HIGH INTERNAL PHASE EMULSIONS AND POROUS MATERIALS PREPARED THEREFROM

Abstract: Polyoxybutylene-polyoxyethylene sulfate-based surfactants particularly useful in preparing high internal phase emulsions. High internal phase emulsions having an internal aqueous phase of greater than 70 percent by volume and an external oil phase comprising a vinyl polymerizable monomer contain a polyoxybutylene-polyoxyethylene-based surfactant. Open-celled polymeric foams having a liquid capacity of greater than about 70 percent of its saturated volume can be prepared from such emulsions.

Description: HIGH INTERNAL PHASE EMULSIONS AND POROUS MATERIALS PREPARED THEREFROM This invention relates to water-in-oil high internal phase emulsions and porous polymeric materials produced therefrom. Water-in-oil emulsions are dispersions of discontinuous or discrete aqueous particles commonly referred to as the "internal" aqueous phase in a continuous or "external" oil phase. Emulsions can contain as much as and more than 70 volume percent internal phase. These are often referred to as high internal phase emulsions (HIPEs). The volume fraction of the internal aqueous phase in such emulsions can be as high as 90 percent and frequently is as high as 95 percent with some HIPEs being reported as high as 98 percent aqueous phase. The use of high internal phase emulsions (HIPEs) in forming porous polymeric materials is well known and is described, for example, in U.S. Patents 5,210,104; 5,200,433; 4,536,521 ; 4,788,225; 5,147,345; 5,331 ,015; 5,260,345; 5,268,224 and 5,318,554. In the described HIPEs, the external oil phase typically comprises a vinyl polymerizable monomer, such as 2-ethylhexyl acrylate and styrene, and a cross-linking monomer such as divinylbenzene. The internal aqueous phase typically comprises water, a radical initiator (if not in the oil phase) and an electrolyte. To form a stable emulsion, a surfactant is added to the oil phase prior to emulsification. Commonly used emulsion stabilizing surfactants include, for example, nonionic surfactants, such as sorbitan esters (for example, sorbitan monooleate and sorbitan monolaurate). Other known stabilizing surfactants include certain poiyglycerol aliphatic esters such as those described in U.S. Patent No. 5,500,451. However, these known surfactants are not efficient, that is, they have to be used in high concentrations to stabilize HIPEs, which can increase the cost of making HIPE foams. When used at concentrations of less than about 2 weight percent, based on the weight of the oil phase, or about 0.06 weight percent based on the weight of the entire emulsion, these known surfactants do not stabilize a HIPE through polymerization to an open-celled foam. HIPE polymerization has gained increasing interest, since open-celled polymeric foams having the capacity to absorb relatively high amounts of water and other liquids can be produced. Unfortunately, in many applications, for example, as absorbents, the emulsion stabilizing surfactant should be removed from the porous polymeric foam prior to use. For example, as described in U.S. Patent 4,788,225, the surfactant may be an extractable residue which can be removed through post-polymerization rinses. If not removed, the surfactant residue may create a problem when it comes in contact with sensitive human skin. Therefore, it is desirable to prepare open-celled polymerized HIPE foams with as little extractable surfactant as possible. One way to reduce the amount of extractable surfactant is to use a polymerizable surfactant, as described in copending patent application U.S. Serial No. 558,333, filed on November 15, 1995. Another way is to include a long hydrophobic component which is sufficient to mechanically bind the surfactant into the foam during polymerization. Using a very small amount of surfactant would also solve the problems associated with extractables, especially in combination with polymerizability or mechanical bindability. However, it is known that using small amounts of surfactants, for example, less than about 5 weight percent, based on the weight of the oil phase, would result in a closed- cell foam. See, for example, J. M. Williams, D. A. Robleski, Langmuir. 4, (1988) 656-662. It would be desirable to provide surfactants which can stabilize HIPEs and form open-celled HIPE foams at relatively low concentrations. In a first aspect, this invention is a polyoxybutylene-polyoxyethylene sulfate- based surfactant. In a second aspect, this invention is a water-in-oil high internal phase emulsion having at least 70 volume percent of an internal aqueous phase and less than 30 volume percent of an external oil phase, and an emulsion stabilizing polyoxybutylene- polyoxyethylene-based surfactant. In a third aspect, this invention is a process for preparing a porous polymeric material which comprises polymerizing the water-in-oil high internal phase emulsion of the second aspect. In a fourth aspect, this invention is an open-cell porous polymeric material prepared by the process of the third aspect. In a fifth aspect, this invention is an open-cell porous polymeric material prepared from the water-in-oil high internal phase emulsion of the second aspect where the external oil phase comprises a vinyl polymerizable monomer and having a liquid capacity greater than about 70 percent of its saturated state volume and containing, after drying without squeezing out any aqueous phase and prior to any rinsing or washing, relatively small amounts of extractable surfactants. The term "relatively small amounts of extractable surfactants" means that less than about 5 percent by weight, preferably less than about 2 percent by weight, more preferably less than about 1 percent by weight and most preferably less than about 0.5 percent by weight surfactant, based on the weight of the polymer, can be extracted from the foam using simple rinses with water or typical solvents for the surfactants, such as, for example, methanol or isopropanol. In a sixth aspect, this invention is an article containing the foam of the fourth aspect that is useful as, for example, an absorbent article, an acoustical modulating article, thermal insulating article, and/or a filtering article. The surfactants of the present invention are useful for preparing high internal phase emulsions with low levels of surfactant. Surfactant applications are broad and anyone skilled in the art would be able to identify a multitude of uses for the surfactants of this invention. Of particular interest are the polymerizable surfactants of this invention which may also be useful in making latexes to, for example, reduce migratory surfactant, and/or enhance the shear stability. The polymerizable surfactants of this invention may also be useful for encapsulation of a phase dispersed into another with the polymerizable surfactant at the interface. By polymerizing the surfactants in the dispersion, the dispersed phase can become encapsulated. Poregens, such as for example an inert surfactant which can be rinsed free after polymerization leaving pores in the polymer, may be used to help render the encapsulation porous, if desired. The HIPEs of the present invention are also useful in preparing low density polymeric foam materials. Highly hydrophilic foam materials made according to the present invention have a particularly useful application in the manufacture of diapers, or other articles which absorb or retain aqueous body fluids. The high internal phase emulsion (HIPE) of the present invention is a water- in-oil emulsion having greater than about 70 volume percent, more preferably, greater than about 90 volume percent and, most preferably, greater than about 95 volume percent of an internal aqueous phase and less than about 30 volume percent, more preferably, less than about 10 volume percent and, most preferably, less than about 5 volume percent of an external oil phase. HIPEs of as much as 98 volume percent or more of internal aqueous phase can be made by the present invention. The external oil phase comprises one or more vinyl polymerizable monomers and a cross-linking monomer. The internal aqueous phase comprises water. Typically, a water-soluble radical initiator is added in the aqueous phase. If an oil-soluble initiator is employed, it is added in the oil phase. Additionally, the HIPE comprises a polyoxybutylene-polyoxyethylene-based surfactant. Vinyl polymerizable monomers which can be employed in the practice of the present invention are any polymerizable monomer having an ethylenic unsaturation. In general, the HIPEs are advantageously prepared from either or both (i) at least one monomer that tends to impart glass-like properties (glassy monomers) to the resulting porous polymeric material and (ii) at least one monomer that tends to impart rubber-like properties (rubbery monomers) to the resulting porous polymeric materials. The glassy monomers are, for the purposes of the present invention, defined as monomeric materials which would produce homopolymers having a glass transition temperature above about 40°C. Preferred glassy monomers include methacrylate-based monomers, such as, for example, methyl methacrylate, and styrene-based monomers, such as, for example, various monovinylidene aromatics such as styrene, o-methylstyrene, chloromethylstyrene, vinylethylbenzene and vinyl toluene. More preferred glassy monomers include styrene, o-methylstyrene, and chloromethylstyrene. The most preferred glassy monomer is styrene. The rubbery monomers are, for the purposes of the present invention, defined as monomeric materials which would produce homopolymers having a glass transition temperature of about 40°C or lower. Preferred rubbery monomers include alkyl esters of ethylenically unsaturated acids ("acrylate esters" or "methacrylate" esters), such as 2- ethylhexyl acrylate, butyl acrylate, hexyl acrylate, butyl methacrylate, lauryl methacrylate, isodecyl methacrylate and mixtures thereof; vinyl aliphatic and alicyclic hydrocarbons such as butadiene; isoprene; and combinations of these comonomers. More preferred rubbery monomers include butyl acrylate, 2-ethylhexyl acrylate, butadiene, isoprene and combinations of these comonomers. The most preferred rubbery monomer is 2-ethylhexyl acrylate. Preferably, the HIPE emulsion includes at least one glassy monomer and at least one rubbery monomer. Without being bound by theory, it is believed that the rubbery monomer provides the foams with flexibility and is used in an amount sufficient to allow compression, bending and twisting during processing, packaging, shipping, storing and use of articles containing such foams, as well as to allow the foam to remain thin until it absorbs liquid, if desired. It is believed the glassy monomer provides the foams with structural integrity and is used in an amount sufficient to minimize the incidence of foam tearing or fragmenting encountered when such foams are subjected to both dynamic and static forces such as, for example, when the wearer of a diaper containing the foam walks, runs, crawls or jumps. The ratio of the glassy monomer to the rubbery monomer generally ranges from 1 :25 to 1.5:1 , more preferably from 1 :9 to 1.5:1. While the amount of the vinyl polymerizable monomers most advantageously employed depends on a variety of factors, such as the specific monomers, in general, the vinyl polymerizable monomer is used in an amount of from 50 to 100 weight percent, preferably from 80 to 95 weight percent, and most preferably from 85 to 93 weight percent, based on the total oil phase. Cross-linking monomers which can be employed in the practice of the present invention for preparing the HIPE include any multifunctional unsaturated monomers capable of reacting with the vinyl monomers. Multifunctional unsaturated cross-linking monomers include, for example, divinylbenzene, ethylene glycol dimethacrylate, 3-butylene dimethacrylate, trimethylolpropane triacrylate and allyl methacrylate. While the amount of cross-linking monomers most advantageously employed depends on a variety of factors, such as the desired polymer modulus, in general, the cross-linking monomer is used in an amount of from 0 to 50 weight percent, preferably from 5 to 20 weight percent, and most preferably from 7 to 15 weight percent, based on the total oil phase. Radical initiators which can be employed in the practice of the present invention for preparing the HIPE include the water-soluble initiators such as, for example, potassium or sodium persulfate and various redox systems such as ammonium persulfate together with sodium metabisulfite and oil-soluble initiators, such as, for example, azobisisobutyronitrile (AIBN), benzoyl peroxide, methyl ethyl ketone peroxide and di-2-ethyl- hexyl-peroxydicarbonate and lauroyl peroxide. The initiator can be added to the aqueous phase or to the oil phase, depending on whether the initiator is water-soluble or oil-soluble. The initiator should be present in an effective amount to polymerize the monomers. Typically, the initiator can be present in an amount of from 0.005 to 20 weight percent, preferably from 0.1 to 10 weight percent and most preferably from 0.1 to 5 weight percent, based on the total oil phase. The internal aqueous phase can include a water-soluble electrolyte for aiding the surfactant in forming a stable emulsion, controlling porosity of the foam and/or enhancing the hydrophilicity of the resulting polymeric foam material if left as a residual component of the foam material. Water-soluble electrolytes which can be employed in the practice of the present invention include inorganic salts (monovalent, divalent, trivalent or mixtures thereof), for example, alkali metal salts, alkaline earth metal salts and heavy metal salts such as halides, sulfates, carbonates, phosphates and mixtures thereof. Such electrolytes include, for example, sodium chloride, sodium sulfate, potassium chloride, potassium sulfate, lithium chloride, magnesium chloride, calcium chloride, magnesium sulfate, aluminum chloride and mixtures thereof. Mono- or divalent salts with monovalent anions, such as halides, are preferred. While the amount of electrolytes most advantageously employed depends on a variety of factors, such as the specific compound, the desired porosity of the foam and the surfactant employed, in general, the electrolytes can be employed up to about 20, more preferably up to about 5 and most preferably up to about 1 weight percent, based on the total aqueous mixture. The internal aqueous phase can additionally comprise a non-electrolyte component, such as, for example, glycerin, as long as a HIPE can still be prepared and polymerized into a foam. Surfactants which can be employed in the practice of the present invention for preparing the water-in-oil high internal phase emulsion include polyoxybutylene- polyoxyethylene-based surfactants. The preferred surfactants which can be employed in the practice of the present invention for preparing the water-in-oil high internal phase emulsion include surfactants represented by any one of the formulas: RO-(BO) m (EO)_SO 3 ( > X RO-(BO) m (EO) n -R' or R"O-(BO) m (EO) n (BO) p -R""" wherein R, R', R" and R'" are any organic, inorganic, or combination of organic and inorganic functionalities which do not prevent the compound from acting as a surfactant.(BO) m and (BO) p are polyoxybutylene blocks of "m" and "p" 1 ,2-butyleneoxide units, respectively; (EO) n is a polyoxyethylene block of "n" ethylene oxide units; X is a counterion and m, n, and p are independently integers greater than zero. Preferably, R is propenyl benzyl, propyl benzyl, vinyl, allyl, linear or branched alkyl, or alkyl-substituted aryl, R' is hydrogen, and R" and R'" are independently hydrogen, propenyl benzyl, propyl benzyl, vinyl, allyl, linear or branched alkyl or alkyl-substituted aryl. Preferably m is a positive number from 10 to 100, more preferably from 20 to 70 and, most preferably, from 20 to 40. Preferably n is a positive number from 1 to 100, more preferably from 1 to 70 and, most preferably, from 5 to 50. Preferably p is a positive number from 10 to 100, more preferably from 20 to 70 and, most preferably, from 20 to 40. The more preferred surfactants which can be employed in the practice of the present invention for preparing the water-in-oil high internal phase emulsion are those represented by the formula: RO-(BO) m (EO) n SO 3 ( ) X wherein R, (BO) m , (EO) n and X are as defined previously. The most preferred surfactants which can be employed in the practice of the present invention for preparing the water-in-oil high internal phase emulsion are those represented by any one of the following formulas: ^- O(BO) 40 (EO) 5 SO 3 - X O O(BO) 30 (EO) 20 SO 3 - X @ O(-BO) 30 (EO) 20 SO 3 - X or CH 3 CH 2 O(BO) 30 (EO) 20 SO 3 - X wherein X is pyridinium, ammonium, or a mixture of both. Generally, the nonionic polyoxybutylene-polyoxyethylene-based surfactants can be prepared by the standard anionic polymerization of monoepoxides, such as, for example, ethylene oxide and butylene oxide, using either a monohydroxyfunctional or dihydroxyfunctional initiator compound and a catalytic amount of a base, as described in "Polymer Syntheses (I)" Organic Chemistry Series Volume I, Stanley R. Sandier, Wolf Karo, 1974, p. 184-189. Polyether sulfates can be prepared through sulfation of the corresponding polyether alcohol using sulfamic acid as described in Organic Functional Group Preparations"; Organic Chemistry Series, Volume 12-111, Second Ed., Stanley R. Sandier, Wolf Karo, 1989, p. 148-149. Preparations of the aforementioned compounds are described in detail in the examples. It has been observed that some of the sulfate-based surfactants tended to lose their efficiency, that is, more surfactant is required to form a HIPE, over time. Although not intended to be bound by theory, it is believed that the sulfate is gradually cleaved over time through a hydrolysis process, producing an alcohol-terminated surfactant. Since sulfates are known to be hydrolytically unstable at a pH below 6 and at a pH above 10, such a hydrolysis can be controlled by controlling the pH of the surfactant. For most of the surfactants tested, the sulfonated form of the surfactant (sulfate-terminated surfactant) has been found to be more efficient than the corresponding alcohol form (alcohol-terminated surfactant) represented, for example, by the formula: RO-(BO) m (EO) n -H However, some of the alcohol-terminated surfactants have been found to be nearly as efficient as the corresponding sulfate-terminated surfactants, such as when m and n in the above formula are 30 and 50, respectively, as demonstrated in Examples 14 to 21. These alcohol-terminated surfactants have also been found to demonstrate high efficiency in forming polymerized HIPE foams. The amount of surfactant used must be such that a water-in-oil high internal phase emulsion will form. Generally, the amount of surfactant needed varies with the specific surfactant and the type of formulation used. As little as about 0.125 weight percent, or- less, based on oil phase can be used. More generally, as little as about 0.25 weight percent based on oil phase can be used. Generally, up to about 25 weight percent or more, based on the oil phase, can be used, if desired. Methods for preparing water-in-oil emulsions are known in the art such as, for example, in U.S. Patents 4,522,953 and 5,210,104, and these methods can be employed in the practice of the present invention. For example, the water-in-oil HIPE can be prepared in batches. In general, to form a water-in-oil HIPE in batch quantities, the water phase is gradually added to a mixture of oil phase and surfactant while the mixture is being agitated. Agitation can be accomplished any number of ways including impeller-type agitation. Alternatively, water-in-oil HIPEs can be prepared in a continuous flow manner. Methods for continuous flow HIPE preparation are also well established in the literature. See, for example, U.S. Patents 4,018,426 and 5,198,472. The following working examples are given to illustrate the invention and should not be construed to limit its scope. Unless otherwise indicated, all parts and percentages are by weight. Example 1 - Preparation of 1 -butylene oxide (401 ethylene oxide (5) 3-propenylphenyl pyridinium sulfate (Surfactant 11 The potassium salt of 2-allylphenol was formed from a 1 :1 molar mixture of potassium ethoxide and 2-allylphenol whereby the ethanol formed during the reaction was removed under high vacuum. Sequential alkoxylation of 1 ,2-butylene oxide (approximately 40 units per molecule) and ethylene oxide (approximately, an average of 5 units per molecule) was conducted utilizing the potassium salt of 2-allylphenol as initiator/catalyst in toluene at 120°C in a Parr reactor. During the course of the polymerization, the allylphenyl moiety undergoes base-catalyzed isomerization to the corresponding 2-propenylphenoxy compound. The resulting diblock copolymer was neutralized with dilute HC1 , filtered and the volatiles were removed by roto-evaporation. The diblock-copolymer was characterized by GPC and NMR. This 2-propenylphenoxypoly BO/EO-monol was heated in the presence of sulfamic acid and pyridine to form the corresponding pyridinium sulfate. This material was heated at 60°C under high vacuum to remove residual pyridine and other volatile components. The degree of sulfamation was determined by 1 H NMR spectroscopy Example 2 - Open-celled Polymerized HIPE Foam using 0.25 weight percent Surfactant 1 Based on the Monomer Phase (0.0125 weight percent Based on Entire Emulsion) Into a monomer phase composed of 4.79 g 2-ethylhexyl acrylate, 1.05 g styrene, 1.64 g divinylbenzene (55 percent active) and 0.10 g lauroyl peroxide initiator was dissolved 0.0188 g of the surfactant from example 1. The components form a clear solution. An aqueous phase was prepared by dissolving 1.42 g calcium chloride dihydrate and 0.17 g potassium persulfate into 141.08 g deionized water. This aqueous phase was added dropwise to the monomer/surfactant solution while mixing in a 250-mL beaker using a 3-paddle agitator at 300 RPM. The resulting HIPE was placed into a dish covered with SARAN™ WRAP (The Dow Chemical Co.) and put in a forced-air oven at 65°C for 15 hours. A water saturated polymeric foam was obtained. The water phase can be squeezed out without fracturing the foam by compressing, indicating an open-celled structure. Example 3 - Preparation of l-polybutyleneoxide(30)-polyethyleneoxide(20. 3-propenylphenyl pyridinium sulfate (Surfactant 2) Another surfactant was prepared as described in Example 1 except the number of 1 ,2-butylene oxide units per molecule was approximately 30 and the number of ethylene oxide units per molecule was approximately 20. Example 4 - Open-celled Polymerized HIPE Foam using 0.25 weight percent Surfactant 2 Based on Monomer Phase (0.0125 weight percent Based on Entire Emulsion. A HIPE was prepared and polymerized as described in Example 2 except Surfactant 2 was used instead of Surfactant 1. Example 5 - Preparation of l-polybutyleneoxide(30)-polyethyleneoxide(20) 3-propylphenyl pyridinium sulfate (Surfactant 3. Another surfactant was prepared as described in Example 3 except the sodium salt of 2-propylphenol was used as the initiator/catalyst instead of the sodium salt of 2-allylphenol. Example 6 - Open-celled Polymerized HIPE Foam using 0.12 weight percent Surfactant 3 based on the Monomer Phase (0.006 weight percent based on Entire Emulsion A polymerized HIPE foam was prepared as described in Example 4 except 0.0095 g of Surfactant 3 was used instead of 0.0188 g of Surfactant 2. The resulting foam was soaked in isopropanol for 2 days and then squeezed free of the internal aqueous phase. The foam was open-celled, as determined by Scanning Electron Microscopy (SEM). Example 7 - Preparation of polvbutyleneoxιde(30,-polvethyleneoxιde(20. pyridinium sulfate (Surfactant 4) Sequential alkoxylation of 1 ,2-butylene oxide (approximately 30 units per molecule) and ethylene oxide (approximately 20 units per molecule) was conducted using potassium ethoxide as initiator/catalyst in toluene at 120°C in a Parr reactor. The resulting diblock copolymer was neutralized with dilute HC1 , filtered, and the volatiles were removed by roto-evaporation. The diblock-copolymer was characterized by GPC and NMR. This polyBO/EO-monol was heated in the presence of sulfamic acid and pyridine to form the corresponding pyridinium sulfate. This material was heated at 60°C under high vacuum to remove residual pyridine and other volatile components. The degree of sulfamation was determined by Η NMR spectroscopy. Example 8 - Open-ceiled Polymerized HIPE Foam using 0.25 weight percent Surfactant 4 based on the Monomer Phase (0.0125 weight percent based on Entire Emulsion) A HIPE was prepared and polymerized as described in Example 2, except Surfactant 4 was used instead of Surfactant 1. Examples 9 to 12 and Comparative Example A The efficiency of Surfactants 1 to 4 was evaluated by determining the minimum amount of surfactant required to form a polymerized open-celled HIPE foam from a 95 percent internal phase HIPE. Several HIPE formulations were prepared with surfactant concentrations ranging from 0.125 to 30 weight-percent based on the weight of the monomer phase while maintaining a 95-weight percent internal phase. The internal phase comprises 4.79 g 2-ethylhexyl acrylate, 1.05 g styrene, 1.64 g divinylbenzene and 0.10 g lauroyl peroxide. The external phase comprised 141.08 g deionized water, 1.42 g CaCI 2 -2H 2 0 and 0.17 g K 2 S 2 O e . The surfactants were generally tested first with the 1 -weight percent formulation (based on weight of monomer phase). If the l-weight percent formulation successfully produced a polymerized open-celled HIPE foam, the 0.5-weight percent formulation was tested next, and so on until a HIPE foam could no longer be produced using the emulsification and polymerization methods described in Example 2. If the l-weight percent recipe failed to produce a polymerized HIPE foam, the 2-weight percent formulation was tested, and so on, until a foam was produced using the emulsification and polymerization methods described in Example 2. For comparative purposes, a known surfactant system (Surfactant A) comprising 75 percent sorbitan monooleate and 25 percent sorbitan trioleate was tested along with Surfactants 1 to 4. Surfactant A was prepared in accordance with the procedure described in Example 1 of U.S. Patent No. 5,260,345. The test results are summarized in Table II, using the ratings shown in Table I. Table Table II The data in Table II show that the surfactants of the present invention were more efficient in forming HIPE foams compared to the known surfactant. The known surfactant system required 15-weight percent surfactant based on the weight of the monomer phase to form a foam, while the surfactants of the present invention produced a stable HIPE foam at a concentration of as little as 0.125 weight percent surfactant based on the weight of the monomer phase (0.0006 weight percent based on the entire HIPE). Furthermore, foams prepared with the surfactants of the present invention at a concentration of 0.125-weight percent surfactant, based on the monomer phase, were open-celled, as determined by SEM. Example 13 - Open-celled Foam Prepared From an Approximately 99 percent Internal Phase Emulsion Into a monomer phase composed of 1.30 g 2-ethylhexyl acrylate, 0.28 g styrene, 0.45 g divinylbenzene (55 percent active) and 0.03 g lauroyl peroxide initiator was dissolved 0.22 g freshly prepared Surfactant 3 from Example 5. An aqueous phase was prepared by dissolving 2.42 g calcium chloride dihydrate and 0.28 g potassium persulfate into 239.3 g of deionized water. All but 53 g of the aqueous phase was slowly emulsified into the monomer/surfactant solution using a dropwise addition while agitating at 115 RPM using a 3-paddle mixer. A thick HIPE resulted. The HIPE was placed into a Pyrex™ (trademark of Corning Glass Works) dish and covered with SARAN™ WRAP (The Dow Chemical Co.) and put into a forced-air oven at 65°C for 21.5 hours. An aqueous filled polymeric foam was produced. The aqueous phase could easily be squeezed from the foam indicating an open- celled foam. Once rinsed with isopropanol, the foam dried to a collapsed state. Upon re- exposure to isopropanol, the clean, dry foam expanded, reabsorbing over 99 mL of isopropanol per gram of dry foam. Examples 14 to 21 - Performance of Alcohol-Terminated Surfactant versus Sulfate- Terminated Surfactant A series of eight surfactants was prepared following a procedure similar to that in Example 7 such that the following block sizes were obtained: a) BO(30)EO(5) b) BO(30)EO(10) c) BO(30)EO(20) d) BO(30)EO(50) A portion of each material (a-d) was isolated as the poly(BO/EO)-monol and a portion of each material (a-d) was sulfonated according to the procedure in Example 7. The following eight surfactants were obtained: EtO-BO(30)EO(5)-H EtO-BO(30)EO(5)-SO 3 ( ) X EtO-BO(30)EO(10)-H EtO-BO(30)EO(10)-SO 3 H X EtO-BO(30)EO(20)-H EtO-BO(30)EO(20)-SO 3 ( ) X EtO-BO(30)EO(50)-H EtO-BO(30)EO(50)-SO 3 ( , X wherein X was either a pyridinium, ammonium, or a combination of both. The efficiency of these eight surfactants was evaluated following the procedure in Examples 9 to 12. The results are summarized in Table III, using the ratings shown in Table I. Table Example 22 - HIPE Foam Prepared without Salt in the Aqueous Phase Into a monomer phase composed of 1.73 g 2-ethylhexyl acrylate, 0.38 g styrene, 0.59 g divinylbenzene (55 percent active) and 0.1 g lauroyl peroxide initiator was dissolved 0.30 g freshly prepared Surfactant 2 from Example 3. To this mixture was slowly added 147.0 g water while stirring at 300 RPM using a 3-paddle mixer. The resulting high internal phase emulsion was poured into PYREX dishes, covered with Saran™ Wrap and cured in a forced-air oven at 65 degrees C for 18 hours. The resulting foam can be squeezed free of aqueous phase. Example 23 - High Temperature Cure of HIPE Into a monomer phase composed of 2.63 g 2-ethylhexyl acrylate, 0.61 g styrene, 0.61 g divinylbenzene (55 percent active) was dissolved 0.04 g lauroyl peroxide and 0.15 g of Surfactant 2 (from Example 3). An aqueous phase was prepared by dissolving 1.96 g calcium chloride dihydrate and 0.33 g potassium persulfate into 194.04 g of water. The aqueous phase was added dropwise to the monomer solution while mixing at 300 RPM with a 3-paddle mixer. The emulsion was mixed an additional 2 minutes after all of the water was added to ensure homogeneity. The resulting high internal phase emulsion was placed into Pyrex dishes, covered with Saran™ Wrap, and placed in a forced-air oven at 95°C for 19.5 hours (overnight) to cure. The resulting foam can be squeezed free of the aqueous phase.

Claims: CLAIMS: 1. A surfactant comprising a compound represented by the general formula: RO-(BO) m (EO) n SO 3 ( ' X wherein R is an organic, inorganic, or combination of organic and inorganic functionality which does not prevent the compound from acting as a surfactant in the desired application;(BO) m is a polyoxybutylene block of "m" 1 ,2-butyleneoxide units; (EO) n is a polyoxyethylene block of "n" ethylene oxide units; X is a counterion and m, and n are independently integers greater than zero. 2. The surfactant of Claim 1 wherein, in the formula, R is propenyl benzyl, propyl benzyl, vinyl, allyl, linear or branched-alkyi or alkyl-substituted aryl and R' and R" are independently hydrogen, propenyl benzyl, propyl benzyl, vinyl, allyl, linear or branched-alkyi or alkyl-substituted aryl. 3. The surfactant of Claim 1 wherein, in the formula, m is a positive number from 10 to 100 and n is a positive number from 1 to 100. 4. The surfactant of Claim 3 wherein, in the formula, m is a positive number from 20 to 40 and n is a positive number from 5 to 50. 5. The surfactant of Claim 1 wherein the compound is represented by any one of the formulas: ^O(BO) 30 (EO) 20 SO 3 - X or CH 3 CH 2 O(BO) 30 (EO) 20 SO 3 - X wherein X is a pyridinium, ammonium, or a mixture of both. 6. A water-in-oil high internal phase emulsion having at least 70 volume percent of an internal aqueous phase and less than 30 volume percent of an external oil phase and an emulsion stabilizing polyoxybutylene-polyoxyethylene-based surfactant. 7. A water-in-oil high internal phase emulsion having at least 70 volume percent of an internal aqueous phase and less than 30 volume percent of an external oil phase and an emulsion stabilizing polyoxybutylene-polyoxyethylene-based surfactant comprising a compound represented by any one of the formulas: RO-(BO) m (EO) n SO 3 ( -» X RO-(BO) m (EO) n -R' or R"O-(BO) m (EO) n (BO) p -R'" wherein R, R', and R" are organic, inorganic, or combination of organic and inorganic functionalities which do not prevent the compound from acting as a surfactant in the oil-in- water emulsion; (BO) m and (BO) p are polyoxybutylene block of "m" and "p" 1 ,2-butyleneoxide units, respectively; (EO) n is a polyoxyethylene block of "n" ethylene oxide units; X is a counterion and m, n, and p are independently integers greater than zero. 8. The emulsion of Claim 7 wherein, in the formula, R is propenyl, benzyl, vinyl, allyl, linear or branched-alkyi or alkyl-substituted aryl, and R' is hydrogen, and R" and R'" are independently hydrogen, propenyl benzyl, propyl benzyl, vinyl, allyl, linear or branched-alkyi or alkyl-substituted aryl. 9. The emulsion of Claim 7 wherein, in the formula, m is a positive number from 10 to 100 and n is a positive number from 1 to 100. 10. The emulsion of Claim 9 wherein, in the formula, m is a positive number from 20 to 40 and n is a positive number from 5 to 50. 11. The emulsion of Claim 7 wherein the surfactant is a compound represented by any one of the formulas: Q^ O(BO) 40 (EO) 5 SO 3 X © O(BO) 30 (EO) 20 SO 3 - X <_^ O(BO) 30 (EO) 20 SO 3 - X or CH 3 CH 2 O(BO) 30 (EO) 20 SO 3 - X wherein X is a pyridinium, ammonium, or a mixture of both. 12. The emulsion of Claim 7 wherein the external oil phase comprises a vinyl polymerizable monomer. 13. The emulsion of Claim 12, wherein the vinyl polymerizable monomer is a glassy monomer, a rubbery monomer or mixtures thereof. 14. The emulsion of Claim 13 wherein the glassy monomer is methyl methacrylate or styrene and the rubbery monomer is 2-ethylhexyl acrylate, butyl acrylate, hexyl acrylate, butyl methacrylate, isodecyl methacrylate, butadiene or isoprene. 15. An open-cell porous polymeric material formed from a water-in-oil high internal phase emulsion having at least 70 volume percent of an internal aqueous phase and less than 30 volume percent of an external oil phase and an emulsion stabilizing polyoxybutylene-polyoxyethylene-based surfactant. 16. An open cell porous polymeric material formed from a water-in-oil high internal phase emulsion having at least 70 volume percent of an internal aqueous phase, less than 30 volume percent of an external oil phase, and containing less than 5 weight percent residual emulsion stabilizing polyoxybutylene-polyoxyethylene-based surfactant upon drying without squeezing free of aqueous phase or rinsing. 17. An open cell porous polymeric material formed from a water-in-oil high internal phase emulsion having at least 70 volume percent of an internal aqueous phase, less than 30 volume percent of an external oil phase comprising vinyl monomers, and an emulsion stabilizing polyoxybutylene-polyoxyethylene-based surfactant comprising a compound represented by any one of the general formulas: RO-(BO) m (EO) n SO 3 ( -' X RO-(BO) m (EO) n -R' or R"O-(BO) m (EO) n (BO) p -R'" wherein R, R', R" and R'" are organic, inorganic, or combination of organic and inorganic functionalities which do not prevent the compound from acting as a surfactant in the oil-in- water emulsion; (BO) m and (BO) p are polyoxybutylene block of "m" and "p" 1 ,2-butyleneoxide units, respectively; (EO) n is a polyoxyethylene block of "n" ethylene oxide unites; X is a counterion and m, n, and p are independently integers greater than zero. 18. The porous polymeric material of Claim 17 wherein, in the formula, R is propenyl benzyl, propyl benzyl vinyl, allyl, linear or branched-alkyi or alkyl-substituted aryl and R' is hydrogen, and R" and R'" are independently hydrogen, propenyl benzyl, propyl benzyl, vinyl, allyl, linear or branched alkyl or alkyl-substituted aryl. 19. The porous polymeric material of Claim 17 wherein, in the formula, m and p are positive integers from 10 to 100 and n is a positive integer from 1 to 100. 20. The porous polymeric material of Claim 17, wherein, in the formula, m and p are positive integers from 20 to 40 and n is a positive integer from 5 to 50. 21. The porous polymeric material of Claim 17 wherein the surfactant is a compound represented by any one of the formula: O F O(BO) 40 (EO) 5 SO 3 - X Q^ O(BO) 30 (EO) 20 SO 3 - X ^F O(BO) 30 (EO) 20 SO 3 - X or CH 3 CH 2 O(BO) 30 (EO) 20 SO 3 - X wherein X is a pyridinium, ammonium, or a mixture of both. 22. A process for preparing a porous polymeric material which comprises polymerizing a water-in-oil high internal phase emulsion having at least 70 volume percent of an external oil phase and less than 30 volume percent of an external oil phase comprising vinyl polymerizable monomers and a polyoxybutyiene-polyoxyethylene-based surfactant. 23. A process for preparing a porous polymeric material which comprises polymerizing a water-in-oil high internal phase emulsion having at least 70 volume percent of an external oil phase and less than 30 volume percent of an external oil phase comprising vinyl polymerizable monomers and a surfactant comprising a compound represented by the general formula: RO-(BO) m (EO) n SO 3 H X RO-(BO) m (EO) n - or R"O-(BO) m (EO) n (BO) p -R"' wherein R, R', R" and R'" are organic, inorganic, or combination of organic and inorganic functionalities which do not prevent the compound from acting as a surfactant in the oil-in- water emulsion; (BO) m and (BO) p are polyoxybutylene block of "m" and "p" 1 ,2-butyleneoxide units, respectively; (EO) n is a polyoxyethylene block of "n" ethylene oxide unites; X is a counterion and m, n, and p are independently integers greater than zero. 24. The process of Claim 23 wherein, in the formula, R is propenyl, benzyl, vinyl, allyl, linear or branched-alkyi or alkyl-substituted aryl, and R' is hydrogen and R" and R'" are independently hydrogen, propenyl benzyl, propyl benzyl, vinyl, allyl, linear or branched-alkyi or alkyl-substituted aryl. 25. The process of Claim 23 wherein, in the formula, m and p are positive integers from 10 to 100 and n is a positive integer from 1 to 100. 26. The process of Claim 23, wherein, in the formula, m and p are positive integers from 20 to 40 and n is a positive integer from 5 to 50. 27. The process of Claim 23, wherein the surfactant is a polymerizable or non-polymerizable compound represented by any one of the formulas: <_^ , O(BO) 40 (EO) 5 SO 3 - X ^O(BO) 30 (EO) 20 SO 3 - X O(BO) 30 (EO) 20 SO 3 - X or CH 3 CH 2 O(BO) 30 (EO) 20 SO 3 - X wherein X is a pyridinium, ammonium, or a mixture of both. 28. An article containing the porous polymeric material of Claim 15. 29. An article containing the porous polymeric material of Claim 16. 30. The porous polymeric material of Claim 15 in the form of an absorbent article. 31. The porous polymeric material of Claim 30 wherein the absorbent article is a diaper. 32. The porous polymeric material of Claim 16 in the form of an absorbent article. 33. The porous polymeric material of Claim 32 wherein the absorbent article is a diaper.

Inventors: GREEN DANIEL PATRICK, MORK STEVE W, ROSE GENE D, GREEN, DANIEL, PATRICK, MORK, STEVE, W., ROSE, GENE, D.
Applicants: DOW CHEMICAL CO, GREEN DANIEL PATRICK, MORK STEVE W, ROSE GENE D, GREEN, DANIEL, PATRICK, MORK, STEVE, W., ROSE, GENE, D., THE DOW CHEMICAL COMPANY
Application year: 1998
Main classification: C08F2
IPC codes: A61L15, B01F17, C08F2, C08G65, C08J9, C11D1