WO2000050501A1 - Method for degassification of high internal phase emulsion components - Google Patents
Method for degassification of high internal phase emulsion components Download PDFInfo
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- WO2000050501A1 WO2000050501A1 PCT/US2000/004354 US0004354W WO0050501A1 WO 2000050501 A1 WO2000050501 A1 WO 2000050501A1 US 0004354 W US0004354 W US 0004354W WO 0050501 A1 WO0050501 A1 WO 0050501A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
- C08J9/286—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum the liquid phase being a solvent for the monomers but not for the resulting macromolecular composition, i.e. macroporous or macroreticular polymers
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- 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
- C08F2/00—Processes of polymerisation
- C08F2/32—Polymerisation in water-in-oil emulsions
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2201/00—Foams characterised by the foaming process
- C08J2201/02—Foams characterised by the foaming process characterised by mechanical pre- or post-treatments
- C08J2201/028—Foaming by preparing of a high internal phase emulsion
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2201/00—Foams characterised by the foaming process
- C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
- C08J2201/05—Elimination by evaporation or heat degradation of a liquid phase
Definitions
- This application relates to flexible, microporous, open-celled polymeric foam materials with physical characteristics that make them suitable for a variety of uses.
- This application particularly relates to methods of degassing the components of the high internal phase emulsions which are subsequently cured to form such foams.
- foams have found utility m various applications, such as thermal, acoustic, electrical, and mechanical (e.g., for cushioning or packaging) insulators, absorbent materials, filters, membranes, floor mats, toys, carriers for inks, dyes, lubricants, and lotions, and the like.
- References describing such uses and properties of foams include Oertel, G., Polyurethane Handbook, Hanser Publishers, Kunststoff, 1985, and Gibson, L. J.; Ashby, M. F., Cellular Solids. Structure and Properties. Pergamon Press, Oxford, 1988.
- Other uses for foams are generally obvious to one skilled m the art.
- Open-celled foams prepared from High Internal Phase Emulsions are particularly useful in a variety of applications including absorbent disposable articles (US Patents 5,331,015 (DesMarais et al.) issued July 19, 1994, 5,260,345 (DesMarais et al.) issued November 9, 1993, 5,268,224 (DesMarais et al.) issued December 7, 1993, 5,632,737 (Stone et al.) issued May 27, 1997, 5,387,207 (Dyer et al.) issued February 7, 1995, 5,786,395 (Stone et al.) July 28, 1998, 5,795,921 (Dyer et al.) issued August 18, 1998), insulation (thermal, acoustic, mechanical) (US Patents 5,770,634 (Dyer et al.) issued June 23, 1998, 5,753,359 (Dyer et al.) issued May 19, 1998, and 5,633,291 (Dyer et al.
- HIPE process provides facile control over the density, cell and pore size and distribution, proportion of cell struts to windows, and porosity m these foams
- the physical properties of HIPE foams are governed by: (1) the properties of the polymer from which the foam is comprised, (2) the density of the foam, (3) the structure of the foam (i.e.
- a key aspect of this process is the rate of polymerization and crosslmking, together referred to as curing, of the oil phase of a HIPE to form a crosslmked polymer network.
- this curing step required that the emulsion be held at an elevated temperature (40°C-82°C) for a relatively long period of time (typically from 2 hours to 18 hours or longer). Such long cure times necessitate relatively low throughput rates, as well as high capital and production costs.
- HIPE foams envisaged placing the emulsion on a layer of impermeable film which would then be coiled and placed m a curing chamber (US Patent 5,670,101 (Nathoo, et al.) issued September 23, 1997). The coiled film/emulsion sandwich could then be cured using the sequential temperature sequence disclosed m the Brownscombe, et al. patents discussed above.
- Deoxygenation of components e.g. monomers and dispersion phases
- components e.g. monomers and dispersion phases
- Such components are deoxygenated in order to reduce the efficiency of polymerization inhibitors typically used to prevent premature polymer formation because typical inhibitors rely on dissolved oxygen.
- a method exemplary of this type is desc ⁇ bed m Japanese patent application Serial No. 06-172406, published on June 21, 1994. Described therein is a method for suspension polymerization of vmyl chloride monomer where the monomer is dispersed m a degassed (deoxygenated to less than 2 ppm 0 2 ) water phase at a temperature lower than a polymerization temperature.
- the dispersed monomer is then raised to a polymerization temperature and an initiator is charged into the aqueous medium.
- This method is said to reduce the amount of scale that is deposited on the polymerization apparatus during polymerization. While such processes may use a degassed water phase, the intent of such degassification is deoxygenation (other processes use sparging to replace dissolved oxygen with nitrogen for the same purpose).
- degassing the phases as opposed to deoxygenation
- the present invention relates to a process for obtaining open-celled foams by polymerizing a High Internal Phase Emulsion, or HIPE, which has a relatively small amount of a continuous oil phase and a relatively greater amount of a discontinuous aqueous phase.
- the present invention particularly relates to relatively high temperature processes for curing the oil phase wherein in one or both of the oil and water phases is/are degassed.
- degassification allows the HIPE to be heated more enabling the foam to be prepared in a much shorter interval than has heretofore been possible with a substantial reduction in the level of internal defects. This enables practical continuous production processes of HIPE foams which have to this point been made via batch processes.
- the process of the present invention generally comprises the steps of: 1) forming a water in oil emulsion (HIPE) wherein the oil phase comprises polyme ⁇ zable monomers; and 2) polymerizing and crosslmkmg the monomers at temperatures greater than 90°C to form a HIPE foam.
- the oil phase comprises: 1) from about 85 to 99% by weight of a monomer component capable of forming a crosslmked copolymer having a Tg of about 90°C or lower, wherein the monomer component comprises a blend of monofunctional monomers, crosslmkng agents, and comonomers capable of modifying foam properties, and 2) from about 1 to about 20% of an emulsifier component capable of forming a stable HIPE.
- the aqueous phase comprises from about 0.2 to about 40% by weight of a water soluble electrolyte and an effective amount of a polymerization initiator.
- the volume to weight ratio of aqueous phase to oil phase is between about 8J and about 140: 1
- the aqueous fraction of the HIPE foam may be removed by a variety of techniques to yield the open-celled, microporous, low density product
- HIPEs in a relatively short time period at elevated temperatures allows increased production and improved economics relative to previously described methods. Either batch or continuous processes can be used. In either case, because the vapor pressure of both phases in the emulsion increases as the temperature is increased, some containment and/or pressurized system may be required to prevent volatilization of HIPE components. Such elevated pressures may also serve to reduce separation of dissolved gasses during the high temperature curing and or emulsification steps. Volatilization to form gas or vapor bubbles may create defects (e.g. voids) that degrade the fine structure, particularly the cell size distribution, of the HIPE and resulting HIPE foam, and is generally to be avoided.
- defects e.g. voids
- This may be accomplished by vacuum degassing one or both of the oil and water phases, by applying pressure from an external source such as a pump or pressurized gas cylinder, by heating the emulsion in a closed container with relatively small headspace volume, by heating a portion of the composition under the surface of the emulsion m an open container such that the "hydrostatic" pressure prevents volatilization of the liquid comprising the emulsion, or by any other method or device generally known to those skilled in the art. Elements of these approaches may be combined to develop a suitable process for rapid curing of HIPE foams
- Figure 1 is an. electron photomicrograph at 500 X magnification of a control HIPE foam in its expanded state wherein the emulsion was formed at 47°C and cured at 65°C under ambient pressure according to the prior art.
- Figure 2 is an electron photomicrographs at 500 X magnification of a representative polymeric foam m its expanded state according to the present invention prepared as described m Example 1.
- Figure 3 is an. electron photomicrograph at 1000 X magnification of a control HIPE foam in its expanded state wherein the emulsion was formed at 47°C and cured at 65°C under ambient pressure according to the prior art.
- Figure 4 is an electron photomicrographs at 1000 X magnification of a representative polymeric foam in its expanded state according to the present invention prepared as described in Example 1.
- Figure 5 is an. electron photomicrograph at 2500 X magnification of a control HIPE foam in its expanded state wherein the emulsion was formed at 47°C and cured at 65°C under ambient pressure according to the prior art.
- Figure 6 is an electron photomicrographs at 2500 X magnification of a representative polymeric foam in its expanded state according to the present invention prepared as described in Example 1.
- Figure 7 is a schematic diagram of the curing chamber used to prepare foams depicted in Figures 1 and 2
- Figure 8 is a schematic diagram of a continuous process for preparing HIPE foams
- “Curing” is the process of converting a HIPE to a HIPE foam. Curing involves the polymerization of monomers into polymers. A further step included the curing process is crosslmkmg. A cured HIPE foam is one which has the physical properties, e.g., mechanical integrity, to be handled m subsequent processing steps (which may include a post-curing treatment to confer the final properties desired). Generally, curing is effected via the application of heat. An indication of the extent of cure is the mechanical strength of the foam, as measured by the yield stress described in the Test Methods section below
- Polymerization is the part of the curing process whereby the monomers of the oil phase are converted to a relatively high molecular weight polymer
- Cross-slmkmg is the part of the curing process whereby the monomers having more than one functional group with respect to free radical polymerization are copolyme ⁇ zed into more than one chain of the growing polymer
- Hydrostatic relates to pressure conferred by a column of liquid in a gravitational field, sometimes referred to as “hydrostatic head”.
- the liquid is not necessarily water, but may be an aqueous solution, emulsion, suspension or other liquid
- defects are irregular pores within the polymeric foam Typically, a defect has an effective diameter much larger than the desired pore size distribution for the foam and can be considered to be a void in the foam.
- Deoxygenation of a liquid is partial or complete removal of dissolved oxygen, usually effected by replacement of the dissolved oxygen by replacement with an inert gas (e.g. N 2 or Ar) Sparging a liquid with N 2 gas is a well known deoxygenation method.
- an inert gas e.g. N 2 or Ar
- the continuous oil phase of the HIPE comprises monomers that are polymerized to form the solid foam structure and the emulsifier necessary to stabilize the emulsion.
- the monomers will include from about 20 to about 95% by weight of at least one substantially water- msoluble monofunctional monomer capable of forming an atactic amorphous polymer having a glass transition temperature (Tg) of about 35°C or lower. This comonomer is added to lower the overall Tg of the resulting HIPE foam.
- Exemplary monomers of this type include C4-C14 alkyl acrylates and Cg-Ci 6 methacrylates such as 2-ethylhexyl acrylate, n-butyl acrylate, hexyl acrylate, n-octyl acrylate, nonyl acrylate, decyl acrylate, isodecyl acrylate, tetradecyl acrylate, benzyl acrylate, nonyl phenyl acrylate, hexyl methacrylate, octyl methacrylate, nonyl methacrylate, decyl methacrylate, isodecyl methacrylate, dodecyl methacrylate, and tetradecyl methacrylate; substituted acrylamides, such as N-octadecyl acrylamide; dienes such as isoprene, butadiene, chloroprene, piperylene, lJ
- the oil phase will also comprise from about 5 to about 80% by weight of at least one substantially water-insoluble, polyfunctional crosslmkmg agent.
- This comonomer is added to confer strength to the resulting HIPE foam.
- Exemplary crosslmkmg monomers of this type encompass a wide variety of monomers containing two or more activated vmyl groups, such as the divinyl benzenes and analogs thereof.
- These analogs include m,p-dwmy ⁇ benzene (including commercially available blends of such divmyl benzenes with ethyl styrene), divmyl naphthalene, trivmyl benzene, divmyl alkyl benzenes, divmyl biphenyls, divmyl phenyl ethers, divmyl ferrocenes, divinyl furans, and the like.
- crosslmkmg agents may be selected from a group derived from the reaction of acrylic acid or methacryhc acid with polyfunctional alcohols and amines
- Nonlimitmg examples of this group include 1,6-hexaned ⁇ old ⁇ acrylate, 1,4- butanedioldimethacrylate, t ⁇ methylolpropane triacrylate, hexamethylene bisacrylamide, and the like.
- Other examples of crosslmkmg monomers include divinyl sulfide, divmyl sulfone, and trivmyl phosphme.
- Other crosshnkers useful in this regard are well known to those skilled m the art.
- the weight fraction of the crosslmkmg component is calculated on the basis of the pure crosslmker m cases wherein the crosslmkmg monomer is commonly used as a mixture (e.g., divmyl benzene often is a 55% pure mixture with the balance being ethyl styrene)
- Any third substantially water-msoluble comonomer may be added to the oil phase m weight percentages of from about 0% to about 70%, preferably from about 15% to about 40%, to modify properties in other ways.
- "toughening" monomers may be desired which impart toughness to the resulting HIPE foam equivalent to that provided by styrene.
- styremcs such as styrene and ethyl styrene and methyl methacrylate.
- styremcs and other compounds which may also help reduce the Tg or enhance the strength of the resulting HIPE foam such as p-n-octyl styrene.
- Monomers may be added to confer flame retardancy as disclosed in commonly assigned copendmg US Patent application Serial No. 09/118,613 (Dyer) filed July 17, 1998. Monomers may be added to confer color, fluorescent properties, radiation resistance, opacity to radiation (e.g., lead tetraacrylate), to disperse charge, to reflect incident infrared light, to absorb radio waves, to form a wettable surface on the HIPE foam struts, or for any other purpose.
- the discontinuous aqueous internal phase of the HIPE is generally an aqueous solution containing one or more dissolved components.
- One essential dissolved component of the water phase is a water-soluble electrolyte.
- the dissolved electrolyte minimizes the tendency of monomers, comonomers, and crosshnkers that are primarily oil soluble to also dissolve m the water phase.
- a water-soluble free-radical initiator is a water-soluble free-radical initiator as may be known to the art.
- the initiator can be present at up to about 20 mole percent based on the total moles of polymerizable monomers present in the oil phase. More preferably, the initiator is present m an amount of from about 0.001 to about 10 mole percent based on the total moles of polymerizable monomers in the oil phase.
- Suitable initiators include ammonium persulfate and potassium persulfate
- the emulsifier is necessary for forming and stabilizing the HIPE.
- the emulsifier is generally included m the oil phase and tends to be relatively hydrophobic in character. (See for example Williams, J. M., Langmuir 1991, 7, 1370-1377, incorporated herein by reference )
- An example emulsifier which functions very well is diglycerol monooleate.
- Other emulsifiers of this general sort also include diglycerol monomy ⁇ state, diglycerol monoisostearate, diglycerol monoesters of coconut fatty acids, sorbitan monooleate, sorbitan monomy ⁇ state, sorbitan monoesters of coconut fatty acids, sorbitan isostearate, and like compounds and mixtures thereof.
- Coemulsifiers may also be used to provide additional control of cell size, cell size distribution, and emulsion stability.
- Exemplary coemulsifiers include phosphatidyl cho nes and phosphatidyl chohne-containing compositions, aliphatic betames, long chain C12-C22 diahphatic, short chain C1 -C4 dialiphatic quaternary ammonium salts, long chain C12-C22 d ⁇ alkoyl(alkenoyl)-2-hydroxyethyl, short chain C1-C4 diahphatic quaternary ammonium salts, long chain C12- 22 diahphatic lmidazolimum quaternary ammonium salts, short chain C1 -C4 diahphatic, long chain C12-C22 monoahphatic benzyl quaternary ammonium salts, the long chain C12-C22 d ⁇ alkoyl(alkenoyl)-2-am ⁇ n
- antioxidants e.g., hindered phenolics, hindered amme light stabilizers, UV absorbers
- plasticizers e.g., dioctyl phthalate, dinonyl sebacate
- flame retardants e.g., halogenated hydrocarbons, phosphates, borates, inorganic salts such as antimony trioxide or ammonium phosphate or magnesium hydroxide
- dyes and pigments e.g., starch, titanium dioxide, carbon black, or calcium carbonate
- fibers e.g., chain transfer agents
- odor absorbers such as activated carbon particulates, dissolved polymers and ohogomers, and such other agents as are commonly added to polymers for a variety of reasons.
- Such additives may be added to confer color, fluorescent properties, radiation resistance, opacity to radiation (e.g., lead compounds), to disperse charge, to reflect incident infrared light, to absorb radio waves, to form a wettable surface on the HIPE foam struts, or for any other purpose.
- radiation e.g., lead compounds
- Foam preparation typically involves the steps of 1) forming a stable high internal phase emulsion (HIPE); 2) curing this stable emulsion under conditions suitable for forming a cellular polymeric structure; 3) optionally squeezing and washing the cellular polymeric structure to remove the original residual water phase from the polymeric foam structure and, if necessary, treating the polymeric foam structure with a hydrophihzmg surfactant and/or hydratable salt to deposit any needed hydrophihzmg surfactant/hydratable salt, and 4) thereafter dewate ⁇ ng this polymeric foam structure.
- HIPE high internal phase emulsion
- the HIPE is formed by combining the water and oil phase components in a ratio between about 8: 1 and 140:1. Preferably, the ratio is between about 10: 1 and about 75:1, more preferably between about 13.1 and about 65: 1.
- the oil phase will typically contain the requisite monomers, comonomers, crosslmkers, and emulsifiers, as well as optional components
- the water phase will typically contain electrolyte or electrolytes and polymerization initiator or initiators.
- the HIPE can be formed from the combined oil and water phases by subjecting these combined phases to shear agitation.
- Shear agitation is generally applied to the extent and for a time period necessary to form a stable emulsion.
- Such a process can be conducted in either batchwise or continuous fashion and is generally carried out under conditions suitable for forming an emulsion where the water phase droplets are dispersed to such an extent that the resulting polymeric foam will have the requisite structural characteristics.
- Emulsification of the oil and water phase combination will frequently involve the use of a mixing or agitation device such as an impeller.
- One preferred method of forming HIPE involves a continuous process that combines and emulsifies the requisite oil and water phases.
- a liquid stream comprising the oil phase is formed.
- a separate liquid stream comprising the water phase is also formed.
- the two separate streams are provided to a suitable mixing chamber or zone at a suitable emulsification pressure and combined therein such that the requisite water to oil phase weight ratios previously specified are achieved.
- the combined streams are generally subjected to shear agitation provided, for example, by an impeller of suitable configuration and dimensions, or by any other means of imparting shear or turbulent mixing generally known to those skilled m the art. Shear will typically be applied to the combined oil/water phase stream at an approp ⁇ ate rate and extent.
- the stable liquid HIPE can then be withdrawn or pumped from the mixing chamber or zone. This preferred method for forming HIPEs via a continuous process is desc ⁇ bed m greater detail in US Patent 5,149,720 (DesMarais et al.), issued September 22, 1992, which is incorporated by reference.
- 60/158,620 (Catalfamo, et al.) filed on October 8, 1999 may be used Degassing one or both of the oil and water phases is particularly important when the required shear is provided by an impeller such as the pm mixer described in the aforementioned US Patents 5,149,720 and 5,827,909. Separation of dissolved gasses due to the relatively lower pressure in the wake of the impeller can cause cavitation with resulting loss of mixing efficiency m addition to being a source of defects m the foam if one or both of the streams is not degassed.
- an impeller such as the pm mixer described in the aforementioned US Patents 5,149,720 and 5,827,909. Separation of dissolved gasses due to the relatively lower pressure in the wake of the impeller can cause cavitation with resulting loss of mixing efficiency m addition to being a source of defects m the foam if one or both of the streams is not degassed.
- the present invention relates to polyme ⁇ zation/curmg of the oil phase of the emulsion at high curing temperatures for short periods.
- the HIPE formed as described above may be polymerized/cured in a batch process, or in a continuous process.
- a measure of the extent of cure of the polymer is the strength of the foam, as measured by the yield stress described m the Test Methods section below.
- Another measure of the extent of cure of the polymer is the extent to which it swells in a good solvent such as toluene (being crosslmked, the HIPE foam does not dissolve without being chemically altered).
- curing comprises two overlapping but distinct processes. The first involves polymerization of the monomers. The second the formation of crosslinks between active sites on adjacent polymer backbones.
- Crosslmkmg is essential to the formation of HIPE foams with strength and integrity essential to their further handling and use.
- the rate controlling step of this crosslmkmg reaction is believed to be related to the rate of diffusion of the active sites attached to the polymer chains. It has been discovered surprisingly that an increase in the rate of production of free-radicals in the HIPE does not accelerate cu ⁇ ng usefully.
- increasing the diffusion rate of the active sites by increasing the temperature of the system in a conventional curing process is limited by the volatility of the components of the emulsion.
- the current invention provides for curing the emulsion under an elevated pressure in order to allow high temperatures and rapid cure times to be attained without excessive volatilization of the emulsion components.
- the present invention requires only degassing one or both of the phases that are used to form the HIPE prior to HIPE formation.
- the oil phase and the aqueous phase of the emulsion may contain dissolved gases. At elevated temperatures, the solubility of these gases in the liquid phases is reduced, and the gas may be released to form bubbles in the emulsion. These bubbles may disrupt the structure of the HIPE and cause undesirable defects in the finished foam structure. The formation of such defects may be reduced or eliminated by: 1) degassing the aqueous and/or oil phases of the emulsion prior to heating, 2) employing sufficient pressure to reduce or eliminate bubble formation at the curing temperature, or combinations of these approaches.
- aqueous phase is typically much larger than the amount of oil phase in the HIPE, most of the dissolved gas in the system may be removed by degassing only the aqueous phase.
- Degassing may be achieved by heating the liquid, or applying a vacuum, with or without a nucleating agent (e.g., boiling media, available from Ald ⁇ ch Chemical Co., Milwaukee, WI), or by any other technique known to those skilled in the art.
- the liquid may be degassed in a batchwise process, or preferably in a continuous process immediately prior to formation of the HIPE. Such degassification is useful at cu ⁇ ng temperatures as low as 40°C.
- the curing temperature will range from about 40°C to about 250°C. Preferred curing temperatures are greater than about 65 °C, more preferred curing temperatures are greater than about 75°C. Still more preferred curing temperatures are greater than about 85°C.
- a stream of the liquid to be degassed may be pumped through an evacuated chamber where the reduced pressure provides a driving force for reducing the amount of dissolved gas in the liquid.
- a chamber may be provided with packing media to increase the surface area of the liquid as it is exposed to the vacuum.
- packing media include glass beads, crenellated glass strips, shaped glass or polymeric pieces (e. g. saddles, Raschig rings, etc.), boiling stones and other solid materials that may serve to increase the surface area of the fluid being exposed to the vacuum.
- Suitable packing materials may be obtained from a large variety of commercial sources, for example, Aldnch Chemicals of Milwaukee, WI.
- a continuous process for degassing the aqueous phase used to form a HIPE according to the present invention is described in Example 2.
- HIPE structural disruption is minimized if one or both of the phases used to form the HIPE is degassed such that the level of a tracer gas (The level of a tracer gas, such as oxygen, is more easily measured and indicates how much other gas, such as nitrogen, may be dissolved in the phase.) is reduced to at least half its initial value after the degassing step and prior to formation of the HIPE.
- the level of tracer gas is reduced to 25% of its initial value by the degassing step More preferably, the tracer gas level is reduced to less than about 15% of its initial value (The amount of the tracer gas in a phase is measured when the phase is at room temperature ( ⁇ 25°C) and at a pressure of 1 atmosphere).
- Exposure to a vacuum of at least about 12 inches of mercury (30 centimeters of mercury) at a residence time wherein the level of a tracer gas is reduced to at least half its initial value is suitable.
- the vacuum is at least about 24 inches of mercury (61 centimeters of mercury).
- exposure of the liquid to be degassed to a vacuum of about 24 inches of mercury (61 centimeters of mercury) with a residence time of at least about 20 seconds has been found to reduce dissolved gas to a suitable level in a reasonable time.
- the residence time under a vacuum of at least about 24 inches of mercury (61 centimeters of mercury) is at least about 60 seconds.
- the residence time is greater than about two minutes.
- variables such as the amount of liquid to be degassed, the level of vacuum, the temperature of the liquid, the surface area of the exposed liquid, and other similar variables all interact to determine the amount of time under vacuum that is required to reduce the initial dissolved gas level to an acceptable level. Such determination is readily done by those having skill in the chemical engineering arts
- the HIPE is formed in a batchwise process, as described m Example 1 below.
- the formed HIPE is transferred to a suitable reaction vessel 200, such as that shown m Figure 7, capable of withstanding pressures (typically from about 2 to about 40 atmospheres) necessary to enable curing at the desired temperature (for example, from about 90° to about 250°C).
- pressure typically from about 2 to about 40 atmospheres
- the desired temperature for example, from about 90° to about 250°C.
- the temperature at which the HIPE is provided to the vessel may be significantly lower than the polyme ⁇ zation/cu ⁇ ng temperature.
- FIG. 7 is an exemplary reaction vessel 200 that is suitable for batch curing of HIPEs according to the present invention.
- the vessel 200 comprises a vessel body 210 having sufficient volume to cure the desired amount of HIPE.
- the vessel body can have any desired shape including cylindrical, cubic, rectangular solid, or other irregular shape as may be desired.
- the container should be constructed such that the polymerized/cured solid foam material can be easily removed for further processing after polyme ⁇ zation/curmg has been carried out to the extent desired.
- a cylindrical shape has been found to be useful.
- the vessel closure 220 has a shape that is complementary to the shape of the vessel body 210 so as to provide a closure therefor.
- the seal 230 is interposed between the closure 220 and the body 210 to provide resistance to leakage of materials enclosed in the reaction vessel 200 during the curing process
- the vessel 200 should be constructed of materials that are capable of withstanding the pressures necessary to cure the HIPE at the desired temperature as is discussed above. Closure means (not shown) capable of resisting such pressure are also necessary m order to maintain the vessel 200 m a sealed condition during the cu ⁇ ng process
- the vessel 200 may further be lined with a material compatible with the HIPE so that it does not cause the HIPE to degrade at the interior surfaces of the vessel which contact the HIPE.
- exemplary surfaces in this regard include: stainless steel, titanium, glass, polyethylene, polypropylene, and polytetrafluoroethylene.
- materials will depend on the environmental factors that the material will experience. For example, cu ⁇ ng temperatures greater than the softening point of a polymer surface would render a polymeric lining unsuitable.
- a titanium or glass surface is suitable for curing conditions requiring the surface to be exposed to high concentration of chloride ion (from the aqueous phase of the HIPE) and the combination of high pressure and temperature which provides the accelerated curing described herein.
- the vessel 200 is filled with HIPE so as to minimize headspace volume before being sealed. Minimizing the headspace volume limits the extent to which volatilization of the emulsion components can occur.
- the vessel 200 may be pressurized simply by heating the container and its contents, for example m an oven. In such a case, the pressure mside the container is determined by the partial vapor pressures of the components of the emulsion.
- pressure can be introduced through an appropriate valve from an external pressure source such as a pump which can provide an incompatible liquid to raise the pressure or pressurized gas cylinder.
- Suitable curing conditions will vary depending upon the composition of the oil and aqueous phases of the emulsion (especially the emulsifier systems used), and the type and amounts of polymerization initiators used.
- the curing temperature will typically range from about 40°C to about 250°C. Frequently, however, it will be desirable to maintain the HIPE at elevated temperatures above about 90°C, more preferably above about 100°C, most preferably between about 125°C and 165°C (2.5 to 7 atmospheres), for a time period ranging from about 20 seconds to about 1 hour, more preferably from about 40 seconds to about 20 minutes, most preferably from about 1 minute to about 10 minutes.
- Figures 1-6 are photomicrographs that compare exemplary foams produced according to the prior art and according to the present invention as described in Example 1 at va ⁇ ous magnifications. Specifically, the foam of Figures 1, 3, and 5 was produced according to Condition 2 of Example 1 and the foam of Figures 2, 4, and 6 was produced according to Condition 7 of Example 1. As can be seen by comparing the process conditions given in table 1 , the only substantial difference in curing is the curing temperature, with the resulting reduction in cunng time. As is clearly evident from the property data m Table 1 below and by compa ⁇ ng the va ⁇ ous pairs of figures, the rapid curing process of the present invention provides foams having essentially the same properties as foams produced according to the prior art using cu ⁇ ng processes that required substantially longer curing times.
- a plurality of reaction vessels 200 may be attached, for example, to a continuous belt which moves the vessels from a HIPE filling station through a heating zone to a section which ejects the cured HIPE foam to a processing line and carriers the containers back to the filling zone (after any washing process that may be needed to restore the containers to usable condition).
- the HIPE is formed m a continuous process, as is shown schematically in Figure 8 and described in Example 2 below.
- Figure 8 describes one method and an apparatus 300 suitable for continuously forming HIPE foams according to the present invention.
- a HIPE is made using the methods generally described in the aforementioned US Patents 5,149,720 and 5,827,909. That is, the oil phase (desired blend of monomers and emulsifier) is prepared and stored m an oil phase supply vessel 305. Similarly, the desired aqueous phase (blend of water, electrolyte and initiator) is prepared and stored in an aqueous phase supply vessel 310. The oil phase and the aqueous phase are supplied m the desired proportions to mixhead 330 by an oil phase supply pump 315 and an aqueous phase supply pump 325. The mixhead 330 supplies the mechanical energy (shear) necessary to form the HIPE. If desired, a HIPE recirculation pump 335 can be used.
- the formed HIPE is pumped into an elongated cu ⁇ ng chamber 340 with specific cross- sectional shape and dimensions as desired for the foam product.
- the oil phase supply pump 315 and the aqueous phase supply pump may be used to pump the HIPE from the mixhead 330 to the curing chamber 340. In this case, emulsification will occur at substantially the curing pressure.
- the emulsification pressure must be somewhat greater than curing pressure to enable flow to occur.
- an optional booster pump 345 may be used to pump the HIPE from the mixhead 330 to the curing chamber 340. In this case, emulsification will occur at a lower pressure and temperature than the curing step.
- multiple systems can be used to make multiple HIPEs having different combinations of properties (e.g., pore dimensions, mechanical properties, etc.).
- Such multiple HIPEs can be introduced into the curing chamber 340 so as to provided a cured foam having regions of varying properties as may be desired for a particular end use.
- the chamber 340 may further be lined with a material compatible with the HIPE so that it does not cause degradation of the HIPE structure at the interior surfaces which contact the HIPE, and is not degraded by the oil or water phase components at the elevated temperatures intended
- a slip layer may be provided between the curing HIPE and the chamber walls to minimize uneven flow patterns as the HIPE progresses through the chamber 340.
- the slip layer must be compatible with the oil and water phase components of the HIPE and have sufficient mechanical stability at the curing temperature so as to be effective.
- Such a slip layer has particular utility when used with curing chamber designs incorporating the "hydrostatic head" as are discussed below.
- At least a portion of the chamber 340 is heated in order to bring the HIPE to the intended curing temperature as it passes through this section or zone. Any manner of heating this section or zone may be employed m order to reach and maintain the desired temperature in a controlled fashion. Examples include heating by resistive electrical elements, steam, hot oil or other fluids, hot air or other gases, or any other method of heating known to those skilled in the art.
- a static mixer/heat exchanger or other forced convection heat exchanger can be utilized in the heated section to improve heat transfer into the HIPE. Once the HIPE begins to gel, the composition can no longer be mixed because of the risk of damaging or even destroying the structure of the foam.
- the chamber 340 should be designed such that the pressure required to pump the emulsion and/or cured foam through the chamber under steady state conditions is sufficient to prevent volatilization of the emulsion components at the cure temperature.
- the chamber 340 may be in a ho ⁇ zontal, inclined, or vertical position The inclined and vertical orientations may be employed to provide additional "hydrostatic" back-pressure to help prevent the volatilization of HIPE components, thereby allowing a shorter curing chamber to be employed
- the length of the optional heated section, the temperature of the optional heated section and the rate at which the emulsion is pumped through the tube are selected to allow for sufficient residence time withm the chamber 340 for adequate heat transfer to the center of the chamber 340 m order to attain complete cure If the optional heating is done in chambers 340, then Chambers 340 with relatively thm cross-sectional dimensions are preferred in order to facilitate rapid heat transfer.
- the HIPE is substantially cured into a HIPE foam by the time it exits the curing chamber 340.
- an elevated extension 350 may be located above and downstream of the cu ⁇ ng chamber 340 so as to provide a hydrostatic head.
- the curing chamber 340 can have any desired cross section that is consistent with the flow requirements of pumping the curing HIPE.
- the cross section can be rectangular, circular, triangular, annular, oval, hourglass, dog bone, asymmetric, etc., as may be desired for a particular use of the cured HIPE.
- the cross sectional dimensions of the chamber 340 are such that the polymerized HIPE foam is produced in sheet-like form with the desired cross- sectional dimensions.
- the cross-sectional shape can be designed to facilitate manufacture of the desired product in subsequent processes.
- an hourglass-shaped cross-section (or conjoined hourglass sections) of the appropriate size may facilitate making disposable absorbent products such as diapers by cutting relatively thm slices or sheets of the shaped HIPE foam.
- Other sizes and shapes may be prepared for making feminine hygiene pads, surgical drapes, face masks, and the like.
- the resultant HIPE foam may be cut or sliced into a sheet-like form with thickness suitable for the intended application.
- the cross-section of the cu ⁇ ng chamber 340 may be varied along the length of the chamber in order to increase or decrease the pressure required to pump the HIPE through the chamber.
- the cross-sectional area of a vertical curing chamber may be increased above the point at which the HIPE foam is cured, in order to reduce the resistance to flow caused by friction between the walls of the chamber and the cured foam.
- the cross-sectional area of a curing chamber may be decreased past the point at which the HIPE foam is cured, m order to increase the pressure required to pump the HIPE through the chamber thereby allowing a shorter curing chamber to be employed.
- a solution of initiator can optionally be injected into the HIPE at a point between the mixhead 330 and the curing chamber 340 (not shown). If the optional injection of initiator is chosen, the aqueous phase, as provided from the aqueous phase supply vessel, is substantially initiator free. Additional mixing means, such as a continuous mixer (not shown) may also be desirable downstream of the injection point and upstream of the curing chamber 340 to ensure the initiator solution is distributed throughout the HIPE Such an arrangement has the advantage of substantially reducing the risk of undesirable curing in the mixhead 330 in the event of an unanticipated equipment shutdown A porous, water-filled, open-celled HIPE foam is the product obtained after curing the reaction chamber.
- the cross sectional dimensions of the chamber 340 are preferably such that the polymerized HIPE foam is produced in sheet-like form with the desired cross-sectional dimensions.
- Alternative cross-sectional dimensions may be employed, but regardless of the shape of the curing chamber 340, the resultant HIPE foam may be cut or sliced into a sheet-like form with thickness suitable for the intended application.
- Sheets of cured HIPE foam are easier to process during subsequent treating/washing and dewate ⁇ ng steps, as well as to prepare the HIPE foam for use m the intended application.
- the product HIPE foam may be cut, ground or otherwise comminuted into particles, cubes, rods, spheres, plates, strands, fibers, or other desired shapes.
- the aqueous phase remaining with the HIPE is typically removed by compressing the foam and/or exposing the foam to a vacuum source. Residual moisture can be removed as desired by conventional evaporative drying techniques.
- the emulsification step may be carried out at a relatively low pressure and the pre-formed emulsion pumped into the curing chamber under relatively high pressure using booster pump 345.
- An alternative process entails pumping the oil phase and the aqueous phase into the mixing chamber under relatively high pressure using oil phase supply pump 315 and aqueous phase supply pump 325.
- the emulsification step occurs under relatively high pressure, and the emulsion exits from the mixing chamber directly into the curing chamber under the requisite pressure. This eliminates the need to actively pump the pre-formed emulsion into the curing chamber.
- the HIPE may comprise at least one monomer with a boiling point less than about 60°C.
- Exemplary monomers include chloroprene, isoprene, and butadiene. These volatile monomers are not easily managed with the HIPE cu ⁇ ng processes disclosed to date. When these are employed in the current invention, the pressure of the process must be sufficient to prevent undue volatilization of these monomers even with the heating necessary to effect rapid cure. Foams using these monomers appropriately may be biodegradable as disclosed m aforementioned US Patent 5,767,168, m which HIPE foams made with isoprene are prepared at a pressure of about 30 psi (2 atmospheres) and a temperature of 50°C for 48 hours or more.
- Foams based on chloroprene may be flame retardant, as disclosed in aforementioned copendmg application Serial No. 09/118,613. As taught in each of these references, the inclusion of antioxidants may be especially preferred for HIPE foams made with 1,3-dienes.
- Swelling ratio may be used as a relative measure of the degree of crosslmkmg of the polymer comprising the HIPE foam.
- the degree of crosslmkmg is the critical part of curing as defined herein above.
- Swelling ratio is determined by cutting a cylindrical sample of the foam 2-6 mm thick, 2.5 cm in diameter. The foam sample is thoroughly washed with water and 2-propanol to remove any residual salts and/or emulsifier. This is be accomplished by placing the sample on a piece of filter paper in a Buchner funnel attached to a filter flask.
- a vacuum is applied to the filter flask by means of a laboratory aspirator and the sample is thoroughly washed with distilled water and then with 2-propanol such that the water and 2-propanol are drawn through the porous foam by the vacuum.
- the washed foam sample is then dried in an oven at 65 °C for three hours, removed from the oven, and allowed to cool to room temperature prior to measurement of the swelling ratio.
- the sample is weighed to within ⁇ 1 mg, to obtain the dry weight of the sample, Wd.
- the sample is then placed m a vacuum flask containing sufficient methanol to completely submerge the foam sample. Remaining air bubbles in the foam structure are removed by gentle reduction of the pressure m the flask by means of a laboratory aspirator.
- the completely saturated foam sample is gently removed from the flask and weighed to within ⁇ 1 mg, taking care not to squeeze any of the methanol out of the sample during the weighing process.
- the sample is again dried by gently expressing most of the methanol followed by oven drying at 65°C for 1 hour.
- the dry sample is then placed into a vacuum flask containing sufficient toluene to completely submerge the foam sample. Residual air trapped within the pores of the foam is removed by gentle application and release of vacuum, as described above.
- the toluene saturated weight of the sample, Wt is also obtained as desc ⁇ bed above.
- the swelling ratio may be calculated from the densities of methanol and toluene, and the weights recorded in the above procedure as follows:
- Yield stress is the most practical measure of the degree of curing and relates to the compression strength of the HIPE foam. Yield stress is the stress at which a marked change m the slope of the stress-strain curve occurs This is practically determined by the intersection of extrapolated regions of the stress-strain curve above and below the yield point, as described m more detail below.
- the general test method for measuring yield stress is disclosed in US Patent 5,753,359. Specifically, for the purposes of this application, the following method is used:
- Rheomet ⁇ cs RSA-2 DMA as is available from Rheomet ⁇ cs Inc., of Piscataway, NJ.
- 31°C oven temperature held for 10 minutes prior to the start of the test, and throughout the test.
- the resulting stress-strain curve can be analyzed by line fitting the initial linear elastic and plateau portions of the plot using a linear regression method. The intersection of the two lines thus obtained provides the yield stress (and yield strain).
- Foam density can be measured on dry, expanded foams using any reasonable method.
- the method used herein is disclosed in the aforementioned US Patent 5,387,207.
- HIPEs are prepared at specified temperatures and placed m suitable containers for specified times at the cure temperatures.
- the HIPE foams so produced are plunged into an ice bath to quench the curing process.
- the cooled foams are removed and processed for analysis, usually comprising removal of water by use of pressure, washing in water and/or organic solvent, and drying followed by slicing and/or cutting to the desired dimensions.
- Anhydrous calcium chloride (22.73 kg) and potassium persulfate (35.5 g) are dissolved in 454 liters of water. This provides the water phase stream to be used in a continuous process for forming a HIPE emulsion. It is degassed continuously as Example 2 before feeding the rest of the process.
- a monomer combination comprising distilled divmylbenzene (42.4% divmylbenzene and 51.6% ethyl styrene) (2640 g), 2-ethylhexyl acrylate (4400 g), and hexanedioldiacrylate (960 g) is added a diglycerol monooleate emulsifier (480 g), ditallow dimethyl ammonium methyl sulfate (80g), and Tmuvm 765 (20 g).
- the diglycerol monooleate emulsifier (G ⁇ ndsted Products; Brabrand, Denmark) comprises approximately 81% diglycerol monooleate, 1% other diglycerol monoesters, 3% polyols, and 15% other polyglycerol esters, imparts a minimum oil/water mterfacial tension value of approximately 2.1 dyne/cm and has an oil/water critical aggregation concentration of approximately 2.8 wt%. After mixing, this combination of mate ⁇ als is allowed to settle overnight. No visible residue is formed and all of the mixture is withdrawn and used as the oil phase in a continuous process for forming a HIPE emulsion.
- the pin impeller comprises a cylindrical shaft of about 36.5 cm in length with a diameter of about 2.9 cm.
- the shaft holds 6 rows of pins, 3 rows having 58 pins and 3 rows having 57 pins, each of the three pins at each level disposed at an angle of 120° to each other, with the next level down disposed at 60° to its neighboring level with each level separated by 0.03 mm, each having a diameter of 0J cm extending outwardly from the central axis of the shaft to a length of 2.3 cm.
- the pin impeller is mounted m a cylindrical sleeve which forms the dynamic mixing apparatus, and the pins have a clearance of 1.5 mm from the walls of the cylindrical sleeve.
- a minor portion of the effluent exiting the dynamic mixing apparatus is withdrawn and enters a recirculation zone, as m Example 1 of US Patent 5,827,909.
- the Waukesha pump in the recirculation zone returns the minor portion to the entry point of the oil and water phase flow streams to the dynamic mixing zone.
- a spiral static mixer is mounted downstream from the dynamic mixing apparatus to provide back pressure in the dynamic mixing apparatus and to provide improved incorporation of components into the HIPE that is eventually formed.
- the static mixer (TAH Industries Model 100-812) is a pipe static mixer with 12 elements with a 1 inch (2.5 cm) diameter.
- a hose is mounted downstream from the static mixer to facilitate delivery of the emulsion to the device used for curing.
- an additional static mixer is used to provide addition back pressure to keep the hose filled.
- the optional static mixer can be a 1 inch (2.5 cm) pipe, 12 element mixer (McMaster-Carr Model 3529K53).
- the combined mixing and recirculation apparatus set-up is filled with oil phase and water phase at a ratio of 4 parts water to 1 part oil.
- the dynamic mixing apparatus is vented to allow air to escape while filling the apparatus completely.
- the flow rates during filling are 7.57 g/sec oil phase and 30J cc/sec water phase.
- agitation is begun m the dynamic mixer, with the impeller turning at 1750 RPM and recirculation is begun at a rate of about 30 cc/sec.
- the flow rate of the water phase is then steadily increased to a rate of 151 J cc/sec over a time pe ⁇ od of about 1 mm., and the oil phase flow rate is reduced to 3.36 g/sec over a time period of about 3 mm.
- the recirculation rate is steadily increased to about 150 cc/sec during the latter time period.
- the back pressure created by the dynamic zone and static mixers at this point is about 19.9 PSI (137 kPa), which represents the total pressure drop of the system.
- the Waukesha pump (Model 30) speed is then steadily decreased to a yield a recirculation rate of about 75 cc/sec.
- the HIPE flowing from the static mixer at this point is collected in a preheated (to approximately 80°C) round polyethylene tub, 40 in. (102 cm) in diameter and 12.5m (31.8 cm) high, with removable sides, much like a sprmgform pan used in cooking cakes.
- a pipe-like polyethylene insert 12.5m (31.8cm) in diameter at its base is firmly affixed to the center of the base and is 12.5m (31.8 cm) high.
- the HIPE-contaimng tubs are kept in a room maintained at 80°C for 2 hours to bring about polymerization and form the foam.
- the cured HIPE foam is removed from the cu ⁇ ng tubs
- the foam at this point has residual water phase (containing dissolved emulsifiers, electrolyte, initiator residues, and initiator) about 43-47 times (43-47X) the weight of polymerized monomers.
- the foam is sliced with a sharp reciprocating saw blade into sheets which are 0J85 inches (4.1 mm) in thickness. These sheets are then subjected to compression in a series of 2 porous nip rolls equipped with vacuum which gradually reduce the residual water phase content of the foam to about 6 times (6X) the weight of the polymerized material.
- the sheets are then resaturated with a 2% CaCl2 solution at 60°C, are squeezed in a series of 3 porous nip rolls equipped with vacuum to a water phase content of about 4X.
- the CaCl2 content of the foam is between 8 and 10 %.
- the foam remains compressed after the final nip at a thickness of about 0.028 in (0.071 cm).
- the foam is then dried m air for about 16 hours. Such drying reduces the moisture content to about 9-17 % by weight of polymerized material. At this point, the foam sheets are very drapeable.
- This example is intended to demonstrate the continuous degassification of the water phase of a HIPE.
- Piping Piping as necessary from a water phase supply to a degasses water phase storage should be used.
- Vacuum Source A multiple stage Thomas Vacuum Pump, model H50A-60 is suitable operated so as to provide a vacuum of at least about 24 inches of mercury (61 centimeters of mercury).
Abstract
Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
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US09/890,999 US6362244B1 (en) | 1999-02-22 | 2000-02-18 | Method for degassification of high internal phase emulsion components |
AU30030/00A AU3003000A (en) | 1999-02-22 | 2000-02-18 | Method for degassification of high internal phase emulsion components |
EP00908742A EP1155069A1 (en) | 1999-02-22 | 2000-02-18 | Method for degassification of high internal phase emulsion components |
CA002363638A CA2363638A1 (en) | 1999-02-22 | 2000-02-18 | Method for degassification of high internal phase emulsion components |
JP2000601072A JP2002537461A (en) | 1999-02-22 | 2000-02-18 | Degassing method for high internal phase emulsion components |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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US12110399P | 1999-02-22 | 1999-02-22 | |
US60/121,103 | 1999-02-22 |
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WO2000050501A1 true WO2000050501A1 (en) | 2000-08-31 |
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PCT/US2000/004354 WO2000050501A1 (en) | 1999-02-22 | 2000-02-18 | Method for degassification of high internal phase emulsion components |
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US (1) | US6362244B1 (en) |
EP (1) | EP1155069A1 (en) |
JP (1) | JP2002537461A (en) |
AU (1) | AU3003000A (en) |
CA (1) | CA2363638A1 (en) |
WO (1) | WO2000050501A1 (en) |
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KR100938787B1 (en) * | 2002-12-12 | 2010-01-27 | 스미또모 가가꾸 가부시끼가이샤 | Method for producing iodine type polarizing film |
EP2226047B1 (en) | 2009-03-06 | 2019-06-26 | The Procter and Gamble Company | Absorbent core |
US20100285096A1 (en) | 2009-05-05 | 2010-11-11 | Fancheng Wang | Hygiene Article Having Calcium Sugar Phosphate |
US8257787B2 (en) * | 2009-12-30 | 2012-09-04 | The Procter & Gamble Company | Method of using a carrier sheet in a continuous high internal phase emulsion foam forming process |
CN104448115B (en) * | 2014-11-28 | 2017-01-04 | 佛山市联塑万嘉新卫材有限公司 | Silver antibacterial ventilative hydrophilic acrylic ester foamed materials of zinc and its preparation method and application |
JP6700095B2 (en) * | 2016-04-27 | 2020-05-27 | 株式会社フジクラ | Glass base material manufacturing method and manufacturing apparatus |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5149720A (en) * | 1991-08-12 | 1992-09-22 | The Procter & Gamble Company | Process for preparing emulsions that are polymerizable to absorbent foam materials |
US5827909A (en) * | 1995-01-10 | 1998-10-27 | The Procter & Gamble Company | Recirculating a portion of high internal phase emulsions prepared in a continuous process |
-
2000
- 2000-02-18 WO PCT/US2000/004354 patent/WO2000050501A1/en not_active Application Discontinuation
- 2000-02-18 JP JP2000601072A patent/JP2002537461A/en not_active Withdrawn
- 2000-02-18 AU AU30030/00A patent/AU3003000A/en not_active Abandoned
- 2000-02-18 CA CA002363638A patent/CA2363638A1/en not_active Abandoned
- 2000-02-18 EP EP00908742A patent/EP1155069A1/en not_active Withdrawn
- 2000-02-18 US US09/890,999 patent/US6362244B1/en not_active Expired - Lifetime
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5149720A (en) * | 1991-08-12 | 1992-09-22 | The Procter & Gamble Company | Process for preparing emulsions that are polymerizable to absorbent foam materials |
US5827909A (en) * | 1995-01-10 | 1998-10-27 | The Procter & Gamble Company | Recirculating a portion of high internal phase emulsions prepared in a continuous process |
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EP1155069A1 (en) | 2001-11-21 |
AU3003000A (en) | 2000-09-14 |
CA2363638A1 (en) | 2000-08-31 |
US6362244B1 (en) | 2002-03-26 |
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