature rose to 50c, and was reduced to 45C
by cooling. After 30 minutes the phases were separated 25 ( settling time 15 minutes), the aqueous phase (first) was stripped to recover isopropanol and epichlorohydrin and discarded (NaOH content; 0.1 %w~.
~i~8433 The organic phase was cooled to 30C, and reacted with a solution of sodium hydroxide (52 g2 in water (208 g) for 5 minutes. The phases were separated (settling time 15 minutes~, and the aqueous phase was (second2 stored.
The resin was recovered from the organic phase by vacuum stripping distillation; the crude resin was dissolved in methyl ethyl ketone (2 12, and the so-lution washed twice with a dilute aqueous sodium dihydro phosphate solution (o.6 l; 0.3 %w NaH2PO4).
Volatiles were distilled off, last traces in vacuum at 120C.
The resin had the following properties:-epoxide equivalent weight 186 saponifiable chlorine (%w) 0.15 phenolic hydroxy (meq./100 g) 3.5Par't B (according to the invention2. The experiment was repeated four times, with the exception that now aqueous sodium hydroxide in the first step was re-placed by the s,tored aqueous phase of the foregoingexperiment.
Here also settling timesof 15 minutes were sufficient, the first aqueous phase was low in alkalinity, and the resin properties were the same (within 1% accuracy).
Exampl'e' 16 Example 15 was repeated, with the difference that 11~8433 the novolac was replaced by the equivalent amount of a technical tetraphenylol ethane (520 g; 10 phenolic equivalents per kg). The resin properties were (1% accuracy):-epoxy equivalent weight 172 saponifiable chlorine (%w) 0.05 phenolic hydroxy (meq/100 g) 2 Here also settling times of 15 minutes were sufficient, and the first aqueous phases of the series were low in alkalinity.
Claims (8)
1. Process for the preparation of a polyglycidyl ether of a polyhydric phenol wherein the polyhydric phenol is reacted with from 2.5 to 10 moles of an.
epihalohydrin per phenolic hydroxy equivalent in the presence of a condensation catalyst, water and a volatile organic solvent, and the reaction product is reacted with aqueous alkali metal hydroxide, with separation of aqueous phase and organic phase in one or more stages and recovery of the polyglycidyl ether from the last organic phase, wherein at least part of at least one separated aqueous phase is recycled to an earlier stage of the process.
epihalohydrin per phenolic hydroxy equivalent in the presence of a condensation catalyst, water and a volatile organic solvent, and the reaction product is reacted with aqueous alkali metal hydroxide, with separation of aqueous phase and organic phase in one or more stages and recovery of the polyglycidyl ether from the last organic phase, wherein at least part of at least one separated aqueous phase is recycled to an earlier stage of the process.
2. Process as claimed in claim 1, comprising the steps of:-(A) reacting in one or more stages (i) a polyhydric phenol;
(ii) an epihalohydrin in an amount of from 2.5 to 10 moles for each phenolic hydroxy equivalent of (i); and (iii) a condensation catalyst, with the proviso that if the condensation catalyst contains an ionizable hydroxide then the amount thereof is at most 0.75 moles for each phenolic hydroxy equivalent of (i);
(C) reacting in one or more stages the reaction product obtained in step A with an aqueous solution of an alkali-metal hydroxide, wherein the total amount of alkali-metal hydroxide reacted, together with the amount of ionizable hydroxide; if any, added in step A, is at least 1.0 moles for each phenolic hydroxy equi-valent of (i) added in step A, separating the reaction product, or each reaction product of each stage, into an aqueous phase and an organic phase and, if two or more reaction stages are used, reacting each separated organic phase, with the exception of the last organic phase, in the next reaction stage of this step C, (D) recycling at least part of an aqueous phase ob-tained in step C to step A or to one or more stages there-of and/or to an earlier stage, if any, of step C, and (E) recovering the polyglycidyl ether of the polyhydric phenol from the organic phase or the last organic phase obtained in step C.
(ii) an epihalohydrin in an amount of from 2.5 to 10 moles for each phenolic hydroxy equivalent of (i); and (iii) a condensation catalyst, with the proviso that if the condensation catalyst contains an ionizable hydroxide then the amount thereof is at most 0.75 moles for each phenolic hydroxy equivalent of (i);
(C) reacting in one or more stages the reaction product obtained in step A with an aqueous solution of an alkali-metal hydroxide, wherein the total amount of alkali-metal hydroxide reacted, together with the amount of ionizable hydroxide; if any, added in step A, is at least 1.0 moles for each phenolic hydroxy equi-valent of (i) added in step A, separating the reaction product, or each reaction product of each stage, into an aqueous phase and an organic phase and, if two or more reaction stages are used, reacting each separated organic phase, with the exception of the last organic phase, in the next reaction stage of this step C, (D) recycling at least part of an aqueous phase ob-tained in step C to step A or to one or more stages there-of and/or to an earlier stage, if any, of step C, and (E) recovering the polyglycidyl ether of the polyhydric phenol from the organic phase or the last organic phase obtained in step C.
3. Process as claimed in claim 1, comprising the steps of:-(A) reacting in one or more stages, at a temperature of below 75°C, (i) a polyhydric phenol;
(ii) an epihalohydrin in an amount of from 2.5 to 10 moles for each phenolic equivalent of (i);
in the presence of (iii) an oxygen-containing volatile organic solvent in such an amount that it represents from 20 to 200 %w based on the weight of (ii) and from 2 to 15 moles for each phenolic equivalent of (i);
(iv) water in an amount of at least 15 %w based on the weight of (ii), and (v) a condensation catalyst, with the proviso that if the condensation catalyst is an ionizable hydroxide the amount thereof is at most 0.75 moles for each phenolic equivalent of (i);
(B) separating the reaction product obtained in step A into an aqueous phase and an organic phase;
(C) reacting, in two or more stages, the organic phase obtained in step B, at a temperature of below 75°C, with an aqueous solution of an alkali-metal hydroxide, wherein the amount of alkali-metal hydroxide added in the first stage, together with the amount of ionizable hydroxide, if any, added in step A, is less than 1.0 moles for each phenolic equivalent of (i) added in step A and wherein the total amount of alkali-metal hydroxide added, together with the amount of ionizable hydroxide, if any, added in step A is at least 1.0 moles for each phenolic equivalent of (i) added in step A, separating the reaction product of each stage into an aqueous phase and an organic phase and reacting each separated organic phase with the exception of the last separated organic phase, in the next reaction stage of this step C;
(D) recycling at least a part of a separated aqueous phase obtained in step C to step A or to one of the stages thereof, and (E) recovering the polyglycidyl ether of the poly-hydric phenol from the last organic phase obtained in step C.
(ii) an epihalohydrin in an amount of from 2.5 to 10 moles for each phenolic equivalent of (i);
in the presence of (iii) an oxygen-containing volatile organic solvent in such an amount that it represents from 20 to 200 %w based on the weight of (ii) and from 2 to 15 moles for each phenolic equivalent of (i);
(iv) water in an amount of at least 15 %w based on the weight of (ii), and (v) a condensation catalyst, with the proviso that if the condensation catalyst is an ionizable hydroxide the amount thereof is at most 0.75 moles for each phenolic equivalent of (i);
(B) separating the reaction product obtained in step A into an aqueous phase and an organic phase;
(C) reacting, in two or more stages, the organic phase obtained in step B, at a temperature of below 75°C, with an aqueous solution of an alkali-metal hydroxide, wherein the amount of alkali-metal hydroxide added in the first stage, together with the amount of ionizable hydroxide, if any, added in step A, is less than 1.0 moles for each phenolic equivalent of (i) added in step A and wherein the total amount of alkali-metal hydroxide added, together with the amount of ionizable hydroxide, if any, added in step A is at least 1.0 moles for each phenolic equivalent of (i) added in step A, separating the reaction product of each stage into an aqueous phase and an organic phase and reacting each separated organic phase with the exception of the last separated organic phase, in the next reaction stage of this step C;
(D) recycling at least a part of a separated aqueous phase obtained in step C to step A or to one of the stages thereof, and (E) recovering the polyglycidyl ether of the poly-hydric phenol from the last organic phase obtained in step C.
4. Process as claimed in any of claims 1 to 3, where-in the polyhydric phenol is a di(hydroxyphenyl) alkane.
5. Process as claimed in any of claims 1 to 3 , where-in the amount of ionizable hydroxide added in the first stage of step A is from 0.025 to 0.425 moles per phenolic hydroxy equivalent of the polyhydric phenol.
6. Process as claimed in any of claim 2 or 3 , where-in the amount of water added in step A is from 30 to 60 percent by weight of the oxygen-containing volatile organic solvent.
7. Process as claimed in any of claim 2 or 3 , wherein the amount of water added in the first stage of step A
is at least 15 percent by weight of the epihalohydrin.
is at least 15 percent by weight of the epihalohydrin.
8. Process as claimed in any of claim 2 or 3 , where-in the temperature in steps A and C is from 35 to 65°C.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB2741177 | 1977-06-30 | ||
| GB27410/77 | 1977-06-30 | ||
| GB2741077 | 1977-06-30 | ||
| GB27411/77 | 1977-06-30 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1118433A true CA1118433A (en) | 1982-02-16 |
Family
ID=26258798
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000304960A Expired CA1118433A (en) | 1977-06-30 | 1978-06-07 | Preparation of polyglycidyl ethers of polyhydric phenols |
Country Status (8)
| Country | Link |
|---|---|
| JP (1) | JPS6057444B2 (en) |
| AU (1) | AU520704B2 (en) |
| CA (1) | CA1118433A (en) |
| CH (1) | CH635089A5 (en) |
| DE (1) | DE2828420A1 (en) |
| FR (1) | FR2396005A1 (en) |
| IT (1) | IT1097374B (en) |
| NL (1) | NL186907C (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4345060A (en) * | 1980-07-08 | 1982-08-17 | Shell Oil Company | Diglycidyl ethers of diphenylol alkanes, their preparation and use in curable compositions |
| JPS591524A (en) * | 1982-06-25 | 1984-01-06 | Sumitomo Chem Co Ltd | Production of novolak epoxy resin |
| AU571499B2 (en) * | 1983-04-01 | 1988-04-21 | Dow Chemical Company, The | Preparing epoxy resins |
| IT1164258B (en) * | 1983-05-31 | 1987-04-08 | Sir Soc Italiana Resine Spa | CATALYTIC PROCEDURE FOR THE PREPARATION OF EPOXY RESINS |
| US4582892A (en) * | 1985-05-28 | 1986-04-15 | The Dow Chemical Company | Process for the preparation of epoxy resins |
| WO2014017524A1 (en) | 2012-07-26 | 2014-01-30 | 電気化学工業株式会社 | Resin composition |
| US11622930B2 (en) | 2020-09-23 | 2023-04-11 | Yoshiharu Masui | Antimicrobial agent |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1154808B (en) * | 1957-07-18 | 1963-09-26 | Union Carbide Corp | Process for the preparation of glycidyl polyethers of polyhydric phenols |
| US2986552A (en) * | 1957-10-04 | 1961-05-30 | Shell Oil Co | Continuous process for preparing glycidyl ethers of phenols |
| US2986551A (en) * | 1957-10-04 | 1961-05-30 | Shell Oil Co | Continuous process for preparing glycidyl polyethers of polyhydric phenols |
| GB1050641A (en) * | 1963-01-18 |
-
1978
- 1978-06-07 CA CA000304960A patent/CA1118433A/en not_active Expired
- 1978-06-28 CH CH705478A patent/CH635089A5/en not_active IP Right Cessation
- 1978-06-28 AU AU37516/78A patent/AU520704B2/en not_active Expired
- 1978-06-28 FR FR7819307A patent/FR2396005A1/en active Granted
- 1978-06-28 IT IT25088/78A patent/IT1097374B/en active
- 1978-06-28 NL NLAANVRAGE7806943,A patent/NL186907C/en not_active IP Right Cessation
- 1978-06-28 DE DE19782828420 patent/DE2828420A1/en active Granted
- 1978-06-28 JP JP53077547A patent/JPS6057444B2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| AU520704B2 (en) | 1982-02-25 |
| JPS5413596A (en) | 1979-02-01 |
| IT1097374B (en) | 1985-08-31 |
| NL186907C (en) | 1991-04-02 |
| IT7825088A0 (en) | 1978-06-28 |
| CH635089A5 (en) | 1983-03-15 |
| FR2396005B1 (en) | 1980-07-18 |
| DE2828420C2 (en) | 1990-04-26 |
| FR2396005A1 (en) | 1979-01-26 |
| NL186907B (en) | 1990-11-01 |
| DE2828420A1 (en) | 1979-01-11 |
| JPS6057444B2 (en) | 1985-12-14 |
| AU3751678A (en) | 1980-01-03 |
| NL7806943A (en) | 1979-01-03 |
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