CA1240444A - N-(2-hydroxy-3-sulfopropyl) amide containing polymers - Google Patents
N-(2-hydroxy-3-sulfopropyl) amide containing polymersInfo
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- CA1240444A CA1240444A CA000522526A CA522526A CA1240444A CA 1240444 A CA1240444 A CA 1240444A CA 000522526 A CA000522526 A CA 000522526A CA 522526 A CA522526 A CA 522526A CA 1240444 A CA1240444 A CA 1240444A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/34—Introducing sulfur atoms or sulfur-containing groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2800/00—Copolymer characterised by the proportions of the comonomers expressed
- C08F2800/10—Copolymer characterised by the proportions of the comonomers expressed as molar percentages
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Separation Of Suspended Particles By Flocculating Agents (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
Abstract
ABSTRACT
A high temperature, pressurized process is described to synthesize sulfonated acrylamide polymers represented by the structure:
A high temperature, pressurized process is described to synthesize sulfonated acrylamide polymers represented by the structure:
Description
~L~
~ he synthesis of water-soluble sulfonated polymers has generally been limited to the use of certain vinyl monomers containing the sulfonate functional group. An example of these monomers are sodium vinyl sulfonate, sùlfonated styrene, and AMP5 (2-acrylamido-2-methyl propane sulfonic acid). In addition, the synthesis of vinylic sulfonated polymers containing the sulfonate group has been limited from the point of view that only certain of these kinds of sulfonated monomers are commercially produced.
As a result, the use of these sulfonated water-soluble polymers is limited only to the structures mentioned above. It would therefore be an advance in the art if other water-soluble polymeric chemical structures could be synthesi~ed on a polymeric backbone which structures would contain the sulfonate group, either in the acid or salt form, and which structures might also contain other functional groups which could enhance the use of these water-soluble sulfonated polymers in certain applications such as dispersants in water treatment, scale inhibitors in natural and industrial waters, flocculants and coagulants, and the like.
It is therefore an obJect of this invention to create water-soluble polymers containing a sulfonate group and, in addition, which polymers may also contain other functional groups which may be useful when applied to aqueous solutions ûr environments.
It is another object of this invention to develop a synthetic procedure which can generally be applicable to the synthesis of various types of water-soluble polymers containing the sulfonate group with or wlthout t~e ad~itional presence o~
other functional groups which may be useful when these polymers are added to aqueous systems.
It is another object of this invention ta synthesize and recover certain types of sulfonate containing water-soluble polymers which polymers may contain other functional groups such as hydroxyl, chloro, bromo, iodo, and/or mixtures tnereof~ which polymers have not heretofor been known or used.
THE_INVENTION
I have discovered a process for modifying water-soluble polymers containing pendant amide functional groups, such polymers primarily derived from acrylamide containing vinylic polymers/copolymers or from alkyl substituted acrylamide containing vinylic polymers or copolymers, and which polymers/copolymers are water soluble and contain pendant amide functional groups derived from acrylamide, methyl acrylamide, ethylacrylamide, and the like.
The process which I have discovered is a process that uses the equivalent of a transamidation reaction with the pendant amide group on the polymer and a chemical reactant represented by the structure:
Formula I.
HN-~R'~ So3M~3n (X)m wherein R is individually chosen, in each occurrence, from the group consisting of hydrogen and lower alkyl groups containing from 1 4 carbon atoms;
M is chosen from the group consisting o~ hydrogen, alkali metal, alkaline earth metal and ammonium ions, and mixtures thereof;
R' is a multi-valent hydrocarbonaceouS bridging group which may be linear, branched, cyc1ic, aromatic, heterocyclic, and mixtures thereof, and having from 1-16 carbon atoms~
X is chosen from Cl, ~r, I, ûH and mixtures thereof;
and wherein, -~
m ranges between 0 and 16, n ranges between 1 and 16, provided that the sum of m + n is between 1-20.
THE CHEMICAL REACTANT
The chemical reactant described above is primarily an amino substituted compound which also contains the sulfonate functional group, and wherein the amine functional group contains at least one active hydrogen substituted on the amino nitrogen.
Although sulfonate compounds having both prlmary and secondary amines can react under my transamidation reaction conditions to achieve modified sulfonate c~ntaining polymers, it is preferable that when a secondary amine is chosen to accomplish this modification of pendant amide containing polymers, that the alkyl group substituted on the amino nitrogen contain no more than 4 carbon atoms, i.e. the alkyl substitution should be limited to methyl, ethyl, propyl and butyl functionality, and ~ . "
isomers thereof.
However, it is most preferred that the amine substitution on the sulfonate contalning chemical reactant be a primary amino functional group. When a prirnary amino functional group is used to accomplish the transamidation reaction, the reaction easily proceeds so as to incorporate at least 25~ and preferably 60, mole percent of the chemical reactant used into the ~ater~soluble polymer chain containing pendent arnide groups, substituting therefore a sulfonate containing functionality for ~hat was originally the pendant amide functionality.
In addition to the amine substitution in the cheMical reactant described above, this chemical reactant does contain at least one sulfonate functional group in either its acid form or its salt form, wherein the salt form is chosen from a salt of an alkali metal, an alkaline earth metal, tertiary amines, and ammonium ions, and mixtures thereof. The saLt form may be in existence prior to the transamidation reaction or it may be synthesized by varying pH with bases containing alkali metals, alkaline earth metals, tertiary amines, or ammonia, either prior to, during the transamidation reaction or aFter the transamidation reaction has been completed.
In addition to the sulfonate functional group and the amine functional group, the chemical reactant may also contain other functional groups chnsen from the groups consisting of chlorine, bromine, hydroxyl, and mixtures thereof. Preferaoly, the chemical reactant is limited to contain a primary amino group responsible for the transamidation reaction, at least one sulfonate group which allows the formation of an anionic sulfonate containing water-soluble polymer, and an hydroxyl group ,or a chloro functional group, the presence of which may enhance the activity of water-soluble sulfonate containing polymers synthesized by my process~
Most preferably, the chemical reactant contains a primary amine, zero or more hydroxyl groups, and one or more sulfonate groups either in the free aci~ form, salt Form, or mixtures of the free acid and salt forms.
Several preferred species of the chemical reactant described above are demonstrated in the following farmulations:
_ 5 _ Formula II.
a. H2N~ CHaS03M
b . H 2N~CH 2 bH--so 3M
c. H2N CH2CH2~SO3M
d. H2N-CH2-CH-CH2503M
THE PENDENT ACRYLAMIDE CONTAINING POLYMERS
The pendant acrylamide containing polymers are water-soluble polymers which have a general structure allowing the presence of a pendant amide group as demonstrated in Formula III:
Formula III.
R
C--O C-^O
Polyme _ ;~ Backbone In Formula III, as one can observe, tne pendant amide group may be a primary amide, a secondary amide, or a tertiary amide compound and mixtures therof. Preferably, to obtain reasonable conversions of these pendant amide groups to the sulfonate containing functional groups described above, the pendant amide group is a primary amide group.
The most likely water-soluble polymers containing pendant amide functionali~y which polymers are easily rnoaified under the conditions of my transamidation reaction, are those water-soluble polymers described by Formula IV:
Formula IV.
CH 2 ~C~c~ 2 ~ ~H~
In Formula IV, R is independently chosen, at each occurrence, from the group consisting of hydrogen, and lo~er alkyl groups containing from 1-4 carbon atoms;
M is independently chosen, at each occurrence, from hydrogen, alkali metals, alkaline earth metal and ammonium ions and mixtures thereof;
and a and b are integers having the following relationships:
a~b ranges between 0 to 100, and a + b is sufficient so as to provide a polymer having a molecular weight of at least 1,000. Preferably the sum a ~ b is sufficient to provide a molecular weight ranging between about 1 t û00-20,0ûO,000.
~4~4~' I
As can be seen, the polymers described above may be homopolymerS of acrylamide or its alkyl homologs, i.e.
methacrylamide and the like, they may be copolyrners of acrylamidé
with acrylic acid or its homologs such as methacrylic acid and the like, or they may be terpolymers and above with other monomers of a vinylic nature which contain acrylamide and acrylic acid, and their homologs such as methacr~,lic acid, methacrylamide,and the-~like.
THE CHEMICAL REACTION
The chemical reaction which is preferred to obtain the sulfonated polymers of this invention is a reaction which can generally be referred to as a transamidation reaction. This reaction substitutes an amine compound which may also contain other functional groups such as the sulfonate function group for the nitrogen portion of a pendant amide group contained on a polymeric backbone as described above. This transamidation reaction has been discovered to be a general reaction which can achieve the substitution of my amine and sulfonate containing moiety for the amide nitrogen group of the pendant amide functionality of a water-soluble polymer, thereby obtaining unique sulfonated polymers.
The reaction conditions requi-re that polymers containing pendant amiae groups be dissolved or readily dispersed in a solvent which is a common solvent for the chemical reactant o~
the class described above. In other words, both the polymer which is to be modified and the chemical reactant should be soluble or dispersible in he ~ame solvent system.
Common solvents which have been found useful in this reaction include, but are not limited to, water, dimethylformamide, dimethylsulfoxide, admixtures thereof, and admixtures of these solvents; either singly or taken together with other miscible solvents such as ethanol, tertiary butanol and the like.
A preferred solvent which is a common solvent for both the polymer containing pendant amide groups and the chemical reactants above is water, particularly if the polymer containing pendant amide group is initially water-soluble, as in the case of most acrylamide containing vinylic polymers. Another preferred comrnon solvent for my reaction is a water in-oil emulsion wherein the dispersed water phase contains dissolved therein both the polymers containing pendant amide groups and the chemical reactants described above.
After having dissolved the polymers containing pendant amide groups in the common solvent, preferably water, the chemical reactant can be added to obtain a solution or dispersion of amide containing polymer and the chemical reactants of this invention Whether the polymer or the reactant is first added to the common solvent is of no consequence. This admixture is then added to or contained in a reaction vessel capable of withstanding a pressurized chemical reaction, for example, a Paar Borr~b type of vessel. The vessel is enclosed and then heated to a temperature of at least 100C, preferably at least llûC, and most preferably to a temperature of at least 120C. If the temperature is increased above lû0C, the vessel contents can expand and the pressure within the vessel can exceed one atmosphere and depending upon the solvent, the sul~onates used or the reactants used, can reach up to about 5 to 15 atmospheres, and possibly more. The pressure within the reaction vessel i5 a non-controlled variable and is controlled only to the extent that the vessel is enclosed, that a reaction temperature of at least 100C or higher is reached, and the vessel may contain solvents or reactants of more or less volatile nature, which solvents and reactants have vapor pressures of such a nature that pressure vessels are required at temperatures above 100C.
Once the reaction vessel contents have reached at least 100C, and preferably 110C, the reaction is allowed to occur for at least 3 minutes at this temperature, and pre~erably for whatever length of time is necessary to accomplish a minimum of at least a 25 percent conversion of the added amount of chemical reactant. The chemical reactant is, of course, converted to a pendant sulfonate containing substituted amide being the product of the transamidation chem~cal reaction summarized above. If the polymer is a homopolymer of acrylamide, methacrylamide, or a copolymer of vinyl amide containing monomers such that no other pendant functional group is present besides amioe functional groups, the condition of the reaction is such that at least some degree o~ amide hydrolysis may also occur in those reactions in which water or a water containing solvent is utilized. In such cases, a carboxylate functional group is also obtained in addition to the sul~onate modified amide and any unreacted starting amide groups From the starting polymer.
Therefore, ~ have described the chemical reaction or process that accomplishes the synthesis of polymers having the structure:
~ ~Æ~
Formula V.
r 1 7~ r t l-f~
~Io~ a OD7 b ~ d M~
(S~3M~4 ) n wherein R is individually chosen at each occurrence from H and lower alkyl (Cl~C4) grûups;
M is chosen from hydrogen, alkali metal, alkaline earth metal, tertiary amines, and ammonium ion and mixtures thereof;
R' is a multi-covalent hydrocarbonaceous bridging group having from one to sixteen carbon atoms and being chosen from linear, branched, cyclic, aromatic, heterocyclic, and mixtures thereof, functional groups;
X is chosen from Cl, Br, OH, and Mixtures thereof;
and wherein a, b, and d are integers with the following relationships;
aJb is from zero to lûO
b/d is from 0.01 to 100 a/d is from zero to 100, and the sum of a+b+d is sufficient to provide a molecular weight of at least 1000, and the ratio of d:(a ~ b) is from 20:1 to 1:100;
and wherein m ranges between O and 16, and n ranges between 1 and 16, provided that when m is zero, R' is from linear, cyclic, heterocyclic, olefinic, aromatic, and mixtures therecf functional groups t an~
~urther provided that the sum o~ m + n i5 between 1-20;
I
which process comprises reacting, in a common solvent, at a temperature of at least 100C:
A. a polymer having a molecular weight o~ at least 500, and having pendant amide functional groups, which polymer is represented by the structure:
~H ~8 ~,~
~- NH2 M~
wherein R, M, a, b have the same meanings as above;
¦ with, ¦ B. a chemical reactant having the structure:
¦ R
l HN-~ R'-~-tS03M)n I Xm ¦ wherein R, R~, M, X, m, and n have the meanings above; wherein ¦ the mole ratio of chemical reactant to pendant amide groups ¦ ranges between about 5:1 to about 1:100; and the reaction occurs ¦ for an effective amount of time to accomplish at least a ¦ 25 percent conversicn of chemical reactant to water-soluble ¦ sulfonated polymer; and then recovering the water-soluble sulfonated polymer.
Polymer recovery may be accomplished in several ways known to the person familiar with the art. For example, the polymers may be precip.ltated by addition of precipitating solvents, or non-solvents, to the reaction mixture~ For example, methanol or acetone may be added to the reaction mixture either as is or after concentration by distillation or vacuum distillation to precipitate the polymers. The polyrners may also be recovered by vacuum distillation of solvent and unreacted chemical reactant from the reaction product mixture. The polymers may also be recovered by gel permeation chromatographic techniques, however, for the most part the polymers are recoverea simply as a solution in the solvent used to perform the transamidation reaction, and used as such.
Preferably, my process is a method to synthesize water-soluble sulfonated polymers having randomly repeated mer units represented by the formula:
r 1 71 ~7 11 r 1 1 l tC_C~f C~f-c-~'~ 0~ 0=~ d M~ ~~Xm (SO3M~
wherein R is individually chosen at each occurrence from H an~lower alkyl (Cl-C4) groups;
M is chosen from hydrogen, alkali metal, alkaline earth metal, tertiary amines 9 and ammonium ions and mixtures thereof;
R' is a multi-covalent hydrocarbonaceous bridging group having from one to sixteen carbon atoms and being chosen from linear alkyl, branched alkyl, cyclic, aromatic, heterocyclic, and mixtures thereof, Functional groups;
X is chosen from Cl, Br, OH, and mixtures thereof;
and wherein a, b, and d are integers with the following relationships;
aJb is from zero to 100 b/d ls from 0.01 to 100 a/d is from zero to 100, and the sum of a+b+d is sufficient to provide a molecular weight of at least 3,000, and the ratio of d:(a + b) is from 20:1 to 1:100;
and wherein m ranges between 0 and 16, and n ranges between 1 and 16, provided that when m is zero, R' is from linear alkyl, cyclic, heterocyclic, olefinic, aromatic, and mixtures thereof functional groups, and further provided that the sum of m + n is from 1 to 20;
which process comprises reacting, in a common solvent, at a temperature of at least 100C:
A. a polymer having a molecular weight of at least 500, and having pendant amide functional groups, and represented by the structure:
O ~ ~EI 2 wherein R, M, a, b have the same meanings as above; with B.a chemical reactant having the structure:
R
HNtR ~S03M)n Xm wherein R, R'1 M, X, m, and n have the meanings above; and wherein the mole ratio of chemical reactant to pendant amide groups ranges between about 5:1 to about l:lûO; and wherein the reaction occurs for an effective amount of time to accomplish at least an 60 percent conversion of chemi.cal reactant to water-soluble sulfonated polymer; and then recovering the water soluble sulfonate~ polymer.
Most preferably, my process is a method for the synthesis o~ water-soluble sulfonated polymers represen-ted by the formula:
CH 2~ C ~ CH 2 - C ~ CH 2 - ~}
O ~C a o~ C b Qo~ d O- 1H a NH
M~ ( ~ I ~Xm (S03 Mi)n wherein R is individually chosen at each occurrence from hydrogen and Cl to C4 lower alkyl groups;
M is individually chosen at each occurrence from hydrogen, alkali metals7 and ammonium ions, ~' is chosen from multi-covalent, branched alkyl, linear alkyl or cyclic hydrocarbonaceous bridging groups having from one to eight carbon atoms;
X is chosen from C17 OH, and mixtures thereof;
m ranges between O to 6;
n ranges between 1 to 4;
~ ~d ~
a~ b, and d are integers with the follo~ing relationships:
a/b ranges from 0 to 100, a/d ranges from 0 to 100, b/d ranges from 0.01 to 100, and the ratio d:(a~b) is between about 5:1 to about 1:25, and wherein the occurrence of mer units of a, b, and d is random and the sum of a+b~d will achieve a molecular weight of at least 1000; which process comprises reacting, in an aqueous solvent:
A. a polymer having pendant amide functional groups and represented by the structure:
~CH 2 ~C~ECH 2 - C ¦_ o~ a O~ ~ b M~
wherein R, M, a, and b have the meanings above and wherein the sum of a~b achieves a molecular weight of at least 500;
and B. a chemical reactant having the structure:
H2N~ R 1_~--t503M ) n Xm wherein R', M, X, m, and n have the meanings above;
under the following reaction conditions:
I. a reaction temperature of at least 100C and preferably at least 110C;
II. a reactîon time of at least L/4 hour and preferably at least 1/2 hour;
~;~4~
III. a mole ratio of chemical reac-~ant to polymer ranging between about 2:1 to abou-t 1:50;
IV. a pressure ranging from atmospheric pressure to 35 times atmospheric pressure, or more;
thereby achieving the synthesis of -the sulfonated polymers described above.
In a most preferred proeess of the present invention R is individually ehosen at each occurrence from hydrogen or methyl M is individually chosen at each occurrence from hydrogen, sodium, potassium, ammonium and mix~ures thereof, R' is a linear alkylene bridging group having from
~ he synthesis of water-soluble sulfonated polymers has generally been limited to the use of certain vinyl monomers containing the sulfonate functional group. An example of these monomers are sodium vinyl sulfonate, sùlfonated styrene, and AMP5 (2-acrylamido-2-methyl propane sulfonic acid). In addition, the synthesis of vinylic sulfonated polymers containing the sulfonate group has been limited from the point of view that only certain of these kinds of sulfonated monomers are commercially produced.
As a result, the use of these sulfonated water-soluble polymers is limited only to the structures mentioned above. It would therefore be an advance in the art if other water-soluble polymeric chemical structures could be synthesi~ed on a polymeric backbone which structures would contain the sulfonate group, either in the acid or salt form, and which structures might also contain other functional groups which could enhance the use of these water-soluble sulfonated polymers in certain applications such as dispersants in water treatment, scale inhibitors in natural and industrial waters, flocculants and coagulants, and the like.
It is therefore an obJect of this invention to create water-soluble polymers containing a sulfonate group and, in addition, which polymers may also contain other functional groups which may be useful when applied to aqueous solutions ûr environments.
It is another object of this invention to develop a synthetic procedure which can generally be applicable to the synthesis of various types of water-soluble polymers containing the sulfonate group with or wlthout t~e ad~itional presence o~
other functional groups which may be useful when these polymers are added to aqueous systems.
It is another object of this invention ta synthesize and recover certain types of sulfonate containing water-soluble polymers which polymers may contain other functional groups such as hydroxyl, chloro, bromo, iodo, and/or mixtures tnereof~ which polymers have not heretofor been known or used.
THE_INVENTION
I have discovered a process for modifying water-soluble polymers containing pendant amide functional groups, such polymers primarily derived from acrylamide containing vinylic polymers/copolymers or from alkyl substituted acrylamide containing vinylic polymers or copolymers, and which polymers/copolymers are water soluble and contain pendant amide functional groups derived from acrylamide, methyl acrylamide, ethylacrylamide, and the like.
The process which I have discovered is a process that uses the equivalent of a transamidation reaction with the pendant amide group on the polymer and a chemical reactant represented by the structure:
Formula I.
HN-~R'~ So3M~3n (X)m wherein R is individually chosen, in each occurrence, from the group consisting of hydrogen and lower alkyl groups containing from 1 4 carbon atoms;
M is chosen from the group consisting o~ hydrogen, alkali metal, alkaline earth metal and ammonium ions, and mixtures thereof;
R' is a multi-valent hydrocarbonaceouS bridging group which may be linear, branched, cyc1ic, aromatic, heterocyclic, and mixtures thereof, and having from 1-16 carbon atoms~
X is chosen from Cl, ~r, I, ûH and mixtures thereof;
and wherein, -~
m ranges between 0 and 16, n ranges between 1 and 16, provided that the sum of m + n is between 1-20.
THE CHEMICAL REACTANT
The chemical reactant described above is primarily an amino substituted compound which also contains the sulfonate functional group, and wherein the amine functional group contains at least one active hydrogen substituted on the amino nitrogen.
Although sulfonate compounds having both prlmary and secondary amines can react under my transamidation reaction conditions to achieve modified sulfonate c~ntaining polymers, it is preferable that when a secondary amine is chosen to accomplish this modification of pendant amide containing polymers, that the alkyl group substituted on the amino nitrogen contain no more than 4 carbon atoms, i.e. the alkyl substitution should be limited to methyl, ethyl, propyl and butyl functionality, and ~ . "
isomers thereof.
However, it is most preferred that the amine substitution on the sulfonate contalning chemical reactant be a primary amino functional group. When a prirnary amino functional group is used to accomplish the transamidation reaction, the reaction easily proceeds so as to incorporate at least 25~ and preferably 60, mole percent of the chemical reactant used into the ~ater~soluble polymer chain containing pendent arnide groups, substituting therefore a sulfonate containing functionality for ~hat was originally the pendant amide functionality.
In addition to the amine substitution in the cheMical reactant described above, this chemical reactant does contain at least one sulfonate functional group in either its acid form or its salt form, wherein the salt form is chosen from a salt of an alkali metal, an alkaline earth metal, tertiary amines, and ammonium ions, and mixtures thereof. The saLt form may be in existence prior to the transamidation reaction or it may be synthesized by varying pH with bases containing alkali metals, alkaline earth metals, tertiary amines, or ammonia, either prior to, during the transamidation reaction or aFter the transamidation reaction has been completed.
In addition to the sulfonate functional group and the amine functional group, the chemical reactant may also contain other functional groups chnsen from the groups consisting of chlorine, bromine, hydroxyl, and mixtures thereof. Preferaoly, the chemical reactant is limited to contain a primary amino group responsible for the transamidation reaction, at least one sulfonate group which allows the formation of an anionic sulfonate containing water-soluble polymer, and an hydroxyl group ,or a chloro functional group, the presence of which may enhance the activity of water-soluble sulfonate containing polymers synthesized by my process~
Most preferably, the chemical reactant contains a primary amine, zero or more hydroxyl groups, and one or more sulfonate groups either in the free aci~ form, salt Form, or mixtures of the free acid and salt forms.
Several preferred species of the chemical reactant described above are demonstrated in the following farmulations:
_ 5 _ Formula II.
a. H2N~ CHaS03M
b . H 2N~CH 2 bH--so 3M
c. H2N CH2CH2~SO3M
d. H2N-CH2-CH-CH2503M
THE PENDENT ACRYLAMIDE CONTAINING POLYMERS
The pendant acrylamide containing polymers are water-soluble polymers which have a general structure allowing the presence of a pendant amide group as demonstrated in Formula III:
Formula III.
R
C--O C-^O
Polyme _ ;~ Backbone In Formula III, as one can observe, tne pendant amide group may be a primary amide, a secondary amide, or a tertiary amide compound and mixtures therof. Preferably, to obtain reasonable conversions of these pendant amide groups to the sulfonate containing functional groups described above, the pendant amide group is a primary amide group.
The most likely water-soluble polymers containing pendant amide functionali~y which polymers are easily rnoaified under the conditions of my transamidation reaction, are those water-soluble polymers described by Formula IV:
Formula IV.
CH 2 ~C~c~ 2 ~ ~H~
In Formula IV, R is independently chosen, at each occurrence, from the group consisting of hydrogen, and lo~er alkyl groups containing from 1-4 carbon atoms;
M is independently chosen, at each occurrence, from hydrogen, alkali metals, alkaline earth metal and ammonium ions and mixtures thereof;
and a and b are integers having the following relationships:
a~b ranges between 0 to 100, and a + b is sufficient so as to provide a polymer having a molecular weight of at least 1,000. Preferably the sum a ~ b is sufficient to provide a molecular weight ranging between about 1 t û00-20,0ûO,000.
~4~4~' I
As can be seen, the polymers described above may be homopolymerS of acrylamide or its alkyl homologs, i.e.
methacrylamide and the like, they may be copolyrners of acrylamidé
with acrylic acid or its homologs such as methacrylic acid and the like, or they may be terpolymers and above with other monomers of a vinylic nature which contain acrylamide and acrylic acid, and their homologs such as methacr~,lic acid, methacrylamide,and the-~like.
THE CHEMICAL REACTION
The chemical reaction which is preferred to obtain the sulfonated polymers of this invention is a reaction which can generally be referred to as a transamidation reaction. This reaction substitutes an amine compound which may also contain other functional groups such as the sulfonate function group for the nitrogen portion of a pendant amide group contained on a polymeric backbone as described above. This transamidation reaction has been discovered to be a general reaction which can achieve the substitution of my amine and sulfonate containing moiety for the amide nitrogen group of the pendant amide functionality of a water-soluble polymer, thereby obtaining unique sulfonated polymers.
The reaction conditions requi-re that polymers containing pendant amiae groups be dissolved or readily dispersed in a solvent which is a common solvent for the chemical reactant o~
the class described above. In other words, both the polymer which is to be modified and the chemical reactant should be soluble or dispersible in he ~ame solvent system.
Common solvents which have been found useful in this reaction include, but are not limited to, water, dimethylformamide, dimethylsulfoxide, admixtures thereof, and admixtures of these solvents; either singly or taken together with other miscible solvents such as ethanol, tertiary butanol and the like.
A preferred solvent which is a common solvent for both the polymer containing pendant amide groups and the chemical reactants above is water, particularly if the polymer containing pendant amide group is initially water-soluble, as in the case of most acrylamide containing vinylic polymers. Another preferred comrnon solvent for my reaction is a water in-oil emulsion wherein the dispersed water phase contains dissolved therein both the polymers containing pendant amide groups and the chemical reactants described above.
After having dissolved the polymers containing pendant amide groups in the common solvent, preferably water, the chemical reactant can be added to obtain a solution or dispersion of amide containing polymer and the chemical reactants of this invention Whether the polymer or the reactant is first added to the common solvent is of no consequence. This admixture is then added to or contained in a reaction vessel capable of withstanding a pressurized chemical reaction, for example, a Paar Borr~b type of vessel. The vessel is enclosed and then heated to a temperature of at least 100C, preferably at least llûC, and most preferably to a temperature of at least 120C. If the temperature is increased above lû0C, the vessel contents can expand and the pressure within the vessel can exceed one atmosphere and depending upon the solvent, the sul~onates used or the reactants used, can reach up to about 5 to 15 atmospheres, and possibly more. The pressure within the reaction vessel i5 a non-controlled variable and is controlled only to the extent that the vessel is enclosed, that a reaction temperature of at least 100C or higher is reached, and the vessel may contain solvents or reactants of more or less volatile nature, which solvents and reactants have vapor pressures of such a nature that pressure vessels are required at temperatures above 100C.
Once the reaction vessel contents have reached at least 100C, and preferably 110C, the reaction is allowed to occur for at least 3 minutes at this temperature, and pre~erably for whatever length of time is necessary to accomplish a minimum of at least a 25 percent conversion of the added amount of chemical reactant. The chemical reactant is, of course, converted to a pendant sulfonate containing substituted amide being the product of the transamidation chem~cal reaction summarized above. If the polymer is a homopolymer of acrylamide, methacrylamide, or a copolymer of vinyl amide containing monomers such that no other pendant functional group is present besides amioe functional groups, the condition of the reaction is such that at least some degree o~ amide hydrolysis may also occur in those reactions in which water or a water containing solvent is utilized. In such cases, a carboxylate functional group is also obtained in addition to the sul~onate modified amide and any unreacted starting amide groups From the starting polymer.
Therefore, ~ have described the chemical reaction or process that accomplishes the synthesis of polymers having the structure:
~ ~Æ~
Formula V.
r 1 7~ r t l-f~
~Io~ a OD7 b ~ d M~
(S~3M~4 ) n wherein R is individually chosen at each occurrence from H and lower alkyl (Cl~C4) grûups;
M is chosen from hydrogen, alkali metal, alkaline earth metal, tertiary amines, and ammonium ion and mixtures thereof;
R' is a multi-covalent hydrocarbonaceous bridging group having from one to sixteen carbon atoms and being chosen from linear, branched, cyclic, aromatic, heterocyclic, and mixtures thereof, functional groups;
X is chosen from Cl, Br, OH, and Mixtures thereof;
and wherein a, b, and d are integers with the following relationships;
aJb is from zero to lûO
b/d is from 0.01 to 100 a/d is from zero to 100, and the sum of a+b+d is sufficient to provide a molecular weight of at least 1000, and the ratio of d:(a ~ b) is from 20:1 to 1:100;
and wherein m ranges between O and 16, and n ranges between 1 and 16, provided that when m is zero, R' is from linear, cyclic, heterocyclic, olefinic, aromatic, and mixtures therecf functional groups t an~
~urther provided that the sum o~ m + n i5 between 1-20;
I
which process comprises reacting, in a common solvent, at a temperature of at least 100C:
A. a polymer having a molecular weight o~ at least 500, and having pendant amide functional groups, which polymer is represented by the structure:
~H ~8 ~,~
~- NH2 M~
wherein R, M, a, b have the same meanings as above;
¦ with, ¦ B. a chemical reactant having the structure:
¦ R
l HN-~ R'-~-tS03M)n I Xm ¦ wherein R, R~, M, X, m, and n have the meanings above; wherein ¦ the mole ratio of chemical reactant to pendant amide groups ¦ ranges between about 5:1 to about 1:100; and the reaction occurs ¦ for an effective amount of time to accomplish at least a ¦ 25 percent conversicn of chemical reactant to water-soluble ¦ sulfonated polymer; and then recovering the water-soluble sulfonated polymer.
Polymer recovery may be accomplished in several ways known to the person familiar with the art. For example, the polymers may be precip.ltated by addition of precipitating solvents, or non-solvents, to the reaction mixture~ For example, methanol or acetone may be added to the reaction mixture either as is or after concentration by distillation or vacuum distillation to precipitate the polymers. The polyrners may also be recovered by vacuum distillation of solvent and unreacted chemical reactant from the reaction product mixture. The polymers may also be recovered by gel permeation chromatographic techniques, however, for the most part the polymers are recoverea simply as a solution in the solvent used to perform the transamidation reaction, and used as such.
Preferably, my process is a method to synthesize water-soluble sulfonated polymers having randomly repeated mer units represented by the formula:
r 1 71 ~7 11 r 1 1 l tC_C~f C~f-c-~'~ 0~ 0=~ d M~ ~~Xm (SO3M~
wherein R is individually chosen at each occurrence from H an~lower alkyl (Cl-C4) groups;
M is chosen from hydrogen, alkali metal, alkaline earth metal, tertiary amines 9 and ammonium ions and mixtures thereof;
R' is a multi-covalent hydrocarbonaceous bridging group having from one to sixteen carbon atoms and being chosen from linear alkyl, branched alkyl, cyclic, aromatic, heterocyclic, and mixtures thereof, Functional groups;
X is chosen from Cl, Br, OH, and mixtures thereof;
and wherein a, b, and d are integers with the following relationships;
aJb is from zero to 100 b/d ls from 0.01 to 100 a/d is from zero to 100, and the sum of a+b+d is sufficient to provide a molecular weight of at least 3,000, and the ratio of d:(a + b) is from 20:1 to 1:100;
and wherein m ranges between 0 and 16, and n ranges between 1 and 16, provided that when m is zero, R' is from linear alkyl, cyclic, heterocyclic, olefinic, aromatic, and mixtures thereof functional groups, and further provided that the sum of m + n is from 1 to 20;
which process comprises reacting, in a common solvent, at a temperature of at least 100C:
A. a polymer having a molecular weight of at least 500, and having pendant amide functional groups, and represented by the structure:
O ~ ~EI 2 wherein R, M, a, b have the same meanings as above; with B.a chemical reactant having the structure:
R
HNtR ~S03M)n Xm wherein R, R'1 M, X, m, and n have the meanings above; and wherein the mole ratio of chemical reactant to pendant amide groups ranges between about 5:1 to about l:lûO; and wherein the reaction occurs for an effective amount of time to accomplish at least an 60 percent conversion of chemi.cal reactant to water-soluble sulfonated polymer; and then recovering the water soluble sulfonate~ polymer.
Most preferably, my process is a method for the synthesis o~ water-soluble sulfonated polymers represen-ted by the formula:
CH 2~ C ~ CH 2 - C ~ CH 2 - ~}
O ~C a o~ C b Qo~ d O- 1H a NH
M~ ( ~ I ~Xm (S03 Mi)n wherein R is individually chosen at each occurrence from hydrogen and Cl to C4 lower alkyl groups;
M is individually chosen at each occurrence from hydrogen, alkali metals7 and ammonium ions, ~' is chosen from multi-covalent, branched alkyl, linear alkyl or cyclic hydrocarbonaceous bridging groups having from one to eight carbon atoms;
X is chosen from C17 OH, and mixtures thereof;
m ranges between O to 6;
n ranges between 1 to 4;
~ ~d ~
a~ b, and d are integers with the follo~ing relationships:
a/b ranges from 0 to 100, a/d ranges from 0 to 100, b/d ranges from 0.01 to 100, and the ratio d:(a~b) is between about 5:1 to about 1:25, and wherein the occurrence of mer units of a, b, and d is random and the sum of a+b~d will achieve a molecular weight of at least 1000; which process comprises reacting, in an aqueous solvent:
A. a polymer having pendant amide functional groups and represented by the structure:
~CH 2 ~C~ECH 2 - C ¦_ o~ a O~ ~ b M~
wherein R, M, a, and b have the meanings above and wherein the sum of a~b achieves a molecular weight of at least 500;
and B. a chemical reactant having the structure:
H2N~ R 1_~--t503M ) n Xm wherein R', M, X, m, and n have the meanings above;
under the following reaction conditions:
I. a reaction temperature of at least 100C and preferably at least 110C;
II. a reactîon time of at least L/4 hour and preferably at least 1/2 hour;
~;~4~
III. a mole ratio of chemical reac-~ant to polymer ranging between about 2:1 to abou-t 1:50;
IV. a pressure ranging from atmospheric pressure to 35 times atmospheric pressure, or more;
thereby achieving the synthesis of -the sulfonated polymers described above.
In a most preferred proeess of the present invention R is individually ehosen at each occurrence from hydrogen or methyl M is individually chosen at each occurrence from hydrogen, sodium, potassium, ammonium and mix~ures thereof, R' is a linear alkylene bridging group having from
2 to 4 carbon atoms;
X is OH;
a, b and d are integers having the following relationships:
a/b ranges from 0 to 50, a/d ranges from 0 to 50, b/d ranges from 0.01 to 10, and d:(a+bl ranges between about 4:1 and 1:20, and the sum of a+b~d is sueh that the sulfonated polymer has a molecular weight ranging from 2,000-20,000,000, and whieh proeess comprises reaeting at a temperature of at least 110C ~or at least 1/2 hour, in a eommon aqueous solvent, A. a polymer having the strueture:
~C~ I--C~CI:~--C--~
~ ~ I
03C 0 - ~
~_ ~H2 M-~
wherein R, M, a, and b have the meanings above and wherein the sum of a+b is such that the molecular weight of the polymer is at least 2,000; with B. a chemical reactant having t:he structure:
H2N J ~R~ --t~3M)n Xm wherein Rl, M, and X are defined above, and m is from 0 to 3, n is -from 1 to 3, and the sum of m+n is from 1 to 4;
and, the ratio of reactant to polymer ranges between about 1:1 to about 1:10, and the reaction pressure is at least 1.25 atmospheres; and then recovering said sulfonated polymer.
It is particularly of interest that my synthetic procedures perrnit the synthesis of a sulfonated polymer represented by:
--E CH2~CH2 c3Ec~2 c~
O= C a o= f b O- f d o NH2 NH
'~H )m ~SO3Mtn wherein: R is individually chosen, at each occurrence, from the group hydrogen, methyl and ethyl groups;
M is individually chosen, at each occurrence~ -from the group hydrogen/ sodium, potassium~ ammonium ions and mixtures -thereoE;
- 17a -L~
R' is linear alkylene bridging group having from 1 to 4 carbon atoms;
m is from 0 to 3;
n is from 1 to 3; and a, b, and d are integers having the relationships:
a/d is from 0 to 50, a/b is from 0 to 50, b/d is from 0.1 to 20, d:(a ~ b~ is from 5:1 to 1:10, - 17b -the sum of a ~ b + d is sufficient to provide a molecular wel~ht of at least 2,000; which process comprises the reaction, in an aqueous solvent, for at least 1/4 hour a~ a temperature of at least llûC, in a pressure controlling reactor, of the ingredients:
A. a reactant:
~ OH)m H2N~ R'X - t ~ S03M )n wherein R', M, m and n have the abûve meanings; and B. a water-soluble vinyl polymer having pendant ami~e groups represented by:
{ ~ 1~
O= 1 a O=C
o NH2 Mt wherein R, M, a, and b have the above meanings; and wherein the mole ratio of reactant to pendant amide groups ranges between about 1:1 to about 1:5;and then recovering the sulfonated polymer.
The invention is further directed to the sulfonated polymer:
O ~ O---C O--~
I ¦ NH
0,~, NH2 CH2 which is synthesized, in a pressure control.l:in~ reac-tor, by react~ cJ a precn-lrsor po:Lymer:
L I ~E I +
o~ a O~ b o~ NH~
M~
with taurine:
H2N- CH2CH2 ~503M
in an aqueous reaction solvent at a temperature of at least 100C, preferably 120C for at least 1~4 hour, l~referably l hour at a mole ratio of precursor polymer to taurine ranging between about 20:1 to about 1:2, preferably lO:l to l:l and wherein:
R is chosen individually, at each occurrence, from hydrogen and methyl groups, preferably hydrogen;
M is chosen individually, at each occurrence, from hydrogen, alkali metal, in particular sodium and potassium tertiary amines, and ammonium ions and mixtures thereof;
a, b, and d are integers having the relationships:
a~d is from 0 to lO0, a/b is from 0 to lO0, b/disfrom 0.01 to lO0, and d:~a ~ b) ranges between about lO:l to about l:lO0, and wherein the sum a ~ b -~ d is such that the sulfonated polymer has a molecular weight of at least 100, preferably about 2000 to about 20lO00,000-- 18a -The invention is also directed to the sulfonated polymer represented by the structure:
--ECH2~--CH3 { CH2~ } ECH2 1 ~
O -C a O~ C b O ~C_ d o NH2 NH
M~ 1H 2 CHOH
l~2 wherein M is individually chosen, at each occurrence, from hydrogen, sodium, ammonium ions;
a, b, d are integers such that:
the sum of a t b -t d iS sufficient to achieve a molecular weight of at least 1000;
a/d is from 0 to 100;
b/d is from 0.01 to 100;
a/b is from 0 to 100~
and the ratio d: (a -t ~) ranges be-tween about 5:1 to 1:50, and to the sulfonated polymer represented by:
.
~CH2--CH3{CH2 C;3--FC~2 1 ~
O -C a O _C ~ O -C d .O NH2 NH
M~ CH 2 CHOH
~H2 wherein M, a, b, d have the above meanincJs~
- l~b -- 6~530-404 Other aspects of the invent.ion are the sulfonated polymer represented by the structure:
- E CH 2-- ~ C~2- C ~ C~52 C
o=f a o= C b O- C d o+ NH 2 1 _~
~ m ( SO 3~ n wherein R is individually chosen, at each occurrence, from hydrogen and methyl yroups;
M is individually chosen, at each occurrence, Erom hydrogen, sodium, potassium, and, ammonium ions, and mixtures -thereof;
R' is a multivalent hydrocarbonaceous bridginc3 group having from 1 - 6 carbon atoms and being from linear alkyl, aromatic, cyclic, and ole~inic groups, and mixtures thereof;
X is from -the group -Oll, and, wherein a, b, and d are integers, the sum of which is such that the ~olecula~ weight of the sulfonated polymer is at least 2,000, and wherein the following relationships e~ist:
a/b is from 0 to 100, a/d is from 0 to 100, b/d i5 from 0.01 to 1000, and the ratio d:(a -~ b) i5 between about 10:1 to about 1:100, and wherein:
m is equal to 0 to 6, n ~s ~3c~uaJ I o 1 I::o 6, ancl ~he ~ulll of m~n is betwee 3c , ~ ~
1-8, and the sulfonated polymer represented by the structure:
R R R
~CH2-C~CH2-C~cH2 C~d O~C O~C O~C
O NH NH
M~
S03M~
wherein R is individually chosen, at each occurrence, from hydrogen and me~hyl groups;
M is individually chosen, at each occurrence, from hydrogen, sodium, potassium, and, ammonium ions, and mixtures thereo~; and, a, bl and d are as mentioned above.
To further illustrate my invention, I provide the following examples.
Example I
In each of the synthetic process below, a low molecular weight copolymer o acrylic acid and acrylamide was reacted with l-amino-2-hydroxy propane sulfonic acid in a homogenous aqueous solution. The reactions were achieved at temperatures of at leas~ 100C and were achieved on acrylic acid/acrylamide polymaric backbones having various molecular weights.
- 18~ -The compositions of the polymers vary from homopolyacrylamide to 50 mole percent acrylamide and acrylic acid copolymers. The polymers and reactants were chargecl as aqueous solutions to a Paar Bomb equipped with temperature and pressure measuring devices and also equipped with means to agitate the contents. Temperatures were increased to at least 100C in each case. Reaction times rangng from about 20 minutes to in excess of 4 hours accomplished the synthesis of the polymers bi~b ~ c~ .n 1~
c o a~
> a~
C ~ æ a~ t + æ ~ ae O C~ o O O O O
X is OH;
a, b and d are integers having the following relationships:
a/b ranges from 0 to 50, a/d ranges from 0 to 50, b/d ranges from 0.01 to 10, and d:(a+bl ranges between about 4:1 and 1:20, and the sum of a+b~d is sueh that the sulfonated polymer has a molecular weight ranging from 2,000-20,000,000, and whieh proeess comprises reaeting at a temperature of at least 110C ~or at least 1/2 hour, in a eommon aqueous solvent, A. a polymer having the strueture:
~C~ I--C~CI:~--C--~
~ ~ I
03C 0 - ~
~_ ~H2 M-~
wherein R, M, a, and b have the meanings above and wherein the sum of a+b is such that the molecular weight of the polymer is at least 2,000; with B. a chemical reactant having t:he structure:
H2N J ~R~ --t~3M)n Xm wherein Rl, M, and X are defined above, and m is from 0 to 3, n is -from 1 to 3, and the sum of m+n is from 1 to 4;
and, the ratio of reactant to polymer ranges between about 1:1 to about 1:10, and the reaction pressure is at least 1.25 atmospheres; and then recovering said sulfonated polymer.
It is particularly of interest that my synthetic procedures perrnit the synthesis of a sulfonated polymer represented by:
--E CH2~CH2 c3Ec~2 c~
O= C a o= f b O- f d o NH2 NH
'~H )m ~SO3Mtn wherein: R is individually chosen, at each occurrence, from the group hydrogen, methyl and ethyl groups;
M is individually chosen, at each occurrence~ -from the group hydrogen/ sodium, potassium~ ammonium ions and mixtures -thereoE;
- 17a -L~
R' is linear alkylene bridging group having from 1 to 4 carbon atoms;
m is from 0 to 3;
n is from 1 to 3; and a, b, and d are integers having the relationships:
a/d is from 0 to 50, a/b is from 0 to 50, b/d is from 0.1 to 20, d:(a ~ b~ is from 5:1 to 1:10, - 17b -the sum of a ~ b + d is sufficient to provide a molecular wel~ht of at least 2,000; which process comprises the reaction, in an aqueous solvent, for at least 1/4 hour a~ a temperature of at least llûC, in a pressure controlling reactor, of the ingredients:
A. a reactant:
~ OH)m H2N~ R'X - t ~ S03M )n wherein R', M, m and n have the abûve meanings; and B. a water-soluble vinyl polymer having pendant ami~e groups represented by:
{ ~ 1~
O= 1 a O=C
o NH2 Mt wherein R, M, a, and b have the above meanings; and wherein the mole ratio of reactant to pendant amide groups ranges between about 1:1 to about 1:5;and then recovering the sulfonated polymer.
The invention is further directed to the sulfonated polymer:
O ~ O---C O--~
I ¦ NH
0,~, NH2 CH2 which is synthesized, in a pressure control.l:in~ reac-tor, by react~ cJ a precn-lrsor po:Lymer:
L I ~E I +
o~ a O~ b o~ NH~
M~
with taurine:
H2N- CH2CH2 ~503M
in an aqueous reaction solvent at a temperature of at least 100C, preferably 120C for at least 1~4 hour, l~referably l hour at a mole ratio of precursor polymer to taurine ranging between about 20:1 to about 1:2, preferably lO:l to l:l and wherein:
R is chosen individually, at each occurrence, from hydrogen and methyl groups, preferably hydrogen;
M is chosen individually, at each occurrence, from hydrogen, alkali metal, in particular sodium and potassium tertiary amines, and ammonium ions and mixtures thereof;
a, b, and d are integers having the relationships:
a~d is from 0 to lO0, a/b is from 0 to lO0, b/disfrom 0.01 to lO0, and d:~a ~ b) ranges between about lO:l to about l:lO0, and wherein the sum a ~ b -~ d is such that the sulfonated polymer has a molecular weight of at least 100, preferably about 2000 to about 20lO00,000-- 18a -The invention is also directed to the sulfonated polymer represented by the structure:
--ECH2~--CH3 { CH2~ } ECH2 1 ~
O -C a O~ C b O ~C_ d o NH2 NH
M~ 1H 2 CHOH
l~2 wherein M is individually chosen, at each occurrence, from hydrogen, sodium, ammonium ions;
a, b, d are integers such that:
the sum of a t b -t d iS sufficient to achieve a molecular weight of at least 1000;
a/d is from 0 to 100;
b/d is from 0.01 to 100;
a/b is from 0 to 100~
and the ratio d: (a -t ~) ranges be-tween about 5:1 to 1:50, and to the sulfonated polymer represented by:
.
~CH2--CH3{CH2 C;3--FC~2 1 ~
O -C a O _C ~ O -C d .O NH2 NH
M~ CH 2 CHOH
~H2 wherein M, a, b, d have the above meanincJs~
- l~b -- 6~530-404 Other aspects of the invent.ion are the sulfonated polymer represented by the structure:
- E CH 2-- ~ C~2- C ~ C~52 C
o=f a o= C b O- C d o+ NH 2 1 _~
~ m ( SO 3~ n wherein R is individually chosen, at each occurrence, from hydrogen and methyl yroups;
M is individually chosen, at each occurrence, Erom hydrogen, sodium, potassium, and, ammonium ions, and mixtures -thereof;
R' is a multivalent hydrocarbonaceous bridginc3 group having from 1 - 6 carbon atoms and being from linear alkyl, aromatic, cyclic, and ole~inic groups, and mixtures thereof;
X is from -the group -Oll, and, wherein a, b, and d are integers, the sum of which is such that the ~olecula~ weight of the sulfonated polymer is at least 2,000, and wherein the following relationships e~ist:
a/b is from 0 to 100, a/d is from 0 to 100, b/d i5 from 0.01 to 1000, and the ratio d:(a -~ b) i5 between about 10:1 to about 1:100, and wherein:
m is equal to 0 to 6, n ~s ~3c~uaJ I o 1 I::o 6, ancl ~he ~ulll of m~n is betwee 3c , ~ ~
1-8, and the sulfonated polymer represented by the structure:
R R R
~CH2-C~CH2-C~cH2 C~d O~C O~C O~C
O NH NH
M~
S03M~
wherein R is individually chosen, at each occurrence, from hydrogen and me~hyl groups;
M is individually chosen, at each occurrence, from hydrogen, sodium, potassium, and, ammonium ions, and mixtures thereo~; and, a, bl and d are as mentioned above.
To further illustrate my invention, I provide the following examples.
Example I
In each of the synthetic process below, a low molecular weight copolymer o acrylic acid and acrylamide was reacted with l-amino-2-hydroxy propane sulfonic acid in a homogenous aqueous solution. The reactions were achieved at temperatures of at leas~ 100C and were achieved on acrylic acid/acrylamide polymaric backbones having various molecular weights.
- 18~ -The compositions of the polymers vary from homopolyacrylamide to 50 mole percent acrylamide and acrylic acid copolymers. The polymers and reactants were chargecl as aqueous solutions to a Paar Bomb equipped with temperature and pressure measuring devices and also equipped with means to agitate the contents. Temperatures were increased to at least 100C in each case. Reaction times rangng from about 20 minutes to in excess of 4 hours accomplished the synthesis of the polymers bi~b ~ c~ .n 1~
c o a~
> a~
C ~ æ a~ t + æ ~ ae O C~ o O O O O
3:
h -~.1~ C~ O O O O O O O
C.) 1~ O O O ~ O O O O
~J O ~ ~ N r~ N a7 ~J ~C
o a~ ~ ~ a~
:~: ~ J 1~~I N N {`J N N
-.
h a) h O ~
O r~ O O U~ O O
N ~1 11~ ~ r'l ~ I` j~
~: O O~ I` ~ O O Il~ O O
j~ ~ ~ ,r~ N --t ~1 ~
h ~: ~ --1 ~ O O O O O O
I N
h _l ~I h C~ ) O O ' ) OC.) O
l_ a~ ~ ~ o o o o c) oo O
o o o o o o In O
N N .
~ S
ta a~ o o o o ~ o o o u~
N N N N N N N N
O~ O ~- I I C~ t~ C )~) C~ v ~
~ ~o ~.o ~c~ O ~o t~-O ~ o c c v v N N I I I I I ~ h h ta ~ z z ~z z ~ z z ~
N N N N N N N N~ aJ
~a C c~ E E ~ E~ E
Cl a: ¢ ~ cc c~ C~~:
a o o o L~ Lr~ Lt'~ u~ Lr, c~ 11 C: t.l ~.) h O Ll~ Lr~ r` r` I~ ~`~~
~ ~ ~ ~ 1 e JJ E ~ Ql ~ X C~ c~ c~ ~ c~ ccCS
C~ O '5 Ci' O CL ~ O O U~ Lt~ L~ L~
O L~ L~ N N N N N~ N
~'f~
In addition, the following polymers would be expected to be synthesized if acrylamide containing polymers were reacted according to the procedures described above with the following chemical reactants: The anticipated products are described in Table II.
TAOLE I I
Starting Chemical Anticipated _~ L~O~L~ Reactant Product Polymer T~ CH2-CH~TH2N-CH2CH250~Na+~cH2~cH3~c~2 F~H2 ~C~I~d O=C 0~ 1 O~C O~C
NH 2 M}1 NH2 M CE~2 ~H2 ~03 Na~
H2N-CH2CH CH CH CH~SO3H {AA~cAm~c~2-cH~d OH OH OH O~C
O~ O.H OH N~
~03SCH2-CH-CE~-CH CH2 " Cl ~12N-Ci~2 C~-cH2-cH2-EAA~ACAI;~tc~2 CH~d Cl NH
~3~; -C~2 -CH-CH-CH 2 H 2N SO 3 ~{AA~AcAm~H2-CH~d OH ~
N~
OH
~AA ~a ~-ACAm~b OH C 1 HN-CH2 CH CH CH2-503H~AA~AcAm~CH2- ~CH~d O~C
CH3 Cl OH N-CH
t 1 3 C1~2 CH-C~-CH2 T~ELE II
(Continued) Starting Chemical Anticipated ~ Reactant Product ~
[AA~AcAm~b C~CH253H {~a~AcAm~b~CH2 CH~d H N \o O~C
1~ 2 5 0 3 H ~"N~
~0~
~AcAm ~ ~2N ~ CH2S03H ~A~ ~ ~cAm ~ CH2 ~]d NH
~AcAm~b CH3 I [AA~ AcAm~Ch2-C~
CH20H HOCH2- C - CH2-NE~
c~3 ~AcAm ~ H2N-CH-CH20H tAA ~ Ac~m ~ CH2-CH
NH
Cl-CH~-CH
~20H
~AcAm3b H2N-CH2~ 503H[AA~EAcAm~CH2-CH~d ~103S ~Et~ -NH
~3 -~66530-404 TABLE~ I l (Continued) Starting Chemical Anticipated Starting Pol~mer Reac-tant Prodllct Polymer ,, ~CH2-ICH ~ A~m~b 12N C~2CH2S03H ~CH2-CH ~ AA]a[ACAm ~ C~l2 lCII~d O=C 0=~ C=O
I
O O NH
1H3 CH3 ~ ICH2) 2 ~AcAm-}H2N-cH2-so3ll ~AA ~AcAm ~ CH
~1035-CH2~N~
~AcAm~b~-IN-cH2C~l2so3H r ~a-fAcAm ~ CH2Cil~d CH2CH2S03H C=O
~IO3S-CH2CH2-NC~I CH SO H
OH
~AcAm~b H-N~ 2 3 [AA ~ AcAm ~ CH2CH~d CH2cHcH2so3H C=O
OH N
HOCH HCOH
ICH2 C1~2 OH
~AA ~ AcAm-~b H2NcH2-cH-cH2so3H ~AA ~ CH2-~CH~d C=O
NH
~CH2 HC-OH
h -~.1~ C~ O O O O O O O
C.) 1~ O O O ~ O O O O
~J O ~ ~ N r~ N a7 ~J ~C
o a~ ~ ~ a~
:~: ~ J 1~~I N N {`J N N
-.
h a) h O ~
O r~ O O U~ O O
N ~1 11~ ~ r'l ~ I` j~
~: O O~ I` ~ O O Il~ O O
j~ ~ ~ ,r~ N --t ~1 ~
h ~: ~ --1 ~ O O O O O O
I N
h _l ~I h C~ ) O O ' ) OC.) O
l_ a~ ~ ~ o o o o c) oo O
o o o o o o In O
N N .
~ S
ta a~ o o o o ~ o o o u~
N N N N N N N N
O~ O ~- I I C~ t~ C )~) C~ v ~
~ ~o ~.o ~c~ O ~o t~-O ~ o c c v v N N I I I I I ~ h h ta ~ z z ~z z ~ z z ~
N N N N N N N N~ aJ
~a C c~ E E ~ E~ E
Cl a: ¢ ~ cc c~ C~~:
a o o o L~ Lr~ Lt'~ u~ Lr, c~ 11 C: t.l ~.) h O Ll~ Lr~ r` r` I~ ~`~~
~ ~ ~ ~ 1 e JJ E ~ Ql ~ X C~ c~ c~ ~ c~ ccCS
C~ O '5 Ci' O CL ~ O O U~ Lt~ L~ L~
O L~ L~ N N N N N~ N
~'f~
In addition, the following polymers would be expected to be synthesized if acrylamide containing polymers were reacted according to the procedures described above with the following chemical reactants: The anticipated products are described in Table II.
TAOLE I I
Starting Chemical Anticipated _~ L~O~L~ Reactant Product Polymer T~ CH2-CH~TH2N-CH2CH250~Na+~cH2~cH3~c~2 F~H2 ~C~I~d O=C 0~ 1 O~C O~C
NH 2 M}1 NH2 M CE~2 ~H2 ~03 Na~
H2N-CH2CH CH CH CH~SO3H {AA~cAm~c~2-cH~d OH OH OH O~C
O~ O.H OH N~
~03SCH2-CH-CE~-CH CH2 " Cl ~12N-Ci~2 C~-cH2-cH2-EAA~ACAI;~tc~2 CH~d Cl NH
~3~; -C~2 -CH-CH-CH 2 H 2N SO 3 ~{AA~AcAm~H2-CH~d OH ~
N~
OH
~AA ~a ~-ACAm~b OH C 1 HN-CH2 CH CH CH2-503H~AA~AcAm~CH2- ~CH~d O~C
CH3 Cl OH N-CH
t 1 3 C1~2 CH-C~-CH2 T~ELE II
(Continued) Starting Chemical Anticipated ~ Reactant Product ~
[AA~AcAm~b C~CH253H {~a~AcAm~b~CH2 CH~d H N \o O~C
1~ 2 5 0 3 H ~"N~
~0~
~AcAm ~ ~2N ~ CH2S03H ~A~ ~ ~cAm ~ CH2 ~]d NH
~AcAm~b CH3 I [AA~ AcAm~Ch2-C~
CH20H HOCH2- C - CH2-NE~
c~3 ~AcAm ~ H2N-CH-CH20H tAA ~ Ac~m ~ CH2-CH
NH
Cl-CH~-CH
~20H
~AcAm3b H2N-CH2~ 503H[AA~EAcAm~CH2-CH~d ~103S ~Et~ -NH
~3 -~66530-404 TABLE~ I l (Continued) Starting Chemical Anticipated Starting Pol~mer Reac-tant Prodllct Polymer ,, ~CH2-ICH ~ A~m~b 12N C~2CH2S03H ~CH2-CH ~ AA]a[ACAm ~ C~l2 lCII~d O=C 0=~ C=O
I
O O NH
1H3 CH3 ~ ICH2) 2 ~AcAm-}H2N-cH2-so3ll ~AA ~AcAm ~ CH
~1035-CH2~N~
~AcAm~b~-IN-cH2C~l2so3H r ~a-fAcAm ~ CH2Cil~d CH2CH2S03H C=O
~IO3S-CH2CH2-NC~I CH SO H
OH
~AcAm~b H-N~ 2 3 [AA ~ AcAm ~ CH2CH~d CH2cHcH2so3H C=O
OH N
HOCH HCOH
ICH2 C1~2 OH
~AA ~ AcAm-~b H2NcH2-cH-cH2so3H ~AA ~ CH2-~CH~d C=O
NH
~CH2 HC-OH
Claims (14)
- THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
l. A process to synthesize water-soluble sulfonated polymers having randomly repeated mer units represented by the formula:
wherein R is individually chosen at each occurrence from H and lower alkyl (C1-C4) groups;
M is chosen from hydrogen, alkali metal, alkaline earth metal, tertiary amines, and ammonium ion, and mixtures thereof;
R' is a multi-covalent hydrocarbonaceous bridging group having from one to sixteen carbon atoms and being chosen from linear alkyl, branched alkyl, cyclic, aromatic, heterocyclic, olefinic and mixtures thereof, functional groups;
X is chosen from Cl, Br, OH, and mixtures thereof;
and wherein a, b, and d are integers with the following relationships;
a/b is from zero to 100 b/d is from 0.01 to 100 a/d is from zero to 100, and the sum of a+b+d is sufficient to provide a molecular weight of at least 1000, and the ratio of d:(a + b) is from 20:1 to 1:100;
- 25 _ and wherein m ranges between 0 and 16, and n ranges between l and 16, provided that when m is zero, R' is from linear, cyclic, heterocyclic, olefinic, aromatic, and mixtures thereof functional groups, and further provided that the sum of m + n is from 1 to 20;
which process comprises reacting, in a common solvent, at a temperature of at least 100°C;
A. a polymer having a molecular weight of at least 500, and having pendant amide functional groups, and represented by the structure:
wherein R, M, a, b have the same meanings as above; with B.a chemical reactant having the structure:
wherein R, R', M, X, m, and n have the meanings above; wherein the mole ratio of chemical reactant to pendant amide groups in the polymer ranges between about 5:1 to about 1:100; and reacting for an effective amount of time to accomplish at least a 25 percent conversion of chemical reactant to water-soluble sulfonated polymer; and then recovering the water-soluble sulfonated polymer. - 2. The process of Claim 1 wherein:
R is individually chosen at each occurrence from hydrogen, methyl, and ethyl groups, M is individually chosen at each occurrence from hydrogen, sodium, potassium, tertiary amines, ammonium and mixtures thereof, R' has at least two carbon atoms and is linear, cyclic, aromatic and mixtures thereof;
X is OH;
m is from 0 to 4;
n is from 1 to 4;
and the molecular weight of the water-soluble sulfonated polymer ranges between about 2000 to about 20,000,000. - 3. The process of Claim 1 or 2 wherein the common solvent is from the group consisting of water, dimethylformamide, dimethylsulfoxide, and mixtures thereof.
- 4. The process of Claim 1 or 2 wherein the solvent is from the group water and water-emulsified in a continuous oil phase such that the water-soluble sulfonated polymer is recovered either as a water-in-oil emulsion or as an aqueous solution.
- 5. The synthesis of water-soluble sulfonated polymers represented by the formula:
wherein R is individually chosen at each occurrence from hydrogen and C1 to C4 lower alkyl, M is individually chosen at each occurrence from hydrogen, alkali metals, tertiary amines, and ammonium ions, R' is chosen from multi-covalent, branched alkyl, linear alkyl or cyclic hydrocarbonaceous bridging groups having from one to eight carbon atoms;
X is chosen from Cl, OH, and mixtures thereof;
m ranges between 0 to 6;
n ranges between 1 to 4;
a, b, and d are integers with the following relationships:
a/b ranges from 0 to 100, a/d ranges from 0 to 100, b/d ranges from 0.01 to 100, and the ratio d:(a+b) is between about 5:1 to about 1:25, and wherein the occurrence of mer units of a, b, and d is random and the sum of a+b+d will achieve a molecular weight of at least 1,000; which process comprises reacting, in an aqueous solvent:
A. a polymer having pendant amide functional groups and represented by the structure:
wherein R, M, a, and b have the meanings above and wherein the sum of a+b achieves a molecular weight of at least 500;
and B. a reactant having the structure:
wherein R', M, X , m, and n have the meanings above;
under the following reaction conditions:
I. a reaction temperature of at least 100°C;
II. a reaction time of at least 1/4 hour;
III. a mole ratio of chemical reactant to polymer ranging between about 2:1 to about 1-50;
IV. a pressure ranging from atmospheric pressure to 35 times atmospheric pressure;
thereby achieving the synthesis, and thereafter recovering said sulfonated polymers. - 6. The process of Claim 5, wherein R is individually chosen at each occurrence from hydrogen or methyl M is individually chosen at each occurrence from hydrogen, sodium, potassium, ammonium and mixtures thereof, R' is a linear alkylene bridging group having from 2 to 4 carbon atoms;
X is OH;
a, b and d are integers having the following relationships:
a/b ranges from 0 to 50, a/d ranges from 0 to 50, b/d ranges from 0.01 to 10, and d:(a+b) ranges between about 4:1 and 1:20, and the sum of a+b+d is such that the sulfonated polymer has a molecular weight ranging from 2,000-20,000,000, and which process comprises reacting at a temperature of at least 110°C for at least 1/2 hour, in a common aqueous solvent, A. a polymer having the structure:
wherein R, M, a, and b have the meanings above and wherein the sum of a+b is such that the molecular weight of the polymer is at least 2,000; with B. a chemical reactant having the structure:
wherein R1, M, and X are defined above, and m is from 0 to 3, n is from 1 to 3, and the sum of m+n is from 1 to 4; and, the ratio of reactant to polymer ranges between about 1:1 to about 1:10, and the reaction pressure is at least 1.25 atmospheres; and then recovering said sulfonated polymer. - 7. The process of Claim 5 or 6 wherein the solvent is a water-in-oil emulsion.
- 8. A process for synthesizing a sulfonated polymer represented by:
wherein: R is individually chosen, at each occurrence, from the group hydrogen, methyl and ethyl groups;
M is individually chosen, at each occurrence, from the group hydrogen, sodium, potassium, tertiary amines, and ammonium ions and mixtures thereof;
R' is a linear alkylene bridging group having from 1 to 4 carbon atoms;
m is from n to 3;
n is from 1 to 3; and the sum, n+m, is from 1-4;
a, b, and d are integers having the relationships:
a/d is from 0 to 50, a/b is from 0 to 50, b/d is from 0.1 to 20, d:(a + b) is from 5:1 to 1:10, the sum of a + b + d is sufficient to provide a molecular weight of at least 2,000; which process comprises reacting in an aqueous solvent, for at least 1/4 hour at a temperature of at least 110°C, in a pressure controlling reactor, the ingredients:
A. a chemical reactant:
wherein R', M, m and n have the above meanings; and B. a water-soluble vinyl polymer having pendant amide groups represented by:
wherein R, M, a, and b have the above meanings; and wherein the mole ratio of reactant to pendant amide groups on the polymer ranges between about 1:1 to about 1:5; and then recovering the sulfonated polymer. - 9. The sulfonated polymer:
which is synthesized, in a pressure controlling reactor, by reacting a precursor polymer:
with taurine:
in an aqueous reaction solvent at a temperature of at least 100°C for at least 1/4 hour at a mole ratio of precursor polymer to taurine ranging between about 20:1 to about 1:2, and wherein:
R is chosen individually, at each occurrence, from hydrogen and methyl groups;
M is chosen individually, at each occurrence, from hydrogen, alkali metal, tertiary amines, and ammonium ions and mixtures thereof;
a, b, and d are integers having the relationships:
a/d is from 0 to 100, a/b is from 0 to 100, b/d is from 0.01 to 100, and d:(a + b) ranges between about 10:1 to about 1:100, and wherein the sum a + b + d is such that the sulfonated polymer has a moleculr weight of at least 1000. - 10. The sulfonated polymer of Claim 9 which is synthesized in an aqueous reaction solvent at a temperature of at least 120°C for at least 1 hour at a mole ratio of precursor polymer to taurine of from 10:1 to 1:1 and wherein:
R is hydrogen, M is from the group H, sodium, potassium, and ammonium ions and mixtures thereof, and the polymer has a molecular weight between about 2000 to about 20,000,000. - 11. The sulfonated polymer represented by the structure:
wherein M is individually chosen, at each occurrence, from hydrogen, sodium, ammonium ions;
a, b, d are integers such that:
the sum of a + b + d is sufficient to achieve a molecular weight of at least 1000;
a/d is from 0 to 100;
b/d is from 0.01 to 100;
a/b is from 0 to 100, and the ratio d:(a + b) ranges between about 5:1 to 1:50. - 12. The sulfonated polymer represented by:
and wherein M, a, b, d have the meanings of Claim 11. - 13. The sulfonated polymer represented by the structure wherein R is individually chosen, at each occurrence, from hydrogen and methyl groups;
M is individually chosen, at each occurrence, from hydrogen, sodium, potassium, and, ammonium ions, and mixtures thereof;
R' is a multivalent hydrocarbonaceous bridging group having from 1 - 6 carbon atoms and being from linear alkyl, aromatic cyclic, and olefinic groups, and mixtures thereof;
X is from the group -OH, and, wherein a, b, and d are integers, the sum of which is such that the molecular weight of the sulfonated polymer is at least 2,000, and wherein the following relationships exist:
a+b is from 0 to 100, a/d is from 0 to 100, b/d is from 0.01 to 1000, and the ratio d:(a + b) is between about 10:1 to about 1:100, and wherein:
m is equal to 0 to 6, n is equal to 1 to 6, and the sum of m+n is between 1-8. - 14. The sulfonated polymer represented by the structure:
wherein R is individually chosen, at each occurrence, from hydrogen and methyl groups;
M is individually chosen, at each occurrence, from hydrogen, sodium, potassium, and, ammonium ions, and mixtures thereof; and, a, b, and d are the same as in Claim 13.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US79645185A | 1985-11-08 | 1985-11-08 | |
| US796,451 | 1985-11-08 | ||
| BR8606292A BR8606292A (en) | 1985-11-08 | 1986-12-19 | PROCESS TO SYNTHESIZE SULPHONATED POLYMERS SOLUBLE IN WATER |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1240444A true CA1240444A (en) | 1988-08-09 |
Family
ID=25664154
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000522526A Expired CA1240444A (en) | 1985-11-08 | 1986-11-10 | N-(2-hydroxy-3-sulfopropyl) amide containing polymers |
Country Status (12)
| Country | Link |
|---|---|
| JP (1) | JPS62115002A (en) |
| AT (1) | AT395592B (en) |
| AU (2) | AU589195B2 (en) |
| BE (1) | BE905996A (en) |
| BR (1) | BR8606292A (en) |
| CA (1) | CA1240444A (en) |
| CH (1) | CH677234A5 (en) |
| DE (1) | DE3616583A1 (en) |
| FR (1) | FR2589864B1 (en) |
| GB (1) | GB2182666B (en) |
| NL (1) | NL191240C (en) |
| SE (1) | SE466260B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4731419A (en) * | 1986-02-24 | 1988-03-15 | Nalco Chemical Company | Alkoxylated/cationically modified amide-containing polymers |
| JPH01167308A (en) * | 1987-11-24 | 1989-07-03 | Nalco Chem Co | Sulfoethylation of polysoap/latex polymer containing high molecular weight acrylamide |
| FR2870246B1 (en) * | 2004-05-14 | 2008-09-12 | Univ Paris 13 | WATER-SOLUBLE COPOLYMERS, PREPARATION AND USES |
Family Cites Families (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1266224A (en) * | 1969-04-02 | 1972-03-08 | ||
| US3692673A (en) * | 1971-02-12 | 1972-09-19 | Lubrizol Corp | Water-soluble sulfonate polymers as flocculants |
| US3709815A (en) * | 1971-07-01 | 1973-01-09 | Calgon Corp | Boiler water treatment |
| US4103742A (en) * | 1975-12-24 | 1978-08-01 | Phillips Petroleum Company | Method for acidizing subterranean formations |
| US4342653A (en) * | 1979-02-15 | 1982-08-03 | American Cyanamid Company | Process for the flocculation of suspended solids |
| DE2931897A1 (en) * | 1979-08-06 | 1981-02-26 | Cassella Ag | WATER-SOLUBLE COPOLYMER AND ITS PRODUCTION |
| DE3027236C2 (en) * | 1980-07-18 | 1985-08-01 | Chemische Fabrik Stockhausen GmbH, 4150 Krefeld | Terpolymers of 2-acrylamido-2-methyl-propanesulfonic acid, acrylamide and acrylic acid in the form of their salts, processes for the production of these terpolymers and use for preventing incrustations in aqueous systems |
| US4471097A (en) * | 1982-01-11 | 1984-09-11 | Klaus Uhl | Water soluble copolymers containing vinyl imidazole as drilling fluid additives |
| CA1225793A (en) * | 1983-03-11 | 1987-08-18 | Union Carbide Corporation | High molecular weight water-soluble polymers and flocculation method using same |
| JPS59223710A (en) * | 1983-06-01 | 1984-12-15 | Sanyo Chem Ind Ltd | Polymer for increasing production of crude petroleum |
| US4545902A (en) * | 1984-09-17 | 1985-10-08 | Nalco Chemical Company | Flocculants for bauxite (red mud) |
| NZ214078A (en) * | 1984-11-10 | 1988-08-30 | Int Computers Ltd | Keyboard subset powered by standby source during mains failure |
| US4652623A (en) * | 1984-11-23 | 1987-03-24 | Calgon Corporation | Polymers for use as filtration control aids in drilling muds |
-
1986
- 1986-05-16 DE DE19863616583 patent/DE3616583A1/en active Granted
- 1986-05-20 FR FR8607129A patent/FR2589864B1/en not_active Expired - Lifetime
- 1986-06-10 JP JP61132894A patent/JPS62115002A/en active Granted
- 1986-07-08 AU AU59841/86A patent/AU589195B2/en not_active Ceased
- 1986-10-14 NL NL8602576A patent/NL191240C/en not_active IP Right Cessation
- 1986-11-10 GB GB8626810A patent/GB2182666B/en not_active Expired
- 1986-11-10 CA CA000522526A patent/CA1240444A/en not_active Expired
- 1986-12-02 CH CH4807/86A patent/CH677234A5/de not_active IP Right Cessation
- 1986-12-05 AT AT0324386A patent/AT395592B/en not_active IP Right Cessation
- 1986-12-18 SE SE8605441A patent/SE466260B/en unknown
- 1986-12-19 BE BE0/217569A patent/BE905996A/en not_active IP Right Cessation
- 1986-12-19 BR BR8606292A patent/BR8606292A/en not_active IP Right Cessation
-
1989
- 1989-06-27 AU AU37094/89A patent/AU625537B2/en not_active Ceased
Also Published As
| Publication number | Publication date |
|---|---|
| AU3709489A (en) | 1989-11-02 |
| ATA324386A (en) | 1992-06-15 |
| JPH0344562B2 (en) | 1991-07-08 |
| AU5984186A (en) | 1987-05-14 |
| DE3616583C2 (en) | 1989-07-20 |
| AU589195B2 (en) | 1989-10-05 |
| AT395592B (en) | 1993-01-25 |
| GB2182666B (en) | 1990-06-13 |
| BE905996A (en) | 1987-06-19 |
| NL191240B (en) | 1994-11-01 |
| SE8605441L (en) | 1988-06-19 |
| JPS62115002A (en) | 1987-05-26 |
| BR8606292A (en) | 1988-07-05 |
| SE8605441D0 (en) | 1986-12-18 |
| SE466260B (en) | 1992-01-20 |
| FR2589864A1 (en) | 1987-05-15 |
| CH677234A5 (en) | 1991-04-30 |
| GB8626810D0 (en) | 1986-12-10 |
| FR2589864B1 (en) | 1992-10-09 |
| NL8602576A (en) | 1987-06-01 |
| DE3616583A1 (en) | 1987-05-21 |
| AU625537B2 (en) | 1992-07-16 |
| NL191240C (en) | 1995-04-03 |
| GB2182666A (en) | 1987-05-20 |
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