CA1173996A - Process for the manufacture of phenol- isobutyraldehyde condensation products - Google Patents
Process for the manufacture of phenol- isobutyraldehyde condensation productsInfo
- Publication number
- CA1173996A CA1173996A CA000388100A CA388100A CA1173996A CA 1173996 A CA1173996 A CA 1173996A CA 000388100 A CA000388100 A CA 000388100A CA 388100 A CA388100 A CA 388100A CA 1173996 A CA1173996 A CA 1173996A
- Authority
- CA
- Canada
- Prior art keywords
- isobutyraldehyde
- phenol
- manufacture
- water
- condensation products
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
Abstract
PROCESS FOR THE MANUFACTURE OF PHENOL-ISOBUTYRALDEHYDE CONDENSATION PRODUCTS
Abstract of the Disclosure A process for the manufacture of condensation products of phenols and isobutyraldehyde by reacting the phenols and isobutyraldehyde at elevated temperature in a mole ratio of 0.5:1 to 1.5:1 in the presence of acid or compounds hydrolyzable to acids as catalysts, subsequent neutralization and removal of the resultant reaction water by distillation wherein the reaction products obtained in this manner are also subjected to a water-vapor distilla-tion.
Abstract of the Disclosure A process for the manufacture of condensation products of phenols and isobutyraldehyde by reacting the phenols and isobutyraldehyde at elevated temperature in a mole ratio of 0.5:1 to 1.5:1 in the presence of acid or compounds hydrolyzable to acids as catalysts, subsequent neutralization and removal of the resultant reaction water by distillation wherein the reaction products obtained in this manner are also subjected to a water-vapor distilla-tion.
Description
~L~73~96 PROCESS FOR THE MANUFACTURE OF PHENOL-ISOBUTYRALDEHYDE CONDENSATION PRODUCTS
Background of the Invention 1. Field of the Invention This invention relates to a process for the manufacture of phenol-isobutyraldehyde condensation products. More specifically, this invention relates to such a process wherein problems presented by odor are eliminated or substantially reduced.
Background of the Invention 1. Field of the Invention This invention relates to a process for the manufacture of phenol-isobutyraldehyde condensation products. More specifically, this invention relates to such a process wherein problems presented by odor are eliminated or substantially reduced.
2. Prior Art Condensation products of phenols and isobutyralde-hyde are well known in the prior art. They are generallyprepared by condensation of isobutyraldehyde with the phenol in the presence of acid catalysts, subsequent neutralization of the resultant products and remGval of the resulting reaction water by distillation. Such process is described in German Published Applications 2,805,763 and 2,805,684.
A drawback of the above described manufacturing methods is the formation of by-products which are produced in quantities of up to 2 percent. These include, for instance, 2,2-dimethylcoumaran which result in considerable odor problems in many technical applications, for instance, in the printing ink industry.
Accordingly, it is a purpose of the instant invention to provide a process for the manufacture of phenol-isobutyraldehyde condensation products wherein odor problems are eliminated or substantially reduced.
~73~6 - Summary of the Invention In accordance with the present invention, the above stated purpose is surprisingly achieved by steam distillation wherein the undesirable by-products can be removed quantita-tively from the end products following the above-described prior art process steps.
Thus the present invention provides a process for the manufacture of condensation products of phenols and isobutyraldehyde by reacting the phenol and isobutyraldehyde at an elevated temperature in a mole ratio of 0.5:1 to 1.5:1 in the presence of acid or compounds hydrolyzable to acids as catalysts, subsequent neutralization and removal of the resultant reaction water by distillation wherein the reaction products obtained in this manner are also subjected to a water-vapor distillation.
Description of the Preferred Embodiments The possibility of solving the odor problem by steam distillation is surprising insofar as one skilled in the art would assume that under the conditions of such an operation - the effect of water and steam at temperatures above 100C for one or more hours - might chemically alter the products, e.g., by hydrolysis or repeated formation of ; the referenced dimethylcoumaran.
The condensation products, referred to herein as resins for simplicity sake, are initially produced in a well known manner such as described in the above-referenced publications. For this purpose/ the appropriate phenol and the catalyst are placed in the reaction vessel and iso-butyraldehyde added wither continuously or in steps. This process may be implemented either without pressure or under pressure. The reactants may also be added to the reaction ~` vessel during the course of the reaction, or all at once.
~.~
.~`' : ~ ~l17399~
The mole ratio of isobutyraldehyde to phenol is about 0.5:1 to 1.5:1, preferably about 0.7:1 to 1.3:1. The reaction temperatures are generally between about 80 and 120C, and the reaction period is about 1 to 6 hours.
.
.
.
~1~73~396 The softening points of the condensates obtainable in this manner, are generally between about 60 and 180C.
Suitable phenols which may be used for the manufacture of such phenol-isobutyraldehyde condensates particularly include those having the formula:
OH
~ R
In this formula, R stands for a hydrogen, chlorine or bromine atom or an alkyl group having 1 to 18 carbon atoms in any of their isomeric forms which are in the o-, m- or p-position to the hydroxyl group, an alicyclic group with 5 to18 carbon atoms, for instance, the cyclopentyl-, cyclo-hexyl-, methylcyclohexyl- or butylcyclohexyl group, an aromatic group or aralkyl group having 6 to 18 carbon atoms such as the phenyl-, ~-methylbenzyl-, benzyl- or cumyl ~roup. In addition to this, phenolic alkyl, cycloalkyl, aryl and aralkyl ketones as well as phenolic alkyl, cyclo-alkyl, aryl and aralkyl carboxylic acids may be used.
Suitable catalysts include acids or substances ;~` which may be hydrolyzed into acids, such as concentrated hydrochloric acid, sulfuric acid, aromatic sulfonic acids as well as halogenated phosphorus, such as phosphoric tri-. chloride, phoshoric xychloride, and phosphoric penta-chloride. The required cataly~t quantity generally arount~
~`
. ~
., ~3~6 to less than 5, particularly 0~1 to l percent by weight, relative to the amount of phenol plus isobutyraldehyde.
It is possible to use a solvent such as xylene which does not participate in the reaction and by which the resultant water can be separated. However, the water can also be removed by means of excess isobutyraldeh~de as solvent. It is therefore more advantageous to work with mole ratios of isobutyraldehyde to phenol above l. This guarantees that the phenol, as the more valuable starting product, will largely react. In addition to this, the softening points will then be above 90C which is of advantage for most applications.
After adding the isobutyraldehyde, the resultant water is removed to the desired degree of condensation at increased temperatures (80 to 120C). Following this, the reaction mixture is neutralized and all volatile products are removed by distillation under reduced pressure if necessary. It is simplest to neutralize the material with ammonia or amines but alkali lye may also be used. If the latter is used, the neutral salts must, in some cases, be removed if they are not desirable in the end product, The neutralization is necessary since large quantities of cleavage products will form upon heating the resultant novolak in the acid range, for instance, upon removing the high boiling impurities. These are primarily unsubstituted and/or suùstituted 2,2-dimethylcoumaran.
.
-1~ ~3~96 In accordance with this invention, the material is now subjected to a steam distillation during which the resultant by-products and/or possibly unreacted raw materials such as phenol are driven out of the resin. The distillation is advantageously carried out under normal pressure with steam having a temperature of up to 160C
within a period of 1 to 3 hours.
., : . .
~ 5 `~`
~73~6 Example I
This example illustrates the manufacture of phenol-isobutyraldehyde condensation products in accordance with the prior art wherein 437.5 kilograms of phenol and 4.7 kilograms of p-tolulene sulfonic acid are placed in a reaction vessel and heated to 50C. 368.5 kilograms of isobutyraldehyde are dripped into the resultant melt with the temperature rising to approximately 80C. Following this, the water is removed at approximately 100C for 4 ` hours in a rotating evaporator. Subsequently, 20.6 kilo-grams of concentrated ammonia solution are added while the mixture is stirred and initially residual water and excess isobutyraldehyde are distilled off under normal pressure, and then the higher boiling components are removed by distillation under reduced pressure at temperatures up to 160C.
Example II
This example illustrates the practice of the instant invention. The initial procedure is the same as that described in Example I above. The ammonia solution necessary for the neutralization is added in two batches, 15.3 kilograms prior to the distillation under normal pressure and 5.3 kilograms prior to the vacuum distilla-. tion. As an additional step, in accordance with the instant invention, a steam distillation follows for a period of one hour.
.1~739~36 The resins produced in the above examples are as follows:
Example II
Example I (According to (Com~arative) this Invention) Softening Point according to DIN 52011 120C 128C
Nonvolatile Component (2 hours 125C) 98.4% 99.8%
Color dark reddishyellow to brown light brown Odor +) odor odor free +) For the odor test, both resins were dissolved on a 50percent basis in ethanol. The solution is applied to uncoated paper and is dried at room temperature for 5 minutes. After this, the samples were enclosed in a twist-off glass and the odor was evaluated.
A drawback of the above described manufacturing methods is the formation of by-products which are produced in quantities of up to 2 percent. These include, for instance, 2,2-dimethylcoumaran which result in considerable odor problems in many technical applications, for instance, in the printing ink industry.
Accordingly, it is a purpose of the instant invention to provide a process for the manufacture of phenol-isobutyraldehyde condensation products wherein odor problems are eliminated or substantially reduced.
~73~6 - Summary of the Invention In accordance with the present invention, the above stated purpose is surprisingly achieved by steam distillation wherein the undesirable by-products can be removed quantita-tively from the end products following the above-described prior art process steps.
Thus the present invention provides a process for the manufacture of condensation products of phenols and isobutyraldehyde by reacting the phenol and isobutyraldehyde at an elevated temperature in a mole ratio of 0.5:1 to 1.5:1 in the presence of acid or compounds hydrolyzable to acids as catalysts, subsequent neutralization and removal of the resultant reaction water by distillation wherein the reaction products obtained in this manner are also subjected to a water-vapor distillation.
Description of the Preferred Embodiments The possibility of solving the odor problem by steam distillation is surprising insofar as one skilled in the art would assume that under the conditions of such an operation - the effect of water and steam at temperatures above 100C for one or more hours - might chemically alter the products, e.g., by hydrolysis or repeated formation of ; the referenced dimethylcoumaran.
The condensation products, referred to herein as resins for simplicity sake, are initially produced in a well known manner such as described in the above-referenced publications. For this purpose/ the appropriate phenol and the catalyst are placed in the reaction vessel and iso-butyraldehyde added wither continuously or in steps. This process may be implemented either without pressure or under pressure. The reactants may also be added to the reaction ~` vessel during the course of the reaction, or all at once.
~.~
.~`' : ~ ~l17399~
The mole ratio of isobutyraldehyde to phenol is about 0.5:1 to 1.5:1, preferably about 0.7:1 to 1.3:1. The reaction temperatures are generally between about 80 and 120C, and the reaction period is about 1 to 6 hours.
.
.
.
~1~73~396 The softening points of the condensates obtainable in this manner, are generally between about 60 and 180C.
Suitable phenols which may be used for the manufacture of such phenol-isobutyraldehyde condensates particularly include those having the formula:
OH
~ R
In this formula, R stands for a hydrogen, chlorine or bromine atom or an alkyl group having 1 to 18 carbon atoms in any of their isomeric forms which are in the o-, m- or p-position to the hydroxyl group, an alicyclic group with 5 to18 carbon atoms, for instance, the cyclopentyl-, cyclo-hexyl-, methylcyclohexyl- or butylcyclohexyl group, an aromatic group or aralkyl group having 6 to 18 carbon atoms such as the phenyl-, ~-methylbenzyl-, benzyl- or cumyl ~roup. In addition to this, phenolic alkyl, cycloalkyl, aryl and aralkyl ketones as well as phenolic alkyl, cyclo-alkyl, aryl and aralkyl carboxylic acids may be used.
Suitable catalysts include acids or substances ;~` which may be hydrolyzed into acids, such as concentrated hydrochloric acid, sulfuric acid, aromatic sulfonic acids as well as halogenated phosphorus, such as phosphoric tri-. chloride, phoshoric xychloride, and phosphoric penta-chloride. The required cataly~t quantity generally arount~
~`
. ~
., ~3~6 to less than 5, particularly 0~1 to l percent by weight, relative to the amount of phenol plus isobutyraldehyde.
It is possible to use a solvent such as xylene which does not participate in the reaction and by which the resultant water can be separated. However, the water can also be removed by means of excess isobutyraldeh~de as solvent. It is therefore more advantageous to work with mole ratios of isobutyraldehyde to phenol above l. This guarantees that the phenol, as the more valuable starting product, will largely react. In addition to this, the softening points will then be above 90C which is of advantage for most applications.
After adding the isobutyraldehyde, the resultant water is removed to the desired degree of condensation at increased temperatures (80 to 120C). Following this, the reaction mixture is neutralized and all volatile products are removed by distillation under reduced pressure if necessary. It is simplest to neutralize the material with ammonia or amines but alkali lye may also be used. If the latter is used, the neutral salts must, in some cases, be removed if they are not desirable in the end product, The neutralization is necessary since large quantities of cleavage products will form upon heating the resultant novolak in the acid range, for instance, upon removing the high boiling impurities. These are primarily unsubstituted and/or suùstituted 2,2-dimethylcoumaran.
.
-1~ ~3~96 In accordance with this invention, the material is now subjected to a steam distillation during which the resultant by-products and/or possibly unreacted raw materials such as phenol are driven out of the resin. The distillation is advantageously carried out under normal pressure with steam having a temperature of up to 160C
within a period of 1 to 3 hours.
., : . .
~ 5 `~`
~73~6 Example I
This example illustrates the manufacture of phenol-isobutyraldehyde condensation products in accordance with the prior art wherein 437.5 kilograms of phenol and 4.7 kilograms of p-tolulene sulfonic acid are placed in a reaction vessel and heated to 50C. 368.5 kilograms of isobutyraldehyde are dripped into the resultant melt with the temperature rising to approximately 80C. Following this, the water is removed at approximately 100C for 4 ` hours in a rotating evaporator. Subsequently, 20.6 kilo-grams of concentrated ammonia solution are added while the mixture is stirred and initially residual water and excess isobutyraldehyde are distilled off under normal pressure, and then the higher boiling components are removed by distillation under reduced pressure at temperatures up to 160C.
Example II
This example illustrates the practice of the instant invention. The initial procedure is the same as that described in Example I above. The ammonia solution necessary for the neutralization is added in two batches, 15.3 kilograms prior to the distillation under normal pressure and 5.3 kilograms prior to the vacuum distilla-. tion. As an additional step, in accordance with the instant invention, a steam distillation follows for a period of one hour.
.1~739~36 The resins produced in the above examples are as follows:
Example II
Example I (According to (Com~arative) this Invention) Softening Point according to DIN 52011 120C 128C
Nonvolatile Component (2 hours 125C) 98.4% 99.8%
Color dark reddishyellow to brown light brown Odor +) odor odor free +) For the odor test, both resins were dissolved on a 50percent basis in ethanol. The solution is applied to uncoated paper and is dried at room temperature for 5 minutes. After this, the samples were enclosed in a twist-off glass and the odor was evaluated.
Claims (6)
1. Process for the manufacture of condensation products of phenols and isobutyraldehyde by reacting the phenol and isobutyraldehyde at an elevated temperature in a mole ratio of 0.5:1 to 1.5:1 in the presence of acid or compounds hydrolyzable to acids as catalysts, subsequent neutralization and removal of the resultant reaction water by distillation wherein the reaction products obtained in this manner are also subjected to a water-vapor distilla-tion.
2. The process of claim 1 wherein said phenol and isobutyraldehyde are reacted at a temperature of about 80°C
to 120°C for about 1 to 6 hours and said steam distillation is performed at a temperature up to about 160°C for about 1 to 3 hours.
to 120°C for about 1 to 6 hours and said steam distillation is performed at a temperature up to about 160°C for about 1 to 3 hours.
3. The process of claim 2 wherein said catalyst is an acid.
4. The process of claim 2 wherein said catalyst is a compound hydrolyzable to an acid.
5. The process of claim 2 wherein a solvent is employed to assist in the removal of water.
6. The process of claim 5 wherein the mole ratio of isobutyraldehyde to the phenol is greater than 1:1 whereby the excess isobutyraldehyde acts as the solvent.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP3039360.3 | 1980-10-18 | ||
| DE19803039360 DE3039360A1 (en) | 1980-10-18 | 1980-10-18 | METHOD FOR THE PRODUCTION OF ODOR-FREE CONDENSATION PRODUCTS FROM PHENOLS AND ISOBUTYRALDEHYDE BY CONDENSATION OF THE MENTIONED SUBSTANCES AND SUBSEQUENT WATER STEAM DISTILLATION |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1173996A true CA1173996A (en) | 1984-09-04 |
Family
ID=6114652
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000388100A Expired CA1173996A (en) | 1980-10-18 | 1981-10-16 | Process for the manufacture of phenol- isobutyraldehyde condensation products |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP0050230B1 (en) |
| CA (1) | CA1173996A (en) |
| DE (2) | DE3039360A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9856406B2 (en) | 2013-03-11 | 2018-01-02 | Covestro Llc | Flame retardant polycarbonate |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2665165B1 (en) * | 1990-07-25 | 1995-02-24 | Ceca Sa | NEW NOVOLAQUE RESINS OF PARA-ALKYLPHENOLS. THEIR PREPARATION PROCESS. |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2176951A (en) * | 1937-09-27 | 1939-10-24 | Resinox Corp | Phenol-butyraldehyde resin |
| US2231860A (en) * | 1937-09-27 | 1941-02-11 | Monsanto Chemicals | Phenol-butyraldehyde-formaldehyde resins |
| GB1302802A (en) * | 1969-01-10 | 1973-01-10 | ||
| DE2805763C2 (en) * | 1978-02-10 | 1982-09-09 | Basf Ag, 6700 Ludwigshafen | Process for the production of isobutyraldehyde-phenol polycondensates and their use |
| DE2805684C2 (en) * | 1978-02-10 | 1983-04-21 | Basf Ag, 6700 Ludwigshafen | Isobutyraldehyde phenolic resins |
-
1980
- 1980-10-18 DE DE19803039360 patent/DE3039360A1/en not_active Withdrawn
-
1981
- 1981-09-21 DE DE8181107489T patent/DE3171130D1/en not_active Expired
- 1981-09-21 EP EP81107489A patent/EP0050230B1/en not_active Expired
- 1981-10-16 CA CA000388100A patent/CA1173996A/en not_active Expired
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9856406B2 (en) | 2013-03-11 | 2018-01-02 | Covestro Llc | Flame retardant polycarbonate |
Also Published As
| Publication number | Publication date |
|---|---|
| DE3039360A1 (en) | 1982-05-27 |
| EP0050230A1 (en) | 1982-04-28 |
| DE3171130D1 (en) | 1985-08-01 |
| EP0050230B1 (en) | 1985-06-26 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEC | Expiry (correction) | ||
| MKEX | Expiry |