CA1090045A

CA1090045A - Amphoteric ion exchange resins

Info

Publication number: CA1090045A
Application number: CA256,215A
Authority: CA
Inventors: Keith O. Wade; Jerry H. Brown
Original assignee: ICI Australia Ltd; Diamond Shamrock Corp
Current assignee: Orica Ltd; Diamond Shamrock Corp
Priority date: 1975-07-01
Filing date: 1976-07-02
Publication date: 1980-11-18
Also published as: IN145110B; DE2629146A1; GB1501307A; FR2316265B1; IT1220912B; NL7607168A; FR2316265A1; US4139499A; MX3363E

Abstract

ABSTRACT

A process for making a thermally reversible amphoteric ion exchange resin suitable for use in the demineralization of water which process comprises dis-persing particles of an ion exchange resin comprising either weakly basic or weakly acidic ionogenic groups in a solution comprising one or more monomers containing an ionogenic group, or organic precursor thereof, of opposite acid-base character to the ionogenic groups of the ion exchange resin particles, a crosslinking agent comprising two or more vinylic or allylic groups, and a porogen;
secondly polymerizing the monomer to give a macroporous crosslinked polymer matrix; and thirdly treating the polymeric composition to convert any organic precursors to ionogenic groups to form an amphoteric ion exchange resin.

Description

- 2 -; This invention relates to thermally regenerable ion ; exchange resins.
: .
Thermally regenerable resins have a potentially im-portant application in water demineralization processes be-cause low-grade heat can be efficiently employed for re-:; ~
generati~n and certain of these resins are of use in the desalination of water.
Processes of ion exchange using thermally regenerable resins are described in the publications:
"An Ion Exchange Process with Thermal Regeneration"~
~- J. Inst. Engr. Aust. (1965) ~ 193 (Part l); Aust. J. Chem.
(1966) 1~ 561 (Part II)~ 589 (Part III)g 765 ~Part IV~ and 791 (Part V); Aust. J. Chem. (1968) 21, 2703 (Part VI);
Desalination (1970) 89 21 (Part VII3; Desalination (1973) 12, ~i 15 217 (Part VIII); Desalination (1973) 1~, 269 (Part IX);
Australian Patent Specification No 274,029.
- We have found a new method of manuPacturing amphoteric resins which leads to a new type of amphoteric resin having enhanced thermally regenerable ion exchange properties.
: ~ , Accordingly we provide a process of making an amphoteric polymeric composition which process comprises dispersing `~ particles of an ion exchange resin comprising either weakly basic or weakly acidic ionogenic groups in a solution com-., ~ , .
prising one or more monomers containing an ionogenic group, ~;~ 25 or organic precursor thereof, of opposite charge to the iono-. . .

. .
~,.,; ~
d~
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-, . . .
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,_ .
j - 3 -. ., ;~ ~enic groups of the ion exchange resin particle, wherein the - ion exchange resin particle and the monomer are not of i- opposite charge, and a crosslinking agent comprising two or more vinylic or allylic groups; secondly polymerizing the `~ 5 monomer to ~ive a macroporous crosslinked polymer matrix; and :, ~- thirdly treating the polymeric composition to con~ert any organic precursors to ionogenic groups to form an amphoteric ~`
~ polymeric composition.
. . .
;~; Suitable monomers for the incorporation vf particles , . , of a weakly basic ion exchange resin in a macroporous polymer ; matrix are acrylamide~ methacrylamide, acrylonitrile, the `'.'.
i~ lower alkyl esters of acrylic acid~ methacrylic acid, ethacrylic .~ .
~s acid, fumaric acid~ maleic acid, itaconic acidg glutaconic .: , ` acid, vinylacetic acid, allylacetic acid and mixtures thereof.
Preferred monomers for the incorporation of particles of a weakly basic ion exchange resin in a macroporous polymer -'~
`-~ matrix are acrylamide~ methacrylamide, acrylonitrile, the lower alkyl esters of acrylic acid, methacrylic acid and ethacrylic acid and mixtures thereof.
"'-"i Suitable monomers for the incorporation of particles -, :
: .
1~ of a weakly acidic ion exchange resin in a macroporous polymer ,:
matrix are ethenylbenzene, acrylonitrile, acrylamide, meth acrylamide and the lower alkyl asters of acrylic acid, meth-i acrylic acid~ ethacrylic acid and mixtures thereof.
Preferred monomer~ for the incorporation of particles of .:, ., .~

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.~ ,, ',''~, .. , ' ~
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, .
.~` a weakly acidic ion exchange resin in a macroporous pol.ymer ~ matrix are ethenylbenzene, acrylonitrile, acrylamide and : ~ -~ methacrylamide.
~ ~:
Throughout this specification and in the claims by ,.-.; ::.j ~ 5 lower alkyl we mean an alkyl group containing 1 to 6 carbon;.: .:
atoms.
The conditions necessary to give a macroporous polymer matrix are well known to those skilled in the art and usually comprise polymerization, in a suspension medium containing .- 10 a dispersing agent, of the required monomers including suit-. able crosslinking agents in a porogen which is normally an , ^~ inert solvent in which the monomer is soluble but in which , ~.~: the polymer is essentially insoluble and which is not soluble :: .:
~.. in the suspension medium.
~ -::. 15 Macroporous polymers are often termed macroreticular ~`- polymers when both macropores and matrix show continuous ~`. structure. These polymers possess a network of microscopic .:, ,., .
~: channels extending through the mass and~ while the micro-`J~
... ~. scopic channels are obviously very small, they are large in .. ~. 20 comparison with the pores in conventional homogeneous cross~
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linked gels, pores of the latter type not being visible in electron photomicrographs and, as is well known, not being ' true pores at all (vide Kunin, "Ion Exchange Resins" page 45, ~' ~ ' !.
` et. seq. John Wiley & Sons Inc. 1958). Macroreticular ` polymers in the dry state usually have surface areas greater ;~ than 1 m2/g, and often of the order of 10 m2/g or greater, ~` with pores whose average diameter is of the order of 20A or more.
It is conventional to proauce these macroreticular . . .
~' 10 polymers in bead form, usually in an overall particle size - of about 10 to 900 microns. Further information on the preparation and structure of macroreticular polymers, which are known materials, may be obtained by referring to British Patent Specification 932,125 and 932,126, U.S. Patent Nos.

3,275,548 and 3,357,158 and Australian Patent No. 450,143.
In the present invention in order to encapsulate the ion exchange resin particles into the macroporous matrix they are dispersed in a solvent suitable as a porogen for the polymerization and the dispersion is added to a solution :i.. :.
of a suitable monomer mixture and initiator. This mixture is then suspended in a suitable medium, preferably aqueous, using one or more suspension agents; the dispersion is : .:
~ maintained by stirring and the mixture polymerized.
: . .
The polymer particles to be encapsulated should be of less than 1/10 the diameter of the composite particles prepared in our process. Most pxeferably the polymer ; particles are in the size range from 0.1 to 5 microns and ..:
.. ..
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:~:

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:1~9~:30~ Cj ..... ;.
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,;~ the composite particles are in the size range from 250 to - ~
, 1000 microns.
`~ To facilitate dispersion of the ion exchange resin .
y~ particles in the monomer solution it is preferable that the particles be in a form compatible with the monomers. Weak base polymers will disperse more readily in organic monomers : in the free base form and weak acid polymers will disperse more readily when in the free acid form.
When, as is preferred, the macroporous polymer matrix is formed by suspension p~lymerization, the mixture of , ., ion exchange resin particles and monomers may be added to ~, the suspension medium which contains a dispersion or ~, . .
,;- suspension agent such as, in the case of an aqueous suspending .~".".~
~ medium, the ammonium salt of a styrene-maleic anydride :, copolymer, carboxymethyl cellulose, polyvinyl alcohol, bentonite or a magnesium silicate dispersion. When this , ; ~ medium is agitated the monomer phase disperses into fine . .
~ droplets containing the ion exchange resin particles. The ~
.~:. :. .
size of the droplets depends on a number of factors such as the amount of dispersion agent and the type and rates of .:: .
!:`'; agitation. Agitation is continued until polymerization is ~s; complete. The polymerized droplets, generally termed "beads", ~, .................................................................... .
~: are then separated from the suspension medium and further , .: .
~: processed if desired.

A suspension polymerization process generally . . ." ~ .
'~i, involves the use of aqueous suspension media.
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When employing water-soluble monomers, however, it ` is not possible to use aqueous suspension media unless the solubility of the monomers is such that they can be salted -: -out. If it is not possible to salt out the monomers, thenliquids in which the monomers are insoluble must be employed as suspension media. Such liquids must be chemically inert in the sense that they do not interfere with the polymerization reaction. Aliphatic hydrocarbons are typical of such media.
Suitable porogens are solvents in which the monomer is :
- 10 soluble but in which the polymer is essentially insoluble ~` and which are essentially insoluble in the suspension media.
. ~ .
-` It is well known that atmospheric oxygen acts as an inhibitor of free radical polymerizations. Preferably, therefore, the polymerization is carried out in the absence ::
j`~ of atmospheric oxygen.
. ,.
` Suitable catalysts which provide free radicals ~` which function as reaction initiators include benzoyl peroxide, ` hydroperoxide, tert-butyl hydroperoxide, cumene hydroperoxide, tetralin peroxide, acetyl peroxide, lauroyl peroxide, .'';
caproyl peroxide, tert-butyl perbenzoate, tert-butyl diperph-thalate and methyl ethyl ketone peroxide.
The amount of peroxidic catalyst required is roughly - proportional to the concentration of the mixture of monomers.
: .
- The usual range is 0.01~ to 3% of catalyst with reference to the weight of the monomer mixture. The preferred range is from . -.

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0.2~ to 1.5~. The optimum amount of catalyst is determined in larse part by the nature of the particular monomers .~:
selected, including the nature of the impurities which ~lay ` accompany said monomers.
Another suitable class of free radical generating . ~, .. .
compounds are the azo catalysts. There may be used, for ;
example, azodiisobutyronitrile, azodiisobutyramide, azobis-(~ ~-dimethylvaleronitrile~, azobis ~ methylbutyronitrile), ` dimethyl, diethyl~ or dibutyl azobis(methylvalerate). These and other similar azo compounds serve as free radical ~;~ - initiators. They contain an -N=N- group attached to aliphatic carbon atoms~ at least one of which is tertiary. An amount of .` 0.01% to 2% of the weight of monomer or monomers is usually sufficient.
Another method of effecting copolymerization is by f~ subjecting the reaction mixture to ultraviolet light in the , .
presence of suitable catalysts at ambicnt or slightly clevate~
temperatures. Such catalysts include benzoin and a~oiso .. .. .
butyronitrile.
Methods o~ forming-the polymer particles for en---~ capsulation will be obvious to those skilled in the art.
Typical methods of suspension polymerization are for example described i~ ~etherland$ Patent Application No.74/07771 and ' ;j '! ' :j U.S. Patent No 3,716,481. The polymer particles to be en-capsulated may also be prepared by crushing larger particles ~'' . .
:, .
, , .
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., ,. :~ . ., "; -, :`

.
formed for example by bulk polymerization.
~ The nature of the weakly basic ion exchange P resin required in thermally regenerable ion exchange resins - is discussed in the publications mentioned hereinbefore and .-in U.S. Patent 3,645,922.
In general any resin comprising unquaternized ` amino groups is suitable. Typical weakly basic ion exchange - resins suitable for use in thermally regenerable ion exchange - resins are crosslinked poly(vinylbenzyldialkylamine), and copolymers derived from N-alkylethyleneimines or N-substituted ,~ aminoalkyl acrylates or methacrylates with suitable crosslinking agents.
- Preferably the basic resin is a polymer or a ....-, copolymer formed from a major proportion of an allylamine monomer.
The nature of the allylamine used to prepare the - particles of polymer or copolymer used in the process of our invention is not narrowly critical and the compositions of our invention may be prepared using any amine or mixture of .
~ 20 amines having one or more allyl substituents. Suitable ,,::
allylamines include, for example, allylamine, diallylamine, triallylamine and alkyldiallylamines. Other suitable ` allylamines include compounds of the general formula II
, . :

: R7~ R3 / II

R :

..,; ,,:

, -. _ g _ `.' ,`.'` .

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:.'' '~

':
. .
.. : . .. - . .

r~ s .` wherein R and R are allyl groups; R , R , R , R , R , R
and R9 separately, is a hydrogen or halogen atom or an alkyl, substituted alkyl, aryl, substituted aryl, nitro, dialkylamine alkyl or :".' R
: -CH2 - N group .~ ~ 2 . R

except that not more than two of R3j R , R , R6 and R7 may 'j~. be the group .: / R
.~- 2 ~
and except that not more than four of R , R , R , R and R
.: may be hydrogen.
:
`.:. 10 Preferably the olefinically unsaturated group is :; .
. allyl. A preferred class of compounds of gneral formula II
., as defined hereinbefore consists of compounds of general . . .
.,: .~ ~ .
~- formula III: -.
.,.
: Y
,..

& N C~2 -~: /
.. V
. : :
.:
- 10 ~ . :
.f~' .
~" .
_, :~.r' ,; :
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7, ' ~ , :',, ;, , ' ."` , : ~
~ wherein RS, R7 and R9 are as defined hereinabove and U, V, :, ; W, X, Y and Z are allyl. A further preferred class of com-pounds of general formula II as defined hereinbefore consists . :.
of compounds of general formula IV.

N - CH~ ~ CH2 ~ N IV

wherein R5, R6, R8 and R9 are as defined hereinabove and W, :
X, Y and Z are allyl.
; Other suitable allylamines include, for example, amines ~ of the general formula V:
, :~, Allyl Allyl '`,~'''' \ /
. 10 N - A - N V
- AllyI Allyl ~`/ where A is an alkylene group containing 2 to 8, preferably 5 to 7 inclusive carbon atoms, for example~ l,6-~is (N,N-. . .
~` diallylamino) hexane.
,.. .
; Preferred allylamines for use in the preparation ;~: 15 thermally regenerable ion c~change resins include, for example:
~ triallylamine, methyldiallylamine, ethyldiallylamine, l,4-bis ,.~.;
~; (N,N-diallylaminomethyl) benzene, 2~4,6-tris(~,N-diallylamino :.~ mcthyl) toluene, 1,2,4~tris(N~N-diallylaminomethyl) ben~ene, j 1,6~bis(N,N-diallylamino) hexane, n-propyl diallylamine, , . ~
,- .i : :, :';~. .

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,.................................... . .
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~ 12 _ :
benzyl diallylamine.
:
~',!,~ It will be understood by those skilled in the art that~
in order to polymerize the allylamines they must normally be ~ present as salts. Hence all references in this specification m~ 5 to the polymerization of allylamines~ even when not specifically ~ described as satls, are to the amines in their polymerizable -`~ form.
-~` Suitable salts are the salts of allylamines with strong acids such as, for example, hydrochloric ~ sulphuric, nitric ,- 10 or phosphoric acid. Generally speaking~ the pH, temperature .....
- and other conditions associated with the polymerization ...
:- process may be those known in the art for the polymerization o~
. ~~
;, the appropriate monomers concerned.
Additional crosslinkers may be added to the polymerization ~; 15 system and to obtain adequate crosslinking it is necessary to :'~ add a crosslinking agent when amines containing only two or less allyl groups are used. Suitable crosslinking agents are well known in the art and include for example, e-thylene glycol dimethacrylate, 1~3-butylene glycol dimethacrylate~
divinylbenzene~ triallyl cyanurate~ the triallyl ether of ` pentaerythritol and bis-diallylamines such as N,N,N',NI-L' .......................................................................... .
tetraallyl-1,6-diaminohexane.
. .
Preferably the crosslinking agent is a salt of triallyl-'L;'~, amine or of a bis(diallylamino)alkane wherein the chain con-~ 25 tains from 2 to 8 carbon atoms.

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,,,' ' ' .. ', , .'~, ~ ,.
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)9~)045 . - 13 -. ".
The amount of crosslinking agent requirecl to ~ive a bead suitable for use in thermally re~enerable ion exchange is "', discussed in U.S. Patent No 3,645,922. The concentration of -- the reaction mixture to some extent controls the amount of ; 5 crosslinking occurring during the reaction.
,. The nature of the weak acid ion exchange resin particles used for encapsulation by the process of the present invention is not narrowly critical. Small particles of crosslinked polymer with weakly acidic functional groups or derivatives thereof may be prepared using suitable derivatives of ethylenic-ally unsaturated carboxylic acids such as the lower alkyl esters ~ :~
of acrylic acid, methacrylic acid, fumaric acid, maleic acid and glutaconic acid.
Suitable crosslinking agents are compounds with more ,. . :
~ 15 than one ethylenically unsaturated group and include divinyl-;~ benzene, divinylpyridine~ divinyltoluenes, divinylnaphthalenes, ~ diallyl phthalate, ethylene glycol diacrylate, ethylene .~ ~
glycol dimethacrylate, divinylxylene, divinylethylbenzene, i divinylsulfone, divinylketone, divinylsulfide, allyl acrylate, .i~ 20 diallyl maleate, diallyl fumarate, diallyl succinate, diallyl ~;- carbonate, diallyl malonate, diallyl oxalate, diallyl adipate, - diallyl sebacate, divinyl sebacate, diallyl tartrate, diallyl , ` silicate, triallyl tricarballylate, triallyl aconitate, . . .
triallyl citrate~ triallyl phosphate, N,NI~methylenedi-~- 25 acrylamicle~ NsNt, methylenedimethacrylamide~ N~NI-ethylenedi-.~ .
; acrylamide, trivinylbenzene, trivinylnaphthalene, poly- ~

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'.';" '~' " ' ' " " ' ' ' , ' ' , ' , ' ' ' ' ' ' ' '.' ' ' ,, ' '. ' ' . ' '' ;
;~,.','.. ' ' ' ' ,' ' ' ''' ' ", ~'`''' ' ' , ' ' '"" ' ' ' , ': ': . ' , ' ' .

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`.,.
.;.`.
-vinylanthrlcenes and the polyallyl and l)olyvinyl ctllers of glycol, glycerol, pentaery-thritol, resorcinol and the monothio or dithio derivatives of glycols.
:: .
~; The macroporous polymer matrix obtained from the -~ 5 polymerization reaction by the process of the present in-vention is treated to convert the functional groups of the ~-~ matrix to functional ion exchange groups to form an amphoteric i~ .
~,. polymeric composition comprising free carboxyl groups and free ` amine groups. Any proçedure known in the art may be employed ~.~, ....
which is capable of converting the blocking group to an ion ex-change site, but is not capable of destroying the polymer chain.
When a weak base ion exchange resin is encapsulated in a polymer matrix produced from unsaturated carboxylic acid derivative precursors, most such matrices may be converted to a weak acid electrolyte by hydrolysis. Thus for example when an ester,amide, imide, nitrile or acid anhydride is used .;
as the precursor, it may be hydrolysed by treatment of the ;. polymeric composition with aqueous solutions of acid or ~`- alkali. We prefer where possible to treat such a polymeric resin with hot aqueous caustic soda solution for several hours.

This alkali treatment will also convert precursors formed from tertiary amines and chlorinated carboxylic acids to the ,~,:;.. ,: .
~- original tertiary amino form.

Methods for the conversion of a polymer matrix encapsu-~;` 25 lating a weak acid ion exchange resin to a weakly basic ., .. , ~ ~ .
, "

:,, J

";
.. ~...
',''.'- ' .

,.. .~ . .
, . . . ~ .

"",, ,~ 0 ,.
electrolyte are also well known to those skilled in the art.
~ For example, catalytic recluction of nitriles and amides with :', hydrogen, reduction of carboxylic acids and esters followed by :
esterification, and chloromethylation of aromatic groups :. .
followed by amination.
Polymeric compositions having appreciable thermally - regenerable ion exchange capacity have a molar ratio of aminegroups to acid groups in the range from 10:90 to 90:10 and preferably from 20:80 to 60:40.
It is preferable to subject the product resin to a pH
equilibration treatment to achieve the optimum ion-exchange performance. Normally, this simply involves stirring the resin -'- in an aqueous salt solution at room temperature (ca. 20C) and ,~, adding hydrochloric acid until the desired pH le~el is obtained, care being taken to ensure that the final equilibrium salt ;~ concentration is at the required level. The salt concentration employed is that of the water to be treated by the desalination ; process. The rcsin is now suitable for use in column operation ~ of a thermally regenerable process, as described in Australian : - .
~ 20 Patent No 274,029. For purposes of evaluation, however, the , . . .
.~ resin may be washed with hot water at ca. 80C to ob-tain it in a regenerated form, and the amount of salt taken up by stirring the regenerated resin in salt solution at room temperature used as a measure of the effectire capacity of ~ 25 the system. The time necessary to achieve salt uptake '"~ :
, . -:
.~'''':.~

.: "
. .

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:: : . , ' . . :
.. . . .
.....

)o~
, - ~6 -., .
equivalent to 50~ of the equilibrium level (the ~half time~) may be used as a convenient measure of the rate of salt ;` . .
r;: adsorption.
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The invention is now illustrated by, but by no means limited to, the following examples:

-;
EXAMPLE I
.
Macroporous AcrYlic Acid/TAA Resin , Polytriallylamine resin consisting of beads of ~`` between 0.5 and 1 microns diameter were washed with 10%
, ;
sodium hydroxide solution to convert it to the free base form. The resin was then washed with water, ethanol, acetone ~twice) and hexane (four times), removing the supernatant liquid at each wash by centrifuging, The solid polytriallylamine (34 g, 137 meq) was then suspended in 100 mls of isooctane and this was added to a solution of ethyl acrylate (38.2 g : 380 meq), ~ . .
~- divinylben~ene (6.0 g) and azo-bis-isobutyronitrile (0.5 g).

~,' The above mixture was suspended in an aqueous ; medium by stirring with a paddle stirrer using a mixture ;~ of suspension agents (water (200 ml), methylcellulose , (0,4 g), polyvinyl alcohol (0.4 g)). Stirring was main-: . ~
'~ 20 tained at just sufficient speed to fully disperse all of , the organic phase in the aqueous phase.

. . ~ .
This suspension was heated by immersing the :':.
s~ vessel in a constant temperature oil bath at 83C

maintaining the reaction temperature at bewteen 75-80C

-- for 21 hours.

'` Reaction allowed to cool and solid collected ,~', on a sieve, washed with ethanol.
: .., . . . .

-;:
., .

, ,; .
,`~
. . ~
.,;;~ .
.,..I
. -.: . ~ , ~ :
~ .. .
: ., ,:

`:

: ? ~ S
~ Hydrolysis :
Above solid placed in round bottom vessel with 200 ml of 20~ sodium hydroxide solution. The mixture was gently ~;:
~`~ stirred and heated at 80C for 21 hours.
~; The reaction mixture was allowed to cool and the white solid collected on a sieve and washed well with water.
The resin was treated by the method described in USP 3,808,158 except that the equilibrium pH was 6.8. The ~, ion exchange properties of the product resin are reported in Example 7.

This example describes the preparation of poly-~- triallylamine granules.
-~~ A mixture of 6.2 g of a 70% triallylamine hydrochloride ~ solution in water, 0.28 g of a 30~ hydrogen peroxide solution .. -, .
;~ and 0.036 g of a 15% ferric chloride solution was sealed in a 25 ml flask under nitrogen and heated at 50C for 4 hours, by which time the mixture had polymerized to a firm gel.
The gel transferred to a blender and macerated with lM hydrochloric acid solution. The solid cake obtained by filtration of the slurry was thoroughly washed with lM
hydrochloric acid followed by prolonged washing with lM
',~ sodium hydroxide solution until no more chloride ion could be ,......
fs: leached from the resin. The resin was finally rinsed free ;;; from sodium hydroxide with water and dried.

!.~,,,.;' :
:~, ~, ~ - 18 -.:

., ,.'.,:
. .
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., ',' ': : ' ~ .
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~:`

he particles were ground to the size range ; 0.3-5 micron diameter.
;; The polymer was obtained in 60~ yield with an anionic ion exchange capacity of 6.4 meq/g and a swelling ratio (ratio of wet volume: dry volume) of 2.2. The pH titration produced a flat curve with a pH of half neutralisation of `
7.9. The change in pH ( pH) from 10~ neutralisation to 60 neutralisati~n was 0.3.

: .
`- 10 A sample of the polytriallylamine granules prepared in Example 2 was converted to the free base form and then -~ suspended in n-butanol by a series of washings in water, -~ ethanol and acetone.
Encapsulation was carried out by a suspension polymerization process. A slurry of polytriallylamine .....
; (11.7 g) in n-butanol (25 ml) was suspended in a solution ofethyl acrylate (20.75 ml; 19.0 g), divinylbenzene (6.6ml; 6.0 g) crosslinking agent, and azobisisobutyronitrile (0.5 g) initiator. This mixture was then suspended in an aqueous phase comprising polyvinylalcohol (1.6 g) in water t200 ml).
.~, ;; The suspension was maintained by stirring with a teflon paddle (semicircular, 6.5 x 2.5 cm) initially at 200 rpm and after 15 minutes at 150 rpm.
Polymerization was effected by heating this suspension :
at 75-80C for 21 hours.
`,:
t.'.' ,.~.
... . .
'' '. ' -- 1 9 ~. .
,''.~'' ' ' .' ' . .
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" .'.
, . . .
.
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' ` ' 9~ S
; ;~
,~..
The product was subjected to a hydrolysis step in 20% NaOH solution at 75-80 C for 21 hours to convert the ,r ethylacrylate ester groups to the functional acid groups.
~-~. The product (29.2 g, 86%) consisted of white ~;~
~; spherical beads mostly between 0.5 and 1 mm in diameter.
No product passed through a British Standard Sieve Size 52 #
(screen opening 0.295 mm), but some spheres appeared to be ~' larger than 1 mm. The beads were of moderate hardness.
The ion exchange properties of the resin are reported in Example 7.
The ~esin water uptake was measured in the Na , free ; ~, .
base form of the resin and, expressed as weight of water :
absorbed as a percentage of total wet weight, was 70~.

. :
Example 3 was repeated exactly except that the ~i 11.7 g of polytriallylamine was replaced with 18.2 g of "Diaion" WA30 (Registered Trade Mark for poly ~,N-dimethyl-N
(4-ethenylphenylmethyl)amine~ ion exchange resin) crushed and sieved to the size range 0.5 to 5 micron diameter.
~,,;:..;,, The ion exchange properties of the resin are reported in Example 7.
~- The resin water uptake as defined in Example 3, ~ was 70%.
;` ':
,~- EXAMPLE 5 :., ~ Example 3 was repeated exactly except that the 11.7 g i~;`' , ,.^~'r .""'""
~;.~ .

.., , ~ . ,.

., ; ~, .
, ~
: :::, ,..~,, ,:

.:.
, .

, .: .

:1 ~)9~
` , :
.~ of polytriallylamine was replaced with 20.3 g of poly-(benzyldiallylamine) crosslinked with 30% N,N,N',N'- tetra-, .~, _ _ _ _ allylhexmethylenediamine crushed and sieved to the size ~ range 0.5 to 5 micron diameter.
The ion exchange prope:rties of the resin are ~ reported in Example 7. The resin water uptake, as defined - in Example 3, was 70%.

~ Example 3 was repeated exactly except that the ; lO 11.7 g of polytriallylamine was replaced with 18.0 g of poly(methyl-diallylamine) crosslinked with 30~ N,N,N',N'-tetra-. allylhexamethylenediamine crushed and sieved to the size . range 0.5 to 5 microns diameter.
The ion exchange properites of the resin are reported .- in Example 7. The resin water uptake, as defined in Example 3, was 70%.
~-: EXAMPLE 7 ~: :
~ The ion exchange properties:of the resins prepared . .; .
.~: in Examples 1, 3, 4, 5 and 6 were measured by the methods . described in U.S. Patent No. 3,808,158 and are shown in ... . .
~ 20 Table l.
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,.,,j'::, Ul Ul ~I CO W ~n 1'- r~ ~
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o o o o o 3 u~ C~
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~ ~rb ~ P~
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, ' :` - ' .

Claims

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. A process of making a thermally reversible amphoteric ion-exchange resin which process comprises:
A. dispersing in a suitable suspension medium a mixture of: either weakly basic or weakly acidic ion-exchange resin particles of particle size in the range from 0.1 to 5 microns; one or more monomers containing either weakly acidic or weakly basic ionogenic groups !
or organic precursors thereof, wherein the ionogenic groups of said monomers are of opposite acid-base character to said ion exchange resin particles; a crosslinking agent comprising two or more vinylic or allylic groups; and a porogen which is an inert solvent in which the monomer is soluble but in which the poly-mer is essentially insoluable and which is not soluble in the suspension medium;
B. polymerizing the monomers to give beads of particle size about 250 to 1000 microns comprising particles of the ion exchange resin in a macroporous crosslinked polymer matrix; and C. treating the polymeric composition from B to convert any organic precursors to ionogenic groups to form an amphoteric polymeric composition wherein the molar ratio of basic ionogenic groups to acidic ionogenic groups is in the range from 10:90 to 90:10.

2. A process according to claim 1 wherein the ion exchange resin particles are weakly basic ion exchange resin particles chosen from crosslinked polymers of allylamine, diallylamine, triallylamine, N-lower alkyl or N-benzyl-N,N-diallylamine, 1,4-bis(N,N-diallylaminomethyl)-benzene, 2,4,6-tris(N,N-diallylaminomethyl)toluene, 1,2,4-tris(N,N-diallylaminomethyl)benzene, 1,6-bis(N,N-diallyl-amino)hexane, N,N-di(lower alkyl)-N-(ethyenylphenylmethyl)-amine and mixtures thereof and crosslinked polymers derived from N-(lower alkyl)ethyleneimines and the N,N-di(lower alkyl)aminoethyl and N,N-di(lower alkyl)aminomethyl esters of acrylic and methacrylic acid; the monomer is chosen from acrylamide, methacrylamide, acrylonitrile, the lower alkyl esters of acrylic acid, methacrylic acid, ethacrylic acid, fumaric acid, maleic acid, itaconic acid, glutaconic acid, vinylacetic acid, allylacetic acid and mixtures thereof;
and wherein lower alkyl means an alkyl group containing from 1 to 6 carbon atoms.

3. A process according to claim 1 wherein the ion exchange resin particles are weakly acidic ion exchange resin particles chosen from crosslinked polymers of acrylic acid, methacrylic acid, ethacrylic acid, fumaric acid, maleic acid, glutaconic acid, itaconic acid, vinylacetic acid, allylacetic acid and mixtures thereof; and the monomer is chosen from ethenylbenzene, acrylonitrile, acrylamide, methacrylamide, the lower alkyl esters of acrylic acid, methacrylic acid, ethacrylic acid and mixtures thereof; and wherein lower alkyl means an alkyl group con-taining from 1 to 6 carbon atoms.

4. A process according to claim 2 wherein the weakly basic ion exchange resin particles are chosen from polymers of triallylamine, crosslinked N,N-di(lower alkyl)-N-(4-ethenylphenylmethyl)amine, N-benzyl-N,N-diallylamine cross-linked with 1,6-bis(N,N-diallylamino)hexane, and N-(lower alkyl)-N,N-diallylamine crosslinked with 1,6-bis(N,N-diallylamino)hexane; and the monomer is chosen from acryl-amide, methacrylamide, acrylonitrile, the lower alkyl esters of acrylic acid, methacrylic acid, ethacrylic acid and mixtures thereof.

5. A process according to claim 1 wherein the molar ratio of basic ionogenic groups to acidic ionogenic groups is in the range from 20:80 to 60:40.

6. An amphoteric resin prepared according to claim 1.

7. An amphoteric resin prepared according to claim 2.

8. An amphoteric resin prepared according to claim 3.

9. An amphoteric resin prepared according to claim 4.

10. An amphteric resin prepared according to claim 5.