CA2215390A1 - Phenolic resin hardener composition - Google Patents
Phenolic resin hardener composition Download PDFInfo
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- CA2215390A1 CA2215390A1 CA002215390A CA2215390A CA2215390A1 CA 2215390 A1 CA2215390 A1 CA 2215390A1 CA 002215390 A CA002215390 A CA 002215390A CA 2215390 A CA2215390 A CA 2215390A CA 2215390 A1 CA2215390 A1 CA 2215390A1
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- sulfonated
- crosslinking
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- 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
- C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
- C08G8/12—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with monohydric phenols having only one hydrocarbon substituent ortho on para to the OH group, e.g. p-tert.-butyl phenol
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
- C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
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- Chemical Kinetics & Catalysis (AREA)
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Abstract
A bridging composition is described and claimed for cross-linking phenolic resols or forming novolac resins. The composition contains at least partially sulphonated cyclic phenolic oligomers, optionally combined with at least partially sulphonated linear phenolic oligomers and/or sulphonated phenol. Unlike conventional catalysts used for cross-linking resols or forming novolac resins, said composition is chemically built into the structure of the final products and provides them with novel or modified properties while accelerating said reactions.
Description
- ~ CA 0221~390 1997-09-1~
. .
PHENOLIC RESIN HARDENER COMPOSITION
The present invention re~ers to a new curing (or bridg-ing) composition for phenolic resins, especially for the 5 polymerization of resols and the formation of novolaks.
Phenolic resins have become known for a rather long time. They may generally be classified in two groups, namely the resols and the novolaks. The resols are ob-tained by a condensation reaction starting from optionally substituted phenols and aldehydes, in particular formalde-hyde, in a basic medium, whereas the condensation of the same starting products but in an acidic medium and gener-ally in using other stoichiometric ratios leads to novolaks which may be hardened by crosslinking at elevated tempera-15 tures in the presence of formaldehyde or a formaldehydeliberating compound, for example hexamethylene tetramine.
For their use in practice, the phenolic resins are crosslinked or cured to the so-called phenoplasts which may be hard ~oams, composite products that contain extenders or 20 fillers such as bakelite, or others. Certain phenolic res-ins are self-curing, especially such resins that are crosslinking via their reactive methylol groups, but this sel~-curing does not yield well-de~ined end products, and the hardening process is very slow.
The crosslinking o~ resols and the formation of no-volaks occur according acidic mechanisms. To this end, sulfuric acid or toluene sulfonic acid are used for exam-CA 022l~390 l997-09-l~
. .
PHENOLIC RESIN HARDENER COMPOSITION
The present invention re~ers to a new curing (or bridg-ing) composition for phenolic resins, especially for the 5 polymerization of resols and the formation of novolaks.
Phenolic resins have become known for a rather long time. They may generally be classified in two groups, namely the resols and the novolaks. The resols are ob-tained by a condensation reaction starting from optionally substituted phenols and aldehydes, in particular formalde-hyde, in a basic medium, whereas the condensation of the same starting products but in an acidic medium and gener-ally in using other stoichiometric ratios leads to novolaks which may be hardened by crosslinking at elevated tempera-15 tures in the presence of formaldehyde or a formaldehydeliberating compound, for example hexamethylene tetramine.
For their use in practice, the phenolic resins are crosslinked or cured to the so-called phenoplasts which may be hard ~oams, composite products that contain extenders or 20 fillers such as bakelite, or others. Certain phenolic res-ins are self-curing, especially such resins that are crosslinking via their reactive methylol groups, but this sel~-curing does not yield well-de~ined end products, and the hardening process is very slow.
The crosslinking o~ resols and the formation of no-volaks occur according acidic mechanisms. To this end, sulfuric acid or toluene sulfonic acid are used for exam-CA 022l~390 l997-09-l~
ple. However, the use of these acids has the major disad-vantage that these acids are imprisoned within the forming polymers during the polycondensation and crosslinking reac-tions; the finished products will therefore contain free 5 acids.
The present invention aims at eliminating this serious and principal disadvantage by replacing the acids that have been used until now, and to improve the polycondensation and crosslinking processes. This object is attained by a 10 new composition which is made the subject of the first in-dependent claim. The second independent claim defines a process for the crosslinking of resols by the use of the new composition, and the third independent claim is di-rected to an analogous process for the formation of no-volaks.
The condensation of the phenol and the formaldehyde (~ormol) may be conducted under predetermined stoichiomet-ric conditions in the presence o~ an acid or a base in such a manner that more or less condensed linear and/or cyclic 20 phenolic oligomers are obtained. The sulfonation of these oligomers, as such or as a mixture, yields partially or to-tally sulfonated linear and/or cyclic phenolic oligomers.
These substances are already partly known, see, for exam-ple, the paper "Synthesis and acid-base properties of 25 calix[4], calix[6] and calix[8]arene p-sul~onic acids" by J.P. Scharff, M. Mahjoubi and R. Perrin, New J. Chem. 1991, 15, 883-887. The cyclic phenolic oligomers are called "calixarenes", and the number of phenolic nuclei per mole-cule is inserted between brackets in the name.
In a surprising manner, it has now been found that these sulfonated phenolic oligomers that are introduced into the resols and/or used for the ~ormation of novolaks CA 022l~390 l997-09-l~
., Substitute Sheet No New page 3 / 26.01.1997 partially but preferably totally the conventional catalyst acid; they do not remain as such within the crosslinked network but are chemically combined in the network struc-5 ture. When used for the formation of novolaks, they re-place in part or better completely the usual catalyst acids and are also incorporated into the chemical structure of the novolak.
In the present document, the composition of matter 10 which is dealt with is named "curing composition" and com-prises the crosslinking agents in the case of resols and the "catalyst" of the novolak formation as well. This com-position is defined by at least one partially or totally sulfonated cyclic phenolic oligomer mixed with at least one 15 partially or totally sulfonated linear phenolic oligomer, and, optionally, a sulfonated phenol. By "phenolic" and "phenol", respectively, a compound is to be understood which has at least one aromatically unsaturated nucleus, substituted by at least one -OH group and having unsubsti-20 tuted ortho positionsi this definition includes phenolsthat are substituted in meta and/or para positions by clas-sic radicals such as alkyl, alkenyl, aryl, ether, nitro, halogen, etc.; these substituents may be selected at will under the only condition that it must not impair the forma-25 tion of the desired resols and novolaks. These substitu-ents may be used for conferring special properties to the final producti the one skilled in the art knows the princi-ples of the action of particular substituents.
In the composition of this invention, the linear and 30 cyclic oligomers may be totally or partially sulfonated.
The ratio between sulfonated linear oligomers, sulfonated phenol and sulfonated cyclic oligomers may vary between all values from 0 to 100%.
The major advantage of the composition according to the 35 invention is that it is normally water soluble. Depending CA 022l~390 l997-09-l~
., . Substitute Sheet No. 2 New page 4 / 26.01.1997 on the proportion of an aqueous solution of sulfonated lin-ear oligomers and/or phenol, added to the cyclic oligomers, the viscosity of the crosslinking agent in the case of phe-5 nols can be modified and adjusted. The final viscosity ofthe crosslinking agent, constituted by the above mentioned mixture of sulfonated phenolic oligomers, may generally vary between 0.03 Pa s and 3 Pa s, measured at 20 ~C.
The use of the totally or partially sulfonated cyclic , 10 phenolic oligomers (calixarenes) as a crosslinking agent according to this invention allows firstly to accelerate the reaction speed; mixtures with sulfonated linear pheno-lic oligomers in ratios of 0.5 to 5% will reduce the cross-linking time of resols until a fifth of the duration re-15 quired until now. Used in combination with sulfonated lin-ear phenolic oligomers, the sulfonated calixarenes permit the condensation of phenol and formol for the formation of novolaks; compared with the current use of p-toluene sulfo-nic acid, the condensation time is divided by about 4.
Secondly, the use of the composition of the invention containing totally or partially sulfonated cyclic phenolic ollgomers (calixarenes) allows to better control the cross-linking and condensation processes. The crosslinking of the resols and the formation of novolaks use acid type me-25 chanisms. The sulfonated cyclic phenolic oligomers show changeable acid-base properties due to their varying acidi-ties. For example, the calix[4]arene p-sulfonic acid has four strong acidities due to the S03H groups and one strong acidity of the OH group (superacid), and three very weak 30 acidities of a pK > 11.
The use of totally or partially sulfonated cyclic phe-nolic oligomers (calixarenes) according to the invention further allows to reinforce the properties of the phenolic resins. The sulfonated phenolic oligomers, having the same =~
CA 0221~390 1997-09-1~
. .
The present invention aims at eliminating this serious and principal disadvantage by replacing the acids that have been used until now, and to improve the polycondensation and crosslinking processes. This object is attained by a 10 new composition which is made the subject of the first in-dependent claim. The second independent claim defines a process for the crosslinking of resols by the use of the new composition, and the third independent claim is di-rected to an analogous process for the formation of no-volaks.
The condensation of the phenol and the formaldehyde (~ormol) may be conducted under predetermined stoichiomet-ric conditions in the presence o~ an acid or a base in such a manner that more or less condensed linear and/or cyclic 20 phenolic oligomers are obtained. The sulfonation of these oligomers, as such or as a mixture, yields partially or to-tally sulfonated linear and/or cyclic phenolic oligomers.
These substances are already partly known, see, for exam-ple, the paper "Synthesis and acid-base properties of 25 calix[4], calix[6] and calix[8]arene p-sul~onic acids" by J.P. Scharff, M. Mahjoubi and R. Perrin, New J. Chem. 1991, 15, 883-887. The cyclic phenolic oligomers are called "calixarenes", and the number of phenolic nuclei per mole-cule is inserted between brackets in the name.
In a surprising manner, it has now been found that these sulfonated phenolic oligomers that are introduced into the resols and/or used for the ~ormation of novolaks CA 022l~390 l997-09-l~
., Substitute Sheet No New page 3 / 26.01.1997 partially but preferably totally the conventional catalyst acid; they do not remain as such within the crosslinked network but are chemically combined in the network struc-5 ture. When used for the formation of novolaks, they re-place in part or better completely the usual catalyst acids and are also incorporated into the chemical structure of the novolak.
In the present document, the composition of matter 10 which is dealt with is named "curing composition" and com-prises the crosslinking agents in the case of resols and the "catalyst" of the novolak formation as well. This com-position is defined by at least one partially or totally sulfonated cyclic phenolic oligomer mixed with at least one 15 partially or totally sulfonated linear phenolic oligomer, and, optionally, a sulfonated phenol. By "phenolic" and "phenol", respectively, a compound is to be understood which has at least one aromatically unsaturated nucleus, substituted by at least one -OH group and having unsubsti-20 tuted ortho positionsi this definition includes phenolsthat are substituted in meta and/or para positions by clas-sic radicals such as alkyl, alkenyl, aryl, ether, nitro, halogen, etc.; these substituents may be selected at will under the only condition that it must not impair the forma-25 tion of the desired resols and novolaks. These substitu-ents may be used for conferring special properties to the final producti the one skilled in the art knows the princi-ples of the action of particular substituents.
In the composition of this invention, the linear and 30 cyclic oligomers may be totally or partially sulfonated.
The ratio between sulfonated linear oligomers, sulfonated phenol and sulfonated cyclic oligomers may vary between all values from 0 to 100%.
The major advantage of the composition according to the 35 invention is that it is normally water soluble. Depending CA 022l~390 l997-09-l~
., . Substitute Sheet No. 2 New page 4 / 26.01.1997 on the proportion of an aqueous solution of sulfonated lin-ear oligomers and/or phenol, added to the cyclic oligomers, the viscosity of the crosslinking agent in the case of phe-5 nols can be modified and adjusted. The final viscosity ofthe crosslinking agent, constituted by the above mentioned mixture of sulfonated phenolic oligomers, may generally vary between 0.03 Pa s and 3 Pa s, measured at 20 ~C.
The use of the totally or partially sulfonated cyclic , 10 phenolic oligomers (calixarenes) as a crosslinking agent according to this invention allows firstly to accelerate the reaction speed; mixtures with sulfonated linear pheno-lic oligomers in ratios of 0.5 to 5% will reduce the cross-linking time of resols until a fifth of the duration re-15 quired until now. Used in combination with sulfonated lin-ear phenolic oligomers, the sulfonated calixarenes permit the condensation of phenol and formol for the formation of novolaks; compared with the current use of p-toluene sulfo-nic acid, the condensation time is divided by about 4.
Secondly, the use of the composition of the invention containing totally or partially sulfonated cyclic phenolic ollgomers (calixarenes) allows to better control the cross-linking and condensation processes. The crosslinking of the resols and the formation of novolaks use acid type me-25 chanisms. The sulfonated cyclic phenolic oligomers show changeable acid-base properties due to their varying acidi-ties. For example, the calix[4]arene p-sulfonic acid has four strong acidities due to the S03H groups and one strong acidity of the OH group (superacid), and three very weak 30 acidities of a pK > 11.
The use of totally or partially sulfonated cyclic phe-nolic oligomers (calixarenes) according to the invention further allows to reinforce the properties of the phenolic resins. The sulfonated phenolic oligomers, having the same =~
CA 0221~390 1997-09-1~
. .
ties. For example, the calix[4]arene p-sulfonic acid has four strong acidities due to the SO3H groups and one strong acidity of the OH group (superacid), and three very weak acidities of a pK > 11.
The use of totally or partlally sulfonated cyclic phe-nolic oligomers (calixarenes) according to the invention further allows to reinforce the properties of the phenolic resins. The sulfonated phenolic oligomers, having the same nature as the phenolic resins, namely the resols and the 10 novolaks, are chemically incorporated into the microstruc-ture of the polymer. They are perfectly compatible with the resins and enhance their mechanical and fire retarding properties. They are thermally and chemically stable and have high melting points. For example, the thermo-15 graphimetric analysis of hydrated calix[6]arene p-sulfonic acid shows the high stability of the product. A first lib-eration of water occurs at about 90 ~C only, then a second liberation of water at about 250 ~C constituting a level that corresponds to the loss of 7 water molecules which is 20 the number of water molecules associated with the calix-arene, thus explaining the fire retarding and fire proof properties. The melting point is above 300 ~C, and the product does not decompose until 800 ~C.
Finally, it has been found that the use of totally or 25 partially sulfonated cyclic phenolic oligomers (calixare-nes) according to the invention allows to obtain phenolic materials having selective complexation properties; the sulfonated cyclic phenolic oligomers which are introduced into the condensation and crosslinking steps of phenolic 30 polymers bring about, further to their acid functions, po-tential complexation sites. Due to their cavities or frac-tions, the calixarenes are privileged and selective sites for the complexation of ions, metals or weakly polar or -CA 022l~390 Is97-og-l~
. . .
even neutral molecules.For example, cone configured calix[4]arenes are able to complex the cations Li+, Na+, K+, Rb+, Cs+, the metals Ti4+, Fe3+, Co2+, certain neutral molecules such as toluene, xylene (selectively p-xylene)i 5 calix[6]arene p-sulfonic acid complexes Uo2+; and calix[8]arenes allow to complex Eu3~ and other lanthanides.
These selectively complexing properties of cyclic phenolic oligomers yield for example phenolic materials having rec-ognizing, separating, depolluting, confining and other ca-10 pacities.
The following Examples further illustrate the inventionin more detail without however limiting the invention re-garding the exemplified compounds and methods.
I. Preparation of phenolic oligomers A. Preparation of linear phenolic oligomers Example 1 10 ml of 95% sul~uric acid are slowly introduced into 220 gms of phenol containing 10% by weight of water under stirring at a temperature o~ 40 ~C. To this mixture, 45 ml 20 O~ 37% aqueous ~ormaline are slowly added under stirring and controlling the temperature which must remain not higher than 40 ~C. Stirring is then continued for one hour.
The solution o~ the oligomers thus obtained is de-25 canted, and the phenolic phase is separated ~rom the aque-ous phase.
According to NMR nuclear magnetic resonance) analyses oi~ the protons and the carbon atoms, it has been ~ound that CA 022l~390 l997-09-l~
. .
the phenolic oligomers that have been formed in this Exam-ple have a condensation degree between 1 and 12 with meth-ylene bridges o-p and p-p, where o-o bridges exist too but are rather seldom.
B. Preparation of cyclic phenolic oligomers Example 2 A mixture is prepared from 33.33 gms of p-tert-butylphenol, 11.67 gms of paraformaldehyde, 0.667 ml of 10N
aqueous NaOH and 200 ml of xylene. The mixture is stirred 10 under nitrogen and brought to reflux during 4 hours, the condensation water being removed by a Dean-Stark apparatus.
The cyclic oligomers obtained form a solid precipitate that is recovered by filtration. Regarding the yield, 91%
by weight of the starting phenol have been transformed to 15 cyclic oligomers.
The HPLC (high performance liquid chromatography) analysis gave the following composition of the reaction product, quoted in % by weight of the total:
p-tert-butylcalix[8]arene 87 %
p-tert-butylcalix[4]arene 3 %
p-tert-butyldihomooxacalix[4]arene 1 %
p-tert-butylcalix[5]arene 1 %
p-tert-butylcalix[6]arene 4 %
p-tert-butylcalix[7]arene 4 %.
Example 3 20 gms of p-tert-butylphenol, 3 gms of KOH in pastille form, 84% purity, and 27 ml of aqueous 37% formaldehyde are CA 022l~390 l997-09-l~
blended. The mixture is stirred under a nitrogen stream and heated until the formation of a viscous yellow mass.
200 ml of xylene are added thereto, and the whole is re-fluxed during 3 hours at 145 ~C with removal of water from 5 the mixture.
The reaction mixture is filtered after cooling, and 21 gms of a solid precipitate are collected that has the fol-lowing composition:
p-tert-butylcalix[6]arene 95 %
p-tert-butylcalix[4]arene 4 %
p-tert-butylcalix[8]arene 1 %.
Example 4 The following components are mixed: 20 gms of p-tert-butylphenol, 12.4 ml of 37% formaline, and 0.24 gm of 98%
NaOH. The mixture is heated during 2 hours to 110 ~C and then cooled to ambient temperature during 30 minutes. 200 ml of diphenyl ether, preheated to 200 ~C, are then added.
15 The reaction mixture, placed under nitrogen, is refluxed during 1.5 hours and then cooled. 300 ml of ethyl acetate are added and the mixture is stirred during 15 minutes.
The mixture is then filtered when cold, and 16 gms of a solid precipitate are formed. This precipitate has the following composition by weight:
p-tert-butylcalix[4~arene 90 %
p-tert-butylcalix[6]arene 5 %
p-tert-butylcalix[7]arene 4 %.
p-tert-butylcalix[8]arene 1 %.
~ CA 022l~390 l997-09-l~
. .
II. Sulfonation of the phenolic oligomers In order to obtain the compositions according to the invention, it is necessary to sulfonate the compounds ob-tained in part I of the Examples.
A. Sulfonation of linear phenolic oligomers Example 5 Into 245 ml of phenolic oligomers, obtained in préced-ing Example 1, 70 ml of 95% sulfuric acid are introduced slowly under stirring in taking care that the temperature 10 does not rise over 50~C. At the end of this introduction, stirring is still maintained for 16 hours. The sulfonated phenolic oligomers are obtained as a solution in water.
The analysis by C13 NMR shows that the oligomers are only little condensed, one methylene bridge for 3 nuclei, 15 that the bridges are of the ortho-para (40%) and para-para type (60%), and that the mixture contains sulfonated mono-mer, sulfonated phenol and partially sulfonated o-p and p-p oligomers.
B. Sulfonation of cyclic oligomers Example 6. Total sulfonation The first step of the preparation comprises a dealkyla-tion of the oligomers in order to liberate sites for sul-fonation.
35 gms of the solid precipitate of Example 2 are dis-25 solved in 350 ml of toluene, and 41 gms of anhydrous alumi-num chloride are added. The mixture is stirred at ambient ~ CA 0221~390 1997-09-1~
temperature during 4 hours, and the dealkylation is :Ein-ished. The reaction is stopped by the addition of 500 ml of lN hydrochloric acid, and the organic phase is collected by decantation. The toluene is then evaporated.
The sulfonation of the dealkylated cyclic oligomers is effected by the addition of 350 ml of 98% sulfuric acid, and the reaction medium is stirred under a nitrogen atmos-phere at 100 ~C during 6 hours. The solids recovered by filtration are treated with ethyl acetate for initiating the crystallization.
It is found in the analysis that all cyclic oligomers are sulfonated, and that the para sites of the calixarenes all bear a -SO3H group.
Example 7. Partial sulfonation For partial sulfonation, a preliminary dealkylation is not required.
35 gms of the solid precipitate of Example 2 are dis-solved in 350 ml of toluene, and 400 ml of 98% sulfuric acid are added. The reaction medium is stirred under a ni-20 trogen atmosphere during 6 hours at 100 ~C. The solids arethen recovered by filtration, and they are treated with ethyl acetate for bringing about their crystallization.
The analysis shows that the cyclic oligomers have been partially sulfonated in that the para sites of the calix-25 arenes carry either a -SO3H group or a tert-butyl group, some of them having been de-tert-butylated during sulfona-tion.
= = _ ~ CA 0221~390 1997-09-1~
., It will be self-understandlng that it is possible to modify the ratios between the reactive components, the con-centrations (especially of the sulfuric acid), etc., in or-der to prepare the sulfonated phenolic oligomers and their 5 modified precursors. Still other modifications are possi-ble, for example the addition of dlluents, finely divided fillers, viscosity or reactivity regulators, coloring agents, etc., to these compositions.
The use of totally or partlally sulfonated cyclic phe-nolic oligomers (calixarenes) according to the invention further allows to reinforce the properties of the phenolic resins. The sulfonated phenolic oligomers, having the same nature as the phenolic resins, namely the resols and the 10 novolaks, are chemically incorporated into the microstruc-ture of the polymer. They are perfectly compatible with the resins and enhance their mechanical and fire retarding properties. They are thermally and chemically stable and have high melting points. For example, the thermo-15 graphimetric analysis of hydrated calix[6]arene p-sulfonic acid shows the high stability of the product. A first lib-eration of water occurs at about 90 ~C only, then a second liberation of water at about 250 ~C constituting a level that corresponds to the loss of 7 water molecules which is 20 the number of water molecules associated with the calix-arene, thus explaining the fire retarding and fire proof properties. The melting point is above 300 ~C, and the product does not decompose until 800 ~C.
Finally, it has been found that the use of totally or 25 partially sulfonated cyclic phenolic oligomers (calixare-nes) according to the invention allows to obtain phenolic materials having selective complexation properties; the sulfonated cyclic phenolic oligomers which are introduced into the condensation and crosslinking steps of phenolic 30 polymers bring about, further to their acid functions, po-tential complexation sites. Due to their cavities or frac-tions, the calixarenes are privileged and selective sites for the complexation of ions, metals or weakly polar or -CA 022l~390 Is97-og-l~
. . .
even neutral molecules.For example, cone configured calix[4]arenes are able to complex the cations Li+, Na+, K+, Rb+, Cs+, the metals Ti4+, Fe3+, Co2+, certain neutral molecules such as toluene, xylene (selectively p-xylene)i 5 calix[6]arene p-sulfonic acid complexes Uo2+; and calix[8]arenes allow to complex Eu3~ and other lanthanides.
These selectively complexing properties of cyclic phenolic oligomers yield for example phenolic materials having rec-ognizing, separating, depolluting, confining and other ca-10 pacities.
The following Examples further illustrate the inventionin more detail without however limiting the invention re-garding the exemplified compounds and methods.
I. Preparation of phenolic oligomers A. Preparation of linear phenolic oligomers Example 1 10 ml of 95% sul~uric acid are slowly introduced into 220 gms of phenol containing 10% by weight of water under stirring at a temperature o~ 40 ~C. To this mixture, 45 ml 20 O~ 37% aqueous ~ormaline are slowly added under stirring and controlling the temperature which must remain not higher than 40 ~C. Stirring is then continued for one hour.
The solution o~ the oligomers thus obtained is de-25 canted, and the phenolic phase is separated ~rom the aque-ous phase.
According to NMR nuclear magnetic resonance) analyses oi~ the protons and the carbon atoms, it has been ~ound that CA 022l~390 l997-09-l~
. .
the phenolic oligomers that have been formed in this Exam-ple have a condensation degree between 1 and 12 with meth-ylene bridges o-p and p-p, where o-o bridges exist too but are rather seldom.
B. Preparation of cyclic phenolic oligomers Example 2 A mixture is prepared from 33.33 gms of p-tert-butylphenol, 11.67 gms of paraformaldehyde, 0.667 ml of 10N
aqueous NaOH and 200 ml of xylene. The mixture is stirred 10 under nitrogen and brought to reflux during 4 hours, the condensation water being removed by a Dean-Stark apparatus.
The cyclic oligomers obtained form a solid precipitate that is recovered by filtration. Regarding the yield, 91%
by weight of the starting phenol have been transformed to 15 cyclic oligomers.
The HPLC (high performance liquid chromatography) analysis gave the following composition of the reaction product, quoted in % by weight of the total:
p-tert-butylcalix[8]arene 87 %
p-tert-butylcalix[4]arene 3 %
p-tert-butyldihomooxacalix[4]arene 1 %
p-tert-butylcalix[5]arene 1 %
p-tert-butylcalix[6]arene 4 %
p-tert-butylcalix[7]arene 4 %.
Example 3 20 gms of p-tert-butylphenol, 3 gms of KOH in pastille form, 84% purity, and 27 ml of aqueous 37% formaldehyde are CA 022l~390 l997-09-l~
blended. The mixture is stirred under a nitrogen stream and heated until the formation of a viscous yellow mass.
200 ml of xylene are added thereto, and the whole is re-fluxed during 3 hours at 145 ~C with removal of water from 5 the mixture.
The reaction mixture is filtered after cooling, and 21 gms of a solid precipitate are collected that has the fol-lowing composition:
p-tert-butylcalix[6]arene 95 %
p-tert-butylcalix[4]arene 4 %
p-tert-butylcalix[8]arene 1 %.
Example 4 The following components are mixed: 20 gms of p-tert-butylphenol, 12.4 ml of 37% formaline, and 0.24 gm of 98%
NaOH. The mixture is heated during 2 hours to 110 ~C and then cooled to ambient temperature during 30 minutes. 200 ml of diphenyl ether, preheated to 200 ~C, are then added.
15 The reaction mixture, placed under nitrogen, is refluxed during 1.5 hours and then cooled. 300 ml of ethyl acetate are added and the mixture is stirred during 15 minutes.
The mixture is then filtered when cold, and 16 gms of a solid precipitate are formed. This precipitate has the following composition by weight:
p-tert-butylcalix[4~arene 90 %
p-tert-butylcalix[6]arene 5 %
p-tert-butylcalix[7]arene 4 %.
p-tert-butylcalix[8]arene 1 %.
~ CA 022l~390 l997-09-l~
. .
II. Sulfonation of the phenolic oligomers In order to obtain the compositions according to the invention, it is necessary to sulfonate the compounds ob-tained in part I of the Examples.
A. Sulfonation of linear phenolic oligomers Example 5 Into 245 ml of phenolic oligomers, obtained in préced-ing Example 1, 70 ml of 95% sulfuric acid are introduced slowly under stirring in taking care that the temperature 10 does not rise over 50~C. At the end of this introduction, stirring is still maintained for 16 hours. The sulfonated phenolic oligomers are obtained as a solution in water.
The analysis by C13 NMR shows that the oligomers are only little condensed, one methylene bridge for 3 nuclei, 15 that the bridges are of the ortho-para (40%) and para-para type (60%), and that the mixture contains sulfonated mono-mer, sulfonated phenol and partially sulfonated o-p and p-p oligomers.
B. Sulfonation of cyclic oligomers Example 6. Total sulfonation The first step of the preparation comprises a dealkyla-tion of the oligomers in order to liberate sites for sul-fonation.
35 gms of the solid precipitate of Example 2 are dis-25 solved in 350 ml of toluene, and 41 gms of anhydrous alumi-num chloride are added. The mixture is stirred at ambient ~ CA 0221~390 1997-09-1~
temperature during 4 hours, and the dealkylation is :Ein-ished. The reaction is stopped by the addition of 500 ml of lN hydrochloric acid, and the organic phase is collected by decantation. The toluene is then evaporated.
The sulfonation of the dealkylated cyclic oligomers is effected by the addition of 350 ml of 98% sulfuric acid, and the reaction medium is stirred under a nitrogen atmos-phere at 100 ~C during 6 hours. The solids recovered by filtration are treated with ethyl acetate for initiating the crystallization.
It is found in the analysis that all cyclic oligomers are sulfonated, and that the para sites of the calixarenes all bear a -SO3H group.
Example 7. Partial sulfonation For partial sulfonation, a preliminary dealkylation is not required.
35 gms of the solid precipitate of Example 2 are dis-solved in 350 ml of toluene, and 400 ml of 98% sulfuric acid are added. The reaction medium is stirred under a ni-20 trogen atmosphere during 6 hours at 100 ~C. The solids arethen recovered by filtration, and they are treated with ethyl acetate for bringing about their crystallization.
The analysis shows that the cyclic oligomers have been partially sulfonated in that the para sites of the calix-25 arenes carry either a -SO3H group or a tert-butyl group, some of them having been de-tert-butylated during sulfona-tion.
= = _ ~ CA 0221~390 1997-09-1~
., It will be self-understandlng that it is possible to modify the ratios between the reactive components, the con-centrations (especially of the sulfuric acid), etc., in or-der to prepare the sulfonated phenolic oligomers and their 5 modified precursors. Still other modifications are possi-ble, for example the addition of dlluents, finely divided fillers, viscosity or reactivity regulators, coloring agents, etc., to these compositions.
Claims (9)
- Claims l Curing composition utilizable in the polycondensation of resols and in the formation of novolaks starting from a phenol and an aldehyde, characterized in that the composition contains at least one partially or totally sulfonated cyclic phenolic oligomer, and at least one partially or totally sulfonated linear phenolic oligomer.
- 2. Composition according to claim 1, characterized in that it further contains at least one sulfonated phenol.
- 3. Composition according to any one of the preceding claims, characterized in that it contains a mixture of totally or partially sulfonated calixarenes [4] to [8].
- 4. Process for the crosslinking of phenolic resols, characterized in that a composition according to any one of claims 1 to 3 is added to a resol and the crosslinking is carried out, the composition replacing at least in part the acid crosslinking catalyst, the composition being further chemically incorporated into the formed crosslinked product.
- 5. Process according to claim 4, characterized in that a crosslinking composition is used comprising a major or exclusive proportion of totally or partially sulfonated calixarenes.
- 6. Process for the formation of novolaks, starting from a phenol and an aldehyde or aldehyde precursor, characterized in that a composition according to any one of claims 1 to 3 is added to the said starting products, said composition replacing at least in part the acid condensation catalyst, the composition being further chemically incorporated into the novolak.
- 7. Process according to claim 6, characterized in that a composition is used comprising totally or partially sulfonated calixarenes [4] to [8].
- 8 Phenolic resin obtained by a polycondensation of a resol, characterized in that it comprises, chemically incorporated into the microstructure of the polymer, the components of the crosslinking composition according to any one of claims 1 to 3.
- 9. Novolak obtained by the polycondensation of an aldehyde and a phenol, characterized that it comprises, chemically incorporated into the microstructure of the polycondensate, the components of the crosslinking composition according to any one of claims 1 to 3.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH768/95-5 | 1995-03-17 | ||
| CH76895 | 1995-03-17 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2215390A1 true CA2215390A1 (en) | 1996-09-26 |
Family
ID=4194727
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002215390A Abandoned CA2215390A1 (en) | 1995-03-17 | 1996-03-14 | Phenolic resin hardener composition |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP0815168B1 (en) |
| JP (1) | JPH11502244A (en) |
| AT (1) | ATE184300T1 (en) |
| AU (1) | AU4936296A (en) |
| CA (1) | CA2215390A1 (en) |
| DE (1) | DE69604162T2 (en) |
| WO (1) | WO1996029363A1 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6465599B1 (en) * | 1995-03-17 | 2002-10-15 | Transdiffusia S.A. | Curing composition for phenolic resins |
| JP4654476B2 (en) * | 1999-06-10 | 2011-03-23 | 味の素株式会社 | Additive composition and method for producing the same |
| CN1214062C (en) | 1999-12-27 | 2005-08-10 | 味之素株式会社 | Resin additive composition and production thereof |
| IT1392545B1 (en) * | 2008-12-18 | 2012-03-09 | Univ Degli Studi Salerno | SKIN PROCESSING PROCESSES BY P-SOLFONATOCALIX (N) ARENI (N = 4-20). |
| JP7312463B2 (en) * | 2018-04-16 | 2023-07-21 | 国立研究開発法人理化学研究所 | Meta-phenolsulfonic acid resin and its use as a catalyst |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1593257A (en) * | 1976-10-08 | 1981-07-15 | Albright & Wilson | Curing catalysts for resinous binders |
| JPH04100890A (en) * | 1990-08-20 | 1992-04-02 | Sugai Kagaku Kogyo Kk | Antioxidant and polymer composition containing the same |
-
1996
- 1996-03-14 AU AU49362/96A patent/AU4936296A/en not_active Abandoned
- 1996-03-14 EP EP96905652A patent/EP0815168B1/en not_active Expired - Lifetime
- 1996-03-14 AT AT96905652T patent/ATE184300T1/en not_active IP Right Cessation
- 1996-03-14 DE DE69604162T patent/DE69604162T2/en not_active Expired - Fee Related
- 1996-03-14 CA CA002215390A patent/CA2215390A1/en not_active Abandoned
- 1996-03-14 WO PCT/CH1996/000095 patent/WO1996029363A1/en active IP Right Grant
- 1996-03-14 JP JP8527945A patent/JPH11502244A/en not_active Ceased
Also Published As
| Publication number | Publication date |
|---|---|
| WO1996029363A1 (en) | 1996-09-26 |
| JPH11502244A (en) | 1999-02-23 |
| ATE184300T1 (en) | 1999-09-15 |
| AU4936296A (en) | 1996-10-08 |
| EP0815168B1 (en) | 1999-09-08 |
| DE69604162D1 (en) | 1999-10-14 |
| DE69604162T2 (en) | 2000-03-09 |
| EP0815168A1 (en) | 1998-01-07 |
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| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| FZDE | Discontinued |