CA1074477A - Dispersions of water soluble polymers in oil - Google Patents
Dispersions of water soluble polymers in oilInfo
- Publication number
- CA1074477A CA1074477A CA217,213A CA217213A CA1074477A CA 1074477 A CA1074477 A CA 1074477A CA 217213 A CA217213 A CA 217213A CA 1074477 A CA1074477 A CA 1074477A
- Authority
- CA
- Canada
- Prior art keywords
- water
- polymer
- oil
- dispersed
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/09—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
- C08G73/0206—Polyalkylene(poly)amines
- C08G73/0213—Preparatory process
- C08G73/022—Preparatory process from polyamines and epihalohydrins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2300/00—Characterised by the use of unspecified polymers
- C08J2300/14—Water soluble or water swellable polymers, e.g. aqueous gels
Abstract
ABSTRACT OF THE DISCLOSURE
Water soluble polymers dispersed in a water-in-oil emulsion are treated to reduce the water content thereof to provide a polymer dispersed in oil which is stable to coagulation or agglomeration during subsequent treatment. The composition can be chemically modified and/or made self dissolving in water by addition of surfac-tant without polymer agglomeration.
Water soluble polymers dispersed in a water-in-oil emulsion are treated to reduce the water content thereof to provide a polymer dispersed in oil which is stable to coagulation or agglomeration during subsequent treatment. The composition can be chemically modified and/or made self dissolving in water by addition of surfac-tant without polymer agglomeration.
Description
4'~'7 DISPERSIONS OF WATER SOLUBLE POLYMERS
i This invention relates to finely divided water soluble po.lymers dispersed in oils. More particularly, the present invention relates to stabiliz`ation of water in oil emulsions having finely divided polymer ~i dispersed therein and to subsequent treatrnent thereof and uses there-for. The invention further relates to the production of water so.luble condensation po.lyrners. ~ :
- Water in oil emulsions having finely divided water so.luble poly- :
rners dispersed therein are known in the art. The primary disadvan-.~ tage of such emulsions is that attempts to further treat such emulsiorE
: 10 generally result in coagulation or agglomeration of the po.lymer whereby the po.lymer does not remain finely divided and dispersed in ~ .
~ .
. the emulsion.
Ttlus, for example, attempts to add surfactants to such emul- .
. 8ions to render the emulsions self dissolvlng.or inverting, whereby ; 1~ the po.lymer can be dispersed in aqueous so:lutions, have generally ~ ~ .
not been successful as a result of coagulation or agglomeration of . ~ th~ po.lymer. As a result, in general, such emulsions are inverted ,`, . ..
, : into water by separate.ly adding the surfactant and emulsion to the . ~:
~ : water, which necessitates separate shipping and har~dling of two .1 20 products. ~-:
..
In U.S. Patent Nos. 3,6Z~,019 and 3,734,873, it is indicated 1 that Lt is possible, in some cases, to prepare a self inverting water- ~
in-oil emulsion having fine.ly dLvided po.lymer and surfactant dispersed : ~
therein; however~ such patents indicate that there are severe limi- ~ -tations in that the addition of the surfactants may tend to interact ' ' , ' . :
i This invention relates to finely divided water soluble po.lymers dispersed in oils. More particularly, the present invention relates to stabiliz`ation of water in oil emulsions having finely divided polymer ~i dispersed therein and to subsequent treatrnent thereof and uses there-for. The invention further relates to the production of water so.luble condensation po.lyrners. ~ :
- Water in oil emulsions having finely divided water so.luble poly- :
rners dispersed therein are known in the art. The primary disadvan-.~ tage of such emulsions is that attempts to further treat such emulsiorE
: 10 generally result in coagulation or agglomeration of the po.lymer whereby the po.lymer does not remain finely divided and dispersed in ~ .
~ .
. the emulsion.
Ttlus, for example, attempts to add surfactants to such emul- .
. 8ions to render the emulsions self dissolvlng.or inverting, whereby ; 1~ the po.lymer can be dispersed in aqueous so:lutions, have generally ~ ~ .
not been successful as a result of coagulation or agglomeration of . ~ th~ po.lymer. As a result, in general, such emulsions are inverted ,`, . ..
, : into water by separate.ly adding the surfactant and emulsion to the . ~:
~ : water, which necessitates separate shipping and har~dling of two .1 20 products. ~-:
..
In U.S. Patent Nos. 3,6Z~,019 and 3,734,873, it is indicated 1 that Lt is possible, in some cases, to prepare a self inverting water- ~
in-oil emulsion having fine.ly dLvided po.lymer and surfactant dispersed : ~
therein; however~ such patents indicate that there are severe limi- ~ -tations in that the addition of the surfactants may tend to interact ' ' , ' . :
2 ~
., ' ' ' .
, . . .
,~ .
.
.:
~ 7g~77 with the eEir~ulsifier or emu.lsion and destroy it prior to use thereof.
Acc~rdingly, there is a need for water solub.le polymers dis-persed ir} a~il, which are more stab.le.
It is further known in the art to chemical.ly modify various , 5 po.lymer~ such as for example, acry.lamide po.lymers by hydrolysis, aminomethylation, etc. Numerous difficulties have been encountered, in effectir~g such modifications, in particular modification of po.lymers having high mo.lecular weights, as a result of the viscous nature thereof ,'~uch problems, includeJ pumping problems, problems in . 10 uniform mixing of reagents to produce uniform reaction; prob.lems in transmitting heat without local overheating, etc.
. According.ly, there is a need for improved means of chemical.ly : - modifying ~arious poly-mers.
It Es also known in the art to produce condensation polymers; ~ .
hc,wever, in order to mitigate the problems associated with the viscous n~}ure of the reaction mixture, it is necessary to effect such : : ~ ~ po.Lymerizations at low Pobrner concentrations. In addition, in some c~ses, it may be necessary to .limit the molecular weight of the . p~lymer~
. : : ~
. 20 :. Accc~rdingly, there is a need for improvements in the technique . : -. .
for producing water so.luble condensation po.lymers .
. ~ a~cordance with one aspect of the present invention, there 1~ is provided an oi.l having finely divided water so.lub.le pobmer , ~ ~ dispersed therein in which the water content thereof is such that the a5 po.lymer remains fine.ly divided and dispersed in the oil when subjec~d to subsec~ent treatment.
., ' ' ' .
, . . .
,~ .
.
.:
~ 7g~77 with the eEir~ulsifier or emu.lsion and destroy it prior to use thereof.
Acc~rdingly, there is a need for water solub.le polymers dis-persed ir} a~il, which are more stab.le.
It is further known in the art to chemical.ly modify various , 5 po.lymer~ such as for example, acry.lamide po.lymers by hydrolysis, aminomethylation, etc. Numerous difficulties have been encountered, in effectir~g such modifications, in particular modification of po.lymers having high mo.lecular weights, as a result of the viscous nature thereof ,'~uch problems, includeJ pumping problems, problems in . 10 uniform mixing of reagents to produce uniform reaction; prob.lems in transmitting heat without local overheating, etc.
. According.ly, there is a need for improved means of chemical.ly : - modifying ~arious poly-mers.
It Es also known in the art to produce condensation polymers; ~ .
hc,wever, in order to mitigate the problems associated with the viscous n~}ure of the reaction mixture, it is necessary to effect such : : ~ ~ po.Lymerizations at low Pobrner concentrations. In addition, in some c~ses, it may be necessary to .limit the molecular weight of the . p~lymer~
. : : ~
. 20 :. Accc~rdingly, there is a need for improvements in the technique . : -. .
for producing water so.luble condensation po.lymers .
. ~ a~cordance with one aspect of the present invention, there 1~ is provided an oi.l having finely divided water so.lub.le pobmer , ~ ~ dispersed therein in which the water content thereof is such that the a5 po.lymer remains fine.ly divided and dispersed in the oil when subjec~d to subsec~ent treatment.
-3- :
, . ... . . . . . .. . : ~ . . . .
~.~37~7'7 In accordance with still another aspect of the present invention, there i5 provided a self-inverting or dissolving composition of finely divid~d polymer and surfactant dispersed in oil in which the water content of the composition is at a value at which the polymer remains finely divided and dispersed in the oil.
In accordance with yet a further aspect of the present invention a self inverting composition of finely divided water soluble polymer dispersed in oil is produced by providing a water in oil emulsion having inely divided water soluble polymer dispersed therein, reducing the water content of the emulsion to a value at which the polymer remains finely divided and dispersed in the oil upon addition of a surfactant, followed by addition of a surfactant to render the composition self inverting.
In yet another aspect of the present invention, a water soluble polymer is chemically modified by forming a water in oil emulsion having finely divided water soluble polymer dispersed therein, reducing the water content of the emulsion to a value at which the polymer remains finely divided and dispersed in the oll during the chemical modification and chemically modifying the polymer.
In still a further aspect of the present invention, a water soluble condensation polymer i5 produced by effecting condensation polymerization of monomers in a water in oil emulsion~
In yet another aspect of the present invention, an acrylamide polymer is neutralized by the use of ammonia. ~ -Thus, in accordance with the present teachings, a self-water dissolving composition of a water soluble -polymer dispersed in oil which is stable to polymer coagulation and agglomeration is provided. The wat~r soluble polymer is C ~ ~4~
., : ,. . .. ,. ... :.
~7~77 selected from the group consisting of ethylenically unsaturated addition pol~mer and polyamines dispersed in oil. The polymers have a wa_er content at which the polymer remains finely divided and dispersed in oil with the wa~er content being less than 40~ by weight based on the polymer and water. The water soluble polymer which is dispersed in oil has been prepared from a water-in-oil emulsion of the water soluble polymer by reduction of the water content. An effective amount of surfactant is provided to render the water soluble polymer self dissolving in wa~er.
In accordance with a further embodiment, a process is provided for producing a self-water dissolving composition of a water soluble polymer dispersed in oil which is stable to polymer coagulation and agglomeration. The process includes reducing tle water content of a water-in-oil emulsion which has a finely c vided water soluble polymer selected from the group consistinc of ethylenically unsaturated addition palymers and polyamines dispersed therein. The emulsion contains from 50 to 95~ by weight of water, based on the polymer and water, with the water content being reduced to a water content which is less than 40~ by weight based on the polymer and water, at which the polymer remains finely divided and dispersed in the oil. ~ surfactant is added in an amount effective to render the water soluble polymer self-dissolving in water.
The polymers used in the present invention are any one of the wide variety of water soluble vinyl addition polymers or water : ' : , ~-:'' -4a-.. . . . . ...
.
:, : :
7~77 .. :
~i .. .
~o.luble c~ndensation po.lymers. The term "water soluble" means that the poLymer is so.luble in water in an arnount of at .least l~lc, by weight, Water so.luble vinyl addition po.lymers are we.ll known in the art, and such po.lymers are preferab.ly used in producing the se.lf inverting compositions in accordance with the present invention. The most preferred vinyl addition polymers are po.lymers (the term poly- ~;
mer as used herein refers to both homopolymers and copolymers containing two or more monomeric units) of acrylamide, such as po.lyacrylamide and copolymers of acrylamide with acrylic acid or salts thereof which contain from 5 to 95 weight percent of acrylamide.
~ .
Also suitable are copolymers of acrylamide with maleic anhydride, ~.
: . vinyl benzene, acrylonitrile, styrene, methacry.lamide, etc.
As representative examples of other suitable water so.luble . 1~ - vinyl addition polymers, there may be mentioned water so.lub.le poly- -mers of acrylic acid, vinyl pyridines, vinyl benzyl dimethyl ammon-: .
ium chloride, methacry.lamide, sul:Eonates of acrylic esters, such . ~ ~ ~ as, 2-su.lfoethyl acrylatie, styrene sulfonates, quaternary or amino . ~ substituted acrylic and rnethacryllc esters, such as 2 aminoethyl : ~ ~ .
methacrylate, and the like.
As representative examples of water so.lub.le condensation : ~
. i ~ ~ po.lymers which are useful In preparing the emulsions of the present . .- .
invention ar which can be prepared by the emulsion technique of the present invention, there may be mentioned, the polyamines, produced ..
25 ~ by condensation of difunctional amine with an epihalohydrin and/or alkyl dihalide. -: . ' : -. ~ 5~
,i : . ' . ...
. ,:,'.. '. . . , ' : . ,. ~ .. . . .
:, :
- : . . , ~
31~79L~7 The polymers used in preparing the emulsion of the present invention may have a molecu.lar weight over a wide range; e. g, lO) 000 - 25, 000, 000; however, the present invention is particuLar.ly applicable to high molecular weight polymers; i. e., in excess of .100, 000, in that such polymer s are more difficult to subject to further ~reatmentJ such as by chemical modification and/or rendering same readily so.luble in water.
The oils which are used in preparing the emulsions of the lpresent invention may be any one of a wide variety of oi.ls which do not adverse1y affect the polymer to be dispersed in the oil. The oi.l may be any one of a wide variety of liquids including hydrocarbons and substituted hydrocarbons. As representative examples, there may be mentioned benzene, xylene, toluene, minera.l oils, kerosenes, aphthas, chlorinated hydrocarbons, such as perchloroethy.lene, etc.
A blend of organics can be used in preparing the oil phase The oil phase preferab.ly has a boiling point in excess oi 10ûC to avoid excess :~ loss of oil phase during water removal; however, lower boi.ling ~materials can be used,provided the oil phase is rep.lenished during water rernoval.
;
~ The water in oil emulsion having fine.ly divided water so.lub.le .-polyrner dispersed therein may be prepared by any one of a wide variety of procedures" and is preferably prepared by the water in oil ; . ~
emulsion pobmerization technique for preparation of vinyl addition ~ ~ ;
polymers. In accordance with such a procedure, a water in oil emulsion of water soluble ethylenically unsaturated monomer(s) is ormed and po.lymerized under free radica.l po.lymerization conditions ! ::
- :
- :
: -6 - . .
', . . .::.
. ':
7~7 to produce a latex of water in oil emulsion having finely divided polymer dispersed therein. A representative example of this technique is disclosed in U.S. Patent No. 3,284,393.
Alternatively, and less preferred, the water in oil emul-sions having finely divided water soluble polymer dispersed therein can be prepared by dispersing previously prepared poly-mer in a water in oil emulsion. Such techniques are known in the art and need not be set forth in detail for a complete understanding of the present invention. In brief, such tech-niques involve, comminuting the polymer to provide finely divided polymer (average particle size is generally less than - 5 millimeter) and then dispersing the polymer in a water in oil emulsion by means of suitable agitation. In most cases, a ~- - .
suitable oil soluble emulsifying agent is used in preparing the emulsion. The ernulsifier should be inert with respect to the ~
components present in the emuIsion or used in the subsequent ~ ~-treatment. In general, the better emulsifiers have HLB numbers (Hydrophobic-liphophobic balance) of below 11 and preferably below 9.
The above techniques and other techniqués for producing such em~lsions are known in the art and no further details are -deemed necessary for a complete understanding of the invention.
The water in oil emulsions having finely divided water .
soluble polymer dispersed therein, which are stabilized to polymer agglomeration, in accordànce with the present : i invention, generally contains from 50% to 95%, by weight, water, and most generally from 60-80% water, based on polymer ;
and water. The amount of oil phase present , : ' . . . . . ' ''' . ~
, ~07~77 In the emulsion Ls generally in the order of 25 to 75 weight percent~
based on oil and water phases.
In accordance with the present invention, the water in oil emul-sions having finely divided water so.lub.le polymer dispersed therein are stabilized with respect to agglomeration or coa~.lation of polymer to permit subsequenttreatment thereo:EJ by reducing the water content thereof to a value at which the polymer remains finely divided and dispersed in the oil during subsequent treatment of the polymer dis-persed ln oil. It is to be understood that the term subsequent treat- ~: .
ment is intended to cover further chemical treatment of the dispersed -po.lyrner and/or addition of components to the po.lymer dispersed In oil, which without stabilization by water removal, wou.ld normal.ly cause coagu1ation or agglomeration of the polymer particles. :
In accordance with the present invention, the water content of t he water-po.lymer phase is reduced to .less than about 40 percent, .j .
by weight, based on water and po.lymer. As should be apparent, the particular amounts of water which can be tolerated in order to provide ... ..
`~ . the desired stabillzation will vary with the po.lymers employed and : -.
the.type of subsequent treatment. In general, the water content of . 20 the polymer and water phase Is reduced to provide a water content In the order of 0% to 40~, by weight, based on po.lymer and water.
In most cases, the water content of the po.lymer and water phase is - .
: ~ reduced to an amount of no less than .l~lc, by weight, based on po.lymer : . .
. .
and water, in that complete water removal is not readily achieved.
The water content is preferably in the order of 1~c to 36~o and most ~`
: preferably Ln the order of l~c, (Ln some cases OYc) to lO~c~ a.ll by . .
8- ~ ~
.
. .
, - , , , , ~ ~ . :
..
~07~77 weight, based on polymer and water. In accordance with the aspect of the present invention wherein the polymer is to be further chemi-cal.ly modified, in most cases, the water content should be at least 5~c, by weight, based on polymer and water, with the upper li-mits be ing as here inabove de scr ibed .
The selection of an optimum water content at which the po.lymer is stabilized with respect to agglomeration or coagulation during .
subsequent treatment is deemed to be within the scope of those skil.led in the art from the teachings herein. It is noted, however, that .lower water contents are required when using water soluble po.lymers containing substantial amounts of amines and/or emulsions which are to be stored over longer periods of time. Similar.ly, greater water removal is generally required for lower molecular weight po1ymers.
It ls ~urther to be understood that in some cases, subsequent to the water removal step, the polyrner may not be present in the oil as an emulsion; 1. e., the polymer rnay be present as a suspension.
It is to be understood, that the termino.logy that the water so.lub.le polymer is ~ine.Ly divided and dispersed in the oil covers both the .
~: ~ - case in which the po.lymer is present in a water in oil emu.lsion, and t he case in which the polymer is suspended in the oil.
App1ieant has surprising.ly found that the water content of the emulsions can be reduced without coagulation or agglomeration of the polymer,which is particularly surprising in view of the fact that such e-mu1sLons are known to be very unstab.le and are often coagula-ted by only mechanical mixing. The water content of the emulsion - is generally reduced by evaporation of water, preferably under-, _g_ . .
.... . . . . .
~L~791 ~77 .
vacuum. The evaporation is general.ly effected at temperatures from ambient to 140C, although higher temperatures could be used The selection of an optimum temperature is deemed to be within the scope , .
of those skilled in the art from the teachings herein Prior to or .
. 5 during the water evaporation, addition al inert organic liquid may be . added for the purpose of reducing viscosity and/or rep.lacing oil dis- :
. . .. .
tilled from the emu.lsion during water remova.l.
. ¦ In accordance with the present invention, the hereinabove des~
cribed technique may also be used for providing the po.lymers as finely divided solids, by evaporating both water and oiL. Applicant :~ surprising.ly found that finely divided po.lymer can be recovered, : .
without adverse agglomeration or coagu.lation, by evaporating water ~ -a~d oil, thereby pro~id ing a simple technique for recovering the sslld po.lymer produced by a water in oil ernulsion polyr.nerization . ~ :
: 15 tec hnique .
As hereinabove noted, ln accordance with one aspect of the ~ .
prescnt invention, the dLsperiion o:E water soluble polymer in oil ~.
having a reduced wa~er content, which renders the cornposition SllS- ~.. ..
~
ceptib.le to further treatment without polymer coagulation, is subse- `
. ; ~. :20 ~ quentb treated by t~e addition of surfactant to provide a self inverting or dissolving compositLon. It has been surprisingly found that any . : : ' ~ one of the wide variety of we.l1 known surfactants which would norma.l- ~
l .
ly cause coagulation of the polymer d~ispersed in a water in oil emulsion, can be added to the composition of the present invention ~:
~25 ~ ~ of po.lymèr dispersed in oil of reduced water content, as hereinabove -.
described, without e:~fecting coagu.lation or agglomeration of the.
:
:: . . -10- ~ ., .
.
:
' . ' ~
": . . , ~. . ;. . ~ ... . , , .;, ' , . . , ' ' , . ' , " . . ,' ' , : , po.lymer. The surfactant added to the composition to render sa-me self inverting may be selected from any one of a wide variety of water soluble cationic, anionic or non-ionic surfactants known in the art.
As known in the art, anionic surfactants include alkali metal, ammo-nium and amine soaps; sa.lts of various sulfonic acids, sulfonated oils, ~tc.
Cationic surfactants inc.lude various long chain amines, quater- ~
nary sa.Us, etc. .
NonLonic surfactants inc.lude condensation products of varial s alcohols, phenols and amides with ethylene oxide; po.lyeth~lene g.lyco.l esters, etc.
The surfactants are well known in the art and representative exa-mples of such surfactants are disclosed in U S. Patent No.
~ .
3, ~24, 0.19. .
The self inverting compositions of the present invention includes :
surfactant in an amount to render the po.lymer se.lf inverting or dis-solving in water. In general, the compositions contain from about û. l~c to about lS~c, preferably from l~c to 7~'1c, by weight, of surfac-tant, based on polymer. The water content is as hereinabove des-: ~ cribed, whereby the po.bmer is fine.ly divided and dispersed inlthe oil after addition of the surfactant. It is to be understood that the .: ~ pr~sent invention is not limLted to sueh il.lustrative amounts of surfactant, and the determination of suitable amounts is deemed ~ :
to be within the scope of those skilled in the art from the teachings herein. In genera.l, the po.lymer is present in the oil in an amount `:
~ 7 ' '' ' ~rom S~c to about 85~c, preferably 25~c to 75~c, all by weight. ~
--11-- . !: ' ` ' " ~ ' .
" ' . . :. . . , ' ~ : ' .
- ' ' " ' , ' ' ' ' ., , ' , ' " '` ' ` ~ ' ' ' ~
' ' . : . . , ' " . ' . ':
:, ,: , , . ~ ' ~L~7~77 The seLi inverting compositions of the present invention are .. . -.
preferably formed from water so.luble ethylenica.lly unsaturated ~` addition polymers, and most preferably from po.lymers of acry.lamides, acry.Lic acids, substituted acrylic esters or substituted acrylamides.
The polymer is readily released into water from the composition by ~- . adding the se.lf inverting composition to water.
It is to be understood that additives other than surfactants can :-.
be added to the selE inverting composition, without effecting coagula-tion or agglomeration of the polymer. Thus, for example, in using the se.lf inverting compositions for water treatment purposes, it may be desira,ble to a.lso add to the composition a biocide and/or corrosion :inhibitorJ etc. J~ and such additives can be added with the surfactant. : .
The se.lf inverting composition of the present invention are particu-: ; larly suitable ior use In water treatment compositions in a manner I ~ 15 known in the art.
As hereinabove noted, in accordance with another aspect of :
. ~ .
th~ present invention, the composition of water so.luble po1ymer . ~ dispersed in oil having a reduced water content can be subsequently treated, in the dispersed phase, to chem~cally modify the po.lymer, . 20 without coagu.latiorl or agglomeration OI the polymer.
The present invention is particu.larly app.licable to the chemical modification of acrylamide polymers, including:
Hydrolysis of amide to carboxyl.
¦ ~ Dimethylaminomethylation of amide. .
: 2 5 ~ : Su.lfomet hylat ion of amide . - ~ .. .
, , .
. : : ~ - Hoffman reaction with chlorine and base.
, ....
, :, "
,.
; . ~
, , ::
,, . , . , .. : . . . .
~7~77 The present invention is a.lso applicable to the exchange of ammonia nitrogen for nitrogen of N,N dimethylamino propylamine.
The present invention is a.lso applicab.le to the quaternization .. . of amine containing po.lymers, and the a.lky.lation of amines by ha.logen .:
., 5 containing polymers, in particu.lar, acry.Lamide copoLymers in which . ~ the comonomer contains an amino or ha.lo group, respectively. Thus, for example, a copolymer of acrylamide and dimethylaminoethyl methacrylate can be quaternized with methy.l chloride or a copo.lymer of acrylamide with chloroethylmethacrylate can be quaternized with :; 10 trimethylamine dispersed in oil having a reduced water content.
, . .
. The fine.ly divided polymer dispersed in oi.L, of reduced water .
content (prepared as hereinabove described by either forming an .
, emulsion by adding polymer to a water in oil emulsion or producing : .
the po.lymer by po.lymerization in a water in oil emulsion; followed : ~.
by reduction of the water content) has an average particle size . . .
genera.l.b in the order of O..l micron to 500 microns, and most frequent.ly, 0. 5 to .lO0 microns. ~Larger particle sizes cou.ld be used, .. ~ but some of the advantages of the inyention are decreased. ::
. .~
: ~ The chemical modifications can be effected by using the reagen~
: ~ :
~ and conditLons generalb known in the art, except that the polymer is treated dispersed in oil, with the:water content thereof being as here-inabove described, Solid reagent emp.loyed in the chemica.l modifi-:
. ~ ., cation may be added as fine powders, aqueous so.lutions or pre- ~ ~
'I ' .
emu.lsified in the same manner as the latex. In some cases, pre-. ~ ' .
. ~ ~ 25 emulsificatlon of the reagent may be required in order to prevent I coa~ulatidn or agglomeration of the polymer. L;quid reagents~-can~
3~
. :-:
.
t.,, ~ :
' ' : ' . . . ' . '': ' '' ~ , , ' ,, ~
.'' ' . ~ , ' , , .:
also be pre-emulsified.
The acrylamide po.lymer, as hereinabove noted, may be chemi- :
cally modlfied with various known reagents, inc.luding, as represen-tative e~amples, bases, dia1kylamine and forma.ldehyde, sodium bLsulfil;e and formalde.hyde; N,N-dialkyldiamines, etc.
The chemical modification of acrylamide polymers may be effected at reaction temperatures known in the art, generally in the order of 15D to 130~C at atmospheric or e.levated pressures The . above conditions are on.ly il.lustrative, and the se.lection of suitab.le conditions is deemed to be within the scope of those skilled in the art.
In accordance with the present invention, it has been found that chemical modification of acrylamide polymers dispersed in oil9 by neutralization, should be effected with gaseous ammonia in that ~ .:
attempts to use GtL~r bases results in agglomeration or coagulation .
~5 of the dispersed po.lymer. The neutralization with ammonia isgenerally efIected at temperatures of 20C to .130C, preferably at a temperature of 50 to 100C. It is to be understood that the present invention is not limlted to such il.lustrative temperatures.
~; . It has also been found iA accordance with the present invention, :.
ao that~advantageous r~sults are obtained by the use of ammonia or :~
ammonium hydro~if3ie, instead OI other conventional bases, for the .-neutralization of acrylamide po.lymers, in particular, those having .
a molecular weigh~ of at least 1009 000 Thus, for example, improve~
ments in conventionaL1 neutralization of acrylamide polymers in ~ :
: 25 aqueous media are ~3btained by the use of ammonia or ammonium . - - . , - hy~oxide.as-a result of the. ability to r~ore effective.ly contr-o1~hydro~
, ~37~7~ :
ys is .
In accordance with still another aspect of the present invention, water soluble condensation po.lymers, in particular, polyamines, are producéd by polymerization in a water in oil emulsion. By proceeding in this manner, concentration of the polymer in the water phase can be increased to concentrations greater than those heretofore used in the art, without the disadvantages which would normally result from the presence of high polymer concentrations.
As known in the art, polyamines are produced by condensation of a po.lyfunctional amine; i. e., having two reactive amine hydrogen atoms, with an epiha.lohydrin or an alky.l diha.lide. ~ -As representative examples of suitable water so.luble amines having two reactive amine hydrogen atoms suitable for the present invention, there may be mentioned: Methylamine, ethylamine, ethan-olamine, propylamine, NJ N-dimethy.lethylenediamine, piperazine anci aniline are suitable. The amLnes need not possess great water . . :
so.lu~ility, and the suitability of any particular amine as a raw ma~erial can be readily determined by laboratory trial. Mixtures . ~ :
of two or more bifunctional amines~may be used.
-: 20 As polyfunctiona.l amines, there may be employed any water soluble amine containing three or mDre reactive amino hydrogen :.
atoms. These amines consequently have a functionality greater than :.
2, and inc.lude amines such as ethylenedlamine, N-rnethylethylene-diamine, the po.lyalkylenepo.lyamines including diethylenetriamine, tetraethylenepentamine and the corresponding po.lypropylenepoly- .
- an~inesj p-phenylenediamine, p,~p'-bisaniline, and l, 3-diamino:.-2- -1 . .. ::: .
,,:
-15- ::
~, ' :
' ~ Q~79~77 propanol.
The epihalohydrin used in this invention has the essentia.1 group ' . ' - C - C X
wherein epoxy group is bonded to two carbon atoms, one of which is bonded adjacently to a carbon atom having the halogen bonded thereto.
The halogen is pre:eerably chlorine for reasons of availability and cost, but may be bromine or iodineO The indicated free valences on .
the carbon atoms are satisfied by hydrogen or lower alkyl groups, ~ .
preferably the methyl or ethyl groups.
The epihalohydrin is preferably epichlorohyclrin but may be -: .
: epibromohydrinJ epiiodohydrin, or one of the higher molecular : .
weight vicinal halohydrins such as 3-chloro-1,,2-epoxybutane, 3- ::
chloro-l,~-epoxypentane, etc. : ~ .
The a.lkyl dihalide used in the invention is preferab.ly a dichlo- .
:~ ride or dibromide of lower alkanes (2-4 carbon ato~ns), w1th the halo ~ -.
group preferab.ly belng on the terminal carbon ato-ms. As represen-: :
tative examp.1es of suitable compounds, there may be mentioned: .:
i ~ ~ : .1,2.-d1ch1Oroethane, i,2-dibromoethane, 1,3~dichloropropane,i1,3 i: ~ 20 dibromopropane, etc.
: :. ' .
- ~ The selection of suitable amines for condensation with a dihalo- : ~ -~: alkane and/or epiha.lohydrin is deemed to be within the scope of those ~ ~ skilled in the art from the teachings herein.
: : : The reaction is general.ly effected at temperatures known in the : .
~ , art; i. e., temperatures in the order of 0-.100C. In addition, the ~ . .
~ reactioh,mixture, as known in the art, preferably includes an~acid, : -16- :. ~
: :
.", , ' ' ~ ~ ' : . '~ '. ' , :~ ' ' ' . .' . . ' .
7~
acceptor; in particularJ an aLka.Li meta.l hydroxide.
As known in the art, the molar ratio of dihalo compound or epihalohydrin to ammonium generally ranges from about l.l:.l to l 8:1.
The general conditions for producing po.lyamine condensation ~.
polymers are known in the art, and such teachings are app.licable to the present invention.
In accordance with the present invention, the mono-mers are condensed in a water in oil emulsion, with the water phase, including monomer, genera.Uy comprising from 25~c to 75~c, by weight, of the . 10 emulsion, based on water and oil.
- The water phase is present in an amount to provide a po.lymer water phase comprised of from 50~c to 90~c, of water, preferably 60%
: to 90~c, al.l by weight, based on po.lymer and water. Subsequent to -comp.letion of the po.lymerization, water may be removed, as hereln- ~.
. 15 above described to provide more concentrated po.lymer in water . solutions. The oil may also be removed, as hereinabove described ::
. ~,:
to provide flowable composition of polymers of concentrations higher than heretofore available in the art. Thus, for examp.le, the oil content could be reduced to the order of 2û~c to 80~, preferab.ly 20'1c ; .
to 70~c, àrld most preferably 20~c to 50~c, of the tota.l composition, : : :
by weight, whichprovides an improvement over the IO~c po.lyamine solutions general.ly available in the art. : -The monorners are emulsified in the oil phase by the use of a : suitable water in oil emu1sifying agent. The emulsifier is general.ly ~ present ~n an amount of from 0 1 to lO percent, by weight, of the oil :
; phase. The emulsiïiers are well known in the art and no further .: ~
: ~, : : :
. : ' ' ,' ~ lq~
, ~ :
,~
: :, ', ' '' ' ' : ' ' .
: ' , . . .
: ' . . .
~()7~47~
details are deemed necessary in this respect for a complete under-standing of the invention.
It is also to be understood that the polyamine could be ; produced by conventional techniques, followed by emulsification of the water polymer solution in oil and evaporation of the water to produce a more concentrated aqueous solution of polyamine.
The invention will be further described with respect to the following examples/ but it is to be understood that the scope of ~ the invention is not to be limited thereby.
; 10 EXAMPLE 1 A commercial acrylamide polymer known as Nalco 623 is a high molecular weight copolymer containing about 93% acrylamide and 7% acrylic acid groups. This polymer is of the type described in U.S. Patent No. 3,284,393, Vanderhoff, an emulsion comprising a continuous phase of hydrocarbon in which are suspended fine particles of acrylamide solution (gel). The composition of Nalco 623 is approximately as follows:
by weight Copolymer 30 ' 20 Water 38 Hydrocarbon 28 ;~
Emulsifier 4 *
A 20 gram sample of Nalco 623 was weighed into a 2 ounce bottle followed by 4.3 grams of toluene. The bottle was then connected to a water aspirator and vacuum was applied. The bottle ;
was held at 20-25C with a water bath for 12 minutes, a~ter which }, -~
the temperature of the bath was raised to 40C for 30 minutes and to 50C for another 10 minutes. The bottle was disconnected and -the product was found to weigh 13.7 grams (loss of 10.6 grams of , 30 water and hydrocarbon combined). A sample of the product was f removed and designated Sample A. To the remainder of the product ~-*
Trademark ~7~7~ `
in the bottle (8.4 grams) was added 4.3 grams of toluene. Vacuum was then applied over a 20 minute period while the bath tempera-ture was raised from 25C to 80C. Distillation was discontinued at this time and the remaining product was found -to weigh 6.1 grams. The proauct was diluted with 3 ml of VM&P naphtha and designated Sample s.
Samples A and s and a sample of untreated Nalco 623 were subjected to a compatibility test with surfactant that was supplied along with the sample of Nalco 623. The surfactant had the designation "Activator" and is a nonionic surfactant of the polyethylene oxide condensate type. The compatibility test con- ~
sisted of adding 2 ml of sample to a vial followed by 0.08 ml of -activator and then mixing. The samples were then observed over a two month period. The results were as follows: ;
Material A~pearance Original Nalco 623 Coagulation in two minutes ~, Sample A CocLgulation in seven minutes Sample B No coagulation observed over a - ; -two month inspection period -Part A. A 500 gram portion of 10% polyacrylamide gel `- (0.703 monomer mole) is placed in a jackèted sigma mixer. This polyacrylamide has an intrlnsic viscosity of 12.6 measured in ~. .. . .
; ! 1 normal NaCl at 25C. Heat is applied to the jacket to bring the polymer mass to 50C and mlxing is started. The reaction mixture is buffered on the alkaline side by addition of 5 g. of Na2HPO4.2H2O and 8 g. of Na3PO4.10H2O. This is followed by 14.2 g. of 37~ formaldehyde solution (0.176 mole). The temperature is held at 50 C with mixing for 80 minutes, after which 20 g. of a ~l 30 40~ dimethylamine solution (0.176 mole) is added and the tempera- --~ * Trademark ., .
, . .
~74477 ture raised to 75C and held for 30 minutes. A sample of the aminomethylated polyacrylamide is dissolved in 1 normal NaCl for determination of its intrinsic viscosity which is found to be 9.8.
Part B. A 30% polyacrylamide latex is prepared by the technique of Vanderhoff and found to have an intrinsic viscosity of 11.9~ The composition of the latex is as follows:
%
~:
Polyacrylamide 30 Water 38 ~;
10 Low Odor Paraffin Solvent(Exxon) 28 Brij* 92 (polyoxyethylene(2)oleate) 4 : .
In a 500 ml three neck round bottom flask equipped with a stirrer ~ -is placed 166.5 g. of the above latex (50 g. polyacrylamide, 0.703 monomer mole). Stirring is started and the latex is heated to 50C after which an emulsion composed of the following is ::
added: Step 1 Grams Na2HPO4.2H2O 1.5 3PO4-10H2O 3.0 ` 20 37~ formaldehyde 14.2(0.176 moles) :.
~, Water 15.0 ~: Low Odor Paraffin 12.0 i, Solvent -:~
", ~ , ,~. Brij* 92 1.4 After 90~minutes at 50C, 29.1 g. of the following emulsion is added: Step 2 ::
, : , Grams ~: 40% dimethylamine 20 (0.176 mole) `
~ Low Odor Paraffin -l ~ 30 Solvent . 8 ;, Brij 92 1.7 The latex is then heated to 75C for 30 minutes, after which a -~ sample is dissolved ln 1 normal NaCl containing 0.04% Triton X-100 ; . .
* Trademarks , ,, , ~ , , ,, : ....... . . .
~ ~74~
for determination of the intrinsic viscosity of the aminomethyl-ated polyacrylamide, which is found to be 11.5.
A 20 g. sample of Nalco 623 is given the same drying treatment as Sample B in Example 1. The product is divided into two equal portions that are treated as follows: -Part A This half of the latex (containin~ 3 g of real polymer, 0.042 monomer mole) is placed in a 1 ounce bottle provided with a ~-heating bath and stirrer. Stirring is started and the bath is heated to 85 C. A solution containing 1.35 g. Na2CO3 (0.0126 ;
mole) and 5.5 g. water is made up, heated to 85C and added drop-wise to the latex with stirring. Heating and stirring are con-tinued at 85C, but after 5 minutes the latex coagulates.
Part B This half of the latex is processed as in A above except that instead of Na2CO3, gaseous ammonia is passed in over the , stirred mixture so as to create saturation. The ammonia atmos-i phere is then maintained over a 4 hour period with stirring at 85C. The product is cooled and blown with air to remove ammonia vapor.
, ,.
EXAMPLE 4 ;
, ~ Part A A 5 g. sample of polyacrylamide (0.703 monomer mole) ~; having a molecular weight of about 6 million is dissolved in water , to give 5~ solution. This so~lution is heated to 85C and 2.26 g.
of 37~ NaOH was added (0.022 mole). The base is mixed into the viscous mass, the reactor is closed, and the mixture is heated at :: , 85C for 6 hours.
Part B This experiment is carried out as in Part A except that instead of NaOH, 1.01 G. of 37~ ammonia (0.022 mole) is used.
The neutralized polymer has improved properties with respect to ', 30 the polymer produced in Part A. ~ ~-'. : , * Trademark ~
.~ . --21- ;
. .
: ~ , . : . .. . .
~L~7~77 Polyacrylamide having a weight average molecular weight of 3 million is made up as 3% solution containing 30 grams of poly-acrylamide (0.4222 monomer mole) and 970 grams of water. To this solution is added 3 grams of Na2PO4.2H2O, 5 grams of Na3PO4Ol0H2O ;
and 3.4 grams of 37% formaldehyde (0.042 mole). The reaction mixture is held at 45-50C for 80 minutes, after which 4.8 grams of 40% dimethylamine solution (0.042 mole) is added. The tempera-ture is then raised to 75C and held for 30 minutes. The mixture 10 is cooled and designated Product A. '~
An emulsion formed from 100 grams of Product A, 96 grams of Low Odor ParafEin Solvent (Exxon ) and 4 grams of Brij 92 (polyoxyethylene(2)oleate) is placed in a 500 ml round bottom flask and attached to a rotary vacuum evaporator that is fitted with a dip tube that can be used to feed or withdraw material from the evaporator.
Concentration is carried out at a pressure of 40 millimeters --of mercury over the temperature range of 40-80C. As the amounts -of water taken overhead reaches approximately 80 ml the contents of the evaporator are removed and emulsified with another 100 ml ~;~ of Product A. The hydrocarbon taken overhead is separated and returned to the emulsion. The new emulsion is returned to the ...
evaporator and the cycle is repeated until all of ~roduct A is concentrated to a stable latex containing .~
Grams Aminomethylated polyacrylamide 33 Water 17 Low Odor Paraffin Solvent 96 Brij 92 4 * Trademarks ~ID'7~'7 A 4 gram sample of the above latex is added with stirring to 600 ml of water containing 0.04% Triton X-100. The polymer dissolves within 10 minutes to give a solution of aminomethylated ; polyacrylamide.
A mixture of 287 grams (9.24 moles) of methylamine (755 grams of 37% aqueous solution), 400 grams of Low Odor Paraffin Solvent and 50 grams of Brij* 92 is emulsified by passage through a Manton Gaulin ~m~e ~ r. The emulsion is placed in a 5 liter ~-flask provided with a stirrer, condenser, thermometer and cooling bath, and 850 grams (9 moles) of epichlorohydrin is added o~er a 2 hour period at 40-45C. Next, 450 grams of 50% aqueous NaOH
:, (4.5 moles) is emulsified with 250 grams of Low Odor Paraffin Solvent and 20 grams of Brij* 92 and added over a one hour period with the temperature heId at 70-80C.~ Heating is continued for one hour at 60C. The product is a free flowing, non-viscous liquid that is readily dissolved in water by use of a water soluble surfactant.
~ .
A 100 gram sample of Nalco 623~is dried by the same pro-` ~ cess~as described for Example 1, Sample B, and the dried latex particles are centrifuged to remove hydrocarbon and then air dried at 50C to drive~off the remaining traces of hydrocarbon. The product is a fine white powder.
The present lnventlon~is particularly advantageous ln that ~
by proceeding in accordance~with the invention, it is possible to ~-, ,~ . .
produce water soluble polymers dispersed in oil which are stable to coagulation or agglomeration when subjected to subsequent treatment. ~ ~-* Trademarks .
, ' ~,''.. ~' :, ,:
~L~374~7~
In accordance with the present invention, it is possible to provide self inverting or dissolving polymer compositions by addition of a surfactant, to a composition of water soluble polymer dispersed in oil, without the polymer agglomera-tion or .;.-~ :
coagulation which would occur without proceeding in accordance with the invention.
Furthermore, the present invention offers the advantage that various water soluble polymers can be chemically modified, without the disadvantages inherent in attempting to modify such 10 polymers, in particular, those of high molecular weight, by -:
ordinary techniquesO .~:.
: As still another advantage, amine condensation polymers .~ .:
can be produced without limiting the polymer concentrations as heretofore required in the art. . .
~ , ' '' ': ' " .,.
,~ '-~ .
..
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'... '': ' , : :
: -24-.
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, . ... . . . . . .. . : ~ . . . .
~.~37~7'7 In accordance with still another aspect of the present invention, there i5 provided a self-inverting or dissolving composition of finely divid~d polymer and surfactant dispersed in oil in which the water content of the composition is at a value at which the polymer remains finely divided and dispersed in the oil.
In accordance with yet a further aspect of the present invention a self inverting composition of finely divided water soluble polymer dispersed in oil is produced by providing a water in oil emulsion having inely divided water soluble polymer dispersed therein, reducing the water content of the emulsion to a value at which the polymer remains finely divided and dispersed in the oil upon addition of a surfactant, followed by addition of a surfactant to render the composition self inverting.
In yet another aspect of the present invention, a water soluble polymer is chemically modified by forming a water in oil emulsion having finely divided water soluble polymer dispersed therein, reducing the water content of the emulsion to a value at which the polymer remains finely divided and dispersed in the oll during the chemical modification and chemically modifying the polymer.
In still a further aspect of the present invention, a water soluble condensation polymer i5 produced by effecting condensation polymerization of monomers in a water in oil emulsion~
In yet another aspect of the present invention, an acrylamide polymer is neutralized by the use of ammonia. ~ -Thus, in accordance with the present teachings, a self-water dissolving composition of a water soluble -polymer dispersed in oil which is stable to polymer coagulation and agglomeration is provided. The wat~r soluble polymer is C ~ ~4~
., : ,. . .. ,. ... :.
~7~77 selected from the group consisting of ethylenically unsaturated addition pol~mer and polyamines dispersed in oil. The polymers have a wa_er content at which the polymer remains finely divided and dispersed in oil with the wa~er content being less than 40~ by weight based on the polymer and water. The water soluble polymer which is dispersed in oil has been prepared from a water-in-oil emulsion of the water soluble polymer by reduction of the water content. An effective amount of surfactant is provided to render the water soluble polymer self dissolving in wa~er.
In accordance with a further embodiment, a process is provided for producing a self-water dissolving composition of a water soluble polymer dispersed in oil which is stable to polymer coagulation and agglomeration. The process includes reducing tle water content of a water-in-oil emulsion which has a finely c vided water soluble polymer selected from the group consistinc of ethylenically unsaturated addition palymers and polyamines dispersed therein. The emulsion contains from 50 to 95~ by weight of water, based on the polymer and water, with the water content being reduced to a water content which is less than 40~ by weight based on the polymer and water, at which the polymer remains finely divided and dispersed in the oil. ~ surfactant is added in an amount effective to render the water soluble polymer self-dissolving in water.
The polymers used in the present invention are any one of the wide variety of water soluble vinyl addition polymers or water : ' : , ~-:'' -4a-.. . . . . ...
.
:, : :
7~77 .. :
~i .. .
~o.luble c~ndensation po.lymers. The term "water soluble" means that the poLymer is so.luble in water in an arnount of at .least l~lc, by weight, Water so.luble vinyl addition po.lymers are we.ll known in the art, and such po.lymers are preferab.ly used in producing the se.lf inverting compositions in accordance with the present invention. The most preferred vinyl addition polymers are po.lymers (the term poly- ~;
mer as used herein refers to both homopolymers and copolymers containing two or more monomeric units) of acrylamide, such as po.lyacrylamide and copolymers of acrylamide with acrylic acid or salts thereof which contain from 5 to 95 weight percent of acrylamide.
~ .
Also suitable are copolymers of acrylamide with maleic anhydride, ~.
: . vinyl benzene, acrylonitrile, styrene, methacry.lamide, etc.
As representative examples of other suitable water so.luble . 1~ - vinyl addition polymers, there may be mentioned water so.lub.le poly- -mers of acrylic acid, vinyl pyridines, vinyl benzyl dimethyl ammon-: .
ium chloride, methacry.lamide, sul:Eonates of acrylic esters, such . ~ ~ ~ as, 2-su.lfoethyl acrylatie, styrene sulfonates, quaternary or amino . ~ substituted acrylic and rnethacryllc esters, such as 2 aminoethyl : ~ ~ .
methacrylate, and the like.
As representative examples of water so.lub.le condensation : ~
. i ~ ~ po.lymers which are useful In preparing the emulsions of the present . .- .
invention ar which can be prepared by the emulsion technique of the present invention, there may be mentioned, the polyamines, produced ..
25 ~ by condensation of difunctional amine with an epihalohydrin and/or alkyl dihalide. -: . ' : -. ~ 5~
,i : . ' . ...
. ,:,'.. '. . . , ' : . ,. ~ .. . . .
:, :
- : . . , ~
31~79L~7 The polymers used in preparing the emulsion of the present invention may have a molecu.lar weight over a wide range; e. g, lO) 000 - 25, 000, 000; however, the present invention is particuLar.ly applicable to high molecular weight polymers; i. e., in excess of .100, 000, in that such polymer s are more difficult to subject to further ~reatmentJ such as by chemical modification and/or rendering same readily so.luble in water.
The oils which are used in preparing the emulsions of the lpresent invention may be any one of a wide variety of oi.ls which do not adverse1y affect the polymer to be dispersed in the oil. The oi.l may be any one of a wide variety of liquids including hydrocarbons and substituted hydrocarbons. As representative examples, there may be mentioned benzene, xylene, toluene, minera.l oils, kerosenes, aphthas, chlorinated hydrocarbons, such as perchloroethy.lene, etc.
A blend of organics can be used in preparing the oil phase The oil phase preferab.ly has a boiling point in excess oi 10ûC to avoid excess :~ loss of oil phase during water removal; however, lower boi.ling ~materials can be used,provided the oil phase is rep.lenished during water rernoval.
;
~ The water in oil emulsion having fine.ly divided water so.lub.le .-polyrner dispersed therein may be prepared by any one of a wide variety of procedures" and is preferably prepared by the water in oil ; . ~
emulsion pobmerization technique for preparation of vinyl addition ~ ~ ;
polymers. In accordance with such a procedure, a water in oil emulsion of water soluble ethylenically unsaturated monomer(s) is ormed and po.lymerized under free radica.l po.lymerization conditions ! ::
- :
- :
: -6 - . .
', . . .::.
. ':
7~7 to produce a latex of water in oil emulsion having finely divided polymer dispersed therein. A representative example of this technique is disclosed in U.S. Patent No. 3,284,393.
Alternatively, and less preferred, the water in oil emul-sions having finely divided water soluble polymer dispersed therein can be prepared by dispersing previously prepared poly-mer in a water in oil emulsion. Such techniques are known in the art and need not be set forth in detail for a complete understanding of the present invention. In brief, such tech-niques involve, comminuting the polymer to provide finely divided polymer (average particle size is generally less than - 5 millimeter) and then dispersing the polymer in a water in oil emulsion by means of suitable agitation. In most cases, a ~- - .
suitable oil soluble emulsifying agent is used in preparing the emulsion. The ernulsifier should be inert with respect to the ~
components present in the emuIsion or used in the subsequent ~ ~-treatment. In general, the better emulsifiers have HLB numbers (Hydrophobic-liphophobic balance) of below 11 and preferably below 9.
The above techniques and other techniqués for producing such em~lsions are known in the art and no further details are -deemed necessary for a complete understanding of the invention.
The water in oil emulsions having finely divided water .
soluble polymer dispersed therein, which are stabilized to polymer agglomeration, in accordànce with the present : i invention, generally contains from 50% to 95%, by weight, water, and most generally from 60-80% water, based on polymer ;
and water. The amount of oil phase present , : ' . . . . . ' ''' . ~
, ~07~77 In the emulsion Ls generally in the order of 25 to 75 weight percent~
based on oil and water phases.
In accordance with the present invention, the water in oil emul-sions having finely divided water so.lub.le polymer dispersed therein are stabilized with respect to agglomeration or coa~.lation of polymer to permit subsequenttreatment thereo:EJ by reducing the water content thereof to a value at which the polymer remains finely divided and dispersed in the oil during subsequent treatment of the polymer dis-persed ln oil. It is to be understood that the term subsequent treat- ~: .
ment is intended to cover further chemical treatment of the dispersed -po.lyrner and/or addition of components to the po.lymer dispersed In oil, which without stabilization by water removal, wou.ld normal.ly cause coagu1ation or agglomeration of the polymer particles. :
In accordance with the present invention, the water content of t he water-po.lymer phase is reduced to .less than about 40 percent, .j .
by weight, based on water and po.lymer. As should be apparent, the particular amounts of water which can be tolerated in order to provide ... ..
`~ . the desired stabillzation will vary with the po.lymers employed and : -.
the.type of subsequent treatment. In general, the water content of . 20 the polymer and water phase Is reduced to provide a water content In the order of 0% to 40~, by weight, based on po.lymer and water.
In most cases, the water content of the po.lymer and water phase is - .
: ~ reduced to an amount of no less than .l~lc, by weight, based on po.lymer : . .
. .
and water, in that complete water removal is not readily achieved.
The water content is preferably in the order of 1~c to 36~o and most ~`
: preferably Ln the order of l~c, (Ln some cases OYc) to lO~c~ a.ll by . .
8- ~ ~
.
. .
, - , , , , ~ ~ . :
..
~07~77 weight, based on polymer and water. In accordance with the aspect of the present invention wherein the polymer is to be further chemi-cal.ly modified, in most cases, the water content should be at least 5~c, by weight, based on polymer and water, with the upper li-mits be ing as here inabove de scr ibed .
The selection of an optimum water content at which the po.lymer is stabilized with respect to agglomeration or coagulation during .
subsequent treatment is deemed to be within the scope of those skil.led in the art from the teachings herein. It is noted, however, that .lower water contents are required when using water soluble po.lymers containing substantial amounts of amines and/or emulsions which are to be stored over longer periods of time. Similar.ly, greater water removal is generally required for lower molecular weight po1ymers.
It ls ~urther to be understood that in some cases, subsequent to the water removal step, the polyrner may not be present in the oil as an emulsion; 1. e., the polymer rnay be present as a suspension.
It is to be understood, that the termino.logy that the water so.lub.le polymer is ~ine.Ly divided and dispersed in the oil covers both the .
~: ~ - case in which the po.lymer is present in a water in oil emu.lsion, and t he case in which the polymer is suspended in the oil.
App1ieant has surprising.ly found that the water content of the emulsions can be reduced without coagulation or agglomeration of the polymer,which is particularly surprising in view of the fact that such e-mu1sLons are known to be very unstab.le and are often coagula-ted by only mechanical mixing. The water content of the emulsion - is generally reduced by evaporation of water, preferably under-, _g_ . .
.... . . . . .
~L~791 ~77 .
vacuum. The evaporation is general.ly effected at temperatures from ambient to 140C, although higher temperatures could be used The selection of an optimum temperature is deemed to be within the scope , .
of those skilled in the art from the teachings herein Prior to or .
. 5 during the water evaporation, addition al inert organic liquid may be . added for the purpose of reducing viscosity and/or rep.lacing oil dis- :
. . .. .
tilled from the emu.lsion during water remova.l.
. ¦ In accordance with the present invention, the hereinabove des~
cribed technique may also be used for providing the po.lymers as finely divided solids, by evaporating both water and oiL. Applicant :~ surprising.ly found that finely divided po.lymer can be recovered, : .
without adverse agglomeration or coagu.lation, by evaporating water ~ -a~d oil, thereby pro~id ing a simple technique for recovering the sslld po.lymer produced by a water in oil ernulsion polyr.nerization . ~ :
: 15 tec hnique .
As hereinabove noted, ln accordance with one aspect of the ~ .
prescnt invention, the dLsperiion o:E water soluble polymer in oil ~.
having a reduced wa~er content, which renders the cornposition SllS- ~.. ..
~
ceptib.le to further treatment without polymer coagulation, is subse- `
. ; ~. :20 ~ quentb treated by t~e addition of surfactant to provide a self inverting or dissolving compositLon. It has been surprisingly found that any . : : ' ~ one of the wide variety of we.l1 known surfactants which would norma.l- ~
l .
ly cause coagulation of the polymer d~ispersed in a water in oil emulsion, can be added to the composition of the present invention ~:
~25 ~ ~ of po.lymèr dispersed in oil of reduced water content, as hereinabove -.
described, without e:~fecting coagu.lation or agglomeration of the.
:
:: . . -10- ~ ., .
.
:
' . ' ~
": . . , ~. . ;. . ~ ... . , , .;, ' , . . , ' ' , . ' , " . . ,' ' , : , po.lymer. The surfactant added to the composition to render sa-me self inverting may be selected from any one of a wide variety of water soluble cationic, anionic or non-ionic surfactants known in the art.
As known in the art, anionic surfactants include alkali metal, ammo-nium and amine soaps; sa.lts of various sulfonic acids, sulfonated oils, ~tc.
Cationic surfactants inc.lude various long chain amines, quater- ~
nary sa.Us, etc. .
NonLonic surfactants inc.lude condensation products of varial s alcohols, phenols and amides with ethylene oxide; po.lyeth~lene g.lyco.l esters, etc.
The surfactants are well known in the art and representative exa-mples of such surfactants are disclosed in U S. Patent No.
~ .
3, ~24, 0.19. .
The self inverting compositions of the present invention includes :
surfactant in an amount to render the po.lymer se.lf inverting or dis-solving in water. In general, the compositions contain from about û. l~c to about lS~c, preferably from l~c to 7~'1c, by weight, of surfac-tant, based on polymer. The water content is as hereinabove des-: ~ cribed, whereby the po.bmer is fine.ly divided and dispersed inlthe oil after addition of the surfactant. It is to be understood that the .: ~ pr~sent invention is not limLted to sueh il.lustrative amounts of surfactant, and the determination of suitable amounts is deemed ~ :
to be within the scope of those skilled in the art from the teachings herein. In genera.l, the po.lymer is present in the oil in an amount `:
~ 7 ' '' ' ~rom S~c to about 85~c, preferably 25~c to 75~c, all by weight. ~
--11-- . !: ' ` ' " ~ ' .
" ' . . :. . . , ' ~ : ' .
- ' ' " ' , ' ' ' ' ., , ' , ' " '` ' ` ~ ' ' ' ~
' ' . : . . , ' " . ' . ':
:, ,: , , . ~ ' ~L~7~77 The seLi inverting compositions of the present invention are .. . -.
preferably formed from water so.luble ethylenica.lly unsaturated ~` addition polymers, and most preferably from po.lymers of acry.lamides, acry.Lic acids, substituted acrylic esters or substituted acrylamides.
The polymer is readily released into water from the composition by ~- . adding the se.lf inverting composition to water.
It is to be understood that additives other than surfactants can :-.
be added to the selE inverting composition, without effecting coagula-tion or agglomeration of the polymer. Thus, for example, in using the se.lf inverting compositions for water treatment purposes, it may be desira,ble to a.lso add to the composition a biocide and/or corrosion :inhibitorJ etc. J~ and such additives can be added with the surfactant. : .
The se.lf inverting composition of the present invention are particu-: ; larly suitable ior use In water treatment compositions in a manner I ~ 15 known in the art.
As hereinabove noted, in accordance with another aspect of :
. ~ .
th~ present invention, the composition of water so.luble po1ymer . ~ dispersed in oil having a reduced water content can be subsequently treated, in the dispersed phase, to chem~cally modify the po.lymer, . 20 without coagu.latiorl or agglomeration OI the polymer.
The present invention is particu.larly app.licable to the chemical modification of acrylamide polymers, including:
Hydrolysis of amide to carboxyl.
¦ ~ Dimethylaminomethylation of amide. .
: 2 5 ~ : Su.lfomet hylat ion of amide . - ~ .. .
, , .
. : : ~ - Hoffman reaction with chlorine and base.
, ....
, :, "
,.
; . ~
, , ::
,, . , . , .. : . . . .
~7~77 The present invention is a.lso applicable to the exchange of ammonia nitrogen for nitrogen of N,N dimethylamino propylamine.
The present invention is a.lso applicab.le to the quaternization .. . of amine containing po.lymers, and the a.lky.lation of amines by ha.logen .:
., 5 containing polymers, in particu.lar, acry.Lamide copoLymers in which . ~ the comonomer contains an amino or ha.lo group, respectively. Thus, for example, a copolymer of acrylamide and dimethylaminoethyl methacrylate can be quaternized with methy.l chloride or a copo.lymer of acrylamide with chloroethylmethacrylate can be quaternized with :; 10 trimethylamine dispersed in oil having a reduced water content.
, . .
. The fine.ly divided polymer dispersed in oi.L, of reduced water .
content (prepared as hereinabove described by either forming an .
, emulsion by adding polymer to a water in oil emulsion or producing : .
the po.lymer by po.lymerization in a water in oil emulsion; followed : ~.
by reduction of the water content) has an average particle size . . .
genera.l.b in the order of O..l micron to 500 microns, and most frequent.ly, 0. 5 to .lO0 microns. ~Larger particle sizes cou.ld be used, .. ~ but some of the advantages of the inyention are decreased. ::
. .~
: ~ The chemical modifications can be effected by using the reagen~
: ~ :
~ and conditLons generalb known in the art, except that the polymer is treated dispersed in oil, with the:water content thereof being as here-inabove described, Solid reagent emp.loyed in the chemica.l modifi-:
. ~ ., cation may be added as fine powders, aqueous so.lutions or pre- ~ ~
'I ' .
emu.lsified in the same manner as the latex. In some cases, pre-. ~ ' .
. ~ ~ 25 emulsificatlon of the reagent may be required in order to prevent I coa~ulatidn or agglomeration of the polymer. L;quid reagents~-can~
3~
. :-:
.
t.,, ~ :
' ' : ' . . . ' . '': ' '' ~ , , ' ,, ~
.'' ' . ~ , ' , , .:
also be pre-emulsified.
The acrylamide po.lymer, as hereinabove noted, may be chemi- :
cally modlfied with various known reagents, inc.luding, as represen-tative e~amples, bases, dia1kylamine and forma.ldehyde, sodium bLsulfil;e and formalde.hyde; N,N-dialkyldiamines, etc.
The chemical modification of acrylamide polymers may be effected at reaction temperatures known in the art, generally in the order of 15D to 130~C at atmospheric or e.levated pressures The . above conditions are on.ly il.lustrative, and the se.lection of suitab.le conditions is deemed to be within the scope of those skilled in the art.
In accordance with the present invention, it has been found that chemical modification of acrylamide polymers dispersed in oil9 by neutralization, should be effected with gaseous ammonia in that ~ .:
attempts to use GtL~r bases results in agglomeration or coagulation .
~5 of the dispersed po.lymer. The neutralization with ammonia isgenerally efIected at temperatures of 20C to .130C, preferably at a temperature of 50 to 100C. It is to be understood that the present invention is not limlted to such il.lustrative temperatures.
~; . It has also been found iA accordance with the present invention, :.
ao that~advantageous r~sults are obtained by the use of ammonia or :~
ammonium hydro~if3ie, instead OI other conventional bases, for the .-neutralization of acrylamide po.lymers, in particular, those having .
a molecular weigh~ of at least 1009 000 Thus, for example, improve~
ments in conventionaL1 neutralization of acrylamide polymers in ~ :
: 25 aqueous media are ~3btained by the use of ammonia or ammonium . - - . , - hy~oxide.as-a result of the. ability to r~ore effective.ly contr-o1~hydro~
, ~37~7~ :
ys is .
In accordance with still another aspect of the present invention, water soluble condensation po.lymers, in particular, polyamines, are producéd by polymerization in a water in oil emulsion. By proceeding in this manner, concentration of the polymer in the water phase can be increased to concentrations greater than those heretofore used in the art, without the disadvantages which would normally result from the presence of high polymer concentrations.
As known in the art, polyamines are produced by condensation of a po.lyfunctional amine; i. e., having two reactive amine hydrogen atoms, with an epiha.lohydrin or an alky.l diha.lide. ~ -As representative examples of suitable water so.luble amines having two reactive amine hydrogen atoms suitable for the present invention, there may be mentioned: Methylamine, ethylamine, ethan-olamine, propylamine, NJ N-dimethy.lethylenediamine, piperazine anci aniline are suitable. The amLnes need not possess great water . . :
so.lu~ility, and the suitability of any particular amine as a raw ma~erial can be readily determined by laboratory trial. Mixtures . ~ :
of two or more bifunctional amines~may be used.
-: 20 As polyfunctiona.l amines, there may be employed any water soluble amine containing three or mDre reactive amino hydrogen :.
atoms. These amines consequently have a functionality greater than :.
2, and inc.lude amines such as ethylenedlamine, N-rnethylethylene-diamine, the po.lyalkylenepo.lyamines including diethylenetriamine, tetraethylenepentamine and the corresponding po.lypropylenepoly- .
- an~inesj p-phenylenediamine, p,~p'-bisaniline, and l, 3-diamino:.-2- -1 . .. ::: .
,,:
-15- ::
~, ' :
' ~ Q~79~77 propanol.
The epihalohydrin used in this invention has the essentia.1 group ' . ' - C - C X
wherein epoxy group is bonded to two carbon atoms, one of which is bonded adjacently to a carbon atom having the halogen bonded thereto.
The halogen is pre:eerably chlorine for reasons of availability and cost, but may be bromine or iodineO The indicated free valences on .
the carbon atoms are satisfied by hydrogen or lower alkyl groups, ~ .
preferably the methyl or ethyl groups.
The epihalohydrin is preferably epichlorohyclrin but may be -: .
: epibromohydrinJ epiiodohydrin, or one of the higher molecular : .
weight vicinal halohydrins such as 3-chloro-1,,2-epoxybutane, 3- ::
chloro-l,~-epoxypentane, etc. : ~ .
The a.lkyl dihalide used in the invention is preferab.ly a dichlo- .
:~ ride or dibromide of lower alkanes (2-4 carbon ato~ns), w1th the halo ~ -.
group preferab.ly belng on the terminal carbon ato-ms. As represen-: :
tative examp.1es of suitable compounds, there may be mentioned: .:
i ~ ~ : .1,2.-d1ch1Oroethane, i,2-dibromoethane, 1,3~dichloropropane,i1,3 i: ~ 20 dibromopropane, etc.
: :. ' .
- ~ The selection of suitable amines for condensation with a dihalo- : ~ -~: alkane and/or epiha.lohydrin is deemed to be within the scope of those ~ ~ skilled in the art from the teachings herein.
: : : The reaction is general.ly effected at temperatures known in the : .
~ , art; i. e., temperatures in the order of 0-.100C. In addition, the ~ . .
~ reactioh,mixture, as known in the art, preferably includes an~acid, : -16- :. ~
: :
.", , ' ' ~ ~ ' : . '~ '. ' , :~ ' ' ' . .' . . ' .
7~
acceptor; in particularJ an aLka.Li meta.l hydroxide.
As known in the art, the molar ratio of dihalo compound or epihalohydrin to ammonium generally ranges from about l.l:.l to l 8:1.
The general conditions for producing po.lyamine condensation ~.
polymers are known in the art, and such teachings are app.licable to the present invention.
In accordance with the present invention, the mono-mers are condensed in a water in oil emulsion, with the water phase, including monomer, genera.Uy comprising from 25~c to 75~c, by weight, of the . 10 emulsion, based on water and oil.
- The water phase is present in an amount to provide a po.lymer water phase comprised of from 50~c to 90~c, of water, preferably 60%
: to 90~c, al.l by weight, based on po.lymer and water. Subsequent to -comp.letion of the po.lymerization, water may be removed, as hereln- ~.
. 15 above described to provide more concentrated po.lymer in water . solutions. The oil may also be removed, as hereinabove described ::
. ~,:
to provide flowable composition of polymers of concentrations higher than heretofore available in the art. Thus, for examp.le, the oil content could be reduced to the order of 2û~c to 80~, preferab.ly 20'1c ; .
to 70~c, àrld most preferably 20~c to 50~c, of the tota.l composition, : : :
by weight, whichprovides an improvement over the IO~c po.lyamine solutions general.ly available in the art. : -The monorners are emulsified in the oil phase by the use of a : suitable water in oil emu1sifying agent. The emulsifier is general.ly ~ present ~n an amount of from 0 1 to lO percent, by weight, of the oil :
; phase. The emulsiïiers are well known in the art and no further .: ~
: ~, : : :
. : ' ' ,' ~ lq~
, ~ :
,~
: :, ', ' '' ' ' : ' ' .
: ' , . . .
: ' . . .
~()7~47~
details are deemed necessary in this respect for a complete under-standing of the invention.
It is also to be understood that the polyamine could be ; produced by conventional techniques, followed by emulsification of the water polymer solution in oil and evaporation of the water to produce a more concentrated aqueous solution of polyamine.
The invention will be further described with respect to the following examples/ but it is to be understood that the scope of ~ the invention is not to be limited thereby.
; 10 EXAMPLE 1 A commercial acrylamide polymer known as Nalco 623 is a high molecular weight copolymer containing about 93% acrylamide and 7% acrylic acid groups. This polymer is of the type described in U.S. Patent No. 3,284,393, Vanderhoff, an emulsion comprising a continuous phase of hydrocarbon in which are suspended fine particles of acrylamide solution (gel). The composition of Nalco 623 is approximately as follows:
by weight Copolymer 30 ' 20 Water 38 Hydrocarbon 28 ;~
Emulsifier 4 *
A 20 gram sample of Nalco 623 was weighed into a 2 ounce bottle followed by 4.3 grams of toluene. The bottle was then connected to a water aspirator and vacuum was applied. The bottle ;
was held at 20-25C with a water bath for 12 minutes, a~ter which }, -~
the temperature of the bath was raised to 40C for 30 minutes and to 50C for another 10 minutes. The bottle was disconnected and -the product was found to weigh 13.7 grams (loss of 10.6 grams of , 30 water and hydrocarbon combined). A sample of the product was f removed and designated Sample A. To the remainder of the product ~-*
Trademark ~7~7~ `
in the bottle (8.4 grams) was added 4.3 grams of toluene. Vacuum was then applied over a 20 minute period while the bath tempera-ture was raised from 25C to 80C. Distillation was discontinued at this time and the remaining product was found -to weigh 6.1 grams. The proauct was diluted with 3 ml of VM&P naphtha and designated Sample s.
Samples A and s and a sample of untreated Nalco 623 were subjected to a compatibility test with surfactant that was supplied along with the sample of Nalco 623. The surfactant had the designation "Activator" and is a nonionic surfactant of the polyethylene oxide condensate type. The compatibility test con- ~
sisted of adding 2 ml of sample to a vial followed by 0.08 ml of -activator and then mixing. The samples were then observed over a two month period. The results were as follows: ;
Material A~pearance Original Nalco 623 Coagulation in two minutes ~, Sample A CocLgulation in seven minutes Sample B No coagulation observed over a - ; -two month inspection period -Part A. A 500 gram portion of 10% polyacrylamide gel `- (0.703 monomer mole) is placed in a jackèted sigma mixer. This polyacrylamide has an intrlnsic viscosity of 12.6 measured in ~. .. . .
; ! 1 normal NaCl at 25C. Heat is applied to the jacket to bring the polymer mass to 50C and mlxing is started. The reaction mixture is buffered on the alkaline side by addition of 5 g. of Na2HPO4.2H2O and 8 g. of Na3PO4.10H2O. This is followed by 14.2 g. of 37~ formaldehyde solution (0.176 mole). The temperature is held at 50 C with mixing for 80 minutes, after which 20 g. of a ~l 30 40~ dimethylamine solution (0.176 mole) is added and the tempera- --~ * Trademark ., .
, . .
~74477 ture raised to 75C and held for 30 minutes. A sample of the aminomethylated polyacrylamide is dissolved in 1 normal NaCl for determination of its intrinsic viscosity which is found to be 9.8.
Part B. A 30% polyacrylamide latex is prepared by the technique of Vanderhoff and found to have an intrinsic viscosity of 11.9~ The composition of the latex is as follows:
%
~:
Polyacrylamide 30 Water 38 ~;
10 Low Odor Paraffin Solvent(Exxon) 28 Brij* 92 (polyoxyethylene(2)oleate) 4 : .
In a 500 ml three neck round bottom flask equipped with a stirrer ~ -is placed 166.5 g. of the above latex (50 g. polyacrylamide, 0.703 monomer mole). Stirring is started and the latex is heated to 50C after which an emulsion composed of the following is ::
added: Step 1 Grams Na2HPO4.2H2O 1.5 3PO4-10H2O 3.0 ` 20 37~ formaldehyde 14.2(0.176 moles) :.
~, Water 15.0 ~: Low Odor Paraffin 12.0 i, Solvent -:~
", ~ , ,~. Brij* 92 1.4 After 90~minutes at 50C, 29.1 g. of the following emulsion is added: Step 2 ::
, : , Grams ~: 40% dimethylamine 20 (0.176 mole) `
~ Low Odor Paraffin -l ~ 30 Solvent . 8 ;, Brij 92 1.7 The latex is then heated to 75C for 30 minutes, after which a -~ sample is dissolved ln 1 normal NaCl containing 0.04% Triton X-100 ; . .
* Trademarks , ,, , ~ , , ,, : ....... . . .
~ ~74~
for determination of the intrinsic viscosity of the aminomethyl-ated polyacrylamide, which is found to be 11.5.
A 20 g. sample of Nalco 623 is given the same drying treatment as Sample B in Example 1. The product is divided into two equal portions that are treated as follows: -Part A This half of the latex (containin~ 3 g of real polymer, 0.042 monomer mole) is placed in a 1 ounce bottle provided with a ~-heating bath and stirrer. Stirring is started and the bath is heated to 85 C. A solution containing 1.35 g. Na2CO3 (0.0126 ;
mole) and 5.5 g. water is made up, heated to 85C and added drop-wise to the latex with stirring. Heating and stirring are con-tinued at 85C, but after 5 minutes the latex coagulates.
Part B This half of the latex is processed as in A above except that instead of Na2CO3, gaseous ammonia is passed in over the , stirred mixture so as to create saturation. The ammonia atmos-i phere is then maintained over a 4 hour period with stirring at 85C. The product is cooled and blown with air to remove ammonia vapor.
, ,.
EXAMPLE 4 ;
, ~ Part A A 5 g. sample of polyacrylamide (0.703 monomer mole) ~; having a molecular weight of about 6 million is dissolved in water , to give 5~ solution. This so~lution is heated to 85C and 2.26 g.
of 37~ NaOH was added (0.022 mole). The base is mixed into the viscous mass, the reactor is closed, and the mixture is heated at :: , 85C for 6 hours.
Part B This experiment is carried out as in Part A except that instead of NaOH, 1.01 G. of 37~ ammonia (0.022 mole) is used.
The neutralized polymer has improved properties with respect to ', 30 the polymer produced in Part A. ~ ~-'. : , * Trademark ~
.~ . --21- ;
. .
: ~ , . : . .. . .
~L~7~77 Polyacrylamide having a weight average molecular weight of 3 million is made up as 3% solution containing 30 grams of poly-acrylamide (0.4222 monomer mole) and 970 grams of water. To this solution is added 3 grams of Na2PO4.2H2O, 5 grams of Na3PO4Ol0H2O ;
and 3.4 grams of 37% formaldehyde (0.042 mole). The reaction mixture is held at 45-50C for 80 minutes, after which 4.8 grams of 40% dimethylamine solution (0.042 mole) is added. The tempera-ture is then raised to 75C and held for 30 minutes. The mixture 10 is cooled and designated Product A. '~
An emulsion formed from 100 grams of Product A, 96 grams of Low Odor ParafEin Solvent (Exxon ) and 4 grams of Brij 92 (polyoxyethylene(2)oleate) is placed in a 500 ml round bottom flask and attached to a rotary vacuum evaporator that is fitted with a dip tube that can be used to feed or withdraw material from the evaporator.
Concentration is carried out at a pressure of 40 millimeters --of mercury over the temperature range of 40-80C. As the amounts -of water taken overhead reaches approximately 80 ml the contents of the evaporator are removed and emulsified with another 100 ml ~;~ of Product A. The hydrocarbon taken overhead is separated and returned to the emulsion. The new emulsion is returned to the ...
evaporator and the cycle is repeated until all of ~roduct A is concentrated to a stable latex containing .~
Grams Aminomethylated polyacrylamide 33 Water 17 Low Odor Paraffin Solvent 96 Brij 92 4 * Trademarks ~ID'7~'7 A 4 gram sample of the above latex is added with stirring to 600 ml of water containing 0.04% Triton X-100. The polymer dissolves within 10 minutes to give a solution of aminomethylated ; polyacrylamide.
A mixture of 287 grams (9.24 moles) of methylamine (755 grams of 37% aqueous solution), 400 grams of Low Odor Paraffin Solvent and 50 grams of Brij* 92 is emulsified by passage through a Manton Gaulin ~m~e ~ r. The emulsion is placed in a 5 liter ~-flask provided with a stirrer, condenser, thermometer and cooling bath, and 850 grams (9 moles) of epichlorohydrin is added o~er a 2 hour period at 40-45C. Next, 450 grams of 50% aqueous NaOH
:, (4.5 moles) is emulsified with 250 grams of Low Odor Paraffin Solvent and 20 grams of Brij* 92 and added over a one hour period with the temperature heId at 70-80C.~ Heating is continued for one hour at 60C. The product is a free flowing, non-viscous liquid that is readily dissolved in water by use of a water soluble surfactant.
~ .
A 100 gram sample of Nalco 623~is dried by the same pro-` ~ cess~as described for Example 1, Sample B, and the dried latex particles are centrifuged to remove hydrocarbon and then air dried at 50C to drive~off the remaining traces of hydrocarbon. The product is a fine white powder.
The present lnventlon~is particularly advantageous ln that ~
by proceeding in accordance~with the invention, it is possible to ~-, ,~ . .
produce water soluble polymers dispersed in oil which are stable to coagulation or agglomeration when subjected to subsequent treatment. ~ ~-* Trademarks .
, ' ~,''.. ~' :, ,:
~L~374~7~
In accordance with the present invention, it is possible to provide self inverting or dissolving polymer compositions by addition of a surfactant, to a composition of water soluble polymer dispersed in oil, without the polymer agglomera-tion or .;.-~ :
coagulation which would occur without proceeding in accordance with the invention.
Furthermore, the present invention offers the advantage that various water soluble polymers can be chemically modified, without the disadvantages inherent in attempting to modify such 10 polymers, in particular, those of high molecular weight, by -:
ordinary techniquesO .~:.
: As still another advantage, amine condensation polymers .~ .:
can be produced without limiting the polymer concentrations as heretofore required in the art. . .
~ , ' '' ': ' " .,.
,~ '-~ .
..
: .
'... '': ' , : :
: -24-.
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.. , . , , . .. . , .. ~ .
Claims (16)
1. A self-water dissolving composition of a water soluble polymer dispersed in oil which is stable to polymer coagulation and agglomeration, comprising:
a water soluble polymer selected from the group consisting of ethylenically unsaturated addition polymers and polyamines dispersed is oil, said polymers having a water content at which the polymer remains finely divided and dispersed in the oil, said water content being less than 40 percent, by weight, based on polymer and water, said water soluble polymer dispersed in oil having been prepared from a water-in-oil emulsion of said water soluble polymer by reduction of the water content thereof; and a surfactant in an amount effective to render the water soluble polymer self-dissolving in water.
a water soluble polymer selected from the group consisting of ethylenically unsaturated addition polymers and polyamines dispersed is oil, said polymers having a water content at which the polymer remains finely divided and dispersed in the oil, said water content being less than 40 percent, by weight, based on polymer and water, said water soluble polymer dispersed in oil having been prepared from a water-in-oil emulsion of said water soluble polymer by reduction of the water content thereof; and a surfactant in an amount effective to render the water soluble polymer self-dissolving in water.
2. The composition of Claim 1 wherein the composition contains no more than 30 percent, of water, by weight, based on polymer and water.
3. The composition according to Claim 2 wherein the composition contains no greater than 10 percent, by weight, of water, based on polymer and water.
4. The composition of Claim 2 wherein the polymer is an ethylenically unsaturated addition polymer.
5. A composition according to Claim 2, 3 or 4 wherein the polymer is a polymer of an acrylamide.
6. A composition according to Claim 2, 3 or 4 wherein the polar has a molecular weight of at least 100,000.
7. A process according to Claim 2, 3 or 4 wherein the polymer is present in an amount of from 5 percent to 85 percent, by weight.
8. The composition according to Claim 2, 3 or 4 wherein the composition is prepared from a water-in-oil emulsion containing from about 50 percent to 95 percent, by weight, water, based on polymer and water.
9. A process for producing a self-water dissolving composition of a water soluble polymer dispersed in oil which is stable to polymer coagulation and aggolmeration, com-prising: reducing the water content of a water-in-oil emulsion having finely divided water soluble polymer selected from the group consisting of ethylenically unsaturated addition polymers and polyamines dispersed therein, said emulsion containing from 50 percent to 95 per-cent, by weight, water, based on polymer and water, said water content being reduced to a water content which is less than 40 percent, by weight, based on polymer and water, at which the polymer remains finely divided and dispersed in the oil;
and adding a surfactant in an amount effective to render the water soluble polymer self-dissolving in water.
and adding a surfactant in an amount effective to render the water soluble polymer self-dissolving in water.
10. A process according to Claim 9 wherein the polymer dispersed in the water-in-oil emulsion was formed by a water-in-oil emulsion polymerization technique.
11. A process according to Claim 10 wherein the water content is reduced to less than 30 percent, by weight, of water based on polymer and water.
12. A process according to Claim 11 wherein the water content is reduced to less than 10 percent, by weight, of water, based on polymer and water.
13. A process according to Claim 11 wherein the polymer is an ethylenically unsaturated addition polymer.
14. A process according to Claim 10, 11 or 13 wherein the polymer is an acrylamide polymer.
15. A process according to Claim 10, 11 or 13 wherein the polymer has a molecular weight of at least 100,000.
16. A process according to Claim 10, 11 or 13 wherein the polymer is present in the oil in an amount of from 5 percent to about 85 percent, by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA327,624A CA1081883A (en) | 1974-01-02 | 1979-05-15 | Dispersions of water soluble polymers in oil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US42954874A | 1974-01-02 | 1974-01-02 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1074477A true CA1074477A (en) | 1980-03-25 |
Family
ID=23703728
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA217,213A Expired CA1074477A (en) | 1974-01-02 | 1974-12-31 | Dispersions of water soluble polymers in oil |
Country Status (8)
| Country | Link |
|---|---|
| JP (2) | JPS604215B2 (en) |
| BR (1) | BR7410936D0 (en) |
| CA (1) | CA1074477A (en) |
| DE (2) | DE2461934C3 (en) |
| FR (1) | FR2256202B1 (en) |
| GB (1) | GB1502779A (en) |
| NL (1) | NL171457C (en) |
| ZA (1) | ZA748222B (en) |
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| DE2840894A1 (en) * | 1978-09-20 | 1980-04-03 | Roehm Gmbh | Stable polymer suspensions |
| JPS6054912B2 (en) * | 1981-12-03 | 1985-12-02 | 洋 小泉 | Inorganic sheet for electrical insulation |
| DE3484407D1 (en) * | 1983-05-17 | 1991-05-16 | Allied Colloids Ltd | POLYMER SUSPENSIONS. |
| DE3426080C2 (en) * | 1984-07-14 | 1996-09-19 | Basf Ag | Process for the preparation of concentrated, stable water-in-oil polymer emulsions of water-soluble or water-swellable polymers |
| JPH01164813U (en) * | 1988-05-10 | 1989-11-17 |
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| US28474A (en) * | 1860-05-29 | Samuel Hall | Coupling for shafting | |
| DE1089173B (en) * | 1957-05-31 | 1960-09-15 | Dow Chemical Co | Inverse emulsion polymerization process for the production of polymers and copolymers of water-soluble monomers |
| DE1204411B (en) * | 1959-04-07 | 1965-11-04 | Hercules Powder Co Ltd | Process for the production of water-soluble polymers |
| US3122203A (en) * | 1959-07-23 | 1964-02-25 | Dow Chemical Co | Well washing process and composition |
| US3284393A (en) * | 1959-11-04 | 1966-11-08 | Dow Chemical Co | Water-in-oil emulsion polymerization process for polymerizing watersoluble monomers |
| NL268017A (en) * | 1960-08-08 | |||
| US3450680A (en) * | 1962-06-27 | 1969-06-17 | Nalco Chemical Co | Acrylamide terpolymers and their use in paper making process |
| US3507840A (en) * | 1967-04-27 | 1970-04-21 | Nalco Chemical Co | Method of removing water from water-soluble polymers |
| US3540680A (en) * | 1968-05-24 | 1970-11-17 | Lockheed Aircraft Corp | Dual rotor system for helicopters |
| GB1319632A (en) * | 1970-03-18 | 1973-06-06 | Ici Ltd | Process for the preparation of water-soluble polymers in solid form |
| US3691124A (en) * | 1970-09-10 | 1972-09-12 | Dow Chemical Co | Stabilized polymer in oil latexes and suspensions |
| US3734873A (en) * | 1970-12-15 | 1973-05-22 | Nalco Chemical Co | Rapid dissolving water-soluble polymers |
| US3624019A (en) * | 1970-12-15 | 1971-11-30 | Nalco Chemical Co | Process for rapidly dissolving water-soluble polymers |
-
1974
- 1974-12-28 JP JP754183A patent/JPS604215B2/en not_active Expired
- 1974-12-30 ZA ZA00748222A patent/ZA748222B/en unknown
- 1974-12-30 BR BR10936/74A patent/BR7410936D0/en unknown
- 1974-12-31 FR FR7443481A patent/FR2256202B1/fr not_active Expired
- 1974-12-31 DE DE19742461934 patent/DE2461934C3/en not_active Expired - Lifetime
- 1974-12-31 CA CA217,213A patent/CA1074477A/en not_active Expired
- 1974-12-31 DE DE2463201A patent/DE2463201C2/de not_active Expired - Lifetime
- 1974-12-31 GB GB56139/74A patent/GB1502779A/en not_active Expired
-
1975
- 1975-01-02 NL NLAANVRAGE7500015,A patent/NL171457C/en not_active IP Right Cessation
-
1980
- 1980-03-31 JP JP4189980A patent/JPS5622303A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6145642B2 (en) | 1986-10-09 |
| NL171457B (en) | 1982-11-01 |
| GB1502779A (en) | 1978-03-01 |
| ZA748222B (en) | 1976-05-26 |
| JPS50105754A (en) | 1975-08-20 |
| DE2463201C2 (en) | 1993-06-09 |
| NL171457C (en) | 1983-04-05 |
| NL7500015A (en) | 1975-07-04 |
| FR2256202B1 (en) | 1978-06-23 |
| FR2256202A1 (en) | 1975-07-25 |
| JPS5622303A (en) | 1981-03-02 |
| DE2461934C2 (en) | 1983-09-01 |
| DE2461934C3 (en) | 1992-08-27 |
| BR7410936D0 (en) | 1975-08-26 |
| JPS604215B2 (en) | 1985-02-02 |
| DE2461934A1 (en) | 1975-07-03 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |