CA1303265C - Water-soluble polymer dispersion - Google Patents
Water-soluble polymer dispersionInfo
- Publication number
- CA1303265C CA1303265C CA000586414A CA586414A CA1303265C CA 1303265 C CA1303265 C CA 1303265C CA 000586414 A CA000586414 A CA 000586414A CA 586414 A CA586414 A CA 586414A CA 1303265 C CA1303265 C CA 1303265C
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- Prior art keywords
- peg
- water
- molecular weight
- soluble polymer
- wsp
- Prior art date
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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
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
- C08L1/08—Cellulose derivatives
-
- 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
- C08J2300/10—Polymers characterised by the presence of specified groups, e.g. terminal or pendant functional groups
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Colloid Chemistry (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Medicinal Preparation (AREA)
Abstract
0607p S. M. Ahmed Case 1 WATER SOLUBLE POLYMER DISPERSION
Abstract of the Disclosure A stable aqueous dispersion comprising a particulate water-soluble polymer and a low-molecular weight polyethylene glycol in which the water-soluble polymer is substantially insoluble, water, and a high molecular weight polyethylene glycol, and a method for making it, are disclosed. The dispersion is easier to handle and has a higher dissolution rate than particulate water-soluble polymers.
Abstract of the Disclosure A stable aqueous dispersion comprising a particulate water-soluble polymer and a low-molecular weight polyethylene glycol in which the water-soluble polymer is substantially insoluble, water, and a high molecular weight polyethylene glycol, and a method for making it, are disclosed. The dispersion is easier to handle and has a higher dissolution rate than particulate water-soluble polymers.
Description
~3032~S
This inYention reLate~ to aqueou~ di~persion~ of partic-ulate water-301uble polymera (WSDs) in which the poly~er i3 disper3ed in polyethyle~e glycol to avoid the fosma~ion of lump~ in the aqueou~ disper3ions, and method~ for making them.
WSPs are often used to modify rheological properties o~
aqueou3 ~olutions, for in~tance, as thickener~ for late~
paints, weLl servicing fluids, cosmetic~, per~onal hygiene products, and ~ood products, and as stabilizers for emul~ion and ~uspension polymerizatlon.
In solution or dispersion ~emulsion) form, WSPs have commercial advantages over tho~e in the dry powder (particulate) form, including ease in handling and in the case of dispersion~, highar di4solution rates. Synthetic WSPs based on liquid or gaseou~ monomers can easily be pre-pared in liquld ~orms, for instance by ~olution or disper-sion polymeri~ation, but WSPs derived from natu~al starting materials are already ~olid polymers. Since they may lump exces~iv~ly when added to water, special care must be taken 2~ when adding such WSP~ to water, to avoid the lu~ping and gel ~ormation that re~ult in very low di~solution rate~.
Unacceptable gel level~ often remain in the~e solutions.
One method for reducing lumping when dispersing hydrp-philic gums ~uch as sodium carbo~ymethyl cellulose (CMC) and guar gum into formulations containing water, i~ described in U.5. Pa~ent 4,453,919: it comprises (a) preparing a blend ~30326S
of water and a water-miscible alcohol that includes poly-ethylene glycol having a preferred molecular weight of 200 to 4000, ~b) introducing the hydrophilic gum into the aqueous alcohol blend, (c~ intimately mising the resultant slurry, and (d) feeding the slurry into a water-containing formulation. Thi~ technique i9 not suitable for making di3per~ions o~ WSP~ that are stable.
The ter~ ''dispersion" i~ u3ed herein to re~r to what might also be termed an "emul ion", "slurry" or "-~ol" and cons~i~ute~ a vehicle containing WSP that can b~ used in application~ where WSP in particulate or li~uid form are conventionally used.
A stabl2 disp~rsion i9 con~idered to be on~ that does not at least immediately separate into two or more distinct lS layers when standing, and in general, stability i~ defined in texms of the purpo~ o~ the digpersion. When the dis-persion will be used within a short period of time, in the order of minutes or hours, it i~ su~icient that the polymer re~ains dispersed or may be readily redispersed within that period ~tabl~ "a~ made" or "moderately" stable), but it is often desixable for the dispersion to re~ain stable d~ring ~torage for periods o~ one to ~ix month3. Conventionally diqpersed WSP tends to agglomerate into gels or soLids that cannot readily redisper~e after standing or more than a few hours or day~ or even much ~horter periods.
Thera is a need for an improved method for making dis-per~ion~ o certain particulate water-soluble polymer3 in aqueous liquids (in~luding polyacrylamide and polyacrylamide derivative , polyvinylpyrrolidone and polyvinylpyrrolidone derivatives, guar gum and guar gum derivatives, and cellulos~ derivatives), ~hat are ef~ctively ~table for their contemplated use before or after ~torage for up to ~i~ month~.
1303Z~iS
According to the invention there is provided an aqueous dispersion comprising a particulate water-soluble polymer selected from polyacrylamide, polyacrylamide derivative, polyvinyl-pyrrolidone, polyvinylpyrrolidone derivative, guar gum, guar gum derivative and cellulose derivative, and a polyethylene glycol of molecular weight 200 to 700 (low molecular weight PEG), characterized in that the dispersion also contains water and a polyethylene glycol of molecular weight greater than 3000 (high molecular weight PEG), and the particulate wa~er-soluble polymer is substantially insoluble in the low molecular weight PEG.
As indlcated "low molecular weight polyethylene glycol"
is a substituted or unsubstituted polyethylene glycol that is llquid at room temperature and has molecular weight of about 200 to about 700, preferahly 250 to 500.
A "hlgh molecular welyht polyethylene glyco]." is a substituted or unsubstituted polyethylene glycol that ls solid at room temperature (preferably in the foxm of a flake or powder), and has a molecular welght greater than about 3,000, preferably o~
about 3,000 to about 50,000, and most pre~erably o~ about 10,000 to about 30,000. Such polyethylene glycols may be readily dlssolved ln water.
With respect to both low or high molecular weight polyethylene glycolæ, one or more of each may be used, and pre~erably, they are either unsubstituted or substituted with a methoxy group.
Polyethylene glycol, also called "polyoxyethylene", "poly(ethylene oxide)" or "polyglycol"r the well known .
i3~13265 condensation polymer of ethylene glycol having the formula CH CH (OCH CH -) -OCH2CH2-OH or H(OCH2C 2)n methoxy polyethylene glycol are commercially available in various grades, for ins~ance, under the trademark "Carbowax" o~ Union Carbide Company. Polyethylene glycol is commonly identi~ied by its molecular weight (MW) and the type of substituents in combination with the initials "PEG". Thus, polyethylene glycol with a molecular weight of 350 that is substituted with a me~hoxy group may be referred to as "methoxy PEG 350". This terminology is used herein when appropriate~
The polymer must not be readily soluble in the LW-PEG
hecause if too much o~ the polymer dissolves in the LW-PEG, the liquid will become too vlscous to be suitable for the purposes of this invention, in some instances forming a gel. The degree of solubility that is permissable obvlously is immediately apparent by trial o~ any particular combination of ingredients.
Examples o~ water-soluble aellulose derivatives that can be used to form the aqueous dispersions of this invention are hydroxyethyl cellulose (HEC), carboxymethyl hydroxyethyl cellulose tCMHEC), hydrophobically modified hydroxyethyl cellulose ~HMHEC), sodium carboxymethyl cellulose (C~C), ethyl hydroxyethyl cellulose, methyl cellulose and hydroxypropyl methyl cellulose, etc.
Dispersible synthetic polymers include polyvinyl-pyrrolidone, polyacrylamide, and their derivatives. Guar, hydroxypropyl guar, xanthan, gum tragacanth, gum karaya, gum arabic, tara gum, and similar polysaccharides can also be ~ 3~)3265 dispersed with this invention.
The water-soluble polymer is polyacrylamide or a polyacrylamide derivative, polyvinylpyrrolidone or a polyvinyl-pyrrolidone derivative, guar gum or a guar gum derivative, or a cellulosic derivative. The preferred cellulose deriva~ives are sodium carboxymethyl cellulose and Garboxymethyl hydroxyethyl cellulose.
Also according to the invention there is provided a method for making an aqueous dispersion of a particulate water-soluble polymer comprises the steps:
(1) mixing a low molecular weight polyethylene glycol (LW-PEG) with a water-soluble polymer (WSP) using a weight ratio of WSP to LW-PEG of from 1:100 to 151; and (2) adding a high molecular weight polyethylene glycol (HW-PEG) using a weight ratio o~ WSP to HW-PEG of S,l to 20:1 along with water uslng a weight ratio of WSP to water of 15:1 to 1:3;
wherein a stable disp~rsfon results.
The resultant dispersion may be stored and added, or directly added, to any aqueous formulation requlring WSP where the end use will tolerate the presence of PEG. It is desirable that the dispersion have suitable fluidity for its intended use, requiring control of the ratio of WSP to 4a ~3~3265 LW-PEG, ~which i~ affected by the solubility of the partic-ular WSP in the LW-PEG), the ratio of WSP to HW-PEG, and the ratio of WSR to water. Generally, higher concentrations of WSP are pre~erred when the disper~ion will be transported or stored for a long period~.
The stability of the di3per~ion~ of this invention tends to be e~tremely sensitive to th~ amount of water used and the amount of water used ~hould not be so great th~
polymer swell~ and a gel is formed, the permissible amount being immediately apparent for any particular combination of ingredients.
Preferably, in th~ mixture of LW-PEG and WSP, the weight ratio o~ WSP to LW-PEG ~hould be about 1:100 to about 1:1, more pre~erably 1:5 to 1:2. Also pr0ferably, the amount of HW-PEG added should be in a weight ratio of WSP to HW-PEG o~ about 5:1 to about 20:1, preferably 10:1 to 15:1, and the amount o~ wat~r added with it should be in a weight ratio of WSP to water o about 15:1 to about 1:3, preferably lOal to 1:1.5.
The ~tability of an lndividual disper~ion~ can be readily determined without undue experimentation by anyone of ordinary skill in the art by a simple test-tube experi-ment in which a WSP iq mixed with LW-PEG to determine it~
compatibility. If the polymer is found to be su~ficiently 2~ in~oluble in the LW-PEG, water and ~-PEG, aqueou~ solutions of HW-PEG, or combinations thereof are added to the ~lurry until the specific combination that provide the desire~
stability and ~luidity i9 determined. For instance, a composition comprising 20~ medium viscosity CMC (ca. 0.7 degree of substitution, medium vi~cosity, i.e., 400-800 ~p~
Brookfield Vis~osity in a 2~ -~olution). 48~ PEG 200, 29~
water and 3~ PEG 20,000, alL based on the total weight of the dispersionq, forms a gel; wherea0, a similaE compo~ition co~taining PEG 300 or PEG 400 instead of PEG 200 form~ a ~table di~per~ion (3table a~ made).
~L~0326~;
It is believed that this invention involves a water-in-water emulsion in which the "disperaion" ha~ two phase3 formed i~ the pres~nce of ~he HW-PEG, a dispergion medium or vehicle co~prising the LW-e~G and water, and a diRpersed phase comprising the WSP and water. The di3tribution of the HW-PEG ia not known. Thus, for the purpo~es o this invention, the term "di3per~ion" iR uged to describe any mixture containing the four components that can be u3ed in applicationY where particulate or liquid water-~oluble polymer are conve~tionally u~ed.
The present invention will b~ illugtrated in the fol-lowing e~amples. In ths examples all percentage3, parts, etc., ar~ by weight unles~ otherwi~e noted.
Example 1 ~he following e~ample show~ the effect of adding water or water containing ~W-PEG to a dispersion of CMC in a LW-PEG vehicle.
A mixture of PEG 300 and CMC (CMC 7M, available from the Aqualon Company, Wilmington, Delaware, having a Brookfield visco~ity o~ about 400-800 Cp9 in a 2 wt ~
~olution at 25C) wa~ prepared and ~ound to be un~table.
Subse~uently, in 3eparate runs, water and water containing mall amounts oi PE~ 20,000 were prepared. Results are shown in the following Table 1. Only the disper~ion containing ~W-PEG was stable.
,o .
~ o I
U~ o CL -^1 ~n o .
t:~ ~ o E C3 C ._ ~L I O
o ~U U~
~ ~10 T
_ ~I L
s ~1 :1~ ~ '0 d9 CL l o.~ X
O ~ ~
~C
. .~ _ :~ ~ ~ to ~
.' ~ 'o' u~ a ~ ~ 8 ,, O ~ ~
;~ 0~
I ~ 01 1 ~ ~
C :~1 _ ~ o~
I ~ Il~ O a~ ~r E ~ ~
_ V ¦ ~ O ~ O
~ ~ o~ ~ ~ .
'~
o :
, ~303Z65 Example 2 This exampls shows that the polymer must be substan-tialLy insoLubLe in thc LW-PEG used for stable disper~ion.
Mixtures of the CMC u~ed in Example 1 and LW-PEG wer~
S prepared to determine their solubility. CMC wag found to be soluble up to 20 wt. ~ with PEG 200, but substantially in301uble in PEG 300 and PEG 400. The blends of the latter two ~ixture~ quickly ceparated into two distinct layer~ upon tanding. Addition of water containing a small amount of PEG 20~000 increased the ~tability of the PEG 300 and PEG
400 disp~r3ions, whereas the PEG 200 composition formed a gel. Results obtained with water and PEG 20,000 are ~hown in ~able 2 below.
~30326S
g o .~ ~ oo . ~ o ~n ~ ~ .-C~ .~ ~
~,7 :~
._ tn O ~5 Q l ._ .~ E ¦ o O
~ ~ ~ ~ .
U~ ~ ~
~ ~ ~.
~ U~ o O ~ ~ -_ O :~ I~
C ,Q~ ._ ~
D I _ ~. ~ ~
_ aL ~S ~ t/1 lJ~
N c l ~ ~
._ ~ 2 .. ~ a~
Cl_ ~ 0~
This inYention reLate~ to aqueou~ di~persion~ of partic-ulate water-301uble polymera (WSDs) in which the poly~er i3 disper3ed in polyethyle~e glycol to avoid the fosma~ion of lump~ in the aqueou~ disper3ions, and method~ for making them.
WSPs are often used to modify rheological properties o~
aqueou3 ~olutions, for in~tance, as thickener~ for late~
paints, weLl servicing fluids, cosmetic~, per~onal hygiene products, and ~ood products, and as stabilizers for emul~ion and ~uspension polymerizatlon.
In solution or dispersion ~emulsion) form, WSPs have commercial advantages over tho~e in the dry powder (particulate) form, including ease in handling and in the case of dispersion~, highar di4solution rates. Synthetic WSPs based on liquid or gaseou~ monomers can easily be pre-pared in liquld ~orms, for instance by ~olution or disper-sion polymeri~ation, but WSPs derived from natu~al starting materials are already ~olid polymers. Since they may lump exces~iv~ly when added to water, special care must be taken 2~ when adding such WSP~ to water, to avoid the lu~ping and gel ~ormation that re~ult in very low di~solution rate~.
Unacceptable gel level~ often remain in the~e solutions.
One method for reducing lumping when dispersing hydrp-philic gums ~uch as sodium carbo~ymethyl cellulose (CMC) and guar gum into formulations containing water, i~ described in U.5. Pa~ent 4,453,919: it comprises (a) preparing a blend ~30326S
of water and a water-miscible alcohol that includes poly-ethylene glycol having a preferred molecular weight of 200 to 4000, ~b) introducing the hydrophilic gum into the aqueous alcohol blend, (c~ intimately mising the resultant slurry, and (d) feeding the slurry into a water-containing formulation. Thi~ technique i9 not suitable for making di3per~ions o~ WSP~ that are stable.
The ter~ ''dispersion" i~ u3ed herein to re~r to what might also be termed an "emul ion", "slurry" or "-~ol" and cons~i~ute~ a vehicle containing WSP that can b~ used in application~ where WSP in particulate or li~uid form are conventionally used.
A stabl2 disp~rsion i9 con~idered to be on~ that does not at least immediately separate into two or more distinct lS layers when standing, and in general, stability i~ defined in texms of the purpo~ o~ the digpersion. When the dis-persion will be used within a short period of time, in the order of minutes or hours, it i~ su~icient that the polymer re~ains dispersed or may be readily redispersed within that period ~tabl~ "a~ made" or "moderately" stable), but it is often desixable for the dispersion to re~ain stable d~ring ~torage for periods o~ one to ~ix month3. Conventionally diqpersed WSP tends to agglomerate into gels or soLids that cannot readily redisper~e after standing or more than a few hours or day~ or even much ~horter periods.
Thera is a need for an improved method for making dis-per~ion~ o certain particulate water-soluble polymer3 in aqueous liquids (in~luding polyacrylamide and polyacrylamide derivative , polyvinylpyrrolidone and polyvinylpyrrolidone derivatives, guar gum and guar gum derivatives, and cellulos~ derivatives), ~hat are ef~ctively ~table for their contemplated use before or after ~torage for up to ~i~ month~.
1303Z~iS
According to the invention there is provided an aqueous dispersion comprising a particulate water-soluble polymer selected from polyacrylamide, polyacrylamide derivative, polyvinyl-pyrrolidone, polyvinylpyrrolidone derivative, guar gum, guar gum derivative and cellulose derivative, and a polyethylene glycol of molecular weight 200 to 700 (low molecular weight PEG), characterized in that the dispersion also contains water and a polyethylene glycol of molecular weight greater than 3000 (high molecular weight PEG), and the particulate wa~er-soluble polymer is substantially insoluble in the low molecular weight PEG.
As indlcated "low molecular weight polyethylene glycol"
is a substituted or unsubstituted polyethylene glycol that is llquid at room temperature and has molecular weight of about 200 to about 700, preferahly 250 to 500.
A "hlgh molecular welyht polyethylene glyco]." is a substituted or unsubstituted polyethylene glycol that ls solid at room temperature (preferably in the foxm of a flake or powder), and has a molecular welght greater than about 3,000, preferably o~
about 3,000 to about 50,000, and most pre~erably o~ about 10,000 to about 30,000. Such polyethylene glycols may be readily dlssolved ln water.
With respect to both low or high molecular weight polyethylene glycolæ, one or more of each may be used, and pre~erably, they are either unsubstituted or substituted with a methoxy group.
Polyethylene glycol, also called "polyoxyethylene", "poly(ethylene oxide)" or "polyglycol"r the well known .
i3~13265 condensation polymer of ethylene glycol having the formula CH CH (OCH CH -) -OCH2CH2-OH or H(OCH2C 2)n methoxy polyethylene glycol are commercially available in various grades, for ins~ance, under the trademark "Carbowax" o~ Union Carbide Company. Polyethylene glycol is commonly identi~ied by its molecular weight (MW) and the type of substituents in combination with the initials "PEG". Thus, polyethylene glycol with a molecular weight of 350 that is substituted with a me~hoxy group may be referred to as "methoxy PEG 350". This terminology is used herein when appropriate~
The polymer must not be readily soluble in the LW-PEG
hecause if too much o~ the polymer dissolves in the LW-PEG, the liquid will become too vlscous to be suitable for the purposes of this invention, in some instances forming a gel. The degree of solubility that is permissable obvlously is immediately apparent by trial o~ any particular combination of ingredients.
Examples o~ water-soluble aellulose derivatives that can be used to form the aqueous dispersions of this invention are hydroxyethyl cellulose (HEC), carboxymethyl hydroxyethyl cellulose tCMHEC), hydrophobically modified hydroxyethyl cellulose ~HMHEC), sodium carboxymethyl cellulose (C~C), ethyl hydroxyethyl cellulose, methyl cellulose and hydroxypropyl methyl cellulose, etc.
Dispersible synthetic polymers include polyvinyl-pyrrolidone, polyacrylamide, and their derivatives. Guar, hydroxypropyl guar, xanthan, gum tragacanth, gum karaya, gum arabic, tara gum, and similar polysaccharides can also be ~ 3~)3265 dispersed with this invention.
The water-soluble polymer is polyacrylamide or a polyacrylamide derivative, polyvinylpyrrolidone or a polyvinyl-pyrrolidone derivative, guar gum or a guar gum derivative, or a cellulosic derivative. The preferred cellulose deriva~ives are sodium carboxymethyl cellulose and Garboxymethyl hydroxyethyl cellulose.
Also according to the invention there is provided a method for making an aqueous dispersion of a particulate water-soluble polymer comprises the steps:
(1) mixing a low molecular weight polyethylene glycol (LW-PEG) with a water-soluble polymer (WSP) using a weight ratio of WSP to LW-PEG of from 1:100 to 151; and (2) adding a high molecular weight polyethylene glycol (HW-PEG) using a weight ratio o~ WSP to HW-PEG of S,l to 20:1 along with water uslng a weight ratio of WSP to water of 15:1 to 1:3;
wherein a stable disp~rsfon results.
The resultant dispersion may be stored and added, or directly added, to any aqueous formulation requlring WSP where the end use will tolerate the presence of PEG. It is desirable that the dispersion have suitable fluidity for its intended use, requiring control of the ratio of WSP to 4a ~3~3265 LW-PEG, ~which i~ affected by the solubility of the partic-ular WSP in the LW-PEG), the ratio of WSP to HW-PEG, and the ratio of WSR to water. Generally, higher concentrations of WSP are pre~erred when the disper~ion will be transported or stored for a long period~.
The stability of the di3per~ion~ of this invention tends to be e~tremely sensitive to th~ amount of water used and the amount of water used ~hould not be so great th~
polymer swell~ and a gel is formed, the permissible amount being immediately apparent for any particular combination of ingredients.
Preferably, in th~ mixture of LW-PEG and WSP, the weight ratio o~ WSP to LW-PEG ~hould be about 1:100 to about 1:1, more pre~erably 1:5 to 1:2. Also pr0ferably, the amount of HW-PEG added should be in a weight ratio of WSP to HW-PEG o~ about 5:1 to about 20:1, preferably 10:1 to 15:1, and the amount o~ wat~r added with it should be in a weight ratio of WSP to water o about 15:1 to about 1:3, preferably lOal to 1:1.5.
The ~tability of an lndividual disper~ion~ can be readily determined without undue experimentation by anyone of ordinary skill in the art by a simple test-tube experi-ment in which a WSP iq mixed with LW-PEG to determine it~
compatibility. If the polymer is found to be su~ficiently 2~ in~oluble in the LW-PEG, water and ~-PEG, aqueou~ solutions of HW-PEG, or combinations thereof are added to the ~lurry until the specific combination that provide the desire~
stability and ~luidity i9 determined. For instance, a composition comprising 20~ medium viscosity CMC (ca. 0.7 degree of substitution, medium vi~cosity, i.e., 400-800 ~p~
Brookfield Vis~osity in a 2~ -~olution). 48~ PEG 200, 29~
water and 3~ PEG 20,000, alL based on the total weight of the dispersionq, forms a gel; wherea0, a similaE compo~ition co~taining PEG 300 or PEG 400 instead of PEG 200 form~ a ~table di~per~ion (3table a~ made).
~L~0326~;
It is believed that this invention involves a water-in-water emulsion in which the "disperaion" ha~ two phase3 formed i~ the pres~nce of ~he HW-PEG, a dispergion medium or vehicle co~prising the LW-e~G and water, and a diRpersed phase comprising the WSP and water. The di3tribution of the HW-PEG ia not known. Thus, for the purpo~es o this invention, the term "di3per~ion" iR uged to describe any mixture containing the four components that can be u3ed in applicationY where particulate or liquid water-~oluble polymer are conve~tionally u~ed.
The present invention will b~ illugtrated in the fol-lowing e~amples. In ths examples all percentage3, parts, etc., ar~ by weight unles~ otherwi~e noted.
Example 1 ~he following e~ample show~ the effect of adding water or water containing ~W-PEG to a dispersion of CMC in a LW-PEG vehicle.
A mixture of PEG 300 and CMC (CMC 7M, available from the Aqualon Company, Wilmington, Delaware, having a Brookfield visco~ity o~ about 400-800 Cp9 in a 2 wt ~
~olution at 25C) wa~ prepared and ~ound to be un~table.
Subse~uently, in 3eparate runs, water and water containing mall amounts oi PE~ 20,000 were prepared. Results are shown in the following Table 1. Only the disper~ion containing ~W-PEG was stable.
,o .
~ o I
U~ o CL -^1 ~n o .
t:~ ~ o E C3 C ._ ~L I O
o ~U U~
~ ~10 T
_ ~I L
s ~1 :1~ ~ '0 d9 CL l o.~ X
O ~ ~
~C
. .~ _ :~ ~ ~ to ~
.' ~ 'o' u~ a ~ ~ 8 ,, O ~ ~
;~ 0~
I ~ 01 1 ~ ~
C :~1 _ ~ o~
I ~ Il~ O a~ ~r E ~ ~
_ V ¦ ~ O ~ O
~ ~ o~ ~ ~ .
'~
o :
, ~303Z65 Example 2 This exampls shows that the polymer must be substan-tialLy insoLubLe in thc LW-PEG used for stable disper~ion.
Mixtures of the CMC u~ed in Example 1 and LW-PEG wer~
S prepared to determine their solubility. CMC wag found to be soluble up to 20 wt. ~ with PEG 200, but substantially in301uble in PEG 300 and PEG 400. The blends of the latter two ~ixture~ quickly ceparated into two distinct layer~ upon tanding. Addition of water containing a small amount of PEG 20~000 increased the ~tability of the PEG 300 and PEG
400 disp~r3ions, whereas the PEG 200 composition formed a gel. Results obtained with water and PEG 20,000 are ~hown in ~able 2 below.
~30326S
g o .~ ~ oo . ~ o ~n ~ ~ .-C~ .~ ~
~,7 :~
._ tn O ~5 Q l ._ .~ E ¦ o O
~ ~ ~ ~ .
U~ ~ ~
~ ~ ~.
~ U~ o O ~ ~ -_ O :~ I~
C ,Q~ ._ ~
D I _ ~. ~ ~
_ aL ~S ~ t/1 lJ~
N c l ~ ~
._ ~ 2 .. ~ a~
Cl_ ~ 0~
3: C I ~Y CO CO CO
O E ~ t .
~~1 0 0 0 UJ
~ O O ~3 ~
UJ 3: O O O lc 1~ ~ ~
q) ~ o c e ~ I l6~
U~ o ' '. '~ .
. . .. . .
~3~;~265 Tha data in Table 2 ~how that the polymer to be dis-persed mugt be su~stantiallY ingoluble in the LW-PEG used for ~table dispersion.
Exam~e 3 Thi~ example show~ the preparation of digpersionq con~aining various amounts of PEG 400, CMC, water and PEG
20,000.
Di~p~r~ion~ of th~ C~C u~ed in Esample 1 in PEG 400 were prepared as in e~ample 2, except that the weights of the co~ponent9 were varied as shown in Table 3 below.
~e3ult~ obtained are ~hown in Table 3 below.
~ 3q~26~
! 1~ ~ o o o ~ u 1~ ~
.~ ~
.
Q 1:~ C!
. .Q~ E O O O O
~ ~ O ~ U~ 11) _ O N ~` ~ ; ;
~1 . ~
l_ ~ L
O :-~ ~
~:: ~ 4~ ~ u~
. .~ ~_ ~5 N
~ D ~
- ' :E gl t`~ C~ O Ul '~I ~ ~ 1 ~
ul C ~ o~ ~i D IUJ 0~ 0 1O c :E ¦ ~ ~ O O A D
U) -to I ~o ,~ n ~o~A t~ A A
U~ O ~
~3~32~
C~C digpsr~ioned With PEG 400 wa5 gtable, a~ made, but was not atable after 24 hou~. Slow phage separation occurred ater 24 hours with ~ample 5.
Example 4 S ~he ~ollowing exampLe ~hows the effect of adding wa~er, and water containing high molecular weight polyethylene glycol to a dispe~ion containing CM~EC and a low molecular weight polyethylene glycol.
CMH~C 420H (available ~rom the Aqualon Company, Wilmington, Delaware, having a Brookfiald ~VF vigcogity in a 1 wt. % agueous ~olution of 1,500 to 2,500 cp~ at 30 rpm with a #3 spindle) was mixed with PEG 200, 300, and 400 and found to be soluble, to varied extentg, a~ evidenced by gradual increa~e~ in visco~ities o~ thc blendgO C~EEC 420~, L5 on the other hand, showed complete inao~ubility with Methosy PEG 350, orming a ~omewhat sta~Le di~pergion on its own.
Samples 9 to 13 were prepared u~ing the methodg o~ Example 2, except that the components shown in Table 4 b~low w~e used. Results obtained are shown in TabLe 4 below.
~3~32~S
C~ o o O
U~ O
a~ ._ _ ~o .~ ~ ~
C:~ ~ Q
on 0~ u e o o o ._ _ N ~
oe a~ ~ c a) U~ _ I -- S -:c ~ ~ cr O ~ ~
_ . '~ ~
a~ o j~n ~E _ _ _ _ ~ u~ ~ a~ ~ ~ ~
~ o ~ ~ ~
~ o ~ ~ C
~ol o o o 0 P~ ~ ~
.;
a~ ~ o ~ r- ~ ~
I ~ ~ ~ ~ t~ CL~-V 1~
I~
a.) ~._.C
~ I ~ ' ~ zce t~7 U~ o ~
~032~S
Tablg 4 hows that due to the inRolubility of, CMH~C
420H in metho~y PEC~ 350 a gomewhzt gtable dic~per3ion results when they are mixQd. Addi~ion o~ water and PEG 20, 000 in proper amou~ts (Samples 12 and 13) produces a much more 5 ~table dispsr ion, i.e., ~table for perio~l:3 of greater thar 6 ~onth~.
Fh~ dispersiorl~ of this invention are u~e~ul in applica-tion~ wher~ dry water-soluble cellulose pol~mer3 have previ-ou~ly been used, as w~ll a~ in applications whera dry water-solubl~ cellulo~e poly~er-~ hava not b~an w~ll guited due to their slow di~olution rate~. Th~ di~p~r~ion9 are e~pecially u~eful for di~persing water-solubl~ polym~r9 in aqUeOU~ ~olu-tion~ 3uch a~, e.g., aqueous pain~sO well gervicing fluid~, co5~0tics, personal hygiene produc~ ood product~, and fluid~ u~ed in the preparation of polymers.
O E ~ t .
~~1 0 0 0 UJ
~ O O ~3 ~
UJ 3: O O O lc 1~ ~ ~
q) ~ o c e ~ I l6~
U~ o ' '. '~ .
. . .. . .
~3~;~265 Tha data in Table 2 ~how that the polymer to be dis-persed mugt be su~stantiallY ingoluble in the LW-PEG used for ~table dispersion.
Exam~e 3 Thi~ example show~ the preparation of digpersionq con~aining various amounts of PEG 400, CMC, water and PEG
20,000.
Di~p~r~ion~ of th~ C~C u~ed in Esample 1 in PEG 400 were prepared as in e~ample 2, except that the weights of the co~ponent9 were varied as shown in Table 3 below.
~e3ult~ obtained are ~hown in Table 3 below.
~ 3q~26~
! 1~ ~ o o o ~ u 1~ ~
.~ ~
.
Q 1:~ C!
. .Q~ E O O O O
~ ~ O ~ U~ 11) _ O N ~` ~ ; ;
~1 . ~
l_ ~ L
O :-~ ~
~:: ~ 4~ ~ u~
. .~ ~_ ~5 N
~ D ~
- ' :E gl t`~ C~ O Ul '~I ~ ~ 1 ~
ul C ~ o~ ~i D IUJ 0~ 0 1O c :E ¦ ~ ~ O O A D
U) -to I ~o ,~ n ~o~A t~ A A
U~ O ~
~3~32~
C~C digpsr~ioned With PEG 400 wa5 gtable, a~ made, but was not atable after 24 hou~. Slow phage separation occurred ater 24 hours with ~ample 5.
Example 4 S ~he ~ollowing exampLe ~hows the effect of adding wa~er, and water containing high molecular weight polyethylene glycol to a dispe~ion containing CM~EC and a low molecular weight polyethylene glycol.
CMH~C 420H (available ~rom the Aqualon Company, Wilmington, Delaware, having a Brookfiald ~VF vigcogity in a 1 wt. % agueous ~olution of 1,500 to 2,500 cp~ at 30 rpm with a #3 spindle) was mixed with PEG 200, 300, and 400 and found to be soluble, to varied extentg, a~ evidenced by gradual increa~e~ in visco~ities o~ thc blendgO C~EEC 420~, L5 on the other hand, showed complete inao~ubility with Methosy PEG 350, orming a ~omewhat sta~Le di~pergion on its own.
Samples 9 to 13 were prepared u~ing the methodg o~ Example 2, except that the components shown in Table 4 b~low w~e used. Results obtained are shown in TabLe 4 below.
~3~32~S
C~ o o O
U~ O
a~ ._ _ ~o .~ ~ ~
C:~ ~ Q
on 0~ u e o o o ._ _ N ~
oe a~ ~ c a) U~ _ I -- S -:c ~ ~ cr O ~ ~
_ . '~ ~
a~ o j~n ~E _ _ _ _ ~ u~ ~ a~ ~ ~ ~
~ o ~ ~ ~
~ o ~ ~ C
~ol o o o 0 P~ ~ ~
.;
a~ ~ o ~ r- ~ ~
I ~ ~ ~ ~ t~ CL~-V 1~
I~
a.) ~._.C
~ I ~ ' ~ zce t~7 U~ o ~
~032~S
Tablg 4 hows that due to the inRolubility of, CMH~C
420H in metho~y PEC~ 350 a gomewhzt gtable dic~per3ion results when they are mixQd. Addi~ion o~ water and PEG 20, 000 in proper amou~ts (Samples 12 and 13) produces a much more 5 ~table dispsr ion, i.e., ~table for perio~l:3 of greater thar 6 ~onth~.
Fh~ dispersiorl~ of this invention are u~e~ul in applica-tion~ wher~ dry water-soluble cellulose pol~mer3 have previ-ou~ly been used, as w~ll a~ in applications whera dry water-solubl~ cellulo~e poly~er-~ hava not b~an w~ll guited due to their slow di~olution rate~. Th~ di~p~r~ion9 are e~pecially u~eful for di~persing water-solubl~ polym~r9 in aqUeOU~ ~olu-tion~ 3uch a~, e.g., aqueous pain~sO well gervicing fluid~, co5~0tics, personal hygiene produc~ ood product~, and fluid~ u~ed in the preparation of polymers.
Claims (12)
1. An aqueous dispersion comprising a particulate water-soluble polymer selected from polyacrylamide, polyacrylamide derivative, polyvinylpyrrolidone, polyvinylpyrrolidone derivative, guar gum, guar gum derivative and cellulose derivative, and a polyethylene glycol of molecular weight 200 to 700 (low molecular weight PEG), characterized in that the dispersion also contains water and a polyethylene glycol of molecular weight greater than 3000 (high molecular weight PEG), and the particulate water-soluble polymer is substantially insoluble in the low molecular weight PEG.
2. The aqueous dispersion of claim 1 where the low molecular weight PEG has a molecular weight of 250 to 500.
3. The aqueous dispersion of claim 2 where the high molecular weight PEG has a molecular weight of 10,000 to 30,000.
4. The aqueous dispersion of claim 1, 2 or 3 where the water-soluble polymer is sodium carboxymethylcellulose.
5. The aqueous dispersion of claim 1, 2 or 3 where the water-soluble polymer is carboxymethylhydroxyethylcellulose.
6. A method for making an aqueous dispersion of a particulate water-soluble polymer comprises the steps:
(1) mixing a low molecular weight polyethylene glycol (LW-PEG) with a water-soluble polymer (WSP) using a weight ratio of WSP to LW-PEG of from 1:100 to 1:1; and (2) adding a high molecular weight polyethylene glycol (HW-PEG) using a weight ratio of WSP to HW-PEG of 5:1 to 20:1 along with water using a weight ratio of WSP to water of 15:1 to 1:3;
wherein a stable dispersion results.
(1) mixing a low molecular weight polyethylene glycol (LW-PEG) with a water-soluble polymer (WSP) using a weight ratio of WSP to LW-PEG of from 1:100 to 1:1; and (2) adding a high molecular weight polyethylene glycol (HW-PEG) using a weight ratio of WSP to HW-PEG of 5:1 to 20:1 along with water using a weight ratio of WSP to water of 15:1 to 1:3;
wherein a stable dispersion results.
7. The method of claim 6 where in step (2) the HW-PEG and water are added as a solution.
8. The method of claim 7 where the WSP to LW-PEG ratio is from 1,5 to 1:2, the WSP to HW-PEG ratio is from 10:1 to 15:1 and the WSP to water ratio is from 10:1 to 1:1.5.
9. The method of claim 8 where the LW-PEG has a molecular weight of 250 to 600.
10. The method of claim 8 where the HW-PEG has a molecular weight of 10,000 to 30,000.
11. The method of any one of claims 6 to 10 where the water-soluble polymer is sodium carboxymethylcellulose.
12. The method of any one of claims 6 to 10 where the water-soluble polymer is carboxymethylhydroxyethylcellulose.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US07/137,841 US4799962A (en) | 1987-12-24 | 1987-12-24 | Water-soluble polymer dispersion |
| US137,841 | 1987-12-24 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1303265C true CA1303265C (en) | 1992-06-09 |
Family
ID=22479266
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000586414A Expired - Fee Related CA1303265C (en) | 1987-12-24 | 1988-12-20 | Water-soluble polymer dispersion |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US4799962A (en) |
| EP (1) | EP0322736B1 (en) |
| JP (1) | JP2812968B2 (en) |
| AU (1) | AU612448B2 (en) |
| BR (1) | BR8806868A (en) |
| CA (1) | CA1303265C (en) |
| DE (1) | DE3880465T2 (en) |
| FI (1) | FI96318C (en) |
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-
1987
- 1987-12-24 US US07/137,841 patent/US4799962A/en not_active Expired - Lifetime
-
1988
- 1988-12-20 CA CA000586414A patent/CA1303265C/en not_active Expired - Fee Related
- 1988-12-21 EP EP88121388A patent/EP0322736B1/en not_active Expired - Lifetime
- 1988-12-21 DE DE8888121388T patent/DE3880465T2/en not_active Expired - Fee Related
- 1988-12-23 AU AU27556/88A patent/AU612448B2/en not_active Ceased
- 1988-12-23 FI FI885969A patent/FI96318C/en not_active IP Right Cessation
- 1988-12-23 JP JP63325710A patent/JP2812968B2/en not_active Expired - Lifetime
- 1988-12-26 BR BR888806868A patent/BR8806868A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| DE3880465D1 (en) | 1993-05-27 |
| BR8806868A (en) | 1989-08-29 |
| JP2812968B2 (en) | 1998-10-22 |
| AU2755688A (en) | 1989-06-29 |
| JPH021764A (en) | 1990-01-08 |
| DE3880465T2 (en) | 1993-08-05 |
| FI96318B (en) | 1996-02-29 |
| FI96318C (en) | 1996-06-10 |
| AU612448B2 (en) | 1991-07-11 |
| EP0322736B1 (en) | 1993-04-21 |
| EP0322736A2 (en) | 1989-07-05 |
| FI885969A (en) | 1989-06-25 |
| EP0322736A3 (en) | 1990-06-27 |
| US4799962A (en) | 1989-01-24 |
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