FR2589864A1 - PROCESS FOR PREPARING WATER-SOLUBLE SULFON POLYMERS AND POLYMERS THUS OBTAINED - Google Patents

Abstract

TO PREPARE THESE POLYMERS SHOWING RANDOM PATTERNS OF FORMULA I, WE REACT IN A COMMON SOLVENT, AT A TEMPERATURE OF AT LEAST 100C, A POLYMER II WITH A MOLECULAR WEIGHT OF AT LEAST 500, HAVING PENDING AMIDE FUNCTIONAL GROUPS, RH, ALKYL IN CC; MH ALKALINE METAL, ALKALINO-EARTH, AMINE TERTIARY, AMMONIUM; HYDROCARBON BRIDGE GROUP IN C-C; XCL, BR, OH; A, B AND D ARE SUCH AS 0AB 100; 0.01 BD 100 ET 0 AD 100, AB D CONDUCTED TO A MOLECULAR WEIGHT OF AT LEAST 1000, ET 20: 1 D: (AB) 1: 100; 0 M 16 AND 1 N 16, 1 M N 20.

Description

PROCESS FOR THE PREPARATION OF SOLUBLE SOLUBLE POLYMERS

WATER AND POLYMERS SO OBTAINED

  The present invention relates to a process for the preparation of water-soluble sulfonated polymers and the polymers obtained by this process. The synthesis of soluble sulphonated polymers in

  water has generally been limited to the use of

  some vinyl monomers containing the functional group

  sulfonate. Examples of these monomers are vinyl sulfonate

  of sodium, sulfonated styrene and 2-acrylamido acid

  2-propane sulfonic acid (AMPS). In addition, the synthesis of

  sulphonated vinyl-containing polymers containing the sulphonate group was limited due to the fact that only some of

  these kinds of sulfonated monomers are manufactured industrially.

  As a result, the use of these polymers

  soluble sulphonated water is limited only to

  mentioned above. So that would be a progress of the technique if other soluble polymer chemical structures

  in water could be synthesized on a poly-

  mother, structures which contain the sulphonate group, either

  in its acid form either in its salt form, and which

  also contain other functional groups that could improve the use of these water-soluble sulfonated polymers in certain applications, for example

  as dispersants in the treatment of water, anti-

  scale in natural and industrial waters,

  culatives and coagulating agents and the like.

  A first objective of this invention is therefore to produce water-soluble polymers containing a

  sulphonate group, polymers which, moreover, can also

  contain other functional groups that may

  be useful when these polymers are applied to

  or aqueous environments.

  Another object of this invention is to develop

  to develop a synthetic process that suffers, as a whole; be applicable to the synthesis of various types of water-soluble polymers containing the sulfonate group, with or

  without the additional presence of other functional groups

  which may be useful when these polymers are added

to aqueous systems.

  Another object of this invention is to synthesize and recover certain types of water-soluble polymers containing sulfonate groups.

  may contain other functional groups such as hy-

  droxyl, chloro, bromo, iodo and / or mixtures thereof,

  polymers are neither known nor used to date.

  The Applicant Company has discovered a process for modifying water-soluble polymers containing

  amide pendant functional groups, such polymers derived from

  mainly vinyl polymers / copolymers

  containing acrylamide residues, or polymers or copolymers

  vinylic polymers containing substitute acrylamide residues

  killed by alkyl residues, said polymers / copolymers

  being soluble in water and containing functional groups

  amide pendants, derived from acrylamide, methyl acry-

  lamide, ethyl acrylamide and the like.

  The process that was discovered by the Company. Of-

  posante, is a process that uses the equivalent of a reac-

  transamidation reaction with the pendant amide group of the polymer and a chemical reagent represented by the structure: Formula I n (X) m wherein R is individually selected, in each case, from the group consisting of hydrogen and lower alkyl groups containing 1-4 carbon atoms;

  M is selected from the group consisting of hydro-

  gene, alkali metals, alkaline earth metals

  and ammonium ions, and mixtures thereof; R 'is a multi-covalent hydrocarbon bridging group, which may be selected from functional groups

  linear, branched, cyclic, aromatic, hetero

  rocyclic compounds and mixtures thereof, and containing 1-16 carbon atoms; X is selected from Cl, Br, I, OH and mixtures thereof and wherein, between 0 and 16, n varies between 1 and 16, with the proviso that

  sum m + n is ----- in the range 1-20.

  The chemical reagent described above is essential

  an amine substituted compound, which also contains the

  sulfonate functional group, and in which the functional group

  amine contains at least one active hydrogen.

  to the nitrogen of the amino group. Although derivatives with

  fonate having both primary and secondary amines

  If they are reactive under the conditions of the transamidation reaction according to the present invention, to result in modified polymers containing sulfonate groups, it is preferable that, when a secondary amine is selected to carry out this modification, polymers containing pendant amide groups the alkyl group attached to the nitrogen of the amino group does not contain more than 4 carbon atoms, that is to say that the substitution with an alkyl group must be limited to the functionalities methyl, ethyl,

  propyl and butyl and their isomers.

  However, we prefer more than substitution

  ---- amine --of --- chemical reagent containing the sulphonyl groups

  fonate is a primary amino functional group. When a primary amino functional group is used to achieve

  the transamidation reaction, the reaction proceeds smoothly

  to incorporate at least 25, and preferably, mole percent of the chemical reagent used, into the chain of the water-soluble polymer containing amide groups

  - pendants thus placing a feature

  sulphonate group to replace what was

  initially the amide pendant functionality.

  In addition to the amine substitution of the chemical reagent described above, this chemical reagent contains at least one sulfonate functional group, either in its acid form or in its salt form, wherein the salt form is selected from salt of an alkali metal, ------- of a metal

  alkaline earth, ----- Tertiary amines and Ammonium ions.

  nium, and their mixtures. The salt form can exist before the transamidation reaction, or it can be synthesized by varying the pH with bases containing alkali metals, alkaline earth metals, tertiary amines,

  or ammonia, either before or during the reaction of

  samidation, ie after the transamidation reaction has

been completed.

  In addition to the sulfonate functional group and the group

  functional amine, the chemical reagent can also contain

  other functional groups, selected from the group consisting of chlorine, bromine, hydroxyl and

  their mixtures. Preferably, the chemical reagent is

  to contain a primary amino group responsible for the transamidation reaction, at least one sulphonate group which

  allows the formation of a water-soluble polymer, anionic

  that, containing sulfonate groups, and a hydroxyl group

  or a chloro functional group, whose presence may

  to improve the activity of water-soluble polymers,

  sulphonate groups, which are synthesized by

  assigned according to the present invention.

  More preferably, the chemical reagent contains a primary amine group, zero, one or more hydroxyl groups, and one or more sulfonate groups in either the free acid form or the salt form, or in

  mixtures of the free acid form and the salt form.

  Several preferred species of the chemical reagent de-

  written above are represented by the following formulas:

- 5 -

  Formula II a. b. c. HaN-CH3 SO3M HaN-CHaCH-SO3M HaN-CaCH2-H-SO3M

H2N-CH2 -CH-CH2SO3M

OH

  Polymers containing acrylamide groups

  are water-soluble polymers, which have a general structure permitting the presence of an amide group during, as shown in Formula III Formula III

H H R

N N

C O

OC C = O

Polvmèr skeleton II NH2

NH RN

H d.

2589S64

  In Formula III, as may be seen, the pendant amide group may be a primary amide group, a secondary amide group, or a tertiary amide group, including

  including mixtures thereof. Preferably, to obtain

  To obtain reasonable conversion rates of these pendant groups into functional groups containing sulfonate groups described above, the amide pendant group is

primary amide group.

  The most suitable water-soluble polymers containing a pendant functional amide, which are easily modified under the conditions of the transamidation reaction according to the present invention, are the water-soluble polymers. represented by Formula IV: Formula IV In Formula IV, R is independently selected, in each case, from the group consisting of hydrogen and lower alkyl groups containing 1-4 carbon atoms; M is independently selected, each time, from

  hydrogen, alkali metals, alkaline earth

  and ammonium ions and their mixtures;

  and a and b are integers satisfying the following relationships

  v: a / b varies --- between 0 and 100, and the sum a + b is sufficient to give a polymer having a molecular weight of at least 1000. Preferably the sum a + b is sufficient to give

  a molecular weight ---------- in the range of

viron 1000-20 000 000.

  As can be seen, the polymers described above can

  be homopolymers of acrylamide or its homologues al-

  kylés, that is, methacrylamide and the like; they may be copolymers of acrylamide with acrylic acid or its homologues, such as methacrylic acid and the like, or they may be terpolymers and polymers consisting of more than three different types of

  monomer units, with other vinyl monomers

  that contain acrylamide and acrylic acid

  that, and their counterparts, such as methacrylic acid and

methacrylamide, and the like.

  The preferred chemical reaction for obtaining the sulfonated polymers of this invention is a reaction which may be referred to generally as a transamidation reaction. This reaction replaces with an amino compound, which may also contain other functional groups, such as the sulfonate functional group, the

  nitrogen portion of an amide group during grafting onto a squeegee

  this polymer as described above. He had been discovered

  that this transamidation reaction is a general reaction

  which can achieve the substitution, by the friendly fraction

  and containing sulfonate groups of the reagent of the invention,

  amide nitrogen group of the pendant amide functionality of a polymeric

  in water, thus allowing the production of

unique fonés.

  The reaction conditions require that the

  polymers containing pendant amide groups are

  under or easily dispersed in a solvent, which is also

  a solvent of the chemical reagent of the class described above

  extra. In other words, both the polymer that needs to be

  modified, and the chemical reagent must be soluble or

  to be dispersed in the same solvent system.

  Common solvents, which have been found useful in this reaction, include, but are not limited to, water, dimethylformamide, dimethylsulfoxide mixtures thereof, and mixtures of these solvents, either alone or in combination between them with other solvents

  such as ethanol, tertiary butanol and similar

  lar. A preferred solvent, which is a common solvent for both the pendant amide group-containing polymer

  and the chemical reagents above, is water, in particular

  bind if the polymer containing pendant amide groups is,

  initially soluble in water, as is the case in most

  vinyl polymers containing acrylic groups

  mide. Another common solvent preferred for the reaction

  according to the present invention is a water-in-water emulsion

  oil in which the dispersed aqueous phase contains

  the state dissolved in it, both the polymers containing

  amide pendant groups and chemical reagents

described above.

  After dissolving the pendant amide-containing polymers in the common solvent, preferably water, the chemical reagent can be added to obtain a solution or dispersion of the polymer containing the

  amide groups and chemical reagents of this invention.

  It is irrelevant whether the polymer or reagent is first added to the common solvent. This mixture is then added to, or placed in, a reactor capable of supporting

  a chemical reaction under pressure, for example, a reaction

  of the type Bomb of Paar. The reactor is -------------

  closed ----, then it is heated to a temperature of at least C, preferably at least 110 C, and more preferably at a temperature of at least 120 C. If the temperature is high above 100 C, the reactor contents may expand and the pressure inside the reactor may exceed 101325Pa (one atmosphere) and, depending on the solvent, the

  The sulfonates used, or the reagents used, may

  to dye approximately 506625Pa at 1519875Pa (5 to 15 atmospheres),

  and maybe more. The pressure inside the reaction

  is an unresolved variable and is set

  only to the extent that the reactor is at -.

  a reaction temperature of at least 100 ° C. or more is reached, and the container may contain solvents or reagents of a more or less volatile nature, said solvents and said reagents having vapor pressures; Such a nature that pressurized reactors are required at temperatures above C. After the reactor contents have reached at least 100 C, and preferably 110 C, the reaction is allowed to proceed for at least 3 minutes. at that temperature, and preferably for any period of time necessary to achieve a minimum of at least 25 percent

  converting the added amount of chemical reagent.

  The chemical reagent is, of course, converted into an amide

  substitute containing pendant sulfonate groups,

  killing the product of the transamidation chemical reaction

  summarized above. If the polymer is a homopolymer of the

  crylamide, methacrylamide, or a copolymer of monomers containing vinyl amides, such that no other functional group is present outside the amide functional groups, the reaction condition is such that at least some degree of hydrolysis amide can also occur in reactions in which water or a solvent containing water is used. In these cases, a carboxylate functional group is also obtained in addition to the sulfonate-modified amide groups and all unreacted starting amide groups from

starting polymer.

  Thus, the reaction or chemical process which carries out the synthesis of structural polymers has been described: Formula V

4X

(SO'3H +) n in which:

  R is chosen individually, each time, from

  mi H and lower alkyl groups (C1-C4);

  M is selected from hydrogen, alkali metals,

  alkaline earth metals, tertiary amines,

  and ammonium ion and mixtures thereof;

  R 'is a multi-covenant hydrocarbon bridging group

  slow, containing from one to sixteen carbon atoms

  and being selected from the functional groups

  neons, branched, cyclic, aromatic, hetero-

  cyclic, and mixtures thereof; X is selected from Cl, Br, OH and mixtures thereof; and wherein:

  a, b and d are integers satisfying the rela-

  the following: a / b varies from zero to 100 b / d varies from 0.01 to 100 a / d varies from zero to 100, and the sum a + b + d is sufficient to give a molecular weight of at least 1000 and the ratio d: (a + b) ranges from 20: 1 to 1: 100; and wherein m varies - between 0 and 16, and

  n varies - between 1 and 16, provided that

  that m is equal to zero, R 'is chosen from among the 11

  functional groups linear, cyclic, hetero-

  cyclic, olefinic and aromatic

  ges, and with the additional condition that the sum m + n is ---- in 1-a range 1-20; said method comprising reacting, in a common solvent, at a temperature of at least 100 ° C: a polymer having a molecular weight of from

  minus 500, and containing functional amide groups.

  said polymer being represented by the structure: NHa Me wherein R, M, a and b have the same meanings as those indicated above; with, B. a structural chemical reagent:

R

  wherein R, R ', M, X, m and n have the meanings

  indicated above; the molar ratio of the reaction

  chemical activity with pendant amide groups ranging from

  5: 1 and about 1: 100; and the reaction occurring during

  a period of time useful for achieving at least one

  25 per cent of the chemical reagent into the

  soluble in water; and then to recover the polymer

sulfonated soluble in water.

  The recovery of the polymer can be carried out in several ways known to those skilled in the art. For example,

  the polymers can be precipitated by addition of soil

  precipitants, or non-solvents to the reaction mixture.

  For example, methanol or acetone may be added to the reaction mixture either as it is or after concentration

  by distillation or vacuum distillation, in order to precipitate

  ter the polymers. The polymers can also be

  recovered by vacuum distillation of the solvent and the unreacted chemical reagent from the product reaction mixture. The polymers can also be recovered by gel permeation chromatography techniques;

  however, for the most part, the polymers are

  simply in the form of a solution in the solvent used to carry out the transamidation reaction, and

are used in this form.

  Preferably, the process according to the present

  The invention is a method for synthesizing sulfated polymers.

  soluble water-soluble compounds having randomly distributed repeating units, represented by the formula: -H R. -g R. RR 2 0 Hg = O = Ho "OC.C O 'NHa NR

WMO

  (S m +) n -in which: R is individually selected, in each case, from H and lower alkyl groups (C1-C4); M is selected from hydrogen, alkali metals, alkaline earth metals, tertiary amines and ammonium ions and mixtures thereof; R 'is a hydrocarbonemulti-covalent bridging group containing from one to sixteen carbon atoms and being

  selected from the linear alkyl functional groups

  branched, cyclic, aromatic, heterocyclic, and mixtures thereof; X is selected from Cl, Br, OH and mixtures thereof; and wherein:

  a, b and d are integers satisfying the rela-

  following: a / b varies from zero to 100, b / d varies from 0.01 to 100, a / d varies from zero to 100, and the sum a + b + d is sufficient to give a molecular weight of minus 3000, and the ratio of d: (a + b) varies from 20: 1 to 1: 100; and wherein: m varies - between 0 and 16, and

  n varies - between 1 and 16, provided that

  m is zero, R 'is selected from linear, cyclic, heterocyclic, olefinic, aromatic alkyl functional groups and mixtures thereof, and with the additional proviso that the sum m + n varies from I to 20; said method comprising reacting, in a common solvent, at a temperature of at least 100 ° C: a polymer having a molecular weight of from

  minus 500, and containing functional amide groups.

  represented by the structure: Ho McN Ha: in which:

  R, M, a and b have the same meanings as

  above; with B. a chemical reagent having the structure: wherein R, R ', M, X, m and n have the meanings indicated above, and wherein the molar ratio

  from chemical reagent to pendant amide groups varies

  be about 5: 1 and about 1: 100; and in which the reaction

  during a period of time to achieve at least a 60 percent conversion of the reagent

  chemical in the sulfonated polymer soluble in water; and in-

  after recovering the sulfonated polymer soluble in water.

  More preferably, the process according to the present invention is a method for synthesizing water-soluble polymers represented by the formula: -wherein: R is individually selected, in each case, from hydrogen and the groups lower alkyl in C! C_ cNb C4; M is individually selected, each time, from

  hydrogen, alkali metals and ammonium ions

niuIm,

  R 'is selected from hydrocarbon bridging groups

  multi-covalent, branched alkyl, linear alkyl

  nonnegative or cyclic, and containing from one to eight carbon atoms; X is selected from Cl, OH and their mixtures m varies - between 0 and 6; n varies - between 1 and 4;

  a, b and d are integers satisfying the rela-

  1 / the following: a / b varies between 0 and 100, a / d -variable between 0 and 100, b / d varies between 0.01 and 100, and the ratio d: (a + b) varies --- between about 5: 1 and about 1:25, and in which the occurrence of repetitive patterns of a, b, and

  d is at random and the sum a + b + d will lead to a molecular weight

  eyepiece of at least 1000; said method comprising reacting, in an aqueous solvent: A. a polymer containing pendant amide functional groups and represented by the structure:

4CHN MCH: 4

O 'NHa MM in which:

  R, M, a and b have the meanings indicated below.

  and in which the sum a + b results in a molecular weight of at least 500; and B. a structural chemical reagent: H2N-t R- ± + SO3M) n I Xm

  in which R ', M, X, m and n have the indicated meanings

  above; under the following reaction conditions: I. a reaction temperature of at least 100 C and preferably at least 110 C; II. a reaction time of at least 1/4 hour and preferably at least one hour;

* III. a molar ratio of chemical reagent to poly-

  mother varies --- between about 2: 1 and about 1:50;

  IV. pressure varying between atmospheric pressure

  and 35 times atmospheric pressure, or more; which makes it possible to carry out the synthesis of sulphonated polymers

described above.

  It is of particular interest that the procedures according to the present invention make it possible to synthesize a sulfonated polymer represented by the formula:

[R R

uCn a3-C CE a - + CE a -C c

<1 1E3

O CIOb O =. C. = d

O. NH

  ## STR2 ## wherein: R is individually selected from hydrogen, methyl and ethyl each, M is individually selected from the group consisting of hydrogen, sodium, potassium, ammonium ions and mixtures thereof;

  R 'is a linear alkylene bridging group, containing

  mantle of 1 to 4 carbon atoms; m varies from 0 to 3; n varies from 1 to 3; and

  a, b, and d are integers satisfying the relations

  tions: a / d varies from 0 to 50, a / b varies from 0 to 50, b / d varies from 0, 1 to 20, d: (a + b) varies from 5: 1 to 1:10, the sum a + b + d is sufficient to give a molecular weight of at least 3000; said method of reacting in an aqueous solvent for at least 1/4

  hour, at a temperature of at least 110 C, in a reaction

  The following ingredients are used: A. a reagent of the formula: ## STR2 ## wherein R ', M, m and n have the meanings given above; and

  B. a water soluble vinyl polymer contains

  amide pendant groups and represented by the structure: wherein R, M, a and b have the meanings indicated above; the molar ratio of reactant to pendant amide groups ranging from about 1: 1 to about 1: 5;

  and then recovering the sulfonated polymer.

  To better illustrate the object of the invention, we will

  describe now several examples of realization.

Example I

  In each of the synthesis processes below, a low molecular weight copolymer of acrylic acid and acrylamide is reacted with 1-amino acid.

  2-hydroxy propanesulfonic acid, in a homogeneous aqueous solution

  gene. The reactions are carried out at temperatures of at least 100 ° C. and are carried out on polymeric backbones

  acrylic acid / acrylamide, having various molecular weight

lar.

2.589864

  The compositions of the polymers vary from

  polyacrylamide copolymer acrylamide at a rate of 50 percent by mole and acrylic acid. The polymers and reagents are loaded, in the form of aqueous solutions, into a Paar bomb equipped with temperature and pressure measuring devices, and also equipped with means for agitating the contents. Temperatures are increased

  up to at least 100 C in each case. The reaction times

  between about 20 minutes and a longer time than

  at 4 hours allow the synthesis of the polymers which are described in Table I.

TABLE I

Polymer of

  proportion (ratio R ci hmqePolymer Produl Molar Weights Reactive Chemical Temperature (AA / Acm / Weight pattern I / AcA2) Starting (mol%) of Repetitive reaction sulfo-P.M.

AA / AcAm) P.M.

  0 AA / 100 AcAm H2N-CH2-CH-CH2SO3M (20) 150 C 31/49/20 43 100 90 +% OH AA / 50 AcAm H2N-CH2-CH-CH2SO3M (20) 150 C 13/37/13 76 600 65% OH AA / 50 AcAm H2NCH2-CH-CH2SO3M (20) 150 C 80/5/15 18 200 75% OH AA / 75 AcAm H2N-CH2-CHCH2SO3M (10) 1500C 40/50/10 21 750 90+ % OH AA / 75 AcAm H2N-CH2-CHCH2SO3M (30) 150 C 50/20/30 24 200 90 +% OH AA / 75 AcAm H2N-CH2-CHCH2SO3M (50) 150 C 50/15/35 25 800 70% ## STR2 ## % OH 1AA = Repetitive pattern acrylic acid 2AcAm = Repetitive pattern acrylamide tD ri% Ln Co oe 0o

  In addition, we can expect to synthesize

  following polymers if acrylamide-containing polymers are reacted according to the procedures described above with the following chemical reagents. The expected products are described in Table II.

TABLE II

  Polymer's Chemical Reagent Polymer Starting Start Expected Product T-f-CH2-CH4-TM2N-CH2CH2SO0Ni * 4 1i-C-CH, -CC-CH4H -Oil b. a 2 NH2; 2 CH2 & 12 * H2N-CH2CH CH CH CM2SO3H1AAv-4AcAEm.fr N-CH2 CH OH OH OaC

OH OH OH NH

2.-cc3SC.2 c H.Hcc.H2.

  w Cl H2NoeCH? .. CM.CH2.CH2 4AA. + ACA .. + c.2OC..C.d

SO3H CO1 N

i NEH

HO3S-CH2 "-CH-CH-CH2

  N r '> tn 0o% 0 Co 0% Nl qJf NO TABLE II (cont'd) Polymer of Polymeric Chemical Reagent Leaving of Product Expected Product T-- CH2-CH-i.-T I b

orC J-C -

N.2 H2N $ y 03H -MtA-Am-t 2-C-d

OH OCNH

  {4AA W - AcAm! OH C1 II HN-CH2 CH CH CH2-SO3H + AA4ACAm R H2-CHHd

CI3 I

  Cl OH N-CH dec 2 CH '-CH-'2 HR03S r4a co o co TABLE II (cont.) Polymer Reactive Chemistry Chemistry Start-up Product Expected

CAA '- "EAcAffmb <CH2503 lA Ac CK-

C H2 3SO3H A

  HO3SCH2 Cx22SO3H - AcAmb H2NCH2SO3H OAA + t4AcAmfCH2. -CI NR X2 n / a 3 S3N + AcAmjb CH3 I, [AAa.--AcAmz.Ch2.?H.d H2N-CH2-C-CH20H Ct CH20M HO CHOH

_M2OM..CH2 2 __ .., H

  TABLE 3 (continued) Polymer of Polymeric Chemical Reagent Starting Flow. Expected Product 4AcAm 0 H2N-CH-CH20H AA t AcAmi t CH ...- Cd CH2C1 C'o sNE

CI-CH2- CH

  LH20H OH fAAcAm ^ H2N-CH2- -SO3H (AA t AcA + tCH2 CH + d

HO3S - CH2-NH

  "ECH2-CH1" 4AcAm H2N-CH2CH2SO3HH2-CH [AC2-Cg x Oec C = O

O-C I I

OC O NH

O H3 (CH2) 2

I

CH] S03H

  fAcAm- H2N-CH2-SO3H (AA tAcAAH tN-CH "[& -ACAt ± AAm + C2-C%.]. d C ao

HO3S-CH2.NE

  Ill, U1% Ln oe o ce GOl TABLE II (cont.) Polymer of Chemical Reagent Polymer Starting Start Expected Product -AcAmi-b H-N-CH2CH2SO3H CH2CH2503H CfO

HO3S-C2CH2-NCH2CH2SO3H

OH (0A + a '+ ACAM ± + bCH2CHtd

I I

A: Am I 'D C = O

-.CH2CHCH2SO3: H I

sCH2CHCH2S03H

CH I'CH

CH2 CH2

2CH F 2

H2 iA & HO HC-OH CH2S3 HC-OH

CH 2SO3H

O1 cn Ln Co% O Os

Claims (13)

  1. Process for synthesizing sulfonated polymers   soluble in water, with repetitive patterns   randomly, represented by the formula: -I- "C-CI-IC - C- --MC --- C- - l -11 1 L_ CCN b UN o O'Ha I NH   (S0M +) n wherein R is individually selected, each time, from H and lower alkyl groups (C1-C4);   M is selected from hydrogen, metals   hulls, alkaline earth metals, tertiary amines and ammonium ions, and mixtures thereof;   R 'is a multi-species hydrocarbon bridging group   covalent, containing from one to sixteen atoms of   carbon and being selected from the functional groups   linear alkyl, branched alkyl, cy-   cliques, aromatic, heterocyclic, olefinic and their mixtures;   X is selected from Cl, Br, OH, and mixtures thereof   ges; and wherein: a, b and d are integers satisfying the following relationships; a / b varies from zero to 100 b / d varies from 0.01 to 100 a / d yvarie from zero to 100,   and the sum a + b + d is sufficient to give   have a molecular weight of at least 1000, and the ratio d: (a + b) varies from 20: 1 to 1: 100;   and wherein m varies between 0 and 16, and n ranges from 1 to 16, with the proviso that when m is zero, R 'is selected from linear, cyclic, heterocyclic, olefinic, aromatic and   their mixtures, and with the additional condition   that the sum m + n varies from 1 to 20; characterized in that it consists in reacting, in a common solvent, at a temperature of at least 100 C; A. a polymer having a molecular weight of from   minus 500, and having functional amide groups   and represented by the structure: NHa Mc   in which R, M, a, b have the same meanings as   above; with B. a structural chemical reagent: R HN '(R' ")" (+ SO 3M) n Xm   in which R, R ', M, X, m and n have the meanings   above; the molar ratio of the chemical reactant to pendant amide groups of the polymer ranging from about 5: 1 to about 1: 100; and conducting the reaction for a period of time useful to achieve at least 25 percent conversion of the chemical reagent to sulfonated pendant groups - 28 -   on the polymer and then recovering the sulfonated polymer soluble in water.   2. Method according to claim 1, characterized in that: R is individually selected, in each case, from hydrogen and methyl and ethyl groups, M is individually chosen, in each case, from hydrogen, sodium, potassium, tertiary amines, ammonium ions and their mixtures, R 'contains at least two carbon atoms and   is chosen from the linear functional groups   res, cyclic, aromatic and their mixtures; X represents OH; m varies from 0 to 4; n varies from 1 to 4; and the molecular weight of the sulfonated polymer soluble in   the water is between about 2000 and about 20 000 000.   3. Method according to one of claims I or 2,   characterized by the fact that the common solvent is chosen in   the group consisting of water, dimethylformamide, dimethyl thylsulfoxide, and mixtures thereof.   4. Method according to one of claims 1 or 2,   characterized in that the solvent is selected from the group   consisting of water and water emulsified in a continuous oily phase, such that the water-soluble sulphonated polymer is recovered either as a water-in-oil emulsion or as a water-in-oil emulsion. an aqueous solution. 5. Process according to claim 1, characterized in that: M is individually selected, each time, from   hydrogen, alkali metals, tertiary amines and ammonium ions,   R 'is selected from hydrocarbon bridging groups   multi-covalent, branched alkyl, linear or cyclic alkyl containing from one to eight carbon atoms; X is selected by Cl, OH, and mixtures thereof; m varies between 0 and 6; n varies between 1 and 4; the ratio d: (a + b) varies between about 5: 1 and about 1:25, and wherein the occurrence of the repeating units of a, b, and d is random and the sum a + b + d leads to a weight molecular weight of at least 2000; and that it consists in reacting, in an aqueous solvent A: A polymer containing pendant amide functional groups and represented by the structure: 15.CH a ... XC} {C a} 0 = famm - NEHa in wherein R, M, a and b have the above meanings and wherein the sum a + b results in a molecular weight of at least 500; and H2N-R '- "- 4SO3M) n Xm   in which R ', M, X, m and n have the meanings given above.   addition; under the following reaction conditions: I. a reaction temperature of at least 10 ° C; II. a reaction time of at least 15 minutes; III. a molar ratio of 2: 1 chemical reactant to polymer ranging from about 2: 1 to about 1:50;   IV. a pressure varying between atmospheric pressure   and 35 times the atmospheric pressure;   thus making it possible to synthesize and,   recovering said sulfonated polymers.   6. Method according to claim 5, characterized by the fact that:   R is chosen individually, each time, from   half the hydrogen and the methyl group,   M is chosen individually, each time,   Hydrogen, sodium, potassium, ammo- nium and their mixtures,   R 'is a linear alkylene bridging group containing   mantle of 2 to 4 carbon atoms; X represents OH;   a, b and d are integers satisfying the rela-   the following: a / b varies between 0 and 50, a / d varies between 0 and 50, b / d varies between 0.01 and 10, and d: (a + b) varies between about 4: 1 and 1:20. , and the sum a + b + d is such that the sulfonated polymer has   a molecular weight ranging in the range of 2000-   000 000, said method comprising reacting at a temperature of at least 110 ° C, for at least 3 hours, in a common aqueous solvent, A. a polymer of structure: in which R, M, a and b have the meanings above   and wherein the sum a + b is such that the molecular weight   the polymer is at least 2000; with B. a chemical reagent of structure: wherein R1, M and X are defined above, and m varies from 0 to 3, n ranges from 1 to 3, and sum m + n varies from 1 to 4; and the ratio of reactant to polymer varies. between about 1: 1 and about 1:10, and the reaction pressure is at least 1.27 × 10 5 Pa (1.25 atmosphere); and then to recover said sulfonated polymer.   7. Method according to one of claims 5 or 6,   characterized in that the solvent used is a water-in-oil emulsion.   8. Process according to claim 5, characterized in that: R is individually selected, in each case, from the group consisting of hydrogen and methyl and ethyl groups; M is individually selected, each time, from the group consisting of hydrogen, sodium, potassium, tertiary amines and ammonium ions and mixtures thereof;   R 'is a linear alkylene bridging group, containing   mantle of 1 to 4 carbon atoms; X represents OH m varies from 0 to 3; n varies from 1 to 3; and the sum n + m is in the range 1-4; a, b and d are integers satisfying the following relations: a / d varies from 0 to 50, a / b varies from 0 to 50, b / d varies from 0.1 to 20, d: (a + b) varies from 5: 1 to 1:10, the sum a + b + d is sufficient to give a molecular weight of at least 2000; this process consisting in reacting, in an aqueous solvent, for at least hour at a temperature of at least 110 ° C., in a reactor regulating the pressure, the following ingredients: A. a chemical reagent: M n in which R ', M, m and n have the above meanings; and   B. a water-soluble vinyl polymer, contains   pendent amide groups, represented by: I I   - Ha M +. wherein R, M, a and b have the above meanings; and the molar ratio of reactant to pendant amide groups of the polymer ranging from about 1: 5 to about 1: 5; and   then recovering the sulfonated polymer.   9. The sulfonated polymer represented by the structure: wherein R is individually selected, each from hydrogen and methyl groups; M is individually selected, each time, from hydrogen, sodium, potassium and ammonium ions, and mixtures thereof; R 'is a multivalent hydrocarbon bridging group containing 16 carbon atoms and being selected from the group consisting of   alkyl groups linear, alkyl branched, cyclic and   finiques, and mixtures thereof; X represents a 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 2000, and wherein the following relationships exist: a / b varies from 0 to 100, a / d varies from 0 to 100, b / d ranges from 0.01 to 100, and the ratio d: (a + b) ranges from about 10: 1 to about 1: 100, and wherein : m varies from 0 to 6,   n varies from 1 to 6, and the sum m + n is in. the namme 1-8.   Polymer according to claim 9, characterized in that it is represented by the structure: R R R 2, to 4, a O = C O -COC I I I O XNH2   in which R is individually chosen, in each case, from hydrogen and methyl groups; H is individually selected, each time, from hydrogen, sodium, potassium and ammonium ions, and mixtures thereof; and a, b and d have the same meanings as those data in claim 9.   11. Polymer according to claim 9, characterized in that it is represented by the structure: _Cl that it is synthesized, in a reactor regulating the pressure, by reaction of a precursor polymer: O = a O_ b oM- With the taurine: H2N-CH 2 CH 2 -SO 3 Bi in a solvent of the aqueous reagents, at a temperature of at least 1000 ° C., for at least 15 minutes, with a molar ratio of the precursor polymer to the taurinese lying between about 20: 1 and about 1: 2, and in the formula of which:   R is chosen individually, each time, from   mi hydrogen and methyl groups;   M is chosen individually, each time,   hydrogen, alkali metals, tertiary amines and ammonium ions, and mixtures thereof;   a, b 'and d are integers satisfying the relations   following conditions; a / d varies from 0 to 100, a / b ranges from 0 to 100, b / d ranges from 0.01 to 100, and d: (a + b) varies from about 10: 1 to about 1: 100,   and the sum a + b + d is such that the sulfonated polymer has   a molecular weight of at least 1000.   12. Polymer according to claim 11, characterized in that it is synthesized in a solvent   aqueous reagents, at a temperature of at least 120 C,   at least 1 hour, with a molar ratio of the polymer   taurine precursor from 10: 1 to 1: 1 and in the form of   from which: R represents hydrogen,   M is selected from the group consisting of H, sodium,   potassium and ammonium ions and mixtures, and the polymer has a   molecular weight of from about 2000 to about 20,000,000.   13. Polymer according to claim 9, characterized by the fact that it is represented by the structure: ## STR2 ## O NH2 NH M CH2 CHOH I CH2   s503 wherein M is individually selected, each time, from hydrogen, sodium, and ammonium ions; a, b, d are integers such that: the sum a + b + d is sufficient to obtain a molecular weight of at least 1000; a / d varies from 0 to 100; b / d varies from 0.01 to 100; a / b varies from 0 to 100,   and the ratio d: (a + b) varies between about 5: 1 and 1:50.   14. Polymer according to claim 9, represented by the structure: ## STR1 ## O 'N NE I M H2 CEH2   CHOH SO3M wherein M is individually selected, in each case, from hydrogen, sodium and ammonium ions; a, b, d are integers such that: the sum a + b + d is sufficient to obtain a molecular weight of at least 1000; a / d varies from 0 to 100; b / d varies from 0.01 to 100; a / b varies from 0 to 100, and the ratio d: (a + b) varies between about 5: 1 and 1:50.