CA1086447A - Water absorbent polymers - Google Patents
Water absorbent polymersInfo
- Publication number
- CA1086447A CA1086447A CA283,430A CA283430A CA1086447A CA 1086447 A CA1086447 A CA 1086447A CA 283430 A CA283430 A CA 283430A CA 1086447 A CA1086447 A CA 1086447A
- Authority
- CA
- Canada
- Prior art keywords
- interpolymer
- weight percent
- methacrylate
- acid
- monomer
- 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
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
-
- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
- Y10S526/93—Water swellable or hydrophilic
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
- Y10S526/932—Thickener or dispersant for aqueous system
Abstract
ABSTRACT OF THE DISCLOSURE
Polymers of unsaturated copolymerizable carboxylic acids, at least one acrylic or methacrylic ester containing an alkyl of 10 to 30 carbon atoms, and another acrylic or methacrylic ester containing and alkyl of 1 to 8 carbon atoms, optionally with a small amount of a cross-linking agent, rapidly absorb and retain large quantities of water and ionic fluids, and are useful in disposable nonwoven articles.
Polymers of unsaturated copolymerizable carboxylic acids, at least one acrylic or methacrylic ester containing an alkyl of 10 to 30 carbon atoms, and another acrylic or methacrylic ester containing and alkyl of 1 to 8 carbon atoms, optionally with a small amount of a cross-linking agent, rapidly absorb and retain large quantities of water and ionic fluids, and are useful in disposable nonwoven articles.
Description
The invention relates to an interpolymer of monomers.
U.S. Patent 3,915,921 discloses copolymers of unsaturated carbo~ylic acid monomers with an alkyl acrylate ester wherein the alkyl group contains about 10 to 30 carbon atoms that are efficient water thickeners, which when neutralized by basic materials have improved resistance to loss in viscosity, even in the presence of substantial amounts of inorganic salts such as sodium chlorideO These copolymers absorb water, but copolymers having improved rates of water absorption and retention are desired.
According to the invention there is provided an interpolymer or copolymer of monomers comprising from about 40 to 87 weight percent of an ole~inically unsaturated carboxylic acid monomer, about 2 to 20 weight percent of at least one acrylic or methacrylic acid ester monomer of the formula R' O
"
CH2=C----C-O-R (I) where R' is hydrogen, methyl or ethyl and R contains 10 to 30 carbon atoms and about 5 to 30 weight percent of at least one other acrylic or methacrylic acid ester monomer of the formula:
R' 0 CH2=C -C-0-R (II) wherein R' is hyd~ogen, methyl or ethyl and R contains 1 to 8 carbon atoms, the interpolymer or copolymer may optionally include a small amount of a cross-linking agent, the copolymer or interpolymer rapidly absorbs and retains large quantities of water and also absorbs and retains ionic aqueous fluids.
In particular R in formula (I) may be alkyl of 10 to 30 carbon atoms or include an alkyl moiety of 10 to 30 carbon atoms~ In formula (II), R may suitably be alkyl of 1 to 8 carbon atoms or include an alkyl moiety of 1 to 8 carbon atoms.
;'i ~ ~' ' ~ ~
- ~ ' 4gL7 ; The copolymers of carboxylic acid monomer and the two .:: acrylic esters of the types and in the amounts defined .,: ' hereinafter provide a much faster rate of absorption of water and aqueous ionic fluids than copolymers not con-~,: taining these ~ssential comonomers in the amounts set forth.
The copolymers also demonstrate improved retention of ~ ., ~ ~ absorbed fluid as compared to prior art polymers. The : :, , ~:: copolymers are readily prepared by copolymerizing the '' .
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~64~L7 ` essential monomers, and optionally o~her comonomexs as defined, by free radical polymeri~ation ~ystems. These copolymers have weiyht avera~e molecular weights from about lo,OOO to greater than 1,000,000. Normally, the molecular weights are from about 50,000 to 900,000. Mole-cular weights of cross-linked polymers may be higher.
The carboxylic monomers useful in the production ..
of the polymers of ~his invention are the olefinically-unsa~urated carboxylic acids con~aining at l~ast one acti-vated carbon-to-carbon olefinic doubla bond, and at least one carboxyl group, that is, an acid containing an olefinic double bond which readily functions in polymerization because of its presence in the monomer molecule either in the alpha-beta position with respect to a carboxyl group thusly, -C=C-COOH, or as a part of a terminal methylene i grouping thusly, CH2=Cf present in the copolymer in amounts from abou~ 40 to 87 weight percent of the copolymer. In the alpha-beta acids the close proximity of the strongly polar carboxyl group to the double-~onded carbon atoms has a strong activating in1uence rendering the substances con-, ;.
taining this structure very readily polymerizable. The ` ::
-; presence of a terminal methylene group~ng in a carboxylic ;~ monomer makes this type of compound much more easily poly-; merizable than if the double bond were intermediate in the carbon structure. Olefinically-unsaturated acids of this class include such widely divergent materials as the acrylic acids typified by acrylic acid itself, methacrylic acid, ethacrylic acid, alpha-chloroacrylic acid, alpha-cyano acrylic acid, beta methyl-acrylic acid (crotonic acid), ~ 30 alpha-phenyl acrylic acid, beta-acryloxy propionic acid, ; _ 3 _ , . .
. :
:, :
~B644t7 i sorbic acid, alpha~chloro sorbic acid, anyelic acid, cin-: namic acid, p-chloro cinnamic acid, beta-styryl acrylic acid (l-carboxy-4-phenyl butadiene-1,3), itaconic acid, citra-- conic acid, mesaconic acid, glutaconic acid, aconitic acid, S maleic acid, fumaric acid, and tricarboxy ethylene. As used ~ herein, the term "carboxylic acid" includes the polycar-.~ boxylic acids and those acid anhydrides, such as maleic ~ anhydride, wherein the anhydride group is formed by the ~ elimination of one molecule of water from two carboxyl groups located on the same polycarboxylic acid molecule.
Maleic anhydride and the other acid anhydrides useful herein ~: have the general structure "
. R- C -,~................................. R'-C -C
.:
wherein R and R' are selected fxom the group consisting of ; 15 hydrogen, halogen and cyanogen (-C-.N) groups and alkyl,aryl, alkaryl, aralkyl, and cycloalkyl groups such as :"
methyl, ethyl, propyl, octyl, decyl, phenyl, tolyl, xylyl, :. benzyl, cyclohexyl and the like.
The preferred carboxylic monomers for use in this invention used in amounts of 40 to 87 weight percent total . ^
.: of the monomers polymerized are the monoolefinic acrylic .~ acids having the general structure :. R
CH2=C-COOH
wherein R is a substituent selected from the class consist-25 ing of hydrogen, halogen, and the cyanogen (-C~N) groups, monovalent alkyl radicals, monovalent aryl radicals, mono-valent aralkyl radicals, monovalent alkaryl radicals and , . .
` ,.i .;: - 4 -'"'''~, ,, .. .. .
8~'7 . ~
monovalent cycloaliphatic radicals. of this class, acrylic - and methacrylic acid are most preferred because of generally lower cost, ready availability, and abili~y to form superior polymers. Another useful carboxylic monomer is maleic ~ 5 anhydride or the acid.
`~ The preferred acrylic ester monomers having long chain aliphatic groups are derivatives of an acrylic acid represented by the formula R' O
: ' "
CH2~C -C--R
wherein R is an alkyl group having from 10 to 30 carbon atoms, preferably 10 to 20 carbon atoms and R' is hydrogen or a methyl or ethyl group presen~ in the copolymer in amount from about 2 to 20 weight percent, more preferably, ; about 5 to 15 weight percent. Representative higher alkyl acrylic esters are decyl acrylate, isodecyl methacrylate~
;........................................................................ .
lauryl acrylate, stearyl acrylate, behenyl acrylate and melissyl acrylate and the corresponding methacrylates.
~ixtures o~ two or three or more long chain acrylic esters may be successfully polymerized wi~h one of the car~oxylic monomers to provide useful thickening resins of this in-vention. Particularly useful are those methacrylates where the alkyl group contains 16 to 21 carbon atoms present in amounts of about S to 15 weight percent of the total mono-mers. Outstanding polymers have been made with 15~5 weight percent isodecyl methacrylate, 10~3 weight percent lauryl methacrylate, 7~3 weight percent stearyl methacrylate.
The other essential acrylic esters are also derivatives of an acrylic acid used in amounts of about . ~ , .
5 to 30 weight percent represented by the formula ` - 5 -.,.",~ .
:
''~. Rl O
CH2=C-C-0-R
wherein R is an alkyl, alkoxy, haloalkyl, cyanoalkyl, and like groups having from 1 to 8 carbon atoms and R' is hydrogen or a methyl or ethyl group. These acrylic esters are present in the copolymer ln amount rom about 5 to 30 weight percent and more preEerably from about 5 to 25 weight percen~. Representative acrylates include methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acry-late, butyl acrylate, isobutyl acrylate, methyl methacry-late, methyl ethacrylate, ethyl methacrylate, octyl acry-;~ late, heptyl acrylate, octyl methacrylate, i~opropyl methacrylate, 2-ethylhexyl acrylate, nonyl acrylate, hexyl acrylate, n~hexyl methacrylate, and the like.
The preferred cross-linking monomer for use in preparing the copolymers, if one is employed, is a poly-;~ alkenyl polyether having more than one alke~yl ether group-ing per molecule. The most useful possess alkenyl groups in which an olefinic double bond is present attached to a terminal methylene grouping, CH2=C~ . They are made by the etherification of a polyhydric alcohol containing at least 4 carbon atoms and at least 3 hydroxyl groups. Compounds of this class may be produced by reacting an alkenyl halide, such as allyl chIoride or allyl bromide with a strongly alkaline aqueous solution of one or more polyhydric alcohols.
The product is a complex mixture of polyethers with varying ~, . .
' numbers oE ether groups. Analysis reveals the average .:, .
~ number of ether groupings on each molecule. Efficiency of , .
- the polyether cross--linking agent increases with the number of potentially polymeri~able groups on the molecule. It is :;
~ - 6 -. . .
:; ~ . .
' preferred to utilize polyethers containing an average of two , . .
or mcre alkenyl ether groupings per molecule. Other cross-linking monomers include for example, diallyl esters, dimethallyl ethers, allyl or methallyl acrylates and acryl-amides, tetraallyl tin, tetravinyl silane, polyalkenyl ; methanes, diacrylates and dimethacrylates, divinyl compounds as divinyl benzene, polyallyl phosphate, diallyloxy com-, pounds and phosphite esters and the like~ Typical agents are allyl pentaerythritol, allyl sucrose, trimethylolpropane triacrylate, 1,6-hexanediol diacrylate, pentaerythritol triacrylate, tetramethylene dimethacrylate, tetramethylene diacrylate, ethylene diacrylate, ethylene dimethacrylate, triethylene glycol dimethacrylate, and the like. Allyl pentaerythritol and allyl sucrose provide excellent polymers in amounts less than 0.5 weight percent. Cross-linking of ; the polymers provides improved ability for the copolymers to swell under a confining pressure.
When the optional cross-linking agent is present, ` ~ polymeric mixtures ~ about 0 to about 3% by weight of cross-linking monomer based on the total of carboxylic acid monomer plus the alkyl acrylate ester monomers, and - more preferably, 0.1 to 0.5 weight percent or phm.
Another method to obtain the desired cross-linking is to use a comonomer which can react to yield cross-links during polymerization. Examples are 2-hydroxyethyl met~--; acrylate and hydroxypropyl methacrylate, and the like.
These units, when copolymerized, cross-link by interchain : esterification with carboxylic yroups. For 2-hydroxyethyl .,~
methacrylate, about 1 to 7 weight percent of monomers based on the total weight of monomers will pro~ide a desired " ' ' . ~
. . . .
6~
degree of cross-linking.
Another method of obtaining cross-linked polymers i~ by reac~ing small amounts of a polyvalent base wi-th the carboxyl-containing polymer. Those materials which yield multivalent cations, for example, include calcium, mag-nesium, zinc, and aluminum. A mixed salt to be used would be one containing potassium or sodium ions wlth small amounts of calcium or aluminum ions, for example, to provide , the multivalent cation to provide cross-linking through ; 10 polymeric carboxyl groups.
It will also be understood that small amounts of other vinylidene monomers, that is, those copolymerizable :~ ., .
~ monomers containing at least one ~erminal CH25 group may .,. ~ .
also be included as a copolymerizable monomer with the essential monomers so long as such monomers do not adversely afect the desired balance of water absorption and retention of the polymeric materials. Such materials include vinyl acetate, vinyl pyrrolidone, methyl vinyl ether, ethyl vinyl ether, methyl vinyl ketone and like in amounts less than about 10 weight percent of the polymer, normally less than 5-weight percent.
The polymers of this invention are preferably made by polymerization in an inert diluent having some solubiliz-ing action on one or more of the monomeric ingredients but ; 25 substantially none on the resultant polymer. Polymerization in mass may be employed but is not preferred because of the . ~
difficulty in working up the solid polymeric masses ob-... .
; tained. Polymerization in an aqueous medium containing a :
water-soluble free radical catalyst peroxygen is useful.
`~ 30 Polymerization in an organic liquid which is a solvent for '.;,.
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, .~ ,;
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.,~ .
~ ~OlYl~j4~L~
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the mono~ers but a non-solvent for the polymer, or in a ~ mixture of such solvents, in the presence of a solvent-: soluble catalyst is most pre$erred because the product is usually obtained as a very fine friable and often fluffy precipitate which, after solvent removal, seldom requires grinding or other treatment before use. Suitable solvents for the ]atter method include benzenel xylene, ~etralin, hexane, heptane, carbon te~rachloride, methyl chloride, ethyl chloride, bromo trichloro methane, dimethyl carbonate, diethyl carbona~e, ethylene dlchloride, and mixture~ of these and other solvent~.
The polymerizations desirably are conducted in the presence of a haloethane or halomethane, preferably con-taining at least four halogen atoms. Representative materials include for example, a fluoroethane, fluoromethane, chloro-fluoromethane, hromofluoroethane, or preferably a chloro-~- fluoroethane or chlorofluoromethane containing at least four halogen atoms including, for example, 1,1,2-trichloro-1,2,2-trichloroethane, trichlorofluoromethane, tetrafluoromethane, .'~ ~ .
chlorotrifluoromethane, bromotri1uoromethane, 1-chloro-~` 1,1,2,2,2-pentafluoroethane, dichlorodifluoromethane, 1,2 difluoro-1,1,2,2-tetrachloroethane and the like. The amounts of these materials used may be varied from the , : , `~ amount just sufficient to make a slurry of the reactants up to where there is a substantial excess of the chlorofluoro-ethane, as will be apparent to those skilled in the art.
Preerred diluents are those which are solvents ~or the monomers but nonsolvents for the polymers.
Polymerization in the diluent medium is carried out in the presence o a free radical catalys~ in a closed :~.
.., ' , ,, ' . : , :
~L(J 8~
vessel in an inert atmosphere and under autogenous pressure or artificially-induced pressure or in an open vessel under reflux at a~mospheric pres wre. Temperature of the poly-merization may be varied from QC. to 100C., depending to a large degree on the molecular weight desired in the polymer.
Polymerization under reflux at 50 to 90~C. under atmos-pheric pressure using a free radical catalyst is generally effective in bringing a polymer yield of 75% to 100% in less than 10 hours. Suitable catalysts include peroxygen com-pounds such as sodium, potassium and ammonium persulfates, caprylyl peroxide, benzoyl peroxide, hydrogen peroxide, pelargonyl peroxide, cumene hydroperoxides, tertiary butyl diperphthalate, tertiary butyl perbenzoate, sodium per-acetate, sodium percarbonate, and the like as well as azo diisobutyryl nitrile, hereinafter referred to as azoiso-butyronitrile. Other catalysts utilizable are the so-called "redox" type of catalyst and the heavy-metal activated catalyst systems.
These polymers generally do not at~ain their maximum properties until converted to a partial alkali, ammonium or amine salt. The neutralizing agent is prefer-ably a monovalent alkali such as sodium, pota~slum, lithium or ammonium hydroxide or the carbonates and bicarbonates , thereof, or mixtures of the same, and also amine bases having not more than one primary or secondary amino group.
5uch amines include, for example, triethanolamine, ethanol-amine, isopropanolamine, triethylamine, trimethyl amine, and the like.
At least 30~ o~ the acid, carboxyl, groups are neutral~zed to an ionic state, that is, -CO2 ~ . Prefer-:, 64~7 ably, about 5~ ~o 90 weight percent of the acid yroups are neutralized to -CO2M. The counter ion M~ is the alkali ca~ion Li~ 9 K~, the ammonia ion NH4~ or quaternary cationic compounds resulting from the neutralization with an organic amine. Excellent results have been obtained with Na+ and K~. Neutxaliza~ion with ~riethanolamine has been parti-cularly useful.
As water absorbent materials these polymers find many uses in powder, lump, film, fiber, fabric form and like form. They are of particular utility in the disposable nonwoven industry where there is need for polymers which will absorb and retain wa~er and ionic physiological fluids.
An important feature of these polymers is their enhanced thickening property even in the presence of a salt. Specific applications include disposable diapers, medical-surgical supplies and personal care produc~s. Such applications require a polymer which must imbibe the liquid to be ab- -sorbed rapidly and be a polymer that will not dissolve.
Further, the fluid must be immobilized or congealed in some way to be retained. The matPrials may also be used as suitable additives to greatly increase the absorptive power of conventional absorbents such as cotton, wood pulp and other cellulosic absorbents used in applications such as wiping cloths, surgical sponges, catamenial devices, and the like. In a specific application, for example, a disposable diaper, there is an inner layer of a soft absorbent nonwoven material that absorbs and passes urine to an inner layer of ; flufy fibrous absorbent material, wherein during the construction of this nonwoven fiber agglomerates or fibers of the polymers of this invention may be included and an - 1 1 i ' '7 additional impervious plastic layer, as polyethylene. A
film of the copolymers of this invention may be used between the outer plastic layer and ~he inner fluffy absorbent layer. Use of the polymers of this invention can result in reducticn in the bulk size of many disposable nonwovens.
The test or absorbency involves enclosing a weighed polymeric sample within a sewn strip of cheesecloth, the assembly resembling a tea bag. In ord~r to determine the amount of fluid absorbed, a blank cheesecloth bag not containing polymer is treated identical~y. Both the blank and polymer containing samples are immersed in the fluid, drained for a definite time and weighed. From the weights of the blank and sample after each immersion, the amount of fluid a~orbed in a specific time is readily calculated.
Powders, fibers, thin films and granule~ may ba tested in this manner. Sample films are cast from a 1% aqueous mucilage of alkali neutralized polymers, and for the Examples a 15 gram sample of a 1~ mucilage is placed in an alumlnum foil cup 5 cc in diameter and dried at atmospheric pressure at 80C. Cheesecloth bags were prepared ~rom 15 mm sq. of cheesecloth folded over and sewn with thread. Samples were placed in the ~luid to be absorbed for periods indicated in the data tables with 15 minutes drainage time between eaah immersion.
The polymers are readily prepared with lauroyl ; peroxide, t-butyl peroxy pivalate, azoisobutyronitrile and the like in a solvent for the monomer/nonsolvent for the copolymer. The polymers were prepared in batch polymeriza-tion at 65C. in 1,1,2-trichloro-1,2,2-trifluoroethane (Freon 113) as the solvent at 65C. using caprylyl pexoxide , - 12 -- ` -6~7 as the catalyst. The resultin~ polymers were i~olated and dried for 15 to 20 hours in a vacuum oven at 60C. The ionic fluid was simulated urine prepared rrom 97.09 weight percent water, 1.4g weight percent urea, 0.80 weight percent sodium chloride, 0~11 weigh~ percent MySO4 ' 7 H2O and 0.06 weight percent CaC12.
EXAMPLE I
A polymer sample (A) was prepared from 62.4 weight parts acrylic acid, 12.0 weight parts methyl methacrylate (MMA) and 5.06 weight parts lauryl methacrylate in 675 weight parts of Freon 113 in the presence of 15 ml of caprylyl peroxide (1% solution in Freon 113). A sample of this polymer was tes~ed for water and ionic fluid absorbency in comparison with a copolymer (B) containing only acrylic acid and lauryl methacrylate, containing 93 weight parts of acrylic acid and 7 weight parts lauryl methacrylate per 100 weight parts of copolymer. The results obtained and the times of immersion are set forth hereinbelow. The absorbed fluid being expressed as fluid/polymer weight ratio.
Total Time of Distilled Water Synthetic Urine Imm~rsion Seconds A(MM~) B A(MMA) B
86.3 13.6 24.5 14.5 116.4 25.6 26.5 24.4 174.3 46.8 32.4 35.4 These data clearly demonstrate the tremendous and unexpected increase in water absorbency of the three-co~ponent ter-polymers A containing methyl methacrylate substituted in part for the acrylic acid, as compared to the copolymer B
not containing methyl methacrylate. In the absorption o~
synthetic urine, note the enhanced absorption rate at 15 seconds of copol~mer A of this invention as compared to the ; - 13 -~0816~L9L~
copolymer B not containing methyl methacrylate. The impor-tant factor is a rapid rate of absorption.
EX~MPLE II
In this Example a series of copolymers were made with increasing amounts of methyl methacrylate to demon-strate the enhanced absorption of wa~er with increasin~
amounts of methyl methacrylate reported as amount of water absorbed times the weight of polymer. The polymers were prepared as described in Example ~. All of the polymers were prepared with 7 weight percent of lauryl methacrylate;
0, 10, 15 and 20 weight percent methyl methacrylate, and 93, 83~ 78 and 73 weight percent acrylic acid. The fluid/
polymer ratio data obtained is as follows:
Weight ~ MMA O 10 15 20 Total Immersion Time - Second 13.6 27.1 86.3 92.1 25.6 34.8 116.~ 131.1 33.3 39.8 128.6 143.2 ~0.4 61.5 141.6 150.4 46.8 70.7 174.3 163.5 The unexpected increase in amount of water absorbed as the methyl methacrylate in the copolymer is increased and the acrylic acld is decreased is readily apparent from these data. A further advantage of the copolymers containing increasing amounts of methyl methacrylate is the enhanced film-forming capabilities of such polymers.
Exa~PLE III
This Example demonstrates the ef fect o~ lauryl methacrylate on water absorbency of a polymer containing a constant amount, 15 weight percent, methyl methacxylate.
These polymers contained 0, 7 and 25 weight percent lauryl methacrylate, 15 weight percent methyl methacrylate and 85, ~86~
78, and 60 weight percent acrylic acid.
Weight % LM~ O 7 25 Total Immer~ion Seconds Fluid/PolYm2r 1~ 0 50O0 5.1 0 74,7 13.0 0 91.9 ~1.5 0 106.6 30.6 0 121.9 37.4 120 0 134.7 44.1 150 0 146.4 49.8 180 0 157.2 57.2 It should be noted that the polymer containing 0 weight percent lauryl methacrylate did not absorb its own weight in water, as compared with 50 times its own weight absorbency with a polymer containing only 7% lauryl methacrylate. The decreased absorbency of lauryl methacrylate as the lauryl methacrylate content of the polymer increased is demon-strated b~ the 25 weight percent polymer.
EXAMP~E IV
The absorbency characteristics in both water and synthetic urine of copolymexs cont~ining lauryl methacrylate and stearyl methacrylate are demonstrated in this example.
The two copolymers prepared as described each contained 83 weight percent acrylic acid~ 10 weight percent methyl methacrylate and 7 weight percent lauryl methacrylate or ~tearyl methacrylate. The weight absorption data obtained are as follows: ~~
Dist~lled Water Synthetic Urine `; 30 LMA SMA LMA SMA
Total Immer-sion-Seconds Fluid/Polymer _ :` :
27.1 29.6 20.7 16.1 34.8 46.5 25.5 31.9 39.~ 55.1 32.5 37.6 61.5 69.7 35.9 ~0.3 70.7 78.7 39.0 43.6 120 55.5 85.8 ~1.0 43.6 150 - 90.3 43.7 4~.1 180 61.g 94.1 44.~ 41,3 ~ !36~1L~7' EX~LE V
To demonstrate the effect of cross-linking on the water absorbent characteristics oE these polymers, -two polymers were prepared: one (MMA) containing 7 weight percent lauryl methacrylate, 10 weight percent methyl meth-acrylate, 10 weight percent acrylic acid; and the other (EA) 7 weight percent lauryl methacrylate, 15 weight percent ethyl acrylate and 78 weight percent acrylic acid. Each was cross-linked with the amount of allyl pentaerythritol (APE) indicated in the data table I below being present during the copolymerization reaction.
-~0~
o co o ~ o~ a7 1` u~ ~
o ~ ~ ...... -. er u~ ~ a~ tn ~r ~D OD
-l h ~ o ~ ~ ~ ~ ~1 ~ N er E~ N ........
.
~1 O u~,~u~er~r~
O ~_1 ~1 ~J N ~1 N N
~ O
o ~ 1~ l ~ ~r N
O 1~ ~ O > u~
O U~ ~ I` OD ~ ~ O 1-.,1 ~:
O ~ ~DO~D~D
N ¦ U~ a~ N ~
H ~1 N ~e~9 1` CO ~ O
~ ~1 Pl ~ U) rl a~ o ~D O ~P U~ I~ CS~
~ ~ O ~ ~ 9 0 U~
a O o li:J ~ N
ll P~ .--1_JNNNNt~
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, .
:~ . o ~1 oo co u~ t~ ~r CT'~
. O ...... .
- I` ~ 1 0 Il') I
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., U~
~1 H U~ Ln 0 1~'1 0 0 0 0 0 _I ~ ~ N 11 Ot~
) ~1 ~'0 ' .~
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It is noted that better absorbe~cy ~or water is obtained with thes~ two copolymers when the allyl pentaery-thritol is present in amounts of less than one part per hundred of other monomers, although the polymers containiny one phm has in~reased absorbency.
EXAMPLE VI
Two other polymers were prepared as described above, each containing 78 weight percent acrylic acid, 15 weight percent ethyl acrylate and 0.2 parts per hundred of total monomers of allyl pentaerythritol, and one polymer (LUA3 7 weight percent lauryl methacrylate and the other (IDMA) 7 weight percent isodecyl methacrylate.
Distilled Water Synthetic Urine LMA_ IDMA LMA IDMA
15 Total Immer-sion Seconds Fluid/Polymer -54.3 49.8 15.0 8.1 114.g 112.5 23.9 14.9 159.2 162.0 25.8 20.5 192.3 196.4 27.1 25.3 222.1 226.8 26.7 2~.0 120 245.1 252.3 27.0 30.5 150 263.2 269.5 27.3 33.0 180 278.~ 287.6 26.g 34~4 6~
EX~MPLE VII
A polymer was prepared a9 described above con-taining methacrylic acid instead of acrylic acid. The ; copolymer was a copolymer of 80 weight percent methacrylicacid, 5 weight percent stearyl methacrylate and 15 weight percent methyl methacrylateO The polymer was neutralized with potassium hydroxide to form the potassium salt and cast into film from the aqueous solution. A 0.16 film was tested for weight absorbency in distilled water. The absorption data was 24.4 times its own weight at 15 seconds, 51.1 at 30 seconds and 60.8 at 45 seconds. More striking was the absorption of simulated urine, 19.9 at 15 seconds, 28.2 at 30 seconds and 30.6 at 45 seconds used in 0.2 gram weight of film.
EXAMPLE ~III
To demonstrate the utility of other lower alkyl acrylates and methacrylates a series of polymers were ; prepared with 80 weight percent acrylic acid, 5 weight percent stearyl methacrylate and 15 weight percent of the monomers indicated in the data table The polymers were converted to the potassium salt, films cast and absorbency in distilled water reported as weight of water absorbed per weight ~f polymer.
. .
n~
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X ~ ~1 al r 1 O ~ N ~D ,1 ,~: ~ ~4 ,~ ~ ~ co o cn ~ u~ u~
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i .. U~
~ ~ U~ o U~ o o o X ~ O ~1 ~ ~ _I
' - ~0 -- : . , , ~.086~LqL7 These samples were then tested ~or abs~rbancy in simulated urine with the ~ollowing results in Data Table III.
~ 21 -6~4~
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,, ,, ~ ~ C ~
O ~ ~ a~
P~
U~ ~
~ ,~
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EXAMPLE IX
Polymers made with 15 weight percent isodecyl methacrylate, 15 weight percent methyl methacrylate and 70 weight percent acrylic acid were prepared as described.
The water absorbency of potassium films in distilled water at 15 seconds was 53.5; at 30 seconds, 79.3; at 45 seconds, 96.8; and at 60 seconds, 115.4.
:
U.S. Patent 3,915,921 discloses copolymers of unsaturated carbo~ylic acid monomers with an alkyl acrylate ester wherein the alkyl group contains about 10 to 30 carbon atoms that are efficient water thickeners, which when neutralized by basic materials have improved resistance to loss in viscosity, even in the presence of substantial amounts of inorganic salts such as sodium chlorideO These copolymers absorb water, but copolymers having improved rates of water absorption and retention are desired.
According to the invention there is provided an interpolymer or copolymer of monomers comprising from about 40 to 87 weight percent of an ole~inically unsaturated carboxylic acid monomer, about 2 to 20 weight percent of at least one acrylic or methacrylic acid ester monomer of the formula R' O
"
CH2=C----C-O-R (I) where R' is hydrogen, methyl or ethyl and R contains 10 to 30 carbon atoms and about 5 to 30 weight percent of at least one other acrylic or methacrylic acid ester monomer of the formula:
R' 0 CH2=C -C-0-R (II) wherein R' is hyd~ogen, methyl or ethyl and R contains 1 to 8 carbon atoms, the interpolymer or copolymer may optionally include a small amount of a cross-linking agent, the copolymer or interpolymer rapidly absorbs and retains large quantities of water and also absorbs and retains ionic aqueous fluids.
In particular R in formula (I) may be alkyl of 10 to 30 carbon atoms or include an alkyl moiety of 10 to 30 carbon atoms~ In formula (II), R may suitably be alkyl of 1 to 8 carbon atoms or include an alkyl moiety of 1 to 8 carbon atoms.
;'i ~ ~' ' ~ ~
- ~ ' 4gL7 ; The copolymers of carboxylic acid monomer and the two .:: acrylic esters of the types and in the amounts defined .,: ' hereinafter provide a much faster rate of absorption of water and aqueous ionic fluids than copolymers not con-~,: taining these ~ssential comonomers in the amounts set forth.
The copolymers also demonstrate improved retention of ~ ., ~ ~ absorbed fluid as compared to prior art polymers. The : :, , ~:: copolymers are readily prepared by copolymerizing the '' .
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~64~L7 ` essential monomers, and optionally o~her comonomexs as defined, by free radical polymeri~ation ~ystems. These copolymers have weiyht avera~e molecular weights from about lo,OOO to greater than 1,000,000. Normally, the molecular weights are from about 50,000 to 900,000. Mole-cular weights of cross-linked polymers may be higher.
The carboxylic monomers useful in the production ..
of the polymers of ~his invention are the olefinically-unsa~urated carboxylic acids con~aining at l~ast one acti-vated carbon-to-carbon olefinic doubla bond, and at least one carboxyl group, that is, an acid containing an olefinic double bond which readily functions in polymerization because of its presence in the monomer molecule either in the alpha-beta position with respect to a carboxyl group thusly, -C=C-COOH, or as a part of a terminal methylene i grouping thusly, CH2=Cf present in the copolymer in amounts from abou~ 40 to 87 weight percent of the copolymer. In the alpha-beta acids the close proximity of the strongly polar carboxyl group to the double-~onded carbon atoms has a strong activating in1uence rendering the substances con-, ;.
taining this structure very readily polymerizable. The ` ::
-; presence of a terminal methylene group~ng in a carboxylic ;~ monomer makes this type of compound much more easily poly-; merizable than if the double bond were intermediate in the carbon structure. Olefinically-unsaturated acids of this class include such widely divergent materials as the acrylic acids typified by acrylic acid itself, methacrylic acid, ethacrylic acid, alpha-chloroacrylic acid, alpha-cyano acrylic acid, beta methyl-acrylic acid (crotonic acid), ~ 30 alpha-phenyl acrylic acid, beta-acryloxy propionic acid, ; _ 3 _ , . .
. :
:, :
~B644t7 i sorbic acid, alpha~chloro sorbic acid, anyelic acid, cin-: namic acid, p-chloro cinnamic acid, beta-styryl acrylic acid (l-carboxy-4-phenyl butadiene-1,3), itaconic acid, citra-- conic acid, mesaconic acid, glutaconic acid, aconitic acid, S maleic acid, fumaric acid, and tricarboxy ethylene. As used ~ herein, the term "carboxylic acid" includes the polycar-.~ boxylic acids and those acid anhydrides, such as maleic ~ anhydride, wherein the anhydride group is formed by the ~ elimination of one molecule of water from two carboxyl groups located on the same polycarboxylic acid molecule.
Maleic anhydride and the other acid anhydrides useful herein ~: have the general structure "
. R- C -,~................................. R'-C -C
.:
wherein R and R' are selected fxom the group consisting of ; 15 hydrogen, halogen and cyanogen (-C-.N) groups and alkyl,aryl, alkaryl, aralkyl, and cycloalkyl groups such as :"
methyl, ethyl, propyl, octyl, decyl, phenyl, tolyl, xylyl, :. benzyl, cyclohexyl and the like.
The preferred carboxylic monomers for use in this invention used in amounts of 40 to 87 weight percent total . ^
.: of the monomers polymerized are the monoolefinic acrylic .~ acids having the general structure :. R
CH2=C-COOH
wherein R is a substituent selected from the class consist-25 ing of hydrogen, halogen, and the cyanogen (-C~N) groups, monovalent alkyl radicals, monovalent aryl radicals, mono-valent aralkyl radicals, monovalent alkaryl radicals and , . .
` ,.i .;: - 4 -'"'''~, ,, .. .. .
8~'7 . ~
monovalent cycloaliphatic radicals. of this class, acrylic - and methacrylic acid are most preferred because of generally lower cost, ready availability, and abili~y to form superior polymers. Another useful carboxylic monomer is maleic ~ 5 anhydride or the acid.
`~ The preferred acrylic ester monomers having long chain aliphatic groups are derivatives of an acrylic acid represented by the formula R' O
: ' "
CH2~C -C--R
wherein R is an alkyl group having from 10 to 30 carbon atoms, preferably 10 to 20 carbon atoms and R' is hydrogen or a methyl or ethyl group presen~ in the copolymer in amount from about 2 to 20 weight percent, more preferably, ; about 5 to 15 weight percent. Representative higher alkyl acrylic esters are decyl acrylate, isodecyl methacrylate~
;........................................................................ .
lauryl acrylate, stearyl acrylate, behenyl acrylate and melissyl acrylate and the corresponding methacrylates.
~ixtures o~ two or three or more long chain acrylic esters may be successfully polymerized wi~h one of the car~oxylic monomers to provide useful thickening resins of this in-vention. Particularly useful are those methacrylates where the alkyl group contains 16 to 21 carbon atoms present in amounts of about S to 15 weight percent of the total mono-mers. Outstanding polymers have been made with 15~5 weight percent isodecyl methacrylate, 10~3 weight percent lauryl methacrylate, 7~3 weight percent stearyl methacrylate.
The other essential acrylic esters are also derivatives of an acrylic acid used in amounts of about . ~ , .
5 to 30 weight percent represented by the formula ` - 5 -.,.",~ .
:
''~. Rl O
CH2=C-C-0-R
wherein R is an alkyl, alkoxy, haloalkyl, cyanoalkyl, and like groups having from 1 to 8 carbon atoms and R' is hydrogen or a methyl or ethyl group. These acrylic esters are present in the copolymer ln amount rom about 5 to 30 weight percent and more preEerably from about 5 to 25 weight percen~. Representative acrylates include methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acry-late, butyl acrylate, isobutyl acrylate, methyl methacry-late, methyl ethacrylate, ethyl methacrylate, octyl acry-;~ late, heptyl acrylate, octyl methacrylate, i~opropyl methacrylate, 2-ethylhexyl acrylate, nonyl acrylate, hexyl acrylate, n~hexyl methacrylate, and the like.
The preferred cross-linking monomer for use in preparing the copolymers, if one is employed, is a poly-;~ alkenyl polyether having more than one alke~yl ether group-ing per molecule. The most useful possess alkenyl groups in which an olefinic double bond is present attached to a terminal methylene grouping, CH2=C~ . They are made by the etherification of a polyhydric alcohol containing at least 4 carbon atoms and at least 3 hydroxyl groups. Compounds of this class may be produced by reacting an alkenyl halide, such as allyl chIoride or allyl bromide with a strongly alkaline aqueous solution of one or more polyhydric alcohols.
The product is a complex mixture of polyethers with varying ~, . .
' numbers oE ether groups. Analysis reveals the average .:, .
~ number of ether groupings on each molecule. Efficiency of , .
- the polyether cross--linking agent increases with the number of potentially polymeri~able groups on the molecule. It is :;
~ - 6 -. . .
:; ~ . .
' preferred to utilize polyethers containing an average of two , . .
or mcre alkenyl ether groupings per molecule. Other cross-linking monomers include for example, diallyl esters, dimethallyl ethers, allyl or methallyl acrylates and acryl-amides, tetraallyl tin, tetravinyl silane, polyalkenyl ; methanes, diacrylates and dimethacrylates, divinyl compounds as divinyl benzene, polyallyl phosphate, diallyloxy com-, pounds and phosphite esters and the like~ Typical agents are allyl pentaerythritol, allyl sucrose, trimethylolpropane triacrylate, 1,6-hexanediol diacrylate, pentaerythritol triacrylate, tetramethylene dimethacrylate, tetramethylene diacrylate, ethylene diacrylate, ethylene dimethacrylate, triethylene glycol dimethacrylate, and the like. Allyl pentaerythritol and allyl sucrose provide excellent polymers in amounts less than 0.5 weight percent. Cross-linking of ; the polymers provides improved ability for the copolymers to swell under a confining pressure.
When the optional cross-linking agent is present, ` ~ polymeric mixtures ~ about 0 to about 3% by weight of cross-linking monomer based on the total of carboxylic acid monomer plus the alkyl acrylate ester monomers, and - more preferably, 0.1 to 0.5 weight percent or phm.
Another method to obtain the desired cross-linking is to use a comonomer which can react to yield cross-links during polymerization. Examples are 2-hydroxyethyl met~--; acrylate and hydroxypropyl methacrylate, and the like.
These units, when copolymerized, cross-link by interchain : esterification with carboxylic yroups. For 2-hydroxyethyl .,~
methacrylate, about 1 to 7 weight percent of monomers based on the total weight of monomers will pro~ide a desired " ' ' . ~
. . . .
6~
degree of cross-linking.
Another method of obtaining cross-linked polymers i~ by reac~ing small amounts of a polyvalent base wi-th the carboxyl-containing polymer. Those materials which yield multivalent cations, for example, include calcium, mag-nesium, zinc, and aluminum. A mixed salt to be used would be one containing potassium or sodium ions wlth small amounts of calcium or aluminum ions, for example, to provide , the multivalent cation to provide cross-linking through ; 10 polymeric carboxyl groups.
It will also be understood that small amounts of other vinylidene monomers, that is, those copolymerizable :~ ., .
~ monomers containing at least one ~erminal CH25 group may .,. ~ .
also be included as a copolymerizable monomer with the essential monomers so long as such monomers do not adversely afect the desired balance of water absorption and retention of the polymeric materials. Such materials include vinyl acetate, vinyl pyrrolidone, methyl vinyl ether, ethyl vinyl ether, methyl vinyl ketone and like in amounts less than about 10 weight percent of the polymer, normally less than 5-weight percent.
The polymers of this invention are preferably made by polymerization in an inert diluent having some solubiliz-ing action on one or more of the monomeric ingredients but ; 25 substantially none on the resultant polymer. Polymerization in mass may be employed but is not preferred because of the . ~
difficulty in working up the solid polymeric masses ob-... .
; tained. Polymerization in an aqueous medium containing a :
water-soluble free radical catalyst peroxygen is useful.
`~ 30 Polymerization in an organic liquid which is a solvent for '.;,.
, .. .
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.,,.,. ~
.
, .~ ,;
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.,~ .
~ ~OlYl~j4~L~
.
the mono~ers but a non-solvent for the polymer, or in a ~ mixture of such solvents, in the presence of a solvent-: soluble catalyst is most pre$erred because the product is usually obtained as a very fine friable and often fluffy precipitate which, after solvent removal, seldom requires grinding or other treatment before use. Suitable solvents for the ]atter method include benzenel xylene, ~etralin, hexane, heptane, carbon te~rachloride, methyl chloride, ethyl chloride, bromo trichloro methane, dimethyl carbonate, diethyl carbona~e, ethylene dlchloride, and mixture~ of these and other solvent~.
The polymerizations desirably are conducted in the presence of a haloethane or halomethane, preferably con-taining at least four halogen atoms. Representative materials include for example, a fluoroethane, fluoromethane, chloro-fluoromethane, hromofluoroethane, or preferably a chloro-~- fluoroethane or chlorofluoromethane containing at least four halogen atoms including, for example, 1,1,2-trichloro-1,2,2-trichloroethane, trichlorofluoromethane, tetrafluoromethane, .'~ ~ .
chlorotrifluoromethane, bromotri1uoromethane, 1-chloro-~` 1,1,2,2,2-pentafluoroethane, dichlorodifluoromethane, 1,2 difluoro-1,1,2,2-tetrachloroethane and the like. The amounts of these materials used may be varied from the , : , `~ amount just sufficient to make a slurry of the reactants up to where there is a substantial excess of the chlorofluoro-ethane, as will be apparent to those skilled in the art.
Preerred diluents are those which are solvents ~or the monomers but nonsolvents for the polymers.
Polymerization in the diluent medium is carried out in the presence o a free radical catalys~ in a closed :~.
.., ' , ,, ' . : , :
~L(J 8~
vessel in an inert atmosphere and under autogenous pressure or artificially-induced pressure or in an open vessel under reflux at a~mospheric pres wre. Temperature of the poly-merization may be varied from QC. to 100C., depending to a large degree on the molecular weight desired in the polymer.
Polymerization under reflux at 50 to 90~C. under atmos-pheric pressure using a free radical catalyst is generally effective in bringing a polymer yield of 75% to 100% in less than 10 hours. Suitable catalysts include peroxygen com-pounds such as sodium, potassium and ammonium persulfates, caprylyl peroxide, benzoyl peroxide, hydrogen peroxide, pelargonyl peroxide, cumene hydroperoxides, tertiary butyl diperphthalate, tertiary butyl perbenzoate, sodium per-acetate, sodium percarbonate, and the like as well as azo diisobutyryl nitrile, hereinafter referred to as azoiso-butyronitrile. Other catalysts utilizable are the so-called "redox" type of catalyst and the heavy-metal activated catalyst systems.
These polymers generally do not at~ain their maximum properties until converted to a partial alkali, ammonium or amine salt. The neutralizing agent is prefer-ably a monovalent alkali such as sodium, pota~slum, lithium or ammonium hydroxide or the carbonates and bicarbonates , thereof, or mixtures of the same, and also amine bases having not more than one primary or secondary amino group.
5uch amines include, for example, triethanolamine, ethanol-amine, isopropanolamine, triethylamine, trimethyl amine, and the like.
At least 30~ o~ the acid, carboxyl, groups are neutral~zed to an ionic state, that is, -CO2 ~ . Prefer-:, 64~7 ably, about 5~ ~o 90 weight percent of the acid yroups are neutralized to -CO2M. The counter ion M~ is the alkali ca~ion Li~ 9 K~, the ammonia ion NH4~ or quaternary cationic compounds resulting from the neutralization with an organic amine. Excellent results have been obtained with Na+ and K~. Neutxaliza~ion with ~riethanolamine has been parti-cularly useful.
As water absorbent materials these polymers find many uses in powder, lump, film, fiber, fabric form and like form. They are of particular utility in the disposable nonwoven industry where there is need for polymers which will absorb and retain wa~er and ionic physiological fluids.
An important feature of these polymers is their enhanced thickening property even in the presence of a salt. Specific applications include disposable diapers, medical-surgical supplies and personal care produc~s. Such applications require a polymer which must imbibe the liquid to be ab- -sorbed rapidly and be a polymer that will not dissolve.
Further, the fluid must be immobilized or congealed in some way to be retained. The matPrials may also be used as suitable additives to greatly increase the absorptive power of conventional absorbents such as cotton, wood pulp and other cellulosic absorbents used in applications such as wiping cloths, surgical sponges, catamenial devices, and the like. In a specific application, for example, a disposable diaper, there is an inner layer of a soft absorbent nonwoven material that absorbs and passes urine to an inner layer of ; flufy fibrous absorbent material, wherein during the construction of this nonwoven fiber agglomerates or fibers of the polymers of this invention may be included and an - 1 1 i ' '7 additional impervious plastic layer, as polyethylene. A
film of the copolymers of this invention may be used between the outer plastic layer and ~he inner fluffy absorbent layer. Use of the polymers of this invention can result in reducticn in the bulk size of many disposable nonwovens.
The test or absorbency involves enclosing a weighed polymeric sample within a sewn strip of cheesecloth, the assembly resembling a tea bag. In ord~r to determine the amount of fluid absorbed, a blank cheesecloth bag not containing polymer is treated identical~y. Both the blank and polymer containing samples are immersed in the fluid, drained for a definite time and weighed. From the weights of the blank and sample after each immersion, the amount of fluid a~orbed in a specific time is readily calculated.
Powders, fibers, thin films and granule~ may ba tested in this manner. Sample films are cast from a 1% aqueous mucilage of alkali neutralized polymers, and for the Examples a 15 gram sample of a 1~ mucilage is placed in an alumlnum foil cup 5 cc in diameter and dried at atmospheric pressure at 80C. Cheesecloth bags were prepared ~rom 15 mm sq. of cheesecloth folded over and sewn with thread. Samples were placed in the ~luid to be absorbed for periods indicated in the data tables with 15 minutes drainage time between eaah immersion.
The polymers are readily prepared with lauroyl ; peroxide, t-butyl peroxy pivalate, azoisobutyronitrile and the like in a solvent for the monomer/nonsolvent for the copolymer. The polymers were prepared in batch polymeriza-tion at 65C. in 1,1,2-trichloro-1,2,2-trifluoroethane (Freon 113) as the solvent at 65C. using caprylyl pexoxide , - 12 -- ` -6~7 as the catalyst. The resultin~ polymers were i~olated and dried for 15 to 20 hours in a vacuum oven at 60C. The ionic fluid was simulated urine prepared rrom 97.09 weight percent water, 1.4g weight percent urea, 0.80 weight percent sodium chloride, 0~11 weigh~ percent MySO4 ' 7 H2O and 0.06 weight percent CaC12.
EXAMPLE I
A polymer sample (A) was prepared from 62.4 weight parts acrylic acid, 12.0 weight parts methyl methacrylate (MMA) and 5.06 weight parts lauryl methacrylate in 675 weight parts of Freon 113 in the presence of 15 ml of caprylyl peroxide (1% solution in Freon 113). A sample of this polymer was tes~ed for water and ionic fluid absorbency in comparison with a copolymer (B) containing only acrylic acid and lauryl methacrylate, containing 93 weight parts of acrylic acid and 7 weight parts lauryl methacrylate per 100 weight parts of copolymer. The results obtained and the times of immersion are set forth hereinbelow. The absorbed fluid being expressed as fluid/polymer weight ratio.
Total Time of Distilled Water Synthetic Urine Imm~rsion Seconds A(MM~) B A(MMA) B
86.3 13.6 24.5 14.5 116.4 25.6 26.5 24.4 174.3 46.8 32.4 35.4 These data clearly demonstrate the tremendous and unexpected increase in water absorbency of the three-co~ponent ter-polymers A containing methyl methacrylate substituted in part for the acrylic acid, as compared to the copolymer B
not containing methyl methacrylate. In the absorption o~
synthetic urine, note the enhanced absorption rate at 15 seconds of copol~mer A of this invention as compared to the ; - 13 -~0816~L9L~
copolymer B not containing methyl methacrylate. The impor-tant factor is a rapid rate of absorption.
EX~MPLE II
In this Example a series of copolymers were made with increasing amounts of methyl methacrylate to demon-strate the enhanced absorption of wa~er with increasin~
amounts of methyl methacrylate reported as amount of water absorbed times the weight of polymer. The polymers were prepared as described in Example ~. All of the polymers were prepared with 7 weight percent of lauryl methacrylate;
0, 10, 15 and 20 weight percent methyl methacrylate, and 93, 83~ 78 and 73 weight percent acrylic acid. The fluid/
polymer ratio data obtained is as follows:
Weight ~ MMA O 10 15 20 Total Immersion Time - Second 13.6 27.1 86.3 92.1 25.6 34.8 116.~ 131.1 33.3 39.8 128.6 143.2 ~0.4 61.5 141.6 150.4 46.8 70.7 174.3 163.5 The unexpected increase in amount of water absorbed as the methyl methacrylate in the copolymer is increased and the acrylic acld is decreased is readily apparent from these data. A further advantage of the copolymers containing increasing amounts of methyl methacrylate is the enhanced film-forming capabilities of such polymers.
Exa~PLE III
This Example demonstrates the ef fect o~ lauryl methacrylate on water absorbency of a polymer containing a constant amount, 15 weight percent, methyl methacxylate.
These polymers contained 0, 7 and 25 weight percent lauryl methacrylate, 15 weight percent methyl methacrylate and 85, ~86~
78, and 60 weight percent acrylic acid.
Weight % LM~ O 7 25 Total Immer~ion Seconds Fluid/PolYm2r 1~ 0 50O0 5.1 0 74,7 13.0 0 91.9 ~1.5 0 106.6 30.6 0 121.9 37.4 120 0 134.7 44.1 150 0 146.4 49.8 180 0 157.2 57.2 It should be noted that the polymer containing 0 weight percent lauryl methacrylate did not absorb its own weight in water, as compared with 50 times its own weight absorbency with a polymer containing only 7% lauryl methacrylate. The decreased absorbency of lauryl methacrylate as the lauryl methacrylate content of the polymer increased is demon-strated b~ the 25 weight percent polymer.
EXAMP~E IV
The absorbency characteristics in both water and synthetic urine of copolymexs cont~ining lauryl methacrylate and stearyl methacrylate are demonstrated in this example.
The two copolymers prepared as described each contained 83 weight percent acrylic acid~ 10 weight percent methyl methacrylate and 7 weight percent lauryl methacrylate or ~tearyl methacrylate. The weight absorption data obtained are as follows: ~~
Dist~lled Water Synthetic Urine `; 30 LMA SMA LMA SMA
Total Immer-sion-Seconds Fluid/Polymer _ :` :
27.1 29.6 20.7 16.1 34.8 46.5 25.5 31.9 39.~ 55.1 32.5 37.6 61.5 69.7 35.9 ~0.3 70.7 78.7 39.0 43.6 120 55.5 85.8 ~1.0 43.6 150 - 90.3 43.7 4~.1 180 61.g 94.1 44.~ 41,3 ~ !36~1L~7' EX~LE V
To demonstrate the effect of cross-linking on the water absorbent characteristics oE these polymers, -two polymers were prepared: one (MMA) containing 7 weight percent lauryl methacrylate, 10 weight percent methyl meth-acrylate, 10 weight percent acrylic acid; and the other (EA) 7 weight percent lauryl methacrylate, 15 weight percent ethyl acrylate and 78 weight percent acrylic acid. Each was cross-linked with the amount of allyl pentaerythritol (APE) indicated in the data table I below being present during the copolymerization reaction.
-~0~
o co o ~ o~ a7 1` u~ ~
o ~ ~ ...... -. er u~ ~ a~ tn ~r ~D OD
-l h ~ o ~ ~ ~ ~ ~1 ~ N er E~ N ........
.
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O ~_1 ~1 ~J N ~1 N N
~ O
o ~ 1~ l ~ ~r N
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It is noted that better absorbe~cy ~or water is obtained with thes~ two copolymers when the allyl pentaery-thritol is present in amounts of less than one part per hundred of other monomers, although the polymers containiny one phm has in~reased absorbency.
EXAMPLE VI
Two other polymers were prepared as described above, each containing 78 weight percent acrylic acid, 15 weight percent ethyl acrylate and 0.2 parts per hundred of total monomers of allyl pentaerythritol, and one polymer (LUA3 7 weight percent lauryl methacrylate and the other (IDMA) 7 weight percent isodecyl methacrylate.
Distilled Water Synthetic Urine LMA_ IDMA LMA IDMA
15 Total Immer-sion Seconds Fluid/Polymer -54.3 49.8 15.0 8.1 114.g 112.5 23.9 14.9 159.2 162.0 25.8 20.5 192.3 196.4 27.1 25.3 222.1 226.8 26.7 2~.0 120 245.1 252.3 27.0 30.5 150 263.2 269.5 27.3 33.0 180 278.~ 287.6 26.g 34~4 6~
EX~MPLE VII
A polymer was prepared a9 described above con-taining methacrylic acid instead of acrylic acid. The ; copolymer was a copolymer of 80 weight percent methacrylicacid, 5 weight percent stearyl methacrylate and 15 weight percent methyl methacrylateO The polymer was neutralized with potassium hydroxide to form the potassium salt and cast into film from the aqueous solution. A 0.16 film was tested for weight absorbency in distilled water. The absorption data was 24.4 times its own weight at 15 seconds, 51.1 at 30 seconds and 60.8 at 45 seconds. More striking was the absorption of simulated urine, 19.9 at 15 seconds, 28.2 at 30 seconds and 30.6 at 45 seconds used in 0.2 gram weight of film.
EXAMPLE ~III
To demonstrate the utility of other lower alkyl acrylates and methacrylates a series of polymers were ; prepared with 80 weight percent acrylic acid, 5 weight percent stearyl methacrylate and 15 weight percent of the monomers indicated in the data table The polymers were converted to the potassium salt, films cast and absorbency in distilled water reported as weight of water absorbed per weight ~f polymer.
. .
n~
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S~ ~ ~ o o O ~ ~1 A
bq ~
~1 ~
X ~ ~1 al r 1 O ~ N ~D ,1 ,~: ~ ~4 ,~ ~ ~ co o cn ~ u~ u~
H ~ ~ t~ O
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' - ~0 -- : . , , ~.086~LqL7 These samples were then tested ~or abs~rbancy in simulated urine with the ~ollowing results in Data Table III.
~ 21 -6~4~
a) ~ u~ ~r o u~ oo ,~ C) o~
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O ~ ~ a~
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U~ ~
~ ,~
X ~ _, a) ~1 O
~ ~ ~ OD r~
Hr l ~1 ~) ~ 00 C~ O O
H.~ 111 ~ ~1 ~1 ~1 H~ ~::
~ ~1~
~ ~rd ~
p u ~ ~
O h ~ l ,1 H
.IJ .
~1 ~ CO O C~
~I h C) . ~ `I N
~ .
~Q
S~ ~ O ~ o o O
O O O t'~
~ ~ ~:
'' '. ' ~ :
EXAMPLE IX
Polymers made with 15 weight percent isodecyl methacrylate, 15 weight percent methyl methacrylate and 70 weight percent acrylic acid were prepared as described.
The water absorbency of potassium films in distilled water at 15 seconds was 53.5; at 30 seconds, 79.3; at 45 seconds, 96.8; and at 60 seconds, 115.4.
:
Claims (19)
1. An interpolymer of monomers comprising from about 40 to 87 weight percent of an olefinically unsaturated carboxylic acid monomer, 2 to 20 weight percent of an (1) acrylic ester monomer of the formula:
where R' is hydrogen, methyl or ethyl and R contains 10 to 30 carbon atoms and 5 to 30 weight percent of (2) at least one other acrylic ester monomer of the formula wherein R' is hydrogen, methyl or ethyl and R contains 1 to 8 carbon atoms.
where R' is hydrogen, methyl or ethyl and R contains 10 to 30 carbon atoms and 5 to 30 weight percent of (2) at least one other acrylic ester monomer of the formula wherein R' is hydrogen, methyl or ethyl and R contains 1 to 8 carbon atoms.
2. An interpolymer of claim 1, containing 0 to 3 weight percent of monomeric cross-linking agent.
3. An interpolymer of claim 2, wherein said carboxylic acid monomer is acrylic acid, (1) is isodecyl methacrylate, lauryl methacrylate or stearyl methacrylate, and (2) is methyl methacrylate or ethyl acrylate.
4. An interpolymer of claim 3, wherein (1) is present in amount from about 5 to 15 weight percent and (2) is present in amount from about 15 to 25 weight percent.
5. An interpolymer of claim 4, wherein the polymer contains about 0.01 to 0.5 weight percent cross-links.
6. An interpolymer of Claim 4 wherein at least about 30 weight percent of the COOH acid groups are neutral ized to structure wherein M is selected from the group consisting of Li, Na, K and NH4 ions and quarternary nitrogen compounds, R3NH.
7. An interpolymer of Claim 2 wherein the acid is acrylic acid, methacrylic acid, maleic acid or the anhydrides thereof.
8. An interpolymer of Claim 4 wherein the cross-linking monomer contains at least a grouping and at least one other polymerizable grouping, said polymerizable groupings being unsaturated nonconjugated bonds.
9. An interpolymer of Claim 8 wherein said cross-linking monomer is a polyalkenyl polyether of a polyhydric alcohol containing more than one alkenyl ether group per molecule and the parent polyhydric alcohol contains at least 3 hydroxyl groups in amounts of 0.01 to less than 0.5 weight percent of the total monomer
10. An interpolymer of Claim 9 wherein said monomer is allyl pentaerythritol.
11. An interpolymer of Claim 9 wherein said monomer is allyl sucrose.
12. An interpolymer of Claim 4 wherein there is 7 to 13 weight percent of (1) lauryl methacrylate and (2) is methyl methacrylate.
13. An interpolymer of Claim 4 wherein there is 7 to 13 weight percent of (1) stearyl methacrylate and (2) is methyl methacrylate.
14. An interpolymer of Claim 9 wherein said acid is acrylic acid, (1) is stearyl methacrylate, (2) is methyl methacrylate and said cross linking agent is allyl pentaery-thritol in amount from 0.05 to 0.2 pHm.
15. An interpolymer of Claim 2 wherein (2) is hexyl methacrylate.
16. An interpolymer of Claim 2 wherein (2) is octyl acrylate.
17. An interpolymer of Claim 2 wherein (2) is 2-ethylhexyl methacrylate.
18. An interpolymer of Claim 2 wherein (2) is isopropyl methacrylate.
19. An interpolymer of Claim 2 wherein there is 10 to 20 weight percent of (1) isodecyl methacrylate and (2) is methyl methacrylate.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US784,099 | 1977-04-04 | ||
| US05/784,099 US4062817A (en) | 1977-04-04 | 1977-04-04 | Water absorbent polymers comprising unsaturated carboxylic acid, acrylic ester containing alkyl group 10-30 carbon atoms, and another acrylic ester containing alkyl group 2-8 carbon atoms |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1086447A true CA1086447A (en) | 1980-09-23 |
Family
ID=25131342
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA283,430A Expired CA1086447A (en) | 1977-04-04 | 1977-07-25 | Water absorbent polymers |
Country Status (15)
| Country | Link |
|---|---|
| US (1) | US4062817A (en) |
| JP (1) | JPS53123490A (en) |
| AU (1) | AU510453B2 (en) |
| BE (1) | BE858800A (en) |
| CA (1) | CA1086447A (en) |
| CH (1) | CH636363A5 (en) |
| DE (1) | DE2734298A1 (en) |
| DK (1) | DK337777A (en) |
| FR (1) | FR2386565A1 (en) |
| GB (1) | GB1589975A (en) |
| IT (1) | IT1085352B (en) |
| MX (1) | MX145592A (en) |
| NL (1) | NL189674C (en) |
| NO (1) | NO772912L (en) |
| SE (1) | SE425974B (en) |
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| US2795564A (en) * | 1953-05-13 | 1957-06-11 | Rohm & Haas | Aqueous paint bases and water-base paints and process for preparing them |
| US2790736A (en) * | 1955-01-31 | 1957-04-30 | Rohm & Haas | Methods of making coated paper products and the products obtained |
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| US3194777A (en) * | 1956-05-14 | 1965-07-13 | Pittsburgh Plate Glass Co | Coating compositions |
| US2892788A (en) * | 1956-07-30 | 1959-06-30 | California Research Corp | Lubricant composition |
| US3317493A (en) * | 1963-11-05 | 1967-05-02 | Du Pont | Terpolymer containing methyl methacrylate, 2-ethylhexyl acrylate and methacrylic acid and compositions containing same |
| US3575911A (en) * | 1964-11-19 | 1971-04-20 | Minnesota Mining & Mfg | Adhesives |
| GB1146155A (en) * | 1965-03-26 | 1969-03-19 | Mitsubishi Rayon Co | Hair lacquers |
| US3657175A (en) * | 1969-06-26 | 1972-04-18 | Standard Brands Chem Ind Inc | Carboxylic acid latices providing unique thickening and dispersing agents |
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| US3957740A (en) * | 1972-04-24 | 1976-05-18 | Hydrophilics International, Inc. | Copolymers |
| FR2218351B1 (en) * | 1973-02-16 | 1976-05-14 | Protex Manuf Prod Chimiq | |
| US3970633A (en) * | 1973-05-16 | 1976-07-20 | Rohm And Haas Company | Thermosetting powder coatings composition |
| CH606154A5 (en) * | 1974-07-02 | 1978-11-15 | Goodrich Co B F | |
| US3940351A (en) * | 1974-07-02 | 1976-02-24 | The B. F. Goodrich Company | Polymerization of carboxylic acid monomers and alkyl acrylate esters in chlorofluoroethane |
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- 1977-07-25 CA CA283,430A patent/CA1086447A/en not_active Expired
- 1977-07-26 AU AU27328/77A patent/AU510453B2/en not_active Expired
- 1977-07-26 DK DK337777A patent/DK337777A/en not_active Application Discontinuation
- 1977-07-29 DE DE19772734298 patent/DE2734298A1/en not_active Withdrawn
- 1977-08-03 IT IT26465/77A patent/IT1085352B/en active
- 1977-08-04 SE SE7708882A patent/SE425974B/en not_active IP Right Cessation
- 1977-08-05 GB GB32858/77A patent/GB1589975A/en not_active Expired
- 1977-08-08 NL NLAANVRAGE7708733,A patent/NL189674C/en not_active IP Right Cessation
- 1977-08-15 JP JP9709477A patent/JPS53123490A/en active Pending
- 1977-08-17 MX MX170268A patent/MX145592A/en unknown
- 1977-08-22 NO NO772912A patent/NO772912L/en unknown
- 1977-09-08 FR FR7727258A patent/FR2386565A1/en active Granted
- 1977-09-16 BE BE180990A patent/BE858800A/en not_active IP Right Cessation
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1978
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| DK337777A (en) | 1978-10-05 |
| BE858800A (en) | 1978-01-16 |
| NL189674C (en) | 1993-06-16 |
| MX145592A (en) | 1982-03-11 |
| IT1085352B (en) | 1985-05-28 |
| CH636363A5 (en) | 1983-05-31 |
| NL189674B (en) | 1993-01-18 |
| FR2386565A1 (en) | 1978-11-03 |
| US4062817A (en) | 1977-12-13 |
| JPS53123490A (en) | 1978-10-27 |
| DE2734298A1 (en) | 1978-10-05 |
| NO772912L (en) | 1978-10-05 |
| NL7708733A (en) | 1978-10-06 |
| GB1589975A (en) | 1981-05-20 |
| FR2386565B1 (en) | 1984-05-25 |
| SE7708882L (en) | 1978-10-05 |
| AU2732877A (en) | 1979-02-01 |
| SE425974B (en) | 1982-11-29 |
| AU510453B2 (en) | 1980-06-26 |
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