US4156675A
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Urea polymer containing a sulfonate radical and method of preparing the same by a polymerization reaction of diaminosulfonate with diisocyanate
Assignee: NHK Spring Co Ltd
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Filing: 1978-02-17
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Granted: 1979-05-29
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Expires: 1998-02-17
Abstract
Abstract A urea compound having a sulfonate radical is obtained by reaction of aminoaminosulfonate represented by the formula: ##STR1## (where R 1 is a hydrocarbon-based radical, and R 3 is propylene radical, a substituted propylene radical, butylene radical or a substituted butylene radical) with diisocyanate, optionally in the presence of diamine and/or water. The reaction may be achieved by interfacial polymerization, solution polymerization, or solvent-free polymerization.
Inventors
- 👤 Shitomi Katayama
- 👤 Takeyasu Iwashita
- 👤 Kiyoshi Jin
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-29 07:20
CPC Classifications
C; C07; C07C; C07C309/00; C07C309/01; C07C309/02; C07C309/03; C07C309/13; C07C309/14; C07C309/15; C08; C08G; C08G18/00; C08G18/06; C08G18/08; C08G18/0804; C08G18/0819; C08G18/0828; C08G18/28; C08G18/30; C08G18/38; C08G18/3855
Claims Analysis
Total Claims: 53
Claim 1
Independent Claim
168 words
A urea compound having sulfonate radical, represented by the general formula: ##STR15## where R 1 is a divalent hydrocarbon-based radical having 2 to 17 carbon atoms, R 2 is a divalent hydrocarbon-based radical having 4 to 29 carbon atoms or polyether or polyester having an average molecular weight of 10,000 or less, R 3 is ##STR16## (wherein Rα; Rα'; Rβ; Rβ'; Rγ; Rγ' and Rα are independently hydrogen, alkyl radicals having 1 to 5 carbon atoms or monovalent radicals excluding hydrogen and alkyl radicals), R 4 is a divalent hydrocarbon-based radical having 2 to 17 carbon atoms, R 5 and R 6 are independently a monovalent hydrocarbon-based radical having 1 to 16 carbon atoms or a divalent hydrocarbon-based radical to form together by mutual bond a carbon chain, X and X' are hydrogen or a biuret bridge, M + is a cation, and x, y and z are values indicating the relative molar proportions of the respective units and complying with the required normalization: x+y+z=1; 0.1<100x/(x+y+z)<100; and 0<100z/x+y+z<50.
Claim 2
Dependent Claim
168 words
A urea compound having sulfonate radical, represented by the general formula: ##STR15## where R 1 is a divalent hydrocarbon-based radical having 2 to 17 carbon atoms, R 2 is a divalent hydrocarbon-based radical having 4 to 29 carbon atoms or polyether or polyester having an average molecular weight of 10,000 or less, R 3 is ##STR16## (wherein Rα; Rα'; Rβ; Rβ'; Rγ; Rγ' and Rα are independently hydrogen, alkyl radicals having 1 to 5 carbon atoms or monovalent radicals excluding hydrogen and alkyl radicals), R 4 is a divalent hydrocarbon-based radical having 2 to 17 carbon atoms, R 5 and R 6 are independently a monovalent hydrocarbon-based radical having 1 to 16 carbon atoms or a divalent hydrocarbon-based radical to form together by mutual bond a carbon chain, X and X' are hydrogen or a biuret bridge, M + is a cation, and x, y and z are values indicating the relative molar proportions of the respective units and complying with the required normalization: x+y+z=1; 0.1<100x/(x+y+z)<100; and 0<100z/x+y+z<50.
Claim 3
Dependent Claim
42 words
A urea compound according to claim 1, wherein said y and z are each zero, and which is represented by the formula: ##STR17## where R 1 , R 2 , R 3 , X, X' and M + are as defined above.
Claim 4
Dependent Claim
71 words
A urea compound according to claim 1, wherein said z is zero, and which is represented by the formula: ##STR18## where R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , X, X' and M + are as defined above, and x and y indicate the relative molar proportions of the respective corresponding units and comply with the required normalization: x+y=1 and 0.1<100x/(x+y)<100.
Claim 5
Dependent Claim
62 words
A urea compound according to claim 1, wherein said y is zero, and which is represented by the formula: ##STR19## where R 1 , R 2 , R 3 , X, X' and M + are as defined above, and x and z indicate the relative molar proportions of the respective corresponding unit and comply with the required normalization: x+z=1 and 0<100z<50.
Claim 6
Dependent Claim
78 words
A urea compound according to claim 1, wherein said x, y and z are each more than zero, and which is represented by the formula: ##STR20## where R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , X, X' and M + are as defined above, and x, y and z indicate the relative molar proportions of the respective corresponding units and comply with the required normalization: x+y+z=1 and 0.1≦100x/(x+y+z)<100.
Claim 7
Dependent Claim
29 words
A urea compound according to claim 1, wherein the molar ratio of the ##STR21## radical occupies 30% or less of the total molar amounts of X and X' radicals.
Claim 8
Dependent Claim
63 words
A urea compound according to claim 1, wherein said R 1 is a radical selected from the group consisting of aliphatic hydrocarbon radicals having 2 to 17 carbon atoms; alicyclic, aliphatic-substituted alicyclic, aromatic, aliphatic-substituted aromatic, alicyclic-substituted aromatic and aliphatic-substituted alicyclic-substituted aromatic hydrocarbon radicals having 6 to 15 carbon atoms; derivatives thereof substituted with halogen; and oxadialkylene radicals having 2 to 17 carbon atoms.
Claim 9
Dependent Claim
20 words
A urea compound according to claim 7, wherein said R 1 is selected from the group consisting of hexamethylene, p-phenylene.
Claim 10
Dependent Claim
68 words
A urea compound according to claim 1, wherein said R 2 is a radical selected from the group consisting of aliphatic hydrocarbon radicals having 4 to 16 carbon atoms, alicyclic hydrocarbon radicals having 8 to 20 carbon atoms, aliphatic-substituted aromatic hydrocarbon radicals having 9 to 20 carbon atoms, alicyclic-substituted aromatic hydrocarbon radicals having 12 to 20 carbon atoms and aromatic hydrocarbon radicals having 8 to 29 carbon atoms.
Claim 11
Dependent Claim
18 words
A urea compound according to claim 9, wherein said R 2 is hexamethylene, 4,4-diphenylmethane, 2,4-tolylene or 2,6-tolylene radical.
Claim 12
Dependent Claim
23 words
A urea compound according to claim 1, wherein said M is one member selected from alkaline metals, alkaline earth metals and tertiary amines.
Claim 13
Dependent Claim
45 words
A urea compound according to claim 1, wherein R 5 and R 6 are independently hydrogen atom, aliphatic hydrocarbon radicals having one to 16 carbon atoms, alicyclic, aliphatic-substituted alicyclic, aromatic, aliphatic-substituted aromatic, alicyclic-substituted aromatic, or aliphatic-substituted alicyclic-substituted aromatic hydrocarbon having 3 to 13 carbon atoms.
Claim 14
Dependent Claim
22 words
A urea compound according to claim 1, R 4 is ethylene or diphenylmethane, and R 5 and R 6 are hydrogen atoms.
Claim 15
Independent Claim
207 words
A method for producing a urea compound having sulfonate radical and represented by the formula: ##STR22## which method comprises reacting an aminoaminosulfonic acid salt represented by the formula: ##STR23## with a diisocyanate represented by the formula: OCNR.sub.2 NCO, optionally in the presence of water and/or a diamine represented by the formula: ##STR24## where R 1 is a divalent hydrocarbon-based radical having 2 to 17 carbon atoms, R 2 is a divalent hydrocarbon-based radical having 4 to 29 carbon atoms or polyether or polyester having an average molecular weight of 10,000 or less, R 3 is ##STR25## (wherein Rα,Rα'; Rβ; Rβ'; Rγ; Rγ' and Rα are independently hydrogen, alkyl radicals having 1 to 5 carbon atoms or monovalent radicals excluding hydrogen and alkyl radicals), R 4 is a divalent hydrocarbon-based radical having 2 to 17 carbon atoms, R 5 and R 6 are independently a monovalent hydrocarbon-based radical having 1 to 16 carbon atoms or a divalent hydrocarbon-based radical to form together by mutual bond a carbon chain, X and X' are hydrogen or a biuret bridge, M + is a cation, and x, y and z are values indicating the relative molar proportions of the respective units and complying with the required normalization: x+y+z=1, 0.1≦100x/(x+y+z)≦100; and 0≦100z/x+y+z≦50.
Claim 16
Independent Claim
207 words
A method for producing a urea compound having sulfonate radical and represented by the formula: ##STR22## which method comprises reacting an aminoaminosulfonic acid salt represented by the formula: ##STR23## with a diisocyanate represented by the formula: OCNR.sub.2 NCO, optionally in the presence of water and/or a diamine represented by the formula: ##STR24## where R 1 is a divalent hydrocarbon-based radical having 2 to 17 carbon atoms, R 2 is a divalent hydrocarbon-based radical having 4 to 29 carbon atoms or polyether or polyester having an average molecular weight of 10,000 or less, R 3 is ##STR25## (wherein Rα,Rα'; Rβ; Rβ'; Rγ; Rγ' and Rα are independently hydrogen, alkyl radicals having 1 to 5 carbon atoms or monovalent radicals excluding hydrogen and alkyl radicals), R 4 is a divalent hydrocarbon-based radical having 2 to 17 carbon atoms, R 5 and R 6 are independently a monovalent hydrocarbon-based radical having 1 to 16 carbon atoms or a divalent hydrocarbon-based radical to form together by mutual bond a carbon chain, X and X' are hydrogen or a biuret bridge, M + is a cation, and x, y and z are values indicating the relative molar proportions of the respective units and complying with the required normalization: x+y+z=1, 0.1≦100x/(x+y+z)≦100; and 0≦100z/x+y+z≦50.
Claim 17
Dependent Claim
49 words
A method according to claim 14, wherein only the aminoaminosulfonic acid salt and the diisocyanate are the indispensable reactants, and which produces a urea compound represented by the formula: ##STR26## where R 1 , R 2 , R 3 , X, X' and M + are as defined above.
Claim 18
Dependent Claim
82 words
A method according to claim 14, wherein the aminoaminosulfonic acid salt, the diisocyanate and the diamine are the indispensable reactants, and which produces a urea compound represented by the formula: ##STR27## where R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , X, X' and M + are as defined above, and x and y indicate the relative molar proportions of the respective corresponding units and comply with the required normalization: x+y=1 and 0.1≦100x/(x+y)<100.
Claim 19
Dependent Claim
72 words
A method according to claim 14, wherein the aminoaminosulfonic acid salt, the diisocyanate and the water are indispensable reactants, and which produces a urea compound represented by the formula: ##STR28## where R 1 , R 2 , R 3 , X, X' and M + are as defined above, and x and z indicate the relative molar proportions of the respective corresponding units and comply with the required normalization: x+z=1 and 0<100z<50.
Claim 20
Dependent Claim
85 words
A method according to claim 14, wherein all the aminoaminosulfonic acid salt, the diisocyanate, the diamine and the water are indispensable reactants, and which produces a urea compound represented by the formula: ##STR29## where R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , X, X' and M + are as defined above, and x, y and z indicate the relative molar proportions of the respective corresponding units and comply with the required normalization: x+y+z=1 and 0.1≦100x/(x+y+z)<100.
Claim 21
Dependent Claim
13 words
A method according to claim 14, wherein said reaction is an interfacial polymerization.
Claim 22
Dependent Claim
43 words
A method according to claim 19, wherein water is used as a solvent for the aminoaminosulfonic acid salt, and a water-insoluble organic solvent which does not react with the aminoaminosulfonic acid salt and the diisocyanate is used as a solvent for the diisocyanate.
Claim 23
Dependent Claim
13 words
A method according to claim 19, wherein said organic solvent is carbon tetrachloride.
Claim 24
Dependent Claim
28 words
A method according to claim 19, wherein said aminoaminosulfonic acid salt is prepared by the addition of the base M to the corresponding aminoaminosulfonic acid before the polymerization.
Claim 25
Dependent Claim
68 words
A method according to claim 19, wherein the reaction is performed through a first step wherein the reaction is carried out at a relatively low temperature and in the absence of a catalyst, a second step wherein the reaction is carried out in the presence of a catalyst, a third step wherein the reaction is carried out at a relatively high temperature or a combination of these steps.
Claim 26
Dependent Claim
41 words
A method according to claim 23, wherein in subsequent to the completion of most of the polymerization reaction, the temperature is raised 5° to 30° C. higher than the previous reaction temperature for attaining a further completion of the polymerization reaction.
Claim 27
Dependent Claim
25 words
A method according to claim 20, wherein the concentration of each of the reactants in each of the solvents is 0.1 to 40% by weight.
Claim 28
Dependent Claim
25 words
A method according to claim 20, wherein the concentration of each of the reactants in each of the solvents is 1% to 30% by weight.
Claim 29
Dependent Claim
31 words
A method according to claim 20, wherein the reaction is carried out at a temperature of more than a freezing point of the reaction system up to less than 100° C.
Claim 30
Dependent Claim
25 words
A method according to claim 27, wherein the reaction is carried out at a temperature of less than a boiling point of the organic solvent.
Claim 31
Dependent Claim
21 words
A method according to claim 20, wherein the reaction is carried out at a temperature of 0° C. to 60° C.
Claim 32
Dependent Claim
21 words
A method according to claim 20, wherein the reaction is carried out at a temperature of 0° C. to 35° C.
Claim 33
Dependent Claim
13 words
A method according to claim 14, wherein the reaction is a solution polymerization.
Claim 34
Dependent Claim
13 words
A method according to claim 31, wherein a polar aprotic solvent is used.
Claim 35
Dependent Claim
29 words
A method according to claim 32, wherein the polar aprotic solvent is selected from the group consisting of tertiary amides, aprotic organic sulfur oxides and triesters of phosphoric acid.
Claim 36
Dependent Claim
31 words
A method according to claim 32, wherein an electrolyte which does not react with the diisocyanate, the aminoaminosulfonic acid salt and the polar aprotic solvent is added as a solubilizing agent.
Claim 37
Dependent Claim
33 words
A method according to claim 32, wherein the corresponding aminoaminosulfonic acid and the base M are added to the polar aprotic solvent to neutralize, thereby forming a solution of the aminoaminosulfonic acid salt.
Claim 38
Dependent Claim
22 words
A method according to claim 35, wherein a neutral dehydrating agent is added so as to remove water produced during the neutralization.
Claim 39
Dependent Claim
23 words
A method according to claim 32, wherein a solution of the diisocyanate is slowly added to a solution of the aminoaminosulfonic acid salt.
Claim 40
Dependent Claim
15 words
A method according to claim 31, wherein the reaction is conducted under an inert atmosphere.
Claim 41
Dependent Claim
28 words
A method according to claim 31, wherein the reaction is performed at a temperature of more than a freezing point of the reaction system up to 200° C.
Claim 42
Dependent Claim
28 words
A method according to claim 39, wherein the reaction is performed at a temperature of more than a freezing point of the reaction system up to 100° C.
Claim 43
Dependent Claim
68 words
A method according to claim 31, wherein the reaction is performed through a first step wherein the reaction is carried out at a relatively low temperature and in the absence of a catalyst, a second step wherein the reaction is carried out in the presence of a catalyst, a third step wherein the reaction is carried out at a relatively high temperature or a combination of these steps.
Claim 44
Dependent Claim
57 words
A method according to claim 40, wherein the reaction is carried out by effecting the first or second step to complete most of the reaction and subsequently conducting the third step at a temperature 5° C. to 100° C. higher than the temperature at which the first or second step is effected to finally complete the reaction.
Claim 45
Dependent Claim
25 words
A method according to claim 31, wherein the concentration of each of the reactants in each of the solvents is 1% to 50% by weight.
Claim 46
Dependent Claim
25 words
A method according to claim 31, wherein the concentration of each of the reactants in each of the solvents is 5% to 30% by weight.
Claim 47
Dependent Claim
13 words
A method according to claim 14, wherein the reaction is a solvent-free polymerization.
Claim 48
Dependent Claim
22 words
A method according to claim 45, wherein the reactants are mixed, charged in a container or a casting mold and reacted there.
Claim 49
Dependent Claim
53 words
A method according to claim 45, wherein the reaction is carried out through a first step wherein the reaction is conducted at a relatively low temperature and in the absence of a catalyst, a second step wherein the reaction is conducted in the presence of a catalyst or a combination of these steps.
Claim 50
Dependent Claim
48 words
A method according to claim 47, wherein the reaction is carried out through the two steps, and the first step is carried out at a temperature of 0° C. to 100° C. and the second step is effected at a temperature higher than that of the first step.
Claim 51
Dependent Claim
21 words
A method according to claim 47, wherein the second step is effected at a temperature of 50° C. to 200° C.
Claim 52
Dependent Claim
12 words
A method according to claim 45, wherein a diluent filler is added.
Claim 53
Dependent Claim
13 words
A method according to claim 50, wherein the diluent filler is silica powder.
References Cited (Backward Citations)
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1982-05-28 | 1982-11-27 | 1983-05-29 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1986-05-28 | 1986-11-27 | 1987-05-29 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1990-05-28 | 1990-11-27 | 1991-05-29 | $7700.00 | Window Closed / Lapsed |