DE2457328A1 - METHOD FOR THE PRODUCTION OF POLYELECTROLYTES - Google Patents

Description

RHONE-POULENC S.A., Paris / France Process for the production of polyelectrolytes

The present invention relates to a method of manufacture complex polyelectrolytes, based on polymers, the sulfonic acid groups and of polymers containing quaternary ammonium groups. For the sake of simplicity, the polymers of these two categories in abbreviated form "sulfonic acid polymer" or called "ammonium polymer".

There are already numerous complex polyelectrolytes that result from an ionic crosslinking between sulfonic acid polymers and Ammonium polymers emerge, described.

The majority of these complex polyelectrolytes came from a reaction of sulfonic acid polymers and ammonium polymers that are individually soluble in water and they were made, by mixing aqueous solutions of the reactive polymers with one another. In this context, one can refer in particular to the U.S. Patents 3,271,496, 3,467,6o4, 3,558,744, 3,565,975, 3 579 6l3 and 3 635 846 refer.

In French patent specification 2 144 922 there is another Class of complex polyelectrolytes, namely those

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those from the conversion of sulfonic acid polymers and ammonium polymers, which are individually insoluble in water emerge. These latter complex polyelectrolytes as well as the above were made by mixing solutions of the reactive polymers.

In contrast to what has been done so far, one has according to the invention found that the complex polyelectrolytes made up of sulfonic acid polymers and ammonium polymers, individually insoluble in water are, derive, can be more easily obtained through intimate Mix one of these two reaction components in solid form (powder) with the other reaction component, this latter being the latter in a solvent, preferably a solvent of the final complex polyelectrolyte, or in solid Form (powder) is present, in which case the mixture of the two powders is then brought into solution, preferably in a solvent for the final complex polyelectrolyte.

The powders used advantageously have a grain size of less than 500 μ and preferably less than 100 μ. In practice, the grain size is often larger than 5 μ and conveniently larger than 20 μ. The limits of 5 and 20 μ are nonetheless by no means critical and only reflect the grain sizes that are obtained using conventional grinding devices.

As far as the exact nature of the complex polyelectrolytes to be produced by the new process according to the invention is concerned, these are Polyelectrolytes characterized in that they / are soluble in an organic medium and of the general formula /% * < ή water

[Losh'cL si ^ ci

5 09823/0887

so

"1

Θ 3-

correspond in the

the symbol N ^ means a quaternary ammonium group, the symbol / ν ^Λ ν / ν \ / \ represents a macromolecular chain which has groups which are capable of becoming -SOJ "by covalent bonding to groups,

bound to

the symbol ^ j \ f \ j \ / \ y \ _ means a macromolecular chain which has groups that can lead to the formation of groups N®, where the chains ΛΑΑΛΑ ^and -f \ S \ f \ f \ J \ " * ^{Considered in} Korotdnation, none. contain antagonistic groups that can lead to the formation of intercatenary covalent bonds,

indicates that the groups ftH at the through

The macromolecular chain shown is bound by at least one covalent bond and
the ratio - ζλ-i is 0.1 and 10,

the symbol

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where the nature of the ^{groups forming the macromolecular chains ΛΑΑΑΛ 1111} Cl _f \ s \ j \ j \ / \ _ , and the values of the symbols η and m are such that a polymer of the formula

ΛΛΑΑΛ

(Sulfonic acid polymer) ί

in which M is a hydrogen ion or an alkali or alkaline earth metal denotes metal ion and χ represents the value 1 or 2,

and a polymer of the formula

(I ₂ )

. ■ (ammonium polymer)

in which A denotes a hydroxyl radical or the anion of an inorganic or organic acid of the formula AHy, where y denotes Value 1, 2 or; 5 represents, each insoluble in water, however soluble in the same liquid organic medium are.

ί For the sake of simplicity, polyelectrolytes will be of the formula

and the part of the formula is called.

the part of the complex a <vw \ C ¹ '-)) "polyanion" ⁰

(SO ₃ ⁰ ) n

- ^ ^Lr \} ^1J1 - (I * ₂ ) "Polycation"

[Vi.

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In general, the presence of ionic groups increases; in the macromolecular chains the solubility of the polymers in water. The polymers used according to the invention of formula (i-) and (Ig) should on the other hand, although they are hydrophilic Groups contain being insoluble in water. The insoluble. on the one hand, by increasing the molecular weight of the polymer and, on the other hand, by limiting the amount of hydrophilic groups attached to the macromolecular Chains / wsaa and _ / \ y \ y \ / \ j "L. Are tied, can be achieved. ·

With regard to the molecular weight, it can generally be said that the specific viscosity of each of the polymers of the formulas (I-) and (I ₂ ) should be in excess of 0.01. It is preferably between 0.05 and 1.5 ( ^{measurement carried out at 25 °} C. with solutions in dimethylformamide at a concentration of 2 g / l).

With regard to the amount of hydrophilic groups, one can generally say that in each of the polymers of the formula (I ₁ ) and (Ip) there should be less than 1 hydrophilic group per 12 carbon atoms and preferably less than 1 hydrophilic group per 20 carbon atoms.

j The hydrophilic groups can only be selected from the groups -SO-, and

N ^ exist. ;

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Number of groups -SO-,

in the polyanion and the ratio

Number of anionic groups

Number of groups
in which the polycation is below 5 % in each case.

The polyanion and the polycation can also be small
Contain quantitative proportion of other hydrophilic groups than the aforementioned ionic groups. These hydrophilic groups can be anionic groups such as Carb ~
oxyl groups, sulfate groups with acidic or salt character, phosphonic acid and phosphate groups and sulfamic acid groups, and cationic groups, such as amine salts, compounds with phosphonium or sulfonium groups

pen, nonionic groups such as hydroxyl,! Ether, carboxylic acid ester, t * or amide groups. If the ί polyanion and polycation contain other hydrophilic groups than the groups -SO, and ISr , it is preferred that these
additional groups are nonionic or ionic groups' of the same charge as the characteristic groups of the
Wear polymers. However, it is within the scope of the invention to use weakly ampholytic polymers, that is to say a: polyanion and / or a polycation which contains a small proportion of cationic or anionic groups.

The expression "small proportion" is to be understood here as meaning that the ratio · · ι

Number of cationic groups:

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In general, both for the polyanion and for the polycation, the ratio

Number of hydrophilic groups other than -SO, or

Number of groups -SOJ ^ or Nn

less than 1. ·. '

The elite macromolecular chains denoted by the symbols' vwvy and _jyj ^ jw \ _ kargest can each be of different types

ι
belong.

In particular, the sulfonic acid polymer from the group from

α Polymerization products of monomers, at least some of which consist of monomers which carry sulfonic acid groups and

ß Products obtained by sulfonation treatment of polymers obtained from monomers free of sulfonic acid groups,

to get voted. · ·

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The term "polymer" is used here in the broad sense of a macromolecular one Chaining used and includes both the polyaddition products, for example, by opening carbon-carbon double bonds are obtained, as well as the polycondensation products according to the generally customary distinction.

Among the polymers of group α, one can in particular find the polymerization products of the vinyl type, which can be defined as products consisting of a number of groupings the formula

f (II)

SO ₃ H

optionally together with groupings of the formula

²³³ ) ₂ - (HI)

consist, where the different radicals H, the same or . can be different from each other, hydrogen

J atoms or _ alkyl radicals with 1 to 4 carbon atoms

to interpret

R either a single valence bond or a divalent pure hydrocarbon group, whose free valences are from a purely aliphatic, saturated or unsaturated, straight-sided or branched chain or carried by an aromatic ring or by a mixed chain, 'one of the free valences of an aliphatic carbon atom and the other free Valence is carried by an aromatic carbon atom

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or a group -0-R ^f - or -SR ¹ -, where R ¹ 'represents a divalent group as previously defined for R,

or a divalent group consisting of aliphatic and / or pure aromatic hydrocarbon groups, which are connected to each other by oxygen or sulfur atoms, j where the free valences are carried by aliphatic and / or aromatic carbon atoms, or

a divalent group, such as those mentioned above, in which one or _; several carbon atoms also carry substituents such as halogen atoms or hydroxyl radicals, "j

means.

i 'ρ ■ ■

In the formula (III), the various symbols R can be used with one another or between different groupings of the formula (III)

ί *

can be the same or different, in each case a hydrogen atom, a halogen atom or an alkyl radical having 1 to 4 carbon atoms mean, and the symbols R, which are the same or different from one another can have the meaning of R ~, or:

a grouping from the group of the remainders of the formulas

-C = N, QR ⁵ , -CR ⁵ , -C-OR ⁵ , -0-CR ⁵ , -C-IIHR ⁵
0 0 0 0

represent, in which. · the symbol R is a hydrogen atom or a linear or branched alkyl radical with 1 to 50 carbon atoms, a cycloalkyl radical with 5 or 6 atoms in the ring or an aryl, alkoxy j.

means aryl or aralkoxy radical. ■.

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As examples of monomers which, by polymerization, lead to ^: groupings of the formula (II), the following can be used; Name acids (possibly converted into salt form):; Vinylsulfonic acid, propene- (1) -sulfonic acid- (1), allylsulfone- _; acid, methallylsulfonic acid, allyloxyethylsulfonic acid; :

Butene (1), butene (2) and butene (3) sulfonic acid (1); |

Hexene sulfonic acids, in particular hexene (1) sulfonic acid (1); | Methylbutene sulfonic acids, methallyloxyethyl sulfonic acid ^,! 3-allyloxypropanol- (2) -sulfonic acid- (1), allylthioethylsulfonic acid, ^ -allylthiopropanol- (2) -sulfonic acid- (1); Vinyl ^; benzenesulfonic acids, in particular 3-vinylbenzenesulfonic acid- (1); Vinyloxybenzenesulfonic acids, in particular 2-vinyloxy- and 4-vinyl- · oxybenzenesulfonic acid- (l); Isopropenylbenzenesulfonic acids, in particular 2-isopropenylbenzene- and 4-isopropenylbenzenesulfonic acid- (l); Bromovinybenzenesulfonic acids, in particular 2-bromo- and 4-bromo-3-vinylbenzenesulfonic acid- (1); α-methylstyrenesulphonic acids, '' a-fithylstyrenesulphonic acids, isopropenylcumene sulphonic acids; Mono-, di- and trihydroxyvinylbenzenesulfonic acids; 2,5-dichloro-vinylbenzenesulfonic acids (1), isopropenynaphthalenesulfonic acids, vinyldichloronaphthalenesulfonic acids; o- and p-allylbenzenesulfonic acid, o- and p-methallylbenzenesulfonic acid; (o- and p-isopropenylphenyl) -4-n-butanesulfonic acid- (i); Vinyl chlorophenylethanesulfonic acids; o- and p-allyloxybenzenesulfonic acid; o- and p-met'hallyloxybenzenesulfonic acid; Vinyl hydroxyphenyl methanesulfonic acids; Vinyl trihydroxyphenylethanesulfonic acids; 2-isopropyl-ethylene-sulfonic acid- (1).

Examples of monomers which lead to groups of the formula (III ) through polymerization and which can be copolymerized with the aforementioned are ethylene, styrene, vinyl bromide, vinyl chloride, vinylidene chloride, acrylonitrile, vinylidenecyanide, methacrylonitrile, allyl alcohol, the vinyl and allyl ethers, such as methyl, ethyl, propyl, cyclohexyl and benzylvinyl or

j -allyl ethers, the vinyl ketones such as methyl vinyl ketone or ethyl ^: vinyl ketone, the unsaturated monocarboxylic acids such as acrylic acid,

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-.11 -

Methacrylic acid, crotonic acid and itaconic acid, and their alkyl. or aryl esters, especially the methyl, ethyl, butyl and \ benzyl ester, the cyano (meth) acrylic esters, such as Ä "thyl-a-oyano- j

I acrylate, the optionally partially saponified vinyl esters; of aliphatic linear monocarboxylic acids such as vinyl acetate; Vinyl propionate, vinyl laurate and vinyl stearate, or of ver _; branched aliphatic 'monocarboxylic acids, such as the vinyl esters j of acids in which the carboxyl group is in the α-position ι

ι a tertiary or quaternary carbon atom is located;

the vinyl esters of aromatic acids, such as vinyl benzoate, which:

unsaturated polycarboxylic acids such as maleic acid or its
Anhydride, acid fumaric acid, citraconic acid, mesaconic acid and aconitic ■ "\, and their mono-, di- or tri-alkyl ^optionally; ester, in particular ethyl, propyl, butyl, hexyl.

2-ethylhexyl, octyl or ß-hydroxyethyl ester, or their

j Cycloalkyl or aryl esters, the amides of unsaturated acids,
such as crotonamide, acrylamide and methacrylamide,
and the reaction products of the aforementioned acids with a
primary monoarnine, 'such as methylamine, ethylamine,
Mention propylamine, cyclohexylamine and aniline.

As particular examples of polymers of the group α which contain groupings of the formulas (il) and (ill j), one can use the
Copolymers of acrylonitrile with methallylsulfonic acid or
name their salts. In these copolymers the proportion is
of groups derived from the acid with groups -SOJtf, im
generally between 1 and J> 0% and preferably between 4- "
and 20 <? o (wt .- ^, based on the total weight of the copolyimers).

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From the foregoing it can be seen that certain of the, groupings of the formula (III) can have hydrophilic groups. It should be noted that the amount of monomer carrying hydrophilic groups used should be such that that before specified proportion of these groups in the macromolecular chain is observed. It is especially easy to get through this To achieve the use of a copolymer derived from monomers of various types, at least a portion of which Monomers is free of hydrophilic groups.

Other examples of polymers of group α are polycondensates, derived from reagents, at least some of which are or carries more substituents -SOJFi.

Specific examples of such polycondensates are those which have a number of groupings of the formula

ι Il

Οη

ι I r

Q - CO -.T ¹ - OC

(iv) or

Ό ο

1 Il 2 Il Q -CLm-T- HNC ■

! in which the symbol Q represents the remainder of a dicarbon

! acid of the formula HOOC - Q - COOH denotes, T ¹ denotes the remainder

! of a diol of the formula HO-T-OH and T is the remainder

i 2

ι a diamine of the formula H _n N - T - NH ₀ , where the

I 1 * - 2 '

■ ". Radical represented by Q as a substituent a group '

^: -SO..H has.

i ' ^ ■ ■

I 12

ί As examples of residues represented by the symbols T and T

i can be used for the aliphatic radicals with even

; or branched chain containing 3 to 10 carbon atoms, the cycloaliphatic radicals with 5 or 6 carbon

i atoms in the ring, the monocyclic aromatic radicals, the

^; not substituted or by 1 or 2 alkyl radicals with 1 to 4

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Carbon atoms can be substituted, or radicals consisting of several cycloaliphatic or aromatic radicals consist of one another directly or through a divalent hydrocarbon radical with 1 to 4 carbon atoms or by a hetero atom, such as oxygen, sulfur and nitrogen, or by a divalent group, such as -SOp-., are connected.

Examples of the radicals represented by the symbol Q include, in particular, the alkylene radicals having 3 "to 10 carbon atoms and name the phenylene radicals, these being different Radicals have a substituent -SOJK.

Sulfosuccinic acid and 5-sulfoisophthalic acid can be used as special examples of dicarboxylic acids of the formula HOOC -Q- COOH to name.

It should be noted that in the preparation of polycondensates of the formulas (IV) and (V) and in particular to adjust the proportion of the sulfonic acid groups in the polycondensate the aforementioned Acid together with other dicarboxylic acids, such as aliphatic dicarboxylic acids, e.g. succinic acid, j glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid ,. Fumaric acid, cycloalkanedi- ! carboxylic acids, e.g. cyclohexanedicarboxylic acid (1,4), and aromatic acids, such as benzene dicarboxylic acids, ver-ί can be turned. . "'

! Examples of diols include ethanediol (1,2), propanediol (1,2) and - (1,3), butanediol (1,2), - (1,3) and - (1,4) , Pentanediol- (1,5), hexanediol- (1,6), decanediol- (1,10), 2,2-dimethyl- \ propanediol- (1,3) and 1,2-diethylpropanediol - call (1,3).

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Examples of diamines are ethylenediamine, 1,2 »diamino ~ propane, 2,2-bis ~ (4-aminocyclohexyl) propane, 1,6-diaminohexane, m-phenylenediamine, 2,2-, 2,7- and 3> 6-diaminocarbazole and N, N'-bis-Ccarbonamldopropylj-hexane-II ^ oJ-diamine name.

The polymers of group ß are formed by bonding sulfonic acid groups obtained on a macromolecular chain. It is possible to attach such groups to polymers, the linkages the formula

0 0 I! , 11

0 0

L.. * Il

Q-CO-T ~ OC f or -Q- CHH - T - HIiO

where the meaning of the various symbols R,

11?
R> T and T: is the one given above and the symbol Q represents a radical like Q, but which is free from groups -S (XH.

Other types of polymers that can be sulfonated are those that have a number of groupings of the formula

Ar> -E-

(VI)

have, in which the symbol Ar, which can be different from one group to the other, is a divalent aromatic Radical or a divalent radical which has at least one aromatic substituent, and that

: Symbol E, which can be different from one group to another, denotes a divalent group selected from the group of -0-, -SOg-, '- (CHg) _v ~, where ν is the value 1 to 4-

represents, and -C (CH,) p- can be selected.

50 9 "82T7Ö8 87"

As examples of aromatic radicals represented by Ar the phenylene radicals optionally substituted by one or two alkyl or aryl radicals, in particular p-phenylene, and the radicals of the formula

in which the symbol L represents an alkylene or alkylidene radical with 1 to 12 carbon atoms or a group -CO-, to name.

As examples of polymers, the linkages of the formula (VI) have, in particular, the phenolic polyethers, such as those described in US Pat. No. 3,306,875, or the polymers having a number of moieties

-CH ₂ -

CH ₂ -Q-Ar

show, name,

As polymers which can be sulfonated, polyaryl ether sulfones are preferably used in the invention general formula

j Such polymers are for example in the French ! U.S. Patent 1,407,30I.

50 9.8 2 3/08 8 7

. The particular sulfonation techniques are in the literature described. In particular, Everet E. Gilbert wrote in “Sulfonation and Related Reactions, "published 1965 by Interscience Publishers provide the means of attaching sulfonic acid groups (or sulfonate groups) to a wide variety of organic Groups defined in detail.

Like the sulfonic acid polymer, the ammonium polymer can be two Belong to categories of polymers. It can consist of:

Products obtained by treating a polymer (α ') bearing tertiary amino groups with a quaternizing agent ! are received, or

j Products which, through the reaction of a tertiary amine with a polymer (ß ^f )> have the substituents capable of quaternizing this amine, which thereby bond with the polymer ß ^! ensure are preserved.

The polymers of group a ^! can be chosen from polymers having a number of groupings of the formula

- C (R ¹ ) ₂ - C (R ¹ ) ~. (VII)

optionally together with a number of groupings of the formula (III) given above, where

the symbol R in the formula (VIl) has the meaning given above and R is a group -N (RZ) ₂ or a monovalent hydrocarbon radical from the group consisting of

5Ö9 82 37Ö8 87

the linear or branched alkyl radicals with

1 to 12 carbon atoms, the cyeloalkyl radicals with 5 or 6 carbon atoms in the ring and the. Phenyl radicals, these various radicals having a substituent -N (R ^) ₂ , and

from a mono- or dinitrogen heterocycle with 5 or 6 chain links, optionally together with one or two aromatic rings, consisting of radicals, where the nitrogen atom, or at least one of the nitrogen atoms of the heterocycle by its 3 valences on adjacent ones Carbon atoms in the heterocycle or through;

2 valences are bonded to these carbon atoms and the third valence to a group -r7,

7 " i

consists, where the different symbols R 'which are the same or' ·; can be different from one another, alkyl radicals with 1 to 6 | Mean carbon atoms. i

As examples of monomers that polymerize into groupings of formula (VII) lead, you can vinyldimethylamine, Allyldimethylamine, 1-Dimethylaminopropen- (1), 2-Dimethylaminopropen- (i), 1-dimethylaminobutene- (2), 4-dimethylaminobutene- (1), 3-dimethylaminobutene- (1), 3-dimethylamino-2-methylpropene- (i), Methylethylallylamine, vinyl diethylamine, 5-dimethylaminopentene- (i), 4-dimethylamino-3-methylbutene- (1), methylpropylallylamine, allyldiethylamine, 6-dimethylaminohexen- (i), ethylvinylbutylamine, Allyldiisopropylamine, 3-dimethylamino-2-propylpentene ~ (1), allyldibutylamine, Dialkylaminostyrenes, especially dimethylaminostyrene and diethylaminostyrene, vinylpyridines, especially N-vinylpyridine, 2-vinylpyridine, 3-vinylpyridine and 4-vinylpyridine, and their substitution derivatives, such as 5-methyl-2-vinylpyridine, 5-ethyl-2-vinylpyridine, 6-methyl-2-vinylpyridine, 4,6-dimethyl-2-vinyl-pyridine and 6-methyl-3-vinyl-

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pyridine, N-vinyl carbazole, 4-vinyl pyrimidine and 2-vinyl benzimidazole to name.

The copolymers of acrylonitrile and a vinyl pyridine can be mentioned as special examples of polymers of group cc. * Which have groupings of the formulas (VII) and (III) between 1 and 50 $ and preferably between K and JO JS>, (wt .- ^, based on the total weight of the copolymer).

The polymers of group a ^! can also consist of condensation products of monomers, at least some of which contain tertiary nitrogen atoms.

Such polycondensates can be defined as products which have a number of groupings of the formula

0 0 Ii 2 Il 3 OC-Q- CO - T-

(VIIl)

or

0 0

Q ² - CiJH - T ⁴ - HHC

(ix)

have, in which the symbol Q denotes the radical of a dicarboxylic acid of the formula HOOC - Q, - COOH, Ί? the remainder of a diol

"5 4

of the formula HO - T - OH and T represents the remainder of a diamine

4 of the formula H ₀ N -T - NH

means, at least one of the

23 4
residues represented by the symbols Q and T or T.

contains tertiary nitrogen atom.

It should be noted that the polycondensate, if there are groupings of formula (viii), consist of these groupings alone can (polyester) or urethane or urea groups may contain. In this latter case the polymer consists of a chain, the series of groupings (VIII) having, with other series of groupings (VIII)

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through groups
"O

KJ-UH-ISQ-MH-CO-l

(ISO means the remainder of a diisocyanate of the formula O = C = N-ISO-N = C = 0) and, if applicable, groups

o -i 3

Ii 8 Μ

OC-ira-ISO-NH-OO-R -CO-ilH-ISO-HH-CO-T

are connected, where R _{1 is} a valence bond or a group of the formula - 0 -, -NH-NH-, -HN - T ⁴ - NH -, - 0 - T ⁵ or -NH-NH-CO-NH-.

The symbol Q is when it is the remainder of a dicarboxylic acid that contains a tertiary nitrogen atom, means an alkylene radical with 2 to 12 carbon atoms which is replaced by a dialkylamino radical substituted or interrupted by an alkylimino radical, a cycloalkylene or arylene radical, which by is substituted by a dialkylamino radical, or a radical in which two of these rings are connected by an alkylimino radical, a nitrogen-containing heterocycle with 5 or 6 chain links, dor contains 1 or 2 nitrogen atoms, where the Nitrogen atom or one of the nitrogen atoms through its j5 valences to adjacent carbon atoms or through 2 valences on neighboring carbon atoms and through the .third Valence is attached to a lower alkyl radical having 1 to 4 carbon atoms. .. ■

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■ - 20 -

ii
The symbol Τ, if it contains the remainder of a diamine with ter-

represents tertiary nitrogen atom, be selected from the radicals represented by Q,.

The symbol T is general when there is a remainder of a Diol represents a tertiary nitrogen atom, a linear or branched aliphatic hydrocarbon radical with 2 to 12 carbon atoms, which is saturated or has ethylenic or acetylenic unsaturation and which only or is at least substituted by a dialkylamino radical or interrupted by an alkylimino radical.

Examples of dicarboxylic acids with a tertiary nitrogen atom include, in particular, methyliminodiacetic acid, 3-di- ! methylaminohexanedioic acid, 1-dimethylaminocyclopentanedicarboxylic ! acid (2,3), dimethylaminoisophthic acid, dimethylaminoterephthalic acid, 1-methyl-pyrimidinedicarboxylic acid and 1-methylimidazole-dicarboxylic acid- (4,5) to name.

Examples of diols with a tertiary nitrogen atom can be in particular the alkylamines substituted on the nitrogen atom by 2 hydroxyalkyl radicals, such as ethyl diethanolamine, or those on a non-hydroxylated carbon atom alkylene glycols substituted by a dialkylamino group, such as! / - Dime thy lamino and P-diethyl aminopropylene glycol.

As examples of diamines that have a tertiary nitrogen atom contain, you can 3-Dimethyiaminohexan-1,6-diamine, 3- (N-Methylpiperazino) -hexan-i ^ -diamine, > -Pyrrolidinohexane-1,6-diamine, 2-piperidinohexane-1,6-diamine, 3-morpholinohexane-1,6-diamine, N-bis- (j5-aminopropyl) -methylamine, N-bis- (3-aminopropyl) -cyclohexylamine and name N-bis (3-aminopropyl) aniline.

50982 3/0887

The dicarboxylic acids, diols. and diamines that do not have a tertiary nitrogen atom and can be used in the preparation of the polycondensates of the formulas (VIII) and (IX), can be chosen from the various dicarboxylic acids, diols and diamines mentioned above.

S As examples of diisocyanates of the formula O = C = N-ISO-N = C = O, which are used for the production of polycondensates of the polyurethane type are usable, one can use 1,6-diisocyanatohexane, 2,4-diisocyanatotoluene, 2,6-diisocyanototoluene, m-diisocyanatobenzene, 2,2-bis- (4-isocyanatocyclohexyl) propane, bis (4-isocyanatocyclohexyl) methane, 1,5-diisocyanatopentane, 1,4-diisocyanatocyclohexane and bis (4-isocyanatophenyl) methane to name. · ■

As examples of compounds, -the together with the above Isocyanates to form groups

O -,

-0-CO-NH-ISO-NH-CO-R -CO-NH-ISO-NH-CO-O-TT-

can be used, you can use water, hydrazine, aminoacetic acid hydrazide, and also the diols and diamines with or without a tertiary nitrogen atom, as mentioned above.

j As special examples of polycondensates, the tertiary embroidery ! contain groups of substances, one can name the polyester urethanes, j those from a diol which has a tertiary nitrogen atom, ι such as Ä'thyldiäthanolamin, adipic acid and diisoj cyanate, such as 4,4 * -diisocyanatodiphenylmethane, j, the coupling agent optionally used is a diol or aminoacetic acid hydrazide. In these polymers, the molecular weight of the polyester intermediate is generally between j500 and 10,000.

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Means for quaternizing tertiary amino groups, as well the handling conditions are described in the literature. In general, esters of mineral acids are used, such as for example alkyl, cycloalkyl and aralkyl halides and sulfates. Preferably contain the alkyl, cycloalkyl and Aralkyl radicals. no more than 14 carbon atoms each. As examples for such quaternizing agents one can use methyl, ethyl, propyl, cyclohexyl and benzyl chloride, bromide and Call iodide and dimethyl and diethyl sulfate. One can also Use halogenated derivatives that have other chemical functions, such as chloroacetaldehyde.

J The substituents of the polymers of the group ß ', which with a; tertiary amine able to react to .quaternary Amoniumj Groups are generally halogen atoms. The polymers of group ß * can therefore be defined as products that are a number of groupings of the formula

: ■ - Δ -Ε -

(X)

have, in which the symbol fc means an organic radical bearing a halogen substituent and the symbol E has the meaning given above.

It should be noted that the polymers of group β ¹ together 'with. the groupings of the formula (x) groupings which are free from; are halogenated groups.

$ 09823/088 7

The presence of halogenated groups in the polymers of group ß * can be caused by polymerization of monomers that containing such groups can be achieved. Examples of this type are the homo- and copolymers of 2-chloroethyl methacrylate. -

In general, the halogenated polymers are obtained by bonding halogenated groups to macromolecular chains free of such groups. The techniques of attaching halogenated groups to polymers are described in the literature. Among the mostly used one can be the halomethylation, in particular the chloromethylation, of polymers which have aromatic groups, such as, for example, the polymers of the formula (VI) ₁ described above, and the treatment of polymers which have hydroxylated groups with epihalohydrins, in particular epichlorohydrin, to name. Particular examples of such hydroxylated polymers are the poly (hydroxy ethers), which are composed of a number of groupings of the formula

0 - Σ - 0 - CH ^ - CII

exist, in which the symbol Σ means a divalent residue, from the group of the remainders of the formulas

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ι ·

Uy ■ ~ <Q

CK ₂ -CH ₃ _.

.CH ₃ .

\ - and

can be chosen.

As an example of tertiary amines that can react with the halogenated polymers described above, one can use the trialkylamines with unsubstituted alkyl radicals, such as trimethylamines, triethylamine and tripropylamine, the trialkylamines in which at least one of the alkyl radicals is substituted by a functional group , such as the N-dialkylalkanolamines, the N-alkyldialkanolamines and the trialkanolamines such as dimethylethanolamine and triethanolamine, the heterocyclic amines such as pyridine, the picolines, the lutidines, the N-alkylpiperidines and the N, N ^! Dialkylpiperazines, quinoxaline, the N-alkylmorpholines and the aromatic amines with an amino group attached to the ring, such as, for example, N, N'-dimethylaniline, or the aromatic amines with an amino group outside the ring. In general, the amines used have from 5 to 12 carbon atoms.

j Among the aforementioned poly (hydroxy ethers) one can name as preferred examples the polymers which

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fetching group

- ^c

3'2

exhibit.

These poly (hydroxy ethers) are preferably mixed with epichlorohydrin treated, the amount of this latter reagent being such that the ratio

Number of moles of epichlorohydrin

] Number of groups OH in the polymer

j - i

S is between 0.2 and 5. . - '.

ι ■;

In the preparation of the complex polyelectrolytes according to the invention, as already indicated above, a Solvent for the reactive polymers, which is preferably also a solvent for the final complex polyelectrolyte represents. This solvent is preferably organic and can be composed of a solvent or a mixture of solvents exist.

The choice of solvent will of course depend on the nature of the various polymers. However, it can be said that in general the aforementioned various polymers in the aprotic polar solvents, such as dimethylformamide, Dimethylacetamide, dimethyl sulfoxide, hexamethylphosphoric acid trisamide, N-methylpyrrolidone- (2), sulfolane and ethylene carbonate, soluble are. It is possible to use mixtures of these solvents with one another and / or with other organic solvents, such as Ketones, esters and the like to use.

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In the pall, in which a reactive polymer in powder form is mixed with a solution of the other reactive polymer, the initial concentration of this solution of the reactive polymer affects the physical nature of the complex polyelectrolyte obtained. In general, in order to achieve continuity in the ionically crosslinked polymer, the polymer concentration of the solution of the starting dissolved polymer should be greater than 0.25 % and preferably greater than 0.5 % (by weight).

The upper limit for the concentration depends essentially on the technological conditions. In general, this limit is in the order of 25 %, although this information is not mandatory.

The preparation of these solutions of the starting polymer

■ can be carried out according to the techniques generally used in the production of polymer solutions. In general, the polymer is in a first stage in the solvent, which is kept at a relatively low temperature (-20 to 20 ⁰ C), dispersed; then the temperature is gradually increased until a clear and homogeneous solution is obtained. The final temperature depends on the type of polymer and the solvent. It is generally between 20 and 100 ^° C.

In the case where the mixture of the two powders of the starting polymers is brought into solution, the conditions of the ratios of the total of the solids with respect to the total of the solids plus the solvent are essentially equivalent, mutatis mutandis, to those indicated above, that is, that the concentration of dissolved polymers in their solution is greater than 0.5 j and preferably greater than 1 % , the upper limit being of the order of 50 % , without this information being intended to be a restriction.

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This solution is carried out under the same conditions as those described above for the solution of a single of the starting polymers have been specified in the solvent.

As can be seen from the value of the ratio given above, the sulfonic acid polymer or the ammonium polymer. j in the reaction mixture in ionic excess. Pre- ^1: Preferably, the ratio is between 0.2 and 5 jj j ·

The formation of the complex polyelectrolyte in the mixture brings about - a strong increase in viscosity from the point in time onwards, to which the two reactants and the solvent are in common contact are. The introduction of a strongly ionized electrolyte, which with the "ionic shields" described in the literature is comparable to this new solution (of the complex polyelectrolyte) causes a considerable decrease in viscosity, which according to the generally accepted interpretation shows that this electrolyte is at least partially between the sulfonic acid polymers and has broken ionic bonds formed in the ammonium polymer.

The solution of the complex polyelectrolyte of the formula (I) can be used as such for the production of films or shaped products be used.

It does happen, however, especially when you have a membrane through Pouring a solution of the complex polyelectrolyte wants to produce that viscosity starting from the reaction medium solution obtained is too high. It is then sufficient to dilute this solution in order to obtain the desired viscosity.

From the foregoing it can be seen that the use of a ionic screen is by no means necessary when processing the complex polyelectrolytes according to the invention. However, it lies within the scope of the invention, a strongly ionized electrolyte, the is soluble in organic medium, such as

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Lithium chloride, to be used to increase the viscosity of the solution of the complex polyelectrolyte.

From solutions of the complex polyelectrolytes according to the invention obtained films or membranes, which can be flat, tubular, spiral or any other shape can have an isotropic or anisotropic structure. One understands membranes with an isotropic structure a membrane that has a dense structure or uniform porosity throughout its thickness. A membrane with an anisotropic structure is generally used to describe a membrane that has a porosity gradient of! one side to the other, wherein one of the sides can be completely free of pores at the boundary.

The isotropic membranes are generally made by simply pouring the solution of the complex polyelectrolyte onto a suitable surface (such as a glass plate or a metal plate, a metal pipe, a metal spiral or a metal tape) and subsequent removal of the solvent. The anisotropic membranes can be immersed the plate carrying the layer of the solution of the complex polyelectrolyte in a coagulation bath (non-solvent for the complex polyelectrolytes). In general, the coagulation bath consists of water or mixtures of Water and organic solvents or from aqueous solutions of electrolytes.

It should be noted that the complex polyelectrolytes produced according to the invention can contain fillers and / or plasticizers, which can be mixed directly with the complex polyelectrolyte in solution or beforehand in the starting sulfonic acid polymer and / or starting ammonium polymers may be introduced.

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Furthermore, the membranes can only consist of the film made from the complex polyelectrolyte with or without filler there is a reinforcement, such as a fabric, a knitted fabric or a net based on natural or synthetic fibers.

The complex polyelectrolytes produced according to the invention can be used in a wide variety of fields. You can in the textile field in the form of threads, fabrics or treatment agents for threads or fabrics that are used to achieve certain properties, such as color affinity, hydrophilicity or antistatic properties, are determined, these properties can be adjusted as a function of the anionic or cationic excess of the complex polyelectrolyte, be used.

In particular, the membranes can be inverted for the fractionation of solutions according to the techniques of ultrafiltration. Osmosis and dialysis can be used. These membranes, especially if they are anisotropic, have a particularly high degree of retention for macromolecular substances, and they have considerable permeability for water. It should be noted that a heat treatment in water allows the structure of the membrane to be modified and its retention zone (limit of the molecular weight of the compounds passing through the membrane) from a high value (for example 10-15,000) to a very low value ( on the order of 2 to 300). In addition to their permeation properties, these membranes have increased mechanical properties which enable them, for example in ultrafiltration, to withstand the use pressures without damage. ^; '

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The films made from the complex polyelectrolytes produced according to the invention can also be used as a separator for batteries.

These polyelectrolytes can also be used for medical purposes, in particular in artificial kidneys and lungs, as a result of their dialysis properties and gas permeation properties of the membranes made from these polyelectrolytes and in general at Manufacture of prostheses and all products that are to come into contact with blood are used, as these are polyelectrolytes possess remarkable antithrombogenic properties.

The complex polyelectrolytes produced according to the invention can also used as synthetic leather or in the production of electrically conductive coatings or antistatic coatings will.

The applications listed above are only examples of the use of the complex polyelectrolytes produced according to the invention and do not constitute a limitation.

The following examples serve to further illustrate the invention.

example 1

Place in a 250 cnr recipient equipped with a stirrer is provided, either separately in order to produce a solution in the recipient by stirring, or together in form an already prepared solution, the following substances:

19 * 6 of a powder g of a copolymer of acrylonitrile and sodium methallyl sulfonate (0.600 milliequivalents / g sulfonate; grain size between 50 and 80 / Uj specific viscosity, measured at 25 ⁰ C in a solution of 2 g / l in dimethylformamide: 0.87);

a mixture of 165.4 cm dimethylformamide and 8.6 cnr water.

After cooling the solution to 0 ^° C., 8 g of a powder of a copolymer of acrylonitrile and 2-methyl-5-pyridine are brought

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(The 0.564 meq / g, tertiary amine groups) which is quaternized by an excess of Methyisulfat and after this quaternization a specific viscosity (measured at 25 ⁰ C in a solution of 2 g / l in dimethylformamide) of l, 6l and a grain size between 50 and 80 u. Can be the whole mixture is stirred at 0 ⁰ C for 1 hour, whereby the copolymer in powder form in the solution in a uniform V / else dispersed.

The temperature of the mixture is brought to 20 ^° C., stirred for 1 hour and the mixture is then left with constant stirring at 65 ^° C. for 5 hours. "You get a clear solution.

This solution is poured onto a glass plate so that a liquid film is formed mm with a thickness of 0.25, which is brought by immersing the whole in a Viasserbad of 20 ⁰ C for coagulation. After removing the solvent by washing with water, a membrane is obtained which can be used for ultrafiltration under a pressure of 2 bar with an aqueous 1 g of lysozyme per liter

(Molecular weight: 15,000) and

5.85 g NaCl / l containing solution is used, this solution being stirred on the surface of the membrane with the aid of a magnetic bar. A permeate with a throughput of 5 4θΟ l / day.m is obtained, the degree of retention of the lysozyme being greater than 90 % .

Example 2

A comminution mill, which is operated with the aid of a rotating knife, is charged with '-' ■

19.6 g of a powder of an acrylonitrile-methallylsulfonate copolymer, which is identical to that of example 1,

8.4 g of a powder of a quaternized copolymer which is identical to that of Example 1.

After achieving an intimate mixture of the two products (or after this is a homogeneous powder, i.e. a powder in which elements of the sulfonic acid polymer can be seen with the naked eye

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can not distinguish elements of ammonium polymers), one adds a mixture of dimethylformamide and 8.6 cm l6j5,4 cnr water at 0 ⁰ C. The whole is then stirred for 1 hour at 0 ^° C., 1 hour at 20 ^° C. and 3 hours at 65 ^° C. This gives a clear solution with a viscosity of 272 poise measured at 25 ^° C.

An ultrafiltration membrane is produced with this solution by proceeding as in Example 1. This membrane has a Flow rate in terms of pure V / water below 2 bar of 4 880 l /

ρ
Day.m.

Example 3

In a. Crushing mill, which is operated with a rotating knife, is brought in:

10 g of a powder of a copolymer of acrylonitrile and sodium methallyl sulfonate (0.570 milliequivalents / g sulfonate; grain size between 50 and 8o / U; specific viscosity measured at 25 ⁰ C to a solution of 2 g / l in dimethylformamide: 1.05);

10 g of a powder of a copolymer of acrylonitrile and 2-methyl-5-vinylpyridine (which contains 0.570 milliequivalents / g of tertiary amine groups), which is quaternized by an excess of methyl sulfate is and after this quaternization a specific viscosity of 1.591 ^ measured as above, and a grain size between

50 and 80 / U;
0.121 g LiCl.

As in Example 2, an intimate mixture is prepared and added

• 5
then at 0 ⁰ C 105 cm dimethylformamide to. The whole is then stirred for 1 hour at 20 ^° C. and 3 hours at 65 ^° C. This gives a clear solution with a viscosity of 445 poise measured at 25 ^° C. (equivalent to the viscosity of the reactive solutions obtained by mixing the individual solutions Polymer solution obtained under homologous conditions).

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Claims (1)

Claims 1.) Process for the production of a complex Polyelectrolytes based on a polymer with sulfonic acid groups (Sulfonic acid polymer) and a polymer with "quaternary ammonium groups (ammonium polymer), which are individually insoluble are in water, characterized in that one of these two reactive polymers is intimately in the form of a powder with the mixes other reactive polymers, the latter being in the form of a solution or in the form of a powder, with one then in this case brings the mixture of the two powders into solution. 2.) The method according to claim 1, characterized in that the complex polyelectrolytes of the category of those that are insoluble in water and soluble in an organic medium and of the general formula SO, (I) J ^- LrLO-TLTL correspond in the the symbol Ν ^{φ represents} a quaternary ammonium group; the symbol. ΛΑΛ / Ά represents a macromolecular chain containing groups that can be bonded to .SO- * ⁰ groups by covalent bonding; the symbol _jT_j ~ UT_n_TL. represents a macromolecular chain which contains groups which give rise ^{to the formation of groups Ν Φ} 509823/0887 can, where the chains A / V \ A / V \ and JTJTJTJTJT in combination considered not to include any antagonistic groups capable of causing the formation of covalent interchain bonds; the symbol 4 ^ - indicates that the groups Ν ^{Φ are} attached to the macromolecular chain represented by JTJTJTJTJL- through at least one covalent bond; the ratio "· is between 0.1 and 10; the nature of the macromolecular chains y \ / VAy \ / \ and JTJTrLTLTL representing groupings as well as the values of the symbols η and m are such that a polymer of the formula ΑΛΛΛΑ so ₃ ^e ι _M x φ (I _1. )
η (sulfonic acid polymer) in the M a proton or an alkali metal or an alkaline earth metal ion represents and χ is 1 or 2, and a polymer of the formula JTJTTLTLTl Ä 1 ± - A ^{y θ} (I ₂ )
(Ammonium polymer) in which A is a hydroxyl radical or the anion of an inorganic or organic acid of the formula AHy, in which y is 1, 2 or 3, means, in each case insoluble in water, but soluble in the same liquid organic medium. 3.) Method according to claim 2, characterized in that that the specific viscosity of each of the formulas 0.0 / f
Is # j4, and preferably between 0.05 and 1.5, measured at 25 ⁰ C in solutions with a concentration of 2 g / l in dimethylformamide - I and Io greater than; is. 509823/0887 -25 - k.) Process according to claim 2, characterized in that each of the polymers of the formulas (I ₁ ) and (I ₂ ) contains less than one hydrophilic group per 12 carbon atoms and preferably less than one hydrophilic group per 20 carbon atoms. 5.) The method according to claim 2, characterized in that the polymer of the formula (I ₁ ) is selected from the group consisting of the polymerization products of monomers, at least some of which consists of monomers with sulfonic acid groups, and the products consisting of Sulphonation of polymers obtained from monomers free of sulphonic acid groups and in that the polymer of formula (Ig) is chosen from the group represented by the products obtained by treating a polymer with tertiary amine groups with a quaternizing agent and the products obtained by reacting a tertiary amine with a polymer which contains substituents which can quaternize this amine, which precisely ensures its bond with this latter polymer. 6.) · Process according to claim 1, characterized in that the powders used have a grain size of less than 500 / U and preferably between 20 and 100 ai . 7.) · The method according to claim 1, characterized in that the solvent used to form the solution is a solvent of the final complex polyelectrolyte _? preferably an organic solvent which can consist of a single solvent or a mixture of solvents. . · " 8.) The method according to claim 1, characterized in that when a reactive polymer in the form of a powder is mixed with a solution of the other reactive polymer, the weight concentration of this solution with respect to this latter polymer is greater than 0.25 % and preferably greater than 0.5 % , the concentration being that in the final 509823/0887 Solution of dissolved polymer is preferably less than 50 % . 9 ·). A method according to claim 1, characterized in that when a mixture of the two powders of the reactive polymers is brought into solution, the weight concentration of the polymers dissolved in the final solution is greater than 0.5 $> and preferably between 1 % and 50 % amounts to. 10.) The method according to claim 1, characterized in that the preparation of the solutions by dispersing the powder or powders in the ^{liquid phase maintained at a temperature of -20 to 20 0} C and then progressively increasing the temperature to a range of 20 to 100 ⁰ C until a clear and homogeneous solution is achieved. 509823/0887