CA1039433A - Disposal of ecologically undesirable liquids - Google Patents
Disposal of ecologically undesirable liquidsInfo
- Publication number
- CA1039433A CA1039433A CA220,179A CA220179A CA1039433A CA 1039433 A CA1039433 A CA 1039433A CA 220179 A CA220179 A CA 220179A CA 1039433 A CA1039433 A CA 1039433A
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- container
- polymer
- liquid
- swelling
- gel
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Abstract
ABSTRACT
Hazardous materials such as askarels, chlorinated hydrocarbons or other ecologically undesireable liquids are disposed of by gelling the liquid within a combustible package and subsequently shipping the package to a quali-fied disposal site, such as an incinerator, which can incinerate halogenated hydrocarbons in an ecologically sound manner.
Hazardous materials such as askarels, chlorinated hydrocarbons or other ecologically undesireable liquids are disposed of by gelling the liquid within a combustible package and subsequently shipping the package to a quali-fied disposal site, such as an incinerator, which can incinerate halogenated hydrocarbons in an ecologically sound manner.
Description
~39~3~
This invention provides a method for the disposi-tion of ecologically undesirable polymer swelling llquid such as polychlorinated biphenyls, the steps of the method .. . ..
comprising containing the liquid within particles of a liquid swellable solid cross-linked vinyl addition resinous polymer which swells but does not dissolve when in contact ; with the liquid, the liquid being present in a quantity at least sufficient to form a gel, containing said gel in a shipping container, and transferring said shipping con-tainer to a disposal site.
Also contemplated within the scope of the present invention is a shipping container particularly suited for the disposal of ecologically undesirable polymer swelling liquids, the shipping container comprising a combustible ecologically undesirable polymer swelling liquid-impermeable hollow body ~efining a space therein, disposed within said space a liquid swellable solid cross-linked vinyl addition resinous polymer which swells but does not dissolve when in contact with the liquid, the polymer being present in a quantity sufficient to form a gel when an ecologlcally undesirable liquid is added to the space.
, .. .. .. . . .. .
Further features and advantages of the present invention will become more apparent from the following specification taken in connection with the drawing wherein:
Figure 1 depicts a partly in-section view of a container suitable for the practice of the present invention.
Figure 2 depicts a container similar to that of Figure 1 filled with a chlorinated hydrocarbon.
17,475-F
~039433 Figure 3 depicts a plurality of containers such as those in Figure 2 prior to closure for shipping.
In Figure 1 there is a schematic partly in--section view of a container in accordance with the ,475-F ~ l,i -la-~3~3 present invention generally designated by the reference numeral 10. The container lO comprises an outer rigid hollow container 11 of a combustible material, advantage-ously a corrugated paperboard. The container ll has the configuration of a parallelepiped and beneficially that of a cube. The container ll defines therein a space 12 and a passageway 13 providing communication between the space 12 and space external to the container ll. Bene-ficially the container ll may be of conventional corrugated paperboard construction. Within the space 12 is disposed a flexible container 14. The flexible container 14 is beneficially generally chlorinated hydrocarbon-impermeable and is of material such as polyethylene, surface sulfonated polyethylene, vinylidene chloride polymers and the like.
The container 14 has a closure 15 and defines an internal space 16 having disposed therein a plurality of swellable poly~er particles 18. Beneficially, the container 14 is o~ sufficient size that when inflated with gas or li~uid it completely or almost completely fills the space 12 within the container ll. The uolume of particles 18 dis-posed within the container 14 beneficially is sufficient on swelling in desired polychlorinated hydrocarbon to completely ~ill the space 12 while the particles are in a gelatinous condition.
In Figure 2 there is a sectional view of a con-tainer lOa generally in accordance with Figure l which has been filled with a chlorinated hydrocarbon. The con-tainer lOa has a rigid outer container lla, a flexible inner container 14a which contains swollen gelatinous material l9 resulting from swelling of particles such as .
,j 17,475-E' -2-~q~ ~
the particles 18 by the addition of an appropriate chlori-nated hydrocarbon such as a polychlorinated hydrocarbon dielectric liquid; that is, an askarel. The gelatinous mass l9 beneficially is sufficiently viscous that on rupture of one or more walls of the container lOa the material does not flow as a low viscosity liquid but can be collected as a gelg for example, with a shovel, and placed in a readily available container such as a plastic bag, box or the like until appropriate disposal can be made.
Figure 3 depicts a container generally designated by the reference numeral 25. The container 25 comprises an addressed or prepaid addressed shipping box 26 which has not yet been closed for shipping. Within the box 26 are disposed four containers designated by the reference numeral lOb which are generally similar to the filled containers lOa of Figure 2.
In the practice of the method of the present invention, a container such as the container 10 of Figure 1 is filled with an askarel or other ecologically undesirable ., _ , .. .. . ...... . . . . . .
polymer-swelling liquid which one wishes to discard. The , . . . .. . ..
container may be either completely or partly filled, depending on the quantity of material available. ~he swellable particles 18 then Lmbibe the liquid to provide a semi-solid gelatinous mass consisting of individual swollen close-packed pol~mer particles. The container is then closed and desirably can be shipped to a disposal site having facilities to dispose of the container liquid in an ecologically desirable manner. Usually such disposal is accomplished by burning, and it is highly desirable 17,475-F -3-that at least a major portion of the container be of a com-bustible material such as synthetic resinous plastic, paper-board and the like.
~lthough as illustrated in Figure 1, the container comprises two portions, a rigid permeable outer member and a flexible generally liquid impermeable inner memberJ in certain instances the outer container 11 may be dispensed with and individual bags packed in a single shipping con-tainer or placed in a suitable shipping container or a plurality of such bags or containers placed in a shipping container in the manner depicted in Figure 3. Oftentimes rigid plastic containers may be employed. However, at the present time the arrangement as depicted in Figure 1 is found to be economical and generally satisfactory, as the rigid outer container provides mechanical protection for the inner flexible container.
Polymers useful in the practice of the present invention are any polymers which swell on contact with pQlychlorinated organic dielectric liquids or other ecolo-gically undesirable organic liquids. Usefu _polymers may swell on contact with water. However, additional swelling . _ _ _ _ _ must occur when contacted with an organic~dielectric liquid.
Selection of a polymer for use with any organic dielectric liquid is readily accomplished by determining a swelling index for the polymer particles. Beneficially, such a swelling lndex is readily determined by measuring the volume of a particulate polymer to be evaluated and sub-sequently adding the desired organic liquid and determining t~e volume of swollen polymer after a period of 48 hours in the organic liquid. The ratio of the volume with 17,475-F _4_ ~)39~33 organic liquid to volume of the unswollen polymer provides the swelling index. If the polymer is soluble, the swelling .. .. . . . . . ... . . .. . .... . ...
index is infinite. If the swelling index is greater than . . .
about 2, the polymer particles are useful in the practice of the present invention. Beneficially ~or most applications, a swelling index of at least 3 and preferably greater than about 5 is desirable. It is critical to the practice of the pre~ent invention to employ a cross-linked polymer which swells but does not dissolve. If the polymer swells in the presence of the oryanic liquid, it is suitable for the practice of the present invention. However, for most application~ it is desirable to employ a polymer which is cross-linked to a sufficient deg.ree that it exhibits a swelling index between about 2 and 50, and preferably bet-ween about 5 and 50. By utilizing the cross-linked polymer, the hazard of dissolution of the polymer over extended periods of tLme is eliminated. A wide variety of polymeric materials are employed with benefit. Such polymers include polymers of styrene and substituted styrenes; copolymers of vinyl chloride such as a copolymer of 60 weight percent vinyl chloride and 40 weight percent vinyl acetate; vinyli-dene chloride copolymers such as a copolymer of 75 percent vinylidene chloride and 25 percent acrylonitrile; acrylic polymers such as polymers o~ methylmethacrylate, ethyl acrylate and the like. In general the chemical composition of the polymers is not critical. The polymers must show significant swelling; that is, at least a 25 percent increase in volume in a period of up to 24 hours in the organic liguid to which the polymers are required to res-pond under desired service conditions of temperature and 17,475-F _5_ ~(133S~33 pressure. Particularly advantageous materials which respond to a wide ~ariety of organic liquids are polymers of styrene such as polystyrene and polymers of styrena and divinylben-zene containing up to about 10 weight percent divinylbenzene.
For general use with polychlorinated hydrocarbons, alkyl-styrene polymers are of particular benefit. Such alkyl-styrene polymers swell ~ery rapidly on contact wi~h ali-phatic and/or aromatic hydrocarbons. ~lkylstyrene polymers usually show substantial swelling when in contact with organic liquids in less than one minute.
Preferably, cross-linked polymers of styrene, and advantageously of alkylstyrenes, are utilized as the imbibing agent in the present in~ention. Those alkyl-styrenes which can be used to prepare these polymers have alkyl groups containing from 1 to 20, and preferably from 4 to 12, carbon atoms, such as: tertiary-alkylstyrenes inc~uding for example p-tert-butylstyrene, p-tert-amyl-styrene, p-tert-hexylstyrene~ p-tert-octylstyrene, p-tert-dodecylstyrene, p-tert-octadecylstyrene, and p-tert-eicosylstyrene n-alkylstyrenes including for example n-butylstyrene, n-amylstyrene, n-hexylstyrene, n-octylstyrene, n-dodecylstyrene, n-octadecylstyrene, and n-eicosylstyrene; sec-alkylstyrenes including for example sec-butylstyrene, sec-hexylstyrene, sec-octylstyrene sec-dodecylstyrene, sec-octadecylstyrene, and sec-eicosyl-styrene; isoalkylstyrenes including for example, isobutyl-styrene, isoamylstyrene~ isohexylstyrene, isooctylstyrene, isododecylstyrene, isooctadecylstyrene and isoeicosyl-styrene, and copolymers thereof.
17,475-F -6-~;39433 Especially preferred for use in the practice of the invention are cross-linked copolymers of such alkylstyrenes as heretofore described and an alkyl es~er derived from a Cl to C18 alcohol and acrylic or methacrylic acid or mixtures thereof.
Suitable monomers which may be employed as comonomers with the alkylstyrene include such materials as vinylnaphthalene~ styrene, a-methylstyrene, ring--substituted a-methylstyrenes, halostyrenes, aryl-styrenes and alkarylstyrenes; methacrylic esters, acryli~ esters, fumarate esters and half esters, maleate esters and half esters, itaconate esters and half esters, vinyl biphenyls, vinyl esters of aliphatic carboxylic - - acid esters, alkyl vinyl ethers, alkyl vinyl ketones, a-olefins, isoolefins, butadiene, isoprene, dimethylbuta-diene~ acrylonitrile, methacrylonitrile and the like.
It is desirable that the polymers used in the process of the invention contain a slight amount of cross-linking agent, preferably in the range of from about 0.01 to 2 percent by weight. The most efficient imbibation of organic liquids occurs when the level of cross-linking agent is less than 1 percent since this permits the polymers to swell easily and imbibe a sub-stantial volume of the organic material.
cross-linking agents which can be used in pre-paring the imbibing polymers suitable for use in the present invention include polyethylenically unsaturated compounds such as divinylbenzene, diethylene glycol dimethacrylate, diisopropenylben2ene, diisopropenyldi-phenyl, diallylmaleate~ diallylphthalate, allylacrylates, 17,475-F _7_ ~(~39~33 allylmethacrylates, allylfumarates, allylitaconates, alkyd resin types, butadiene or isoprene polymers, cyclooctadiene, methylene norbornylenes, divinyl phthalates~ vinyl iso-propenylbenzene, divinylbiphenyl, as well as any other di-or poly-functional compound known to be of use as a cross--linking agent in polymeric vinyl-addition compositions.
~ormally, the polymer containing the cross-linking agent swells with the imbibed organic materials. If there is too much cross-linking agent, the quantity of material imbibed is often insufficient for most applications. If the imbibitional polymer particles contain no cross-linking agent or too little cross-linking agent, then it will dissolve eventually in the organic material resulting, for example, in a non-discrete, non-particulate mass of polymer-thickened organic liquid which is sticky and gathered together with more difficulty than when cross--linked particles are employed.
Polymers for the practice of the method of the present invention may be prepared by any convenient tech-nique, either suspension, emulsion or mass polymerization.
Generally, the method of preparation is selected to pro-vide polymer in the most convenient form for any particular application. Thus, if it is desired to have free-flowing, readily packed beads or particles, generally suspension polymerization is employed to provide a plurality of small beads. If it is desired to obtain beads or particles having the maximum amount of polymer suxface and a rela-tively high imbibition rate, it is oftentimes desirable to employ an emulsion polymerization technique and recover the polymer by spray drying. If it is desired to obtain 17,475-F -8-1~3~43;3~
! a body or particles of pre-determined configuration, it is oftentimes beneficial to employ a mass polymerization technique wherein a polymer-insoluble diluent is employed.
Porous polymers can also be prepared by either suspension - or mass polymerization. Alternately, satisfactory par-ticles are prepared by mass or suspension polymerization with subsequent comminution of the polymer prepared by the mass technique. The particle size of such polymers is selected in accordance with the desired rate of imbibi-tion, larger particles being employed for slower imbibi-tion, smaller particles ~or rapid imbibition. For most applications, such particles are from about 0.1 to 5 millimetars in diameter. Alternately, porous polymer particles may be polymerized in desired shapes. The size of the particles has a significant effect on the rate of imbibing by the particles. For rapid imbibition usually it is desirable to employ particles having di-amet~rs of 500 microns or less, and to periodically shake the container and contents until gelation or swelling is complete. In order to optimize each application, factors such as temperature, configurationJ quantity of fluid, the presence of water and the like must be considered. If the polymer body has water therein, imbibition is somewhat slower than when the water is absent.
The selection of materials for the containers such as the container 14 is well within the skill of anyone in the art. The containers need only be generally impermeable to the liquid to be packaged therein under normal shipping conditions. Materials such as polyethylene, polypropylene, surface sulfonated polyethylene, polypropylene 17,475-F -9-~ 03~33 and resinous copolymers thereof are eminently satisfactory.
Other materials are readily evaluated by placing a portion of the material to be handled within a pouch prepared from the material and allowing it to remain within the pouch at 100F. for a period of one week. If the pouch does not rupture, it is satisfactory for use in the present inven-tion.
By way of further illustration, a commercially available container of one gallon size generally as depicted in Figure 1 is employed. Approximately 1.33 pounds of styrene polymer beads ~as ng 20 mesh and being retained on 80 mesh (U.S. Sieve Size) screens and lightly cross-linked with 0.1 part by weight divinylbenzene per 100 parts by weight of styrene t~ provide a polymer having a swelli~g---index--in tQl~ene of_l2.5, are positioned within the container. By "swelling index" is meant the ratio of the volume of t~e toluene-swollen be~ds to the unswollen polymer particles as determined at 25C. at equilibrium swelling. ~he container is subsequently filled with a commercially available askarel removed for sampling pur-poses rom transformers. Within a period of about one half hour no li~uid is observed within the container and the contents appear to be a rigi~ gel. Three like containers are prepared and all four containers are placed in a ship-ping container and shipped by commercial carrier a distance of about 600 miles. ~o dama~e to either the inner containers or the shipping containers is observed. One of the sample containers is opened and a portion of the contents expelled onto a concrete floor from which it is readily recovered by means of a scoop shovel. The containers are subsequently destroyed by incineration at an approved site.
This invention provides a method for the disposi-tion of ecologically undesirable polymer swelling llquid such as polychlorinated biphenyls, the steps of the method .. . ..
comprising containing the liquid within particles of a liquid swellable solid cross-linked vinyl addition resinous polymer which swells but does not dissolve when in contact ; with the liquid, the liquid being present in a quantity at least sufficient to form a gel, containing said gel in a shipping container, and transferring said shipping con-tainer to a disposal site.
Also contemplated within the scope of the present invention is a shipping container particularly suited for the disposal of ecologically undesirable polymer swelling liquids, the shipping container comprising a combustible ecologically undesirable polymer swelling liquid-impermeable hollow body ~efining a space therein, disposed within said space a liquid swellable solid cross-linked vinyl addition resinous polymer which swells but does not dissolve when in contact with the liquid, the polymer being present in a quantity sufficient to form a gel when an ecologlcally undesirable liquid is added to the space.
, .. .. .. . . .. .
Further features and advantages of the present invention will become more apparent from the following specification taken in connection with the drawing wherein:
Figure 1 depicts a partly in-section view of a container suitable for the practice of the present invention.
Figure 2 depicts a container similar to that of Figure 1 filled with a chlorinated hydrocarbon.
17,475-F
~039433 Figure 3 depicts a plurality of containers such as those in Figure 2 prior to closure for shipping.
In Figure 1 there is a schematic partly in--section view of a container in accordance with the ,475-F ~ l,i -la-~3~3 present invention generally designated by the reference numeral 10. The container lO comprises an outer rigid hollow container 11 of a combustible material, advantage-ously a corrugated paperboard. The container ll has the configuration of a parallelepiped and beneficially that of a cube. The container ll defines therein a space 12 and a passageway 13 providing communication between the space 12 and space external to the container ll. Bene-ficially the container ll may be of conventional corrugated paperboard construction. Within the space 12 is disposed a flexible container 14. The flexible container 14 is beneficially generally chlorinated hydrocarbon-impermeable and is of material such as polyethylene, surface sulfonated polyethylene, vinylidene chloride polymers and the like.
The container 14 has a closure 15 and defines an internal space 16 having disposed therein a plurality of swellable poly~er particles 18. Beneficially, the container 14 is o~ sufficient size that when inflated with gas or li~uid it completely or almost completely fills the space 12 within the container ll. The uolume of particles 18 dis-posed within the container 14 beneficially is sufficient on swelling in desired polychlorinated hydrocarbon to completely ~ill the space 12 while the particles are in a gelatinous condition.
In Figure 2 there is a sectional view of a con-tainer lOa generally in accordance with Figure l which has been filled with a chlorinated hydrocarbon. The con-tainer lOa has a rigid outer container lla, a flexible inner container 14a which contains swollen gelatinous material l9 resulting from swelling of particles such as .
,j 17,475-E' -2-~q~ ~
the particles 18 by the addition of an appropriate chlori-nated hydrocarbon such as a polychlorinated hydrocarbon dielectric liquid; that is, an askarel. The gelatinous mass l9 beneficially is sufficiently viscous that on rupture of one or more walls of the container lOa the material does not flow as a low viscosity liquid but can be collected as a gelg for example, with a shovel, and placed in a readily available container such as a plastic bag, box or the like until appropriate disposal can be made.
Figure 3 depicts a container generally designated by the reference numeral 25. The container 25 comprises an addressed or prepaid addressed shipping box 26 which has not yet been closed for shipping. Within the box 26 are disposed four containers designated by the reference numeral lOb which are generally similar to the filled containers lOa of Figure 2.
In the practice of the method of the present invention, a container such as the container 10 of Figure 1 is filled with an askarel or other ecologically undesirable ., _ , .. .. . ...... . . . . . .
polymer-swelling liquid which one wishes to discard. The , . . . .. . ..
container may be either completely or partly filled, depending on the quantity of material available. ~he swellable particles 18 then Lmbibe the liquid to provide a semi-solid gelatinous mass consisting of individual swollen close-packed pol~mer particles. The container is then closed and desirably can be shipped to a disposal site having facilities to dispose of the container liquid in an ecologically desirable manner. Usually such disposal is accomplished by burning, and it is highly desirable 17,475-F -3-that at least a major portion of the container be of a com-bustible material such as synthetic resinous plastic, paper-board and the like.
~lthough as illustrated in Figure 1, the container comprises two portions, a rigid permeable outer member and a flexible generally liquid impermeable inner memberJ in certain instances the outer container 11 may be dispensed with and individual bags packed in a single shipping con-tainer or placed in a suitable shipping container or a plurality of such bags or containers placed in a shipping container in the manner depicted in Figure 3. Oftentimes rigid plastic containers may be employed. However, at the present time the arrangement as depicted in Figure 1 is found to be economical and generally satisfactory, as the rigid outer container provides mechanical protection for the inner flexible container.
Polymers useful in the practice of the present invention are any polymers which swell on contact with pQlychlorinated organic dielectric liquids or other ecolo-gically undesirable organic liquids. Usefu _polymers may swell on contact with water. However, additional swelling . _ _ _ _ _ must occur when contacted with an organic~dielectric liquid.
Selection of a polymer for use with any organic dielectric liquid is readily accomplished by determining a swelling index for the polymer particles. Beneficially, such a swelling lndex is readily determined by measuring the volume of a particulate polymer to be evaluated and sub-sequently adding the desired organic liquid and determining t~e volume of swollen polymer after a period of 48 hours in the organic liquid. The ratio of the volume with 17,475-F _4_ ~)39~33 organic liquid to volume of the unswollen polymer provides the swelling index. If the polymer is soluble, the swelling .. .. . . . . . ... . . .. . .... . ...
index is infinite. If the swelling index is greater than . . .
about 2, the polymer particles are useful in the practice of the present invention. Beneficially ~or most applications, a swelling index of at least 3 and preferably greater than about 5 is desirable. It is critical to the practice of the pre~ent invention to employ a cross-linked polymer which swells but does not dissolve. If the polymer swells in the presence of the oryanic liquid, it is suitable for the practice of the present invention. However, for most application~ it is desirable to employ a polymer which is cross-linked to a sufficient deg.ree that it exhibits a swelling index between about 2 and 50, and preferably bet-ween about 5 and 50. By utilizing the cross-linked polymer, the hazard of dissolution of the polymer over extended periods of tLme is eliminated. A wide variety of polymeric materials are employed with benefit. Such polymers include polymers of styrene and substituted styrenes; copolymers of vinyl chloride such as a copolymer of 60 weight percent vinyl chloride and 40 weight percent vinyl acetate; vinyli-dene chloride copolymers such as a copolymer of 75 percent vinylidene chloride and 25 percent acrylonitrile; acrylic polymers such as polymers o~ methylmethacrylate, ethyl acrylate and the like. In general the chemical composition of the polymers is not critical. The polymers must show significant swelling; that is, at least a 25 percent increase in volume in a period of up to 24 hours in the organic liguid to which the polymers are required to res-pond under desired service conditions of temperature and 17,475-F _5_ ~(133S~33 pressure. Particularly advantageous materials which respond to a wide ~ariety of organic liquids are polymers of styrene such as polystyrene and polymers of styrena and divinylben-zene containing up to about 10 weight percent divinylbenzene.
For general use with polychlorinated hydrocarbons, alkyl-styrene polymers are of particular benefit. Such alkyl-styrene polymers swell ~ery rapidly on contact wi~h ali-phatic and/or aromatic hydrocarbons. ~lkylstyrene polymers usually show substantial swelling when in contact with organic liquids in less than one minute.
Preferably, cross-linked polymers of styrene, and advantageously of alkylstyrenes, are utilized as the imbibing agent in the present in~ention. Those alkyl-styrenes which can be used to prepare these polymers have alkyl groups containing from 1 to 20, and preferably from 4 to 12, carbon atoms, such as: tertiary-alkylstyrenes inc~uding for example p-tert-butylstyrene, p-tert-amyl-styrene, p-tert-hexylstyrene~ p-tert-octylstyrene, p-tert-dodecylstyrene, p-tert-octadecylstyrene, and p-tert-eicosylstyrene n-alkylstyrenes including for example n-butylstyrene, n-amylstyrene, n-hexylstyrene, n-octylstyrene, n-dodecylstyrene, n-octadecylstyrene, and n-eicosylstyrene; sec-alkylstyrenes including for example sec-butylstyrene, sec-hexylstyrene, sec-octylstyrene sec-dodecylstyrene, sec-octadecylstyrene, and sec-eicosyl-styrene; isoalkylstyrenes including for example, isobutyl-styrene, isoamylstyrene~ isohexylstyrene, isooctylstyrene, isododecylstyrene, isooctadecylstyrene and isoeicosyl-styrene, and copolymers thereof.
17,475-F -6-~;39433 Especially preferred for use in the practice of the invention are cross-linked copolymers of such alkylstyrenes as heretofore described and an alkyl es~er derived from a Cl to C18 alcohol and acrylic or methacrylic acid or mixtures thereof.
Suitable monomers which may be employed as comonomers with the alkylstyrene include such materials as vinylnaphthalene~ styrene, a-methylstyrene, ring--substituted a-methylstyrenes, halostyrenes, aryl-styrenes and alkarylstyrenes; methacrylic esters, acryli~ esters, fumarate esters and half esters, maleate esters and half esters, itaconate esters and half esters, vinyl biphenyls, vinyl esters of aliphatic carboxylic - - acid esters, alkyl vinyl ethers, alkyl vinyl ketones, a-olefins, isoolefins, butadiene, isoprene, dimethylbuta-diene~ acrylonitrile, methacrylonitrile and the like.
It is desirable that the polymers used in the process of the invention contain a slight amount of cross-linking agent, preferably in the range of from about 0.01 to 2 percent by weight. The most efficient imbibation of organic liquids occurs when the level of cross-linking agent is less than 1 percent since this permits the polymers to swell easily and imbibe a sub-stantial volume of the organic material.
cross-linking agents which can be used in pre-paring the imbibing polymers suitable for use in the present invention include polyethylenically unsaturated compounds such as divinylbenzene, diethylene glycol dimethacrylate, diisopropenylben2ene, diisopropenyldi-phenyl, diallylmaleate~ diallylphthalate, allylacrylates, 17,475-F _7_ ~(~39~33 allylmethacrylates, allylfumarates, allylitaconates, alkyd resin types, butadiene or isoprene polymers, cyclooctadiene, methylene norbornylenes, divinyl phthalates~ vinyl iso-propenylbenzene, divinylbiphenyl, as well as any other di-or poly-functional compound known to be of use as a cross--linking agent in polymeric vinyl-addition compositions.
~ormally, the polymer containing the cross-linking agent swells with the imbibed organic materials. If there is too much cross-linking agent, the quantity of material imbibed is often insufficient for most applications. If the imbibitional polymer particles contain no cross-linking agent or too little cross-linking agent, then it will dissolve eventually in the organic material resulting, for example, in a non-discrete, non-particulate mass of polymer-thickened organic liquid which is sticky and gathered together with more difficulty than when cross--linked particles are employed.
Polymers for the practice of the method of the present invention may be prepared by any convenient tech-nique, either suspension, emulsion or mass polymerization.
Generally, the method of preparation is selected to pro-vide polymer in the most convenient form for any particular application. Thus, if it is desired to have free-flowing, readily packed beads or particles, generally suspension polymerization is employed to provide a plurality of small beads. If it is desired to obtain beads or particles having the maximum amount of polymer suxface and a rela-tively high imbibition rate, it is oftentimes desirable to employ an emulsion polymerization technique and recover the polymer by spray drying. If it is desired to obtain 17,475-F -8-1~3~43;3~
! a body or particles of pre-determined configuration, it is oftentimes beneficial to employ a mass polymerization technique wherein a polymer-insoluble diluent is employed.
Porous polymers can also be prepared by either suspension - or mass polymerization. Alternately, satisfactory par-ticles are prepared by mass or suspension polymerization with subsequent comminution of the polymer prepared by the mass technique. The particle size of such polymers is selected in accordance with the desired rate of imbibi-tion, larger particles being employed for slower imbibi-tion, smaller particles ~or rapid imbibition. For most applications, such particles are from about 0.1 to 5 millimetars in diameter. Alternately, porous polymer particles may be polymerized in desired shapes. The size of the particles has a significant effect on the rate of imbibing by the particles. For rapid imbibition usually it is desirable to employ particles having di-amet~rs of 500 microns or less, and to periodically shake the container and contents until gelation or swelling is complete. In order to optimize each application, factors such as temperature, configurationJ quantity of fluid, the presence of water and the like must be considered. If the polymer body has water therein, imbibition is somewhat slower than when the water is absent.
The selection of materials for the containers such as the container 14 is well within the skill of anyone in the art. The containers need only be generally impermeable to the liquid to be packaged therein under normal shipping conditions. Materials such as polyethylene, polypropylene, surface sulfonated polyethylene, polypropylene 17,475-F -9-~ 03~33 and resinous copolymers thereof are eminently satisfactory.
Other materials are readily evaluated by placing a portion of the material to be handled within a pouch prepared from the material and allowing it to remain within the pouch at 100F. for a period of one week. If the pouch does not rupture, it is satisfactory for use in the present inven-tion.
By way of further illustration, a commercially available container of one gallon size generally as depicted in Figure 1 is employed. Approximately 1.33 pounds of styrene polymer beads ~as ng 20 mesh and being retained on 80 mesh (U.S. Sieve Size) screens and lightly cross-linked with 0.1 part by weight divinylbenzene per 100 parts by weight of styrene t~ provide a polymer having a swelli~g---index--in tQl~ene of_l2.5, are positioned within the container. By "swelling index" is meant the ratio of the volume of t~e toluene-swollen be~ds to the unswollen polymer particles as determined at 25C. at equilibrium swelling. ~he container is subsequently filled with a commercially available askarel removed for sampling pur-poses rom transformers. Within a period of about one half hour no li~uid is observed within the container and the contents appear to be a rigi~ gel. Three like containers are prepared and all four containers are placed in a ship-ping container and shipped by commercial carrier a distance of about 600 miles. ~o dama~e to either the inner containers or the shipping containers is observed. One of the sample containers is opened and a portion of the contents expelled onto a concrete floor from which it is readily recovered by means of a scoop shovel. The containers are subsequently destroyed by incineration at an approved site.
Claims (10)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A method for the disposition of ecologically undesirable polymer swelling liquid, the steps of the method comprising containing the liquid within particles of a liquid swellable solid cross-linked vinyl addition resinous polymer which swells but does not dissolve when in contact with the liquid, the liquid being present in a quantity at least sufficient to form a gel, containing said gel in a shipping container, and transferring said shipping container to a disposal site.
2. The method of Claim 1 wherein the undesirable polymer swelling liquid is an askarel.
3. The method of Claim 2 wherein the swellable resinous polymer is a styrene polymer.
4. The method of Claim 1 wherein the shipping container has a plastic layer adjacent the gel.
5. The method of Claim 4 wherein a corrugated paperboard container surrounds the plastic container.
6. A shipping container particularly suited for the disposal of ecologically undesirable polymer swelling liquids, the shipping container comprising a combustible ecologically undesirable polymer swelling liquid-impermeable hollow body defining a space therein, disposed within said space a liquid swellable solid cross-linked vinyl addition resinous polymer which swells but does not dissolve when in contact with the liquid, the polymer being present in a quantity sufficient to form a gel when an ecologically undesirable liquid is added to the space.
7. The container of Claim 6 wherein the polymer is a styrene polymer.
8. The container of Claim 6 wherein the hollow body comprises a first or inner layer of a plastic and a second or outer layer of corrugated paperboard.
9. The container of Claim 6 wherein the hollow body has a generally parallelepiped configuration.
10. A plurality of containers in accordance with Claim 6 disposed within a container.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA220,179A CA1039433A (en) | 1975-02-14 | 1975-02-14 | Disposal of ecologically undesirable liquids |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA220,179A CA1039433A (en) | 1975-02-14 | 1975-02-14 | Disposal of ecologically undesirable liquids |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1039433A true CA1039433A (en) | 1978-09-26 |
Family
ID=4102301
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA220,179A Expired CA1039433A (en) | 1975-02-14 | 1975-02-14 | Disposal of ecologically undesirable liquids |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1039433A (en) |
-
1975
- 1975-02-14 CA CA220,179A patent/CA1039433A/en not_active Expired
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