CA1237131A - Gelling composition with sulfonated diphenyldiissocyanate - Google Patents
Gelling composition with sulfonated diphenyldiissocyanateInfo
- Publication number
- CA1237131A CA1237131A CA000465351A CA465351A CA1237131A CA 1237131 A CA1237131 A CA 1237131A CA 000465351 A CA000465351 A CA 000465351A CA 465351 A CA465351 A CA 465351A CA 1237131 A CA1237131 A CA 1237131A
- Authority
- CA
- Canada
- Prior art keywords
- sulfonated
- composition
- sulfur trioxide
- gelling agent
- diisocyanate
- 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
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
Novel gelling agents are prepared by reacting diphenyldiisocyanates with sulfur trioxide in a molar concentration of about 1:2. When the sulfonated diphenyldiisocyanate is added to water in concentrations above 2%, a gel is produced which is stable under acidic conditions at pH levels of about 4 or less.
Novel gelling agents are prepared by reacting diphenyldiisocyanates with sulfur trioxide in a molar concentration of about 1:2. When the sulfonated diphenyldiisocyanate is added to water in concentrations above 2%, a gel is produced which is stable under acidic conditions at pH levels of about 4 or less.
Description
7 ~L3 ~L
NOVEL GELLING COMPOSITION
This invention relates to novel sulfonated diphenyldiisocyanates.
It also relates to novel gels produced from the sulfonated diphenyl-diisocyanates upon their addition to water. These novel gels are stable under acidic conditions and at elevated temperatures.
It is known that sulfonation of various aromatic mono- and poly-isocyanates yields compounds containing both isocyanate and sulfonic acid functionalities on one molecule wherein the sulfo group exclusive-ly enters at the ortho position to the isocyanate group on the aromatic ring. This position is favored due to the formation of a six-membered heterocyclic ring by the ortho sulfonic acid group with the isocyanate group, referred to as a cyclic carbamic acid-sulfonic acid anhydride.
See Angew. Chem. Int. Ed. Eng. 21~ No. 11 (1982), pgs. 867-868.
U.S. Pat. No. 4,176,118 issued November 27, 1979 to M. Petinaux et al. describes the partial sulfonation of 4,4'-diphenyl diisocyanates which yields exclusively tetranuclear uretdione diisocyanate disulfonic acids. The reaction is carried out employing molar ratios ln the range of from about 1:1 to about 1:1.4 of diisocyanate to SO3 reagent, how-ever it is disclosed that larger amounts of SO3 may be used without substantially altering the course of the reaction. The compositions of , . . . .:
--,~
Petinaux et al. are described as being useful as crosslinking agents as well as useful in the polymer synthesis of, for example, polyisocyanur-ates, polycarbodiimides, polyimides, and polyurethanes.
Neither of the above references disclose or suggest the novel com-positions herein or the unique gel forming ability they possess upon addition to water.
This invention provides a gelling agPnt prepared by the steps of:
(a) sulfonating a diphenyldiisocyanate of the formula OCN ~ X ~ NCO
wherein X is -CH2-, -C-, -O-, -S-, -S-, -C=C-, or -C-with sulfur trioxide in a molar ratio greater than 1:1.5 and less than 1-3 of diisocyanate to sulfur trioxide in an anhydrous inert organic solvent at a temperature of -30 to ~100C, and (b) recovering the gelling agent.
The preferred temperature is 10-30C. The present invention also relates to the gel produced by the addition of these compositions to water and to the novel properties of the gel.
The diphenyldiisocyanates useful herein have the general formula OCN ~ X ~ NCO
wherein X is defined above. These diisocyanates may be sulfonated by procedures commonly known in the art. Sulfur trioxide or other sulfur-containing materials capable of rendering S03 available may be employ-ed. Use of sulfur trioxide is preferred. Accordingly, the diphenyl-~3'~3~
diisocyanates are treated with sulfur trioxide in a molar concentration of about 2 moles of sulfur trioxide to one mole of diisocyanate.
The sulfonation is carried out in a solvent which mus-t be chemical-ly inert to both S03 and the diisocyanates under the reaction conditions employed. Suitable solvents for the present invention include various halogenated hydrocarbons, dioxane, and tetrahydrofuran. The preferred solvent is 1,2-dichloroethane.
A typical sulfonation procedure useful herein involves simultane-ously adding sulfur trioxide and a solution containing the diisocyanate and the inert solvent to a reaction vessel already charged with the solvent and purged with nitrogen. The reactants are introduced by slow addition being careful to keep the reaction temperature below 30C in order to achieve a uniform reaction with a controlled exotherm. The resultant sulfonated product precipitates from solution and may then be recovered in quantitative yields by filtration.
As described in the Angew. Chem. reference mentioned above, sul-fonated isocyanates exist in equilibrium in the form of the cyclic carb-amic acid-sulfonic acid anhydride or in the open form. In a similar fashion, the proposed structures of the sulfonated diphenyldiisocyanates herein, existing in equilibrium, are H H
OCN ~ X ~ NCO ~ N ~ X ~ N
H03S S03H o - S2 2 o wherein X has been previously described. These structures are con-sistent with elemental analysis results. Upon addition to water, the sulfonated compositions are believed to hydrolyze, with the evolution of carbon dioxide, to form zwitterions consisting of amino and sulfonic , ~3~ ~3'~
acid functionalities having the Formula ~H3N- ~ ~ X- ~ -NH3 wherein X is described above.
It has been discovered that the sulfonated diphenyldiisocyanates herein form a gel upon addition to water when added in concentrations above 2%. The amount of time necessary for gelling to occur is a function of the concentration of the sulfonated diisocyanate in aqueous solution. Generally, solutions containing 5% or more of the sulfonated diisocyanate will gel in less than thirty minutes at room temperature.
In order to prepare the novel gelling agent herein, it is necessary to react a suitable diphenyldiisocyanate with S03 in molar concentrations of about 1 mole diisocyanate to 2 moles S03, or in other words about stoichiometric amounts of S03 to isocyanate concentration are necessary.
When diisocyanate:S03 molar ratios as low as 1:1.5 or as high as 1:3 are used, it was found that products without gel-forming capabilities are produced.
The sulfonated products described herein, when added to water in concentrations of about 5%, will normally alter the pH of the water to about 2. Stability studies on the gels at various pH's were carried out by adjusting samples containing 5% sulfonated diisocyanate to pH
values from 0.5 to 10. It was found that the gel formation was rever-sible and that gels were only stable under acidic conditions at pH
levels of about 4 or less. ~hile not wishing to be bound to any theory or mechanism, it is currently believed that at higher pH levels the hydrolyzed sulfonates carry a negative charge and as a result, the gel will not form due to charge repulsion between the molecules.
~33'7.~
The novel gels are stable upon extended holding times at elevated temperatures. For instance, gels maintained at 70C for 12 hours re-mained firm showing no sign of instability.
Oftentimes gels may be sensitive to various salt or polymer im-S purities present in solution. The novel gels herein were found to be insensitive to salts containing monovalent cations as well as to synthetic and natural polymers. The gels were, however, sensitive to salts containing divalent or multivalent cations. Such cations destroy-ed gel formation and resulted in fluffy precipitates.
The sulfonated diisocyanates of the present invention are useful, for example, as thickeners in aqueous systems and as absorbants.
In the examples which follow, all parts and percentages are given b~ weight and all temperatures are given in degress Celsius unless otherwise indicated.
This example illustrates the preparation of sulfonated 4,4'-diiso-cyanato-diphenyl methane (MDI).
A five-liter Morton flask equipped with a stirrer, thermometer, addition funnels, condenser with drying tube and a gas inlet adapter was purged with nitrogen for 15 minutes. Seven hundred twenty five (725) 9. of 1,2-dichloroethane (DCE) was added to the flask. Using two ad-dition funnels, 81.4 g. of sulfur trioxide (1.00 mole) and 440 ml. of MDI solution in DCE were added simultaneuosly while maintaining the internal temperature between 15-20C. The MDI solution which contained 125 g. MDI (0.5 mole) in DCE was added at a rate of 10 ml./ minute.
The sulfur trioxide was added at a rate of 1 ml./minute. The ~3~ L3~
sulfonated MDI precipitated as it formed. After completing sulfona-tion, the sulfona-ted MDI was filtered and dried at 60C. A total of 210 y.
of the sulfonate, a pink powder, was collected.
Elemental analysis for C15HlON208S2 Calculated: C, 43.9%; H, 2.4%; N, 6.8%; 0, 31.3%; S, 15.6%.
Found: C, 42.1%; H, 2.9%, N, 6.2%; 0, 33.2%; S, 15.5%.
This example illustrates the gel forming capabilities of MDI sul-fonate from Example 1 in water at various concentrations.
Aqueous solutions of MDI sulfonate were prepared at pH=2 and ob-served for gel formation. The results are given in Table I.
TABLE I
Concentration of MDI
Sulfonate Solution (%) Gel Time
NOVEL GELLING COMPOSITION
This invention relates to novel sulfonated diphenyldiisocyanates.
It also relates to novel gels produced from the sulfonated diphenyl-diisocyanates upon their addition to water. These novel gels are stable under acidic conditions and at elevated temperatures.
It is known that sulfonation of various aromatic mono- and poly-isocyanates yields compounds containing both isocyanate and sulfonic acid functionalities on one molecule wherein the sulfo group exclusive-ly enters at the ortho position to the isocyanate group on the aromatic ring. This position is favored due to the formation of a six-membered heterocyclic ring by the ortho sulfonic acid group with the isocyanate group, referred to as a cyclic carbamic acid-sulfonic acid anhydride.
See Angew. Chem. Int. Ed. Eng. 21~ No. 11 (1982), pgs. 867-868.
U.S. Pat. No. 4,176,118 issued November 27, 1979 to M. Petinaux et al. describes the partial sulfonation of 4,4'-diphenyl diisocyanates which yields exclusively tetranuclear uretdione diisocyanate disulfonic acids. The reaction is carried out employing molar ratios ln the range of from about 1:1 to about 1:1.4 of diisocyanate to SO3 reagent, how-ever it is disclosed that larger amounts of SO3 may be used without substantially altering the course of the reaction. The compositions of , . . . .:
--,~
Petinaux et al. are described as being useful as crosslinking agents as well as useful in the polymer synthesis of, for example, polyisocyanur-ates, polycarbodiimides, polyimides, and polyurethanes.
Neither of the above references disclose or suggest the novel com-positions herein or the unique gel forming ability they possess upon addition to water.
This invention provides a gelling agPnt prepared by the steps of:
(a) sulfonating a diphenyldiisocyanate of the formula OCN ~ X ~ NCO
wherein X is -CH2-, -C-, -O-, -S-, -S-, -C=C-, or -C-with sulfur trioxide in a molar ratio greater than 1:1.5 and less than 1-3 of diisocyanate to sulfur trioxide in an anhydrous inert organic solvent at a temperature of -30 to ~100C, and (b) recovering the gelling agent.
The preferred temperature is 10-30C. The present invention also relates to the gel produced by the addition of these compositions to water and to the novel properties of the gel.
The diphenyldiisocyanates useful herein have the general formula OCN ~ X ~ NCO
wherein X is defined above. These diisocyanates may be sulfonated by procedures commonly known in the art. Sulfur trioxide or other sulfur-containing materials capable of rendering S03 available may be employ-ed. Use of sulfur trioxide is preferred. Accordingly, the diphenyl-~3'~3~
diisocyanates are treated with sulfur trioxide in a molar concentration of about 2 moles of sulfur trioxide to one mole of diisocyanate.
The sulfonation is carried out in a solvent which mus-t be chemical-ly inert to both S03 and the diisocyanates under the reaction conditions employed. Suitable solvents for the present invention include various halogenated hydrocarbons, dioxane, and tetrahydrofuran. The preferred solvent is 1,2-dichloroethane.
A typical sulfonation procedure useful herein involves simultane-ously adding sulfur trioxide and a solution containing the diisocyanate and the inert solvent to a reaction vessel already charged with the solvent and purged with nitrogen. The reactants are introduced by slow addition being careful to keep the reaction temperature below 30C in order to achieve a uniform reaction with a controlled exotherm. The resultant sulfonated product precipitates from solution and may then be recovered in quantitative yields by filtration.
As described in the Angew. Chem. reference mentioned above, sul-fonated isocyanates exist in equilibrium in the form of the cyclic carb-amic acid-sulfonic acid anhydride or in the open form. In a similar fashion, the proposed structures of the sulfonated diphenyldiisocyanates herein, existing in equilibrium, are H H
OCN ~ X ~ NCO ~ N ~ X ~ N
H03S S03H o - S2 2 o wherein X has been previously described. These structures are con-sistent with elemental analysis results. Upon addition to water, the sulfonated compositions are believed to hydrolyze, with the evolution of carbon dioxide, to form zwitterions consisting of amino and sulfonic , ~3~ ~3'~
acid functionalities having the Formula ~H3N- ~ ~ X- ~ -NH3 wherein X is described above.
It has been discovered that the sulfonated diphenyldiisocyanates herein form a gel upon addition to water when added in concentrations above 2%. The amount of time necessary for gelling to occur is a function of the concentration of the sulfonated diisocyanate in aqueous solution. Generally, solutions containing 5% or more of the sulfonated diisocyanate will gel in less than thirty minutes at room temperature.
In order to prepare the novel gelling agent herein, it is necessary to react a suitable diphenyldiisocyanate with S03 in molar concentrations of about 1 mole diisocyanate to 2 moles S03, or in other words about stoichiometric amounts of S03 to isocyanate concentration are necessary.
When diisocyanate:S03 molar ratios as low as 1:1.5 or as high as 1:3 are used, it was found that products without gel-forming capabilities are produced.
The sulfonated products described herein, when added to water in concentrations of about 5%, will normally alter the pH of the water to about 2. Stability studies on the gels at various pH's were carried out by adjusting samples containing 5% sulfonated diisocyanate to pH
values from 0.5 to 10. It was found that the gel formation was rever-sible and that gels were only stable under acidic conditions at pH
levels of about 4 or less. ~hile not wishing to be bound to any theory or mechanism, it is currently believed that at higher pH levels the hydrolyzed sulfonates carry a negative charge and as a result, the gel will not form due to charge repulsion between the molecules.
~33'7.~
The novel gels are stable upon extended holding times at elevated temperatures. For instance, gels maintained at 70C for 12 hours re-mained firm showing no sign of instability.
Oftentimes gels may be sensitive to various salt or polymer im-S purities present in solution. The novel gels herein were found to be insensitive to salts containing monovalent cations as well as to synthetic and natural polymers. The gels were, however, sensitive to salts containing divalent or multivalent cations. Such cations destroy-ed gel formation and resulted in fluffy precipitates.
The sulfonated diisocyanates of the present invention are useful, for example, as thickeners in aqueous systems and as absorbants.
In the examples which follow, all parts and percentages are given b~ weight and all temperatures are given in degress Celsius unless otherwise indicated.
This example illustrates the preparation of sulfonated 4,4'-diiso-cyanato-diphenyl methane (MDI).
A five-liter Morton flask equipped with a stirrer, thermometer, addition funnels, condenser with drying tube and a gas inlet adapter was purged with nitrogen for 15 minutes. Seven hundred twenty five (725) 9. of 1,2-dichloroethane (DCE) was added to the flask. Using two ad-dition funnels, 81.4 g. of sulfur trioxide (1.00 mole) and 440 ml. of MDI solution in DCE were added simultaneuosly while maintaining the internal temperature between 15-20C. The MDI solution which contained 125 g. MDI (0.5 mole) in DCE was added at a rate of 10 ml./ minute.
The sulfur trioxide was added at a rate of 1 ml./minute. The ~3~ L3~
sulfonated MDI precipitated as it formed. After completing sulfona-tion, the sulfona-ted MDI was filtered and dried at 60C. A total of 210 y.
of the sulfonate, a pink powder, was collected.
Elemental analysis for C15HlON208S2 Calculated: C, 43.9%; H, 2.4%; N, 6.8%; 0, 31.3%; S, 15.6%.
Found: C, 42.1%; H, 2.9%, N, 6.2%; 0, 33.2%; S, 15.5%.
This example illustrates the gel forming capabilities of MDI sul-fonate from Example 1 in water at various concentrations.
Aqueous solutions of MDI sulfonate were prepared at pH=2 and ob-served for gel formation. The results are given in Table I.
TABLE I
Concentration of MDI
Sulfonate Solution (%) Gel Time
2.0 no gel formation on prolonged standing 2.5 18 hours 5.0 30 minutes 10.0 5 minutes The gel time was reduced drastically as the concentration of MDI
sulfonate was increased with no gel formation observed for solutions containing 2.0~ or less of the sulfonate.
This example illustrates the criticality of the molar ratio of sulfur trioxide to diisocyanate necessary to produce a composition which is gel-forming upon addition to water.
MDI was sulfonated with sulfur trioxide in molar ratios of 1 mole MDI and from 1 to 3 moles sulfur trioxide. The sulfonated MDI products s3~3'~
were prepared as in Example 1. The products were added at a 2.5~ ad-dition level to water and compared with the sulfonated procluct of Example 1. Results shown in Table II indicate that only sulfonated diisocyanates prepared with about 2 moles of sulfur trioxide for every mole of diiso-cyanate will produce a composition which is gel-forming in water.
TABLE II
Sample Diisocyanate:S0~ Molar ~atio Solubility in Water A 1:1 not soluble no gel Formation B 1:1.5 not 'soluble no gel formation C 1:2 soluble formed gel upon standing D 1:3 soluble initially precipiated upon standing no gel formation This example illustrates the inability of other sulfonated phenyl isocyanates to form gels upon addition to water.
~ ther typical phenyl isocyanates were sulfonated as in Example 1 employing stoichiometric amounts of sulfur trioxide according to the isocyanate content of the composition. The isocyanates sulfonated in-cluded: phenyl isocyanate, 3,3'-dimethyl-4,4'-biphenylene isocyanate, and Rubinate ~ ~a mixture of 70 mole percent of diethylene triphenylene isocyanate and 30 mole percent of MDI available from Rubicon Chemicals).
The sulfonated samples were compared with sulfonated MDI of Example 1 by preparing 5~ aqueous solutions of each at pH=2 to observe yel formation. Resu1ts after 4 hours standing are shown in Table III.
Trade Mark ~3'7~3~.
TABLE III
Sulfonat d Sample Final Appearance of the Solution phenyl isocyanate brown powdery precipitate formed in water 5 3,3'-dimethyl-4,4'-biphenylene brown powdery precipitate formed isocyanate in water Rubinate M clear, brown solution MDI yellow, translucent gel The results show that only diphenyldiisocyanates herein have gel forming capabilities in water after solution.
This example illustrates the effect of added salts on the gel formation of the sulfonated diphenyldiisocyanates herein.
Aqueous solutions containing 5% sulfonated MDI from Example 1 and 10% of various salts were prepared at pH=2. The salts employed includ ed those containing monovalent cations: LiCl, NaCl, KCl, Na2S04 and NH4Cl; and those containing divalent or multivalent cations: MgCl2, CaCl2, and Al2(S04)3.
The samples which contained salts with monovalent cations formed firm gels while the other samples produced mixtures containing fluffy - precipitates, This example illustrates the effect of added synthetic or natural polymers on the novel gel formation of the sulfonated diphenyldiisocyan-ates.
Aqueous solutions containing 5% sulfonated MDI from Example 1 and1% of various polymers were prepared at pH=2. The polymers employed included: gelatinized corn starch, carboxymethyl cellulose, hydroxy-~'7~3~.
g ethyl cellulose, sulfonated polystyrene, polyacrylamide and polyethy-lene oxide.
All samples produced gels indicating -that natural and synthetic polymers have no detrimental effect on gel formation.
,
sulfonate was increased with no gel formation observed for solutions containing 2.0~ or less of the sulfonate.
This example illustrates the criticality of the molar ratio of sulfur trioxide to diisocyanate necessary to produce a composition which is gel-forming upon addition to water.
MDI was sulfonated with sulfur trioxide in molar ratios of 1 mole MDI and from 1 to 3 moles sulfur trioxide. The sulfonated MDI products s3~3'~
were prepared as in Example 1. The products were added at a 2.5~ ad-dition level to water and compared with the sulfonated procluct of Example 1. Results shown in Table II indicate that only sulfonated diisocyanates prepared with about 2 moles of sulfur trioxide for every mole of diiso-cyanate will produce a composition which is gel-forming in water.
TABLE II
Sample Diisocyanate:S0~ Molar ~atio Solubility in Water A 1:1 not soluble no gel Formation B 1:1.5 not 'soluble no gel formation C 1:2 soluble formed gel upon standing D 1:3 soluble initially precipiated upon standing no gel formation This example illustrates the inability of other sulfonated phenyl isocyanates to form gels upon addition to water.
~ ther typical phenyl isocyanates were sulfonated as in Example 1 employing stoichiometric amounts of sulfur trioxide according to the isocyanate content of the composition. The isocyanates sulfonated in-cluded: phenyl isocyanate, 3,3'-dimethyl-4,4'-biphenylene isocyanate, and Rubinate ~ ~a mixture of 70 mole percent of diethylene triphenylene isocyanate and 30 mole percent of MDI available from Rubicon Chemicals).
The sulfonated samples were compared with sulfonated MDI of Example 1 by preparing 5~ aqueous solutions of each at pH=2 to observe yel formation. Resu1ts after 4 hours standing are shown in Table III.
Trade Mark ~3'7~3~.
TABLE III
Sulfonat d Sample Final Appearance of the Solution phenyl isocyanate brown powdery precipitate formed in water 5 3,3'-dimethyl-4,4'-biphenylene brown powdery precipitate formed isocyanate in water Rubinate M clear, brown solution MDI yellow, translucent gel The results show that only diphenyldiisocyanates herein have gel forming capabilities in water after solution.
This example illustrates the effect of added salts on the gel formation of the sulfonated diphenyldiisocyanates herein.
Aqueous solutions containing 5% sulfonated MDI from Example 1 and 10% of various salts were prepared at pH=2. The salts employed includ ed those containing monovalent cations: LiCl, NaCl, KCl, Na2S04 and NH4Cl; and those containing divalent or multivalent cations: MgCl2, CaCl2, and Al2(S04)3.
The samples which contained salts with monovalent cations formed firm gels while the other samples produced mixtures containing fluffy - precipitates, This example illustrates the effect of added synthetic or natural polymers on the novel gel formation of the sulfonated diphenyldiisocyan-ates.
Aqueous solutions containing 5% sulfonated MDI from Example 1 and1% of various polymers were prepared at pH=2. The polymers employed included: gelatinized corn starch, carboxymethyl cellulose, hydroxy-~'7~3~.
g ethyl cellulose, sulfonated polystyrene, polyacrylamide and polyethy-lene oxide.
All samples produced gels indicating -that natural and synthetic polymers have no detrimental effect on gel formation.
,
Claims (15)
IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A gel-forming composition having a pH less than 4 comprising (a) water and (b) an amount greater than 2 percent of a sulfonated diphenyldiisocyanate prepared by sulfonating a diphenyldiisocyanate of the formula wherein X is with sulfur trioxide in a molar ratio greater than 1:1.5 and less than 1:3 of the diyhenyldiisocyanate to sulfur trioxide.
2. The composition of claim 1 containing up to 10% of the sulfonated diphenyldiisocyanate.
3. The composition of claim 1 further comprising a synthetic or natural polymer.
4. The composition of claim 3, wherein said synthetic or natural polymer is selected from the group consisting of gelatinized starch, carboxymethyl cellulose, hydroxyethyl cellulose, sulfonated polystyrene, polyacrylamide, and polyethylene oxide.
5. The composition of claim 1, further comprising a monovalent cation.
6. The composition of claim 5, wherein said monovalent cation is selected from the group consisting of Li+, Na+ , K+, and NH?.
7. The composition of claim 1, 3 or 5, wherein X is -CH2-.
8. The composition of claim 1, 3 or 5, wherein the molar ratio of diisocyanate to sulfur trioxide is 1:2.
9. The composition of claim 1, 3 or 5, wherein said sulfonated diphenyldiisocyanate has the formula C15H10N2O8S2.
10. A gelling agent prepared by the steps of:
(a) sulfonating a dipheny1diisocyanate of the formula wherein X is with sulfur trioxide in a molar ratio greater than 1:1.5 and less than 1:3 of diisocyanate to sulfur trioxide in an anhydrous inert organic solvent at a temperature of -30 to +100°C; and (b) recovering said gelling agent.
(a) sulfonating a dipheny1diisocyanate of the formula wherein X is with sulfur trioxide in a molar ratio greater than 1:1.5 and less than 1:3 of diisocyanate to sulfur trioxide in an anhydrous inert organic solvent at a temperature of -30 to +100°C; and (b) recovering said gelling agent.
11. The gelling agent of Claim 10, wherein the molar ratio of diisocyanate to sulfur trioxide is 1:2.
12. The gelling agent of Claim 10, wherein X is -CH2-.
13. The gelling agent of Claim 12, having the formula C15H10N2O8S2.
14. The gelling. agent of Claim 10, wherein the temperature is 0 to 30°C and wherein the inert organic solvent is 1,2-dichloroethane.
15. The gelling agent of Claim 10, wherein recovery is by filtration.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US55032783A | 1983-11-10 | 1983-11-10 | |
| US550,327 | 1983-11-10 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1237131A true CA1237131A (en) | 1988-05-24 |
Family
ID=24196711
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000465351A Expired CA1237131A (en) | 1983-11-10 | 1984-10-12 | Gelling composition with sulfonated diphenyldiissocyanate |
Country Status (2)
| Country | Link |
|---|---|
| CA (1) | CA1237131A (en) |
| GB (1) | GB2149787B (en) |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2615876C2 (en) * | 1976-04-10 | 1986-05-15 | Bayer Ag, 5090 Leverkusen | Aromatic isocyanato-polysulphonic acids and process for their preparation |
| DE2640103C2 (en) * | 1976-09-07 | 1986-05-07 | Bayer Ag, 5090 Leverkusen | Storage-stable mixtures of aromatic isocyanatosulphonic acids and organic liquids and processes for their production |
-
1984
- 1984-10-12 CA CA000465351A patent/CA1237131A/en not_active Expired
- 1984-10-31 GB GB08427562A patent/GB2149787B/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| GB2149787A (en) | 1985-06-19 |
| GB8427562D0 (en) | 1984-12-05 |
| GB2149787B (en) | 1987-12-02 |
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