CA2024508A1 - Water-absorbent, high capacity polyurethane foams - Google Patents
Water-absorbent, high capacity polyurethane foamsInfo
- Publication number
- CA2024508A1 CA2024508A1 CA002024508A CA2024508A CA2024508A1 CA 2024508 A1 CA2024508 A1 CA 2024508A1 CA 002024508 A CA002024508 A CA 002024508A CA 2024508 A CA2024508 A CA 2024508A CA 2024508 A1 CA2024508 A1 CA 2024508A1
- Authority
- CA
- Canada
- Prior art keywords
- foam
- water
- process according
- polyoxyethylene
- crosslinking agent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
- C08G18/6677—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203 having at least three hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/22—Catalysts containing metal compounds
- C08G18/225—Catalysts containing metal compounds of alkali or alkaline earth metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6688—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3271
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/758—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing two or more cycloaliphatic rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2110/00—Foam properties
- C08G2110/0008—Foam properties flexible
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2110/00—Foam properties
- C08G2110/0041—Foam properties having specified density
- C08G2110/005—< 50kg/m3
Abstract
ABSTRACT
A water absorbent, relatively dimensionally stable foam is formed from a prepolymer prepared from a polyoxyethylene containing diol, a crosslinking agent and a polyisocyanate. The preferred polyisocyanate is methylene bis(cyclohexyl isocyanate). The foam also demonstrates the ability to hold substantial amounts of water, even under pressure, and can be used in various personal and medical care products such as diapers and surgical sponges.
A water absorbent, relatively dimensionally stable foam is formed from a prepolymer prepared from a polyoxyethylene containing diol, a crosslinking agent and a polyisocyanate. The preferred polyisocyanate is methylene bis(cyclohexyl isocyanate). The foam also demonstrates the ability to hold substantial amounts of water, even under pressure, and can be used in various personal and medical care products such as diapers and surgical sponges.
Description
BACKGROUND OF THE INVENTION
1. Field of the Invention Generally, the invention relates to urethane prepolymers used to make polyurethane foams, and more specifically, urethane prepolymers used to make water absorbent polyuret~ane and high water capacity foams.
1. Field of the Invention Generally, the invention relates to urethane prepolymers used to make polyurethane foams, and more specifically, urethane prepolymers used to make water absorbent polyuret~ane and high water capacity foams.
2. Description of Prior Art The prior art discloses various compositions and methods used to make polyurethane prepolymers and water absorbent polyurethane foams resulting from such prepolymers. Recently, there have been attempts to achieve highly water absorbent foams which also exhibit dimensional stability, e.g. ability to retain shape and rigidity, and hold the absorbed water even under pressure.
See Non Wovens Market and Fiber Structures Report, p. 3, _ July 14, 1989. This ability to retain water under pressure also reflects the foam's load bearing characteristics. Further, materials possessing these characteristics have also been recognized as useful in products such as surgical dressings, diapers, bedpads, etc. See U.S. Patent 3,939,123 to Matthews et al, Col. l, lines 13-23.
One known method for making prepolymers for water absorbent foams is to make the prepolymer with hydrophilic components such as polyoxyethylene oxide containing polyols. See U. S. Patent 3,903,232 to Wood and Frisch.
However, when wet, such foams undergo a large amount of swelling and water plasticization of the polymer matrix.
Further, Wood and Frisch disclose that they can compress their foams to form soft dense materials and upon exposure to water, regenerate them to the original volume, e.g.
fifteen to twenty times expansion. See Column 2, lines 38-42 and lines 52-57. Because of this expansion and the accompanying swelling and plasticization, the Wood et al 2 ~
foams lose their structural rigidity and release substantial amounts of water when handled. Thus their ability to hold water is diminished. Also see U.S. Patent 4,160,076. (hydrophilic polyurethane sponge which absorbs six times its weight in water) More recent methods achieve a water absorbent foam by incorporating hydrophilic components into the prepolymer.
For instance, U.S. Patent 4,738,992 to Larson and Hedrick discloses the incorporation of ionic hydrophilic functional groups, such as sulfonate groups, into a polyurea/urethane, isocyanate terminated prepolymer used to make water absorbent sponges. Of course, the hydrophilicity of the functional groups enhances the overall water absorption properties of the foam. See also U.S. Patent 4,638,017 to Larson and ~edrick.
The addition of hydrophilic polycarbonyl moieties, e.g. those found on acrylates, to the polyurethane structure of a foam represents a similar approach to Larson and Hendrick's method. See U.S. Patent 4,725,628 to Garvey et al. See also U.S. Patent 4,725,629 to Garvey and Pazos.
Water absorbent foams also have been made using hydrophobic materials. For instance, U.S. Patent 4,377,645 to Guthrie and Arquette discloses foaming ` 25 prepolymers wherein isocyanate capped prepolymers are prepared from hydrophobic methylene diphenyl isocyanate, (MDI), trimethyolpropane and a polyoxyalkylene diol.
While the foam resulting from the MDI terminated prepolymer only swells 19~ by volume, it is only able to hold a little over 20 times its weight in water. These foams are suitable for household sponges and substrates for flocked wall coverings, as well as suitable for flexible foams used in medical or personal care items.
See also U.S. Patents 4,384,050 and 4,384,051 to Guthrie.
To enhance a foam's dimensional stability, additives have been used in making water absorbent foams.
~ ~ .
~ 3 ~
Typically, additives are also used to improve the durability and the load bearing characteristics of the foam. A popular method for achieving these characteristics is the addition of reinforcing agents.
For instance, U.S. Patent 4,314,034 to Fulmer and Vollmerhausen discloses the addition of polyester fibers to provide structural rigidity. See also U.S. Patent 4,201,846 to Kehr et al. (polyvinyl alcohol fibers used for reinforcement in polyurethane foams) and U.S. Patent 3,959,191 to Kehr and Marans (addition of solid materials such as fibrous materials to improve load bearing characteristics.) However, the prior art approaches for achieving water absorbency and dimensional stability have disadvantages.
For example, the super absorbent foams disclosed by Larson and Hedrick are made by the attachment of ionic groups to the urethane prepolymer and thus involves additional chemical processing to achieve the desired water absorbent properties. Garvey et al's use of the methacrylates results in foams which undergo undue swelling when wet.
The foams made from MDI and reinforcing agents, while they have relatively good structural stability, do not have sufficient water capacity characteristics because the reinforcing agents increase foam density and deplete void space. As mentioned above, MDI-based foams without reinforcing agents were only able to hold water in an amount up to about twenty times their weight.
SUMMARY OF THE INVENTION
Accordingly, it is an object of the invention to obtain foams having improved water capacity properties.
It is also an object of this invention to obtain a foam which holds water under pressure.
It is an object of the invention to obtain foams with improved water absorbent properties, yet which undergo relatively little swelling.
c~
It is an object o$ the invention to provide a novel method to produce water absorbent foams.
It is also an object to produce a novel water absorbent foam composition as well as an object to use the novel foams in articles of manufacture which require good water absorbent and wicking properties, as well as structural stability. These and other objects will be apparent from the following description.
DESCRI PT I ON OF PREFERRED EMBODIMENTS
Prepolymers used to make the invention are prepared using the well known prepolymer approach and can be made with polyoxyethylene containing diols and particular polyisocyanates. Crosslinking agents are also used to make the prepolymer. The resulting prepolymer is then foamed in water and surfactants.
The polyoxyethylene containing diols used are those having an average molecular weight, i.e. number average, of 2500 or less. The diol should also have at least 50%, preferably 80% and most preferably substantially 100~ by weight, oxyethylene groups. By using a diol with higher oxyethylene content, hydrophilicity and, ultimately, good water absorption is maintained. A preferred diol is a polyoxyethylene diol from Union Carbide which has a molecular weight of between about 950 and 1050 and is commercially available as Carbowax 1000. However, other polyethylene glycol formulations having higher or lower ` molecular weights can also be used.
As mentioned earlier, when a diol such as Carbowax 1000 is used, a crosslinking agent is required to provide sufficient crosslinking and strength to the final foam.
Typical crosslinking agents include low molecular weight polyols having 3 or 4 hydroxyl equivalents per mole.
Examples are trimethylolethane, trimethylolpropane, glycerol, triethanolamine, pentaerythritol or mixtures thereof. The preferred crosslinking agent is trimethylol ' 2 i~
propane ~TMP). In general the molar ratio of diol to TMP
should be in the range of about 1:1 to 4:1, with the preferred ratio being about 2:1 to 3:1. Of course, the higher the molecular weight diol used, the more crosslinker needed to get the proper crosslinking. By using the crosslinking agent in these proportions, sufficient hydroxyl equivalents are present for reaction with the isocyanate function groups of the polyisocyanates. Thus, the addition of the crosslinking agent to the diol and the polyisocyanate provides a prepolymer which has a number of branches and terminal isocyanates. The resulting terminal isocyanate groups are thus present in sufficient numbers to provide a relatively strong crosslinked foam.
The preferred isocyanate is methylene bis(cyclohexyl isocyanate) and is available as DesmodurR W from Mobay, Corp. However, other similar isocyanates are envisioned and could be used for this invention.
The polyol component, i.e. the diol and hydroxyl containing crosslinking agent, and the polyisocyanate component are preferably mixed at a ratio of about 1:1 by weightO
Catalysts can also be used to make the prepolymer.
Examples include organo tin compounds such as stannous octoate, stannous oleate, dibutyltin dilaurate, dibutyltin di-2-ethyl hexoate and the like. Tertiary amine catalysts such as triethyl amines may also be used. Such catalysts are disclosed in Flexible Polyurethane Foams: Chemistry and Technology; Woods, pp. 50-55, 1982, the contents of which are incorporated herein by reference. The amount of catalyst employed varies between 0.0005% and to about 0.1%
by weight of catalyst to the weight of all components of the prepolymer, i.e. polyol, crosslinking agent and polyisocyanate.
The prepolymer is formed, using the above mentioned proportions, at a temperature in the range of 50C to about 90C and a residence time in the range of 0.5h to s~
48h, depending on the amount and type of catalyst used.
Preferably the reaction is maintained at about 70C
throughout the reaction.
Further, during the prepolymer forming reaction, it has been helpful to measure the isocyanate level by titration periodically during the reaction. From these periodic measurements, one can determine the theoretical point at which all the hydroxyl groups of the polyol (and crosslinking agent) will have reacted with an isocyanate.
If the theoretical point has not been reached, additional reaction time will be required. However, if the reaction is carried out too far, the viscosity of the resulting prepolymer increases to the point where it becomes difficult to mix the prepolymer with water.
After the prepolymer is made, it is added to water to produce the foam. Surfactants can also be added to adjust the texture and appearance of the foam, i.e. such as the cell size, shape, etc., as well as preventing the formation of splits in the resulting foam buns. Examples of surfactants include silicone-polyether copolymer surfactants such as L-520 from Union Carbide and DC-198 from Dow Corning. Fluorocarbon copolymers such as the Zonyl (from Dupont) or FluoradR (from Minnesota Mining and Manufacturing) surfactant families can also be used.
The polyether silicones are preferred when water absorbent foams containing small, fine cell-sized foams are desired.
Polyoxyethylene/polyoxypropylene block copolymer surfactants such as Pluronic surfactants can also be used. The preferred Pluronic surfactants, e~g. L-62, L-92 and L-122, contain 20 percent by weight or less of polyoxyethylene and are preferably employed in 1-2%
solution, the use of which is well known to one skilled in the art of foam formation.
It is also often desirable to add about 0.5 to 2.0%
by weight of an inorganic base to catalyze the foaming , .
~7~
reaction for aliphatic isocyanate-based prepolymers.
Sodium bicarbonate or sodium carbonate are two examples of such catalysts.
The prepolymer and surfactant containing aqueous solution are then mixed in a high shear mixer in a volume amount ratio of prepolymer:water of about 2:1 to 6:1, with a ratio of about 3:1 preferred.
The resulting foams typically have a low density and have been shown to be water absorbent. While the density of the foams obtained have been in the range of 0.020g/cc to 0.060g/cc, higher density foams should also show good water absorbency.
The foams demonstrate high water absorbency as measured by vertical wicking rates of up to about 3cms in one minute. The capillary wicking tests used are similar to those used to measure vertical wicking in paper products, e.g. the well known Xlemm test. The wicking results for the foams tested are found in Table I.
The wate~- capacities of the foams are found in Table II and are expressed as the amount(s) of water absorbed per gram of foam. As indicated by the results in Table II, the invention shows improved water capacity than that of prior art foams, e.g. improvements of up to two times as much capacity. Examples F and G also indicate improvements in water absorption properties, e.g. wicking.
The foam's dimensional stability is evidenced by its load bearing characteristics and rigidity when wet; i.e.
it does not collapse under its own weight as well as the weight of the water. Further when wet, the foam transforms from a flexible structure to one that is quite firm and undergoes only a relatively small amount of swelling after complete saturation.
In addition, after it has been wetted and water has been absorbed, the foams show the ability to retain a substantial amount of water, even under pressure. See Table III.
In view of the above properties, it is envisioned that the invention can be used in various personal and medical care areas. Personal products include incontinence pads, tampons, sweat bands, household sponges, etc. Medical care products include surgical sponges, wound dressings, surgical drapes, mattress covers, etc.
The following examples illustrate the basic concepts of the invention, but are in no way to be used to limit the scope of the claims below.
Example A - Prepolymer 1 (Pl) A mixture of 500g (0.5 moles) of Carbowax 1000 and 33.5g (0.25 moles) of trimethylolpropane was degassed by heating for two hours @ 70C and about 2 Torr. To this was added 542g (2.07 moles, 18% excess) of Desmodur W, i.e.
methylene bis(cyclohexyl isocyanate). The temperature was raised to 70C and 0.5g of stannous octoate was added as catalyst. After 35 minut~s, the isocyanate content of the reaction product was 2.19 meq/g and the product was poured into a bottle for storage. After a few days at ambient temperature, the isocyanate content and viscosity had stabilized at 2.00 meq/g and 73,000 cp at 25C.
Example B - Foam 1 (Fl) A foam was made from Pl by mixing lOOg of Pl with 33g of water con~aining 1.6g of sodium bicarbonate and 0.7g of Dow Corning's polyether-polysiloxane surfactant DC-198.
The dried foam had a fine-celled structure and a density of 0.037 g/cc. After soaking in water, the foam contained approximately 35 times its weight of water and its volume had swelled by 50%. Upon application of 0.2 psi, the foam retained 34g water per gram of foam. See Tables II and III.
_9_ 2~2~
Example C - Prepolymer 2 (P2) In another illustration, three batches of a prepolymer were made by mixing lOOOg (1.0 mole) of Carbowax 1000 and 67.0g (0.5 mole) of trimethylolpropane and degassed as in the previous example. To this mixture was added 1084 g (4.14 moles) of Desmodur W, the temperature was raised to 70C and l.Og of stannous octoate was added. Of the several preparations made, each had an isocyanate content of 2.15-2.25 meq/g at the completion of the reaction. The products were poured into bottles for storage as described in Example A.
Example D - Foam 2 (F2) Approximately two quarts of P2 were loaded into the "prepolymer (isocyanate) side" of a UNIPRE Type M-10/2 two-component meter, mix, and disperse system equipped with two five-liter stainless steel tanks, each tank connected to a metering pump drive unit controlled by two separately adjustable electric motors driving independent metering pumps, connected by means of teflon-lined hoses to a high capacity mixing head containing a high-shear dynamic mixer containing a rotor and stator. (Ashby-Cross Co., Inc., Topsfield, MA).
Approximately two quarts of an aqueous solution containing two wt% Pluronic L-62 surfactant and 2~ sodium bicarbonate was used. By a computer controlled metering system a 3:1 (volumetric) ratio of prepolymer-to-aqueous was metered through the mix head and into an open container, where the foaming reaction proceeded. The dry foam had a density of 0.030 g/cc and had a very fine celled structure composed primarily of open cells. Immersion of the foam into an aqueous saline solution led to sinking of the foam into the water and an immediate retention of 38-40 g saline solution/g polymer-foam in three different samples. A
volume expansion of about 40% was observed after ' 2 ~ 2 `~ '3~ ~
immersion. After gentle application and releasing of pressure on the foam while submerged in water, the samples of foam were able to hold 41-45g of water per gram of foam. Upon application of 0.2 psi, 40-43g of water per gram of foam remained and upon application of 1 psi 22g-29g of water per gram of foam remained. See Tables II
and III.
Example E - Foam 3 (F3~
P2 was again used to make a foam except an aqueous phase of 2% Pluronic L62 and 2% sodium bicarbonate and a 2:1 volumetric ratio of prepolymer:aqueous as controlled by the computer was used. When dry, the foam had a density of 0.050 g/cc and a higher portion of open cells than the foam of Example D, e.g. F2. After submersion the foam contained 31g of water per gram of foam. At 0.2 psi the foam retained 30-31g of water per gram of foam. This foam exhibited vertical wicking of saline solution of 2.0-2.7 cm in 1 minute, 4.7-5.2 cm in 20 minutes, and 8 cm in three hours.
Example F
A piece of the foam (Cl), e.g. a foam produced according to Example 7 of U.S. Patent 4,377,645, weighing 2.6g was allowed to float on water for one day. It was observed that only the bottom surface was wet and that no wicking had occurred in the foam's interior. The foam was then compressed under water to expel as much air as possible.
The foam was then removed from the water and allowed to drain for five minutes. It was reweighed and was found to hold 23.4g of water per gram of foam (See Table III) and was observed that the foam had become soft. It was also observed that the foam had expanded 19% in volume. When squeezed, it released the water easily due to the softness of the foam, but required several minutes to return to its original wet dimensions because of its lack of resilience in the wet state.
2 ~
Example G
A prepolymer produced according to Example 1 of U.S.
Patent 4,377,645 was converted into a foam (C2) by mixing the prepolymer on an Ashby-Cross Foam Machine with an equal volume of water containing 2% by weight of Pluronic 25-R2 as a surfactant. After drying, the foam had a density of 0.047g/cc and has cells somewhat smaller than Cl of Example F. A piece of the resulting foam weighing 2.6g was floated on water and required three hours to become saturated. It held 22.8g of water per gram of foam (See Table III) and its volume expanded by 19%. When wet, C2 was much like Cl, but C2 was somewhat harder to squeeze because of its finer cell structure. Recovery of original dimensions required even more time to return to its original dimensions than Cl.
Table I
Water Absorbency Foam Wicking Height (cm) Elapsed Time (min) F2 1.2 2.4 20 F3 2.0-2.7 4.7-5.2 20 8.0 180 Table II
Water Capacity (O psi) Foam (g watertg foam) Fl 35 Cl 23 : , -Table III
Water Retention Foam Pressureg water/g foam Fl 0.2 34 F2 0.2 40-43 F2 1.0 22-29 F3 0.2 30-31 '', ., .
:,~
.~
:`
"~
See Non Wovens Market and Fiber Structures Report, p. 3, _ July 14, 1989. This ability to retain water under pressure also reflects the foam's load bearing characteristics. Further, materials possessing these characteristics have also been recognized as useful in products such as surgical dressings, diapers, bedpads, etc. See U.S. Patent 3,939,123 to Matthews et al, Col. l, lines 13-23.
One known method for making prepolymers for water absorbent foams is to make the prepolymer with hydrophilic components such as polyoxyethylene oxide containing polyols. See U. S. Patent 3,903,232 to Wood and Frisch.
However, when wet, such foams undergo a large amount of swelling and water plasticization of the polymer matrix.
Further, Wood and Frisch disclose that they can compress their foams to form soft dense materials and upon exposure to water, regenerate them to the original volume, e.g.
fifteen to twenty times expansion. See Column 2, lines 38-42 and lines 52-57. Because of this expansion and the accompanying swelling and plasticization, the Wood et al 2 ~
foams lose their structural rigidity and release substantial amounts of water when handled. Thus their ability to hold water is diminished. Also see U.S. Patent 4,160,076. (hydrophilic polyurethane sponge which absorbs six times its weight in water) More recent methods achieve a water absorbent foam by incorporating hydrophilic components into the prepolymer.
For instance, U.S. Patent 4,738,992 to Larson and Hedrick discloses the incorporation of ionic hydrophilic functional groups, such as sulfonate groups, into a polyurea/urethane, isocyanate terminated prepolymer used to make water absorbent sponges. Of course, the hydrophilicity of the functional groups enhances the overall water absorption properties of the foam. See also U.S. Patent 4,638,017 to Larson and ~edrick.
The addition of hydrophilic polycarbonyl moieties, e.g. those found on acrylates, to the polyurethane structure of a foam represents a similar approach to Larson and Hendrick's method. See U.S. Patent 4,725,628 to Garvey et al. See also U.S. Patent 4,725,629 to Garvey and Pazos.
Water absorbent foams also have been made using hydrophobic materials. For instance, U.S. Patent 4,377,645 to Guthrie and Arquette discloses foaming ` 25 prepolymers wherein isocyanate capped prepolymers are prepared from hydrophobic methylene diphenyl isocyanate, (MDI), trimethyolpropane and a polyoxyalkylene diol.
While the foam resulting from the MDI terminated prepolymer only swells 19~ by volume, it is only able to hold a little over 20 times its weight in water. These foams are suitable for household sponges and substrates for flocked wall coverings, as well as suitable for flexible foams used in medical or personal care items.
See also U.S. Patents 4,384,050 and 4,384,051 to Guthrie.
To enhance a foam's dimensional stability, additives have been used in making water absorbent foams.
~ ~ .
~ 3 ~
Typically, additives are also used to improve the durability and the load bearing characteristics of the foam. A popular method for achieving these characteristics is the addition of reinforcing agents.
For instance, U.S. Patent 4,314,034 to Fulmer and Vollmerhausen discloses the addition of polyester fibers to provide structural rigidity. See also U.S. Patent 4,201,846 to Kehr et al. (polyvinyl alcohol fibers used for reinforcement in polyurethane foams) and U.S. Patent 3,959,191 to Kehr and Marans (addition of solid materials such as fibrous materials to improve load bearing characteristics.) However, the prior art approaches for achieving water absorbency and dimensional stability have disadvantages.
For example, the super absorbent foams disclosed by Larson and Hedrick are made by the attachment of ionic groups to the urethane prepolymer and thus involves additional chemical processing to achieve the desired water absorbent properties. Garvey et al's use of the methacrylates results in foams which undergo undue swelling when wet.
The foams made from MDI and reinforcing agents, while they have relatively good structural stability, do not have sufficient water capacity characteristics because the reinforcing agents increase foam density and deplete void space. As mentioned above, MDI-based foams without reinforcing agents were only able to hold water in an amount up to about twenty times their weight.
SUMMARY OF THE INVENTION
Accordingly, it is an object of the invention to obtain foams having improved water capacity properties.
It is also an object of this invention to obtain a foam which holds water under pressure.
It is an object of the invention to obtain foams with improved water absorbent properties, yet which undergo relatively little swelling.
c~
It is an object o$ the invention to provide a novel method to produce water absorbent foams.
It is also an object to produce a novel water absorbent foam composition as well as an object to use the novel foams in articles of manufacture which require good water absorbent and wicking properties, as well as structural stability. These and other objects will be apparent from the following description.
DESCRI PT I ON OF PREFERRED EMBODIMENTS
Prepolymers used to make the invention are prepared using the well known prepolymer approach and can be made with polyoxyethylene containing diols and particular polyisocyanates. Crosslinking agents are also used to make the prepolymer. The resulting prepolymer is then foamed in water and surfactants.
The polyoxyethylene containing diols used are those having an average molecular weight, i.e. number average, of 2500 or less. The diol should also have at least 50%, preferably 80% and most preferably substantially 100~ by weight, oxyethylene groups. By using a diol with higher oxyethylene content, hydrophilicity and, ultimately, good water absorption is maintained. A preferred diol is a polyoxyethylene diol from Union Carbide which has a molecular weight of between about 950 and 1050 and is commercially available as Carbowax 1000. However, other polyethylene glycol formulations having higher or lower ` molecular weights can also be used.
As mentioned earlier, when a diol such as Carbowax 1000 is used, a crosslinking agent is required to provide sufficient crosslinking and strength to the final foam.
Typical crosslinking agents include low molecular weight polyols having 3 or 4 hydroxyl equivalents per mole.
Examples are trimethylolethane, trimethylolpropane, glycerol, triethanolamine, pentaerythritol or mixtures thereof. The preferred crosslinking agent is trimethylol ' 2 i~
propane ~TMP). In general the molar ratio of diol to TMP
should be in the range of about 1:1 to 4:1, with the preferred ratio being about 2:1 to 3:1. Of course, the higher the molecular weight diol used, the more crosslinker needed to get the proper crosslinking. By using the crosslinking agent in these proportions, sufficient hydroxyl equivalents are present for reaction with the isocyanate function groups of the polyisocyanates. Thus, the addition of the crosslinking agent to the diol and the polyisocyanate provides a prepolymer which has a number of branches and terminal isocyanates. The resulting terminal isocyanate groups are thus present in sufficient numbers to provide a relatively strong crosslinked foam.
The preferred isocyanate is methylene bis(cyclohexyl isocyanate) and is available as DesmodurR W from Mobay, Corp. However, other similar isocyanates are envisioned and could be used for this invention.
The polyol component, i.e. the diol and hydroxyl containing crosslinking agent, and the polyisocyanate component are preferably mixed at a ratio of about 1:1 by weightO
Catalysts can also be used to make the prepolymer.
Examples include organo tin compounds such as stannous octoate, stannous oleate, dibutyltin dilaurate, dibutyltin di-2-ethyl hexoate and the like. Tertiary amine catalysts such as triethyl amines may also be used. Such catalysts are disclosed in Flexible Polyurethane Foams: Chemistry and Technology; Woods, pp. 50-55, 1982, the contents of which are incorporated herein by reference. The amount of catalyst employed varies between 0.0005% and to about 0.1%
by weight of catalyst to the weight of all components of the prepolymer, i.e. polyol, crosslinking agent and polyisocyanate.
The prepolymer is formed, using the above mentioned proportions, at a temperature in the range of 50C to about 90C and a residence time in the range of 0.5h to s~
48h, depending on the amount and type of catalyst used.
Preferably the reaction is maintained at about 70C
throughout the reaction.
Further, during the prepolymer forming reaction, it has been helpful to measure the isocyanate level by titration periodically during the reaction. From these periodic measurements, one can determine the theoretical point at which all the hydroxyl groups of the polyol (and crosslinking agent) will have reacted with an isocyanate.
If the theoretical point has not been reached, additional reaction time will be required. However, if the reaction is carried out too far, the viscosity of the resulting prepolymer increases to the point where it becomes difficult to mix the prepolymer with water.
After the prepolymer is made, it is added to water to produce the foam. Surfactants can also be added to adjust the texture and appearance of the foam, i.e. such as the cell size, shape, etc., as well as preventing the formation of splits in the resulting foam buns. Examples of surfactants include silicone-polyether copolymer surfactants such as L-520 from Union Carbide and DC-198 from Dow Corning. Fluorocarbon copolymers such as the Zonyl (from Dupont) or FluoradR (from Minnesota Mining and Manufacturing) surfactant families can also be used.
The polyether silicones are preferred when water absorbent foams containing small, fine cell-sized foams are desired.
Polyoxyethylene/polyoxypropylene block copolymer surfactants such as Pluronic surfactants can also be used. The preferred Pluronic surfactants, e~g. L-62, L-92 and L-122, contain 20 percent by weight or less of polyoxyethylene and are preferably employed in 1-2%
solution, the use of which is well known to one skilled in the art of foam formation.
It is also often desirable to add about 0.5 to 2.0%
by weight of an inorganic base to catalyze the foaming , .
~7~
reaction for aliphatic isocyanate-based prepolymers.
Sodium bicarbonate or sodium carbonate are two examples of such catalysts.
The prepolymer and surfactant containing aqueous solution are then mixed in a high shear mixer in a volume amount ratio of prepolymer:water of about 2:1 to 6:1, with a ratio of about 3:1 preferred.
The resulting foams typically have a low density and have been shown to be water absorbent. While the density of the foams obtained have been in the range of 0.020g/cc to 0.060g/cc, higher density foams should also show good water absorbency.
The foams demonstrate high water absorbency as measured by vertical wicking rates of up to about 3cms in one minute. The capillary wicking tests used are similar to those used to measure vertical wicking in paper products, e.g. the well known Xlemm test. The wicking results for the foams tested are found in Table I.
The wate~- capacities of the foams are found in Table II and are expressed as the amount(s) of water absorbed per gram of foam. As indicated by the results in Table II, the invention shows improved water capacity than that of prior art foams, e.g. improvements of up to two times as much capacity. Examples F and G also indicate improvements in water absorption properties, e.g. wicking.
The foam's dimensional stability is evidenced by its load bearing characteristics and rigidity when wet; i.e.
it does not collapse under its own weight as well as the weight of the water. Further when wet, the foam transforms from a flexible structure to one that is quite firm and undergoes only a relatively small amount of swelling after complete saturation.
In addition, after it has been wetted and water has been absorbed, the foams show the ability to retain a substantial amount of water, even under pressure. See Table III.
In view of the above properties, it is envisioned that the invention can be used in various personal and medical care areas. Personal products include incontinence pads, tampons, sweat bands, household sponges, etc. Medical care products include surgical sponges, wound dressings, surgical drapes, mattress covers, etc.
The following examples illustrate the basic concepts of the invention, but are in no way to be used to limit the scope of the claims below.
Example A - Prepolymer 1 (Pl) A mixture of 500g (0.5 moles) of Carbowax 1000 and 33.5g (0.25 moles) of trimethylolpropane was degassed by heating for two hours @ 70C and about 2 Torr. To this was added 542g (2.07 moles, 18% excess) of Desmodur W, i.e.
methylene bis(cyclohexyl isocyanate). The temperature was raised to 70C and 0.5g of stannous octoate was added as catalyst. After 35 minut~s, the isocyanate content of the reaction product was 2.19 meq/g and the product was poured into a bottle for storage. After a few days at ambient temperature, the isocyanate content and viscosity had stabilized at 2.00 meq/g and 73,000 cp at 25C.
Example B - Foam 1 (Fl) A foam was made from Pl by mixing lOOg of Pl with 33g of water con~aining 1.6g of sodium bicarbonate and 0.7g of Dow Corning's polyether-polysiloxane surfactant DC-198.
The dried foam had a fine-celled structure and a density of 0.037 g/cc. After soaking in water, the foam contained approximately 35 times its weight of water and its volume had swelled by 50%. Upon application of 0.2 psi, the foam retained 34g water per gram of foam. See Tables II and III.
_9_ 2~2~
Example C - Prepolymer 2 (P2) In another illustration, three batches of a prepolymer were made by mixing lOOOg (1.0 mole) of Carbowax 1000 and 67.0g (0.5 mole) of trimethylolpropane and degassed as in the previous example. To this mixture was added 1084 g (4.14 moles) of Desmodur W, the temperature was raised to 70C and l.Og of stannous octoate was added. Of the several preparations made, each had an isocyanate content of 2.15-2.25 meq/g at the completion of the reaction. The products were poured into bottles for storage as described in Example A.
Example D - Foam 2 (F2) Approximately two quarts of P2 were loaded into the "prepolymer (isocyanate) side" of a UNIPRE Type M-10/2 two-component meter, mix, and disperse system equipped with two five-liter stainless steel tanks, each tank connected to a metering pump drive unit controlled by two separately adjustable electric motors driving independent metering pumps, connected by means of teflon-lined hoses to a high capacity mixing head containing a high-shear dynamic mixer containing a rotor and stator. (Ashby-Cross Co., Inc., Topsfield, MA).
Approximately two quarts of an aqueous solution containing two wt% Pluronic L-62 surfactant and 2~ sodium bicarbonate was used. By a computer controlled metering system a 3:1 (volumetric) ratio of prepolymer-to-aqueous was metered through the mix head and into an open container, where the foaming reaction proceeded. The dry foam had a density of 0.030 g/cc and had a very fine celled structure composed primarily of open cells. Immersion of the foam into an aqueous saline solution led to sinking of the foam into the water and an immediate retention of 38-40 g saline solution/g polymer-foam in three different samples. A
volume expansion of about 40% was observed after ' 2 ~ 2 `~ '3~ ~
immersion. After gentle application and releasing of pressure on the foam while submerged in water, the samples of foam were able to hold 41-45g of water per gram of foam. Upon application of 0.2 psi, 40-43g of water per gram of foam remained and upon application of 1 psi 22g-29g of water per gram of foam remained. See Tables II
and III.
Example E - Foam 3 (F3~
P2 was again used to make a foam except an aqueous phase of 2% Pluronic L62 and 2% sodium bicarbonate and a 2:1 volumetric ratio of prepolymer:aqueous as controlled by the computer was used. When dry, the foam had a density of 0.050 g/cc and a higher portion of open cells than the foam of Example D, e.g. F2. After submersion the foam contained 31g of water per gram of foam. At 0.2 psi the foam retained 30-31g of water per gram of foam. This foam exhibited vertical wicking of saline solution of 2.0-2.7 cm in 1 minute, 4.7-5.2 cm in 20 minutes, and 8 cm in three hours.
Example F
A piece of the foam (Cl), e.g. a foam produced according to Example 7 of U.S. Patent 4,377,645, weighing 2.6g was allowed to float on water for one day. It was observed that only the bottom surface was wet and that no wicking had occurred in the foam's interior. The foam was then compressed under water to expel as much air as possible.
The foam was then removed from the water and allowed to drain for five minutes. It was reweighed and was found to hold 23.4g of water per gram of foam (See Table III) and was observed that the foam had become soft. It was also observed that the foam had expanded 19% in volume. When squeezed, it released the water easily due to the softness of the foam, but required several minutes to return to its original wet dimensions because of its lack of resilience in the wet state.
2 ~
Example G
A prepolymer produced according to Example 1 of U.S.
Patent 4,377,645 was converted into a foam (C2) by mixing the prepolymer on an Ashby-Cross Foam Machine with an equal volume of water containing 2% by weight of Pluronic 25-R2 as a surfactant. After drying, the foam had a density of 0.047g/cc and has cells somewhat smaller than Cl of Example F. A piece of the resulting foam weighing 2.6g was floated on water and required three hours to become saturated. It held 22.8g of water per gram of foam (See Table III) and its volume expanded by 19%. When wet, C2 was much like Cl, but C2 was somewhat harder to squeeze because of its finer cell structure. Recovery of original dimensions required even more time to return to its original dimensions than Cl.
Table I
Water Absorbency Foam Wicking Height (cm) Elapsed Time (min) F2 1.2 2.4 20 F3 2.0-2.7 4.7-5.2 20 8.0 180 Table II
Water Capacity (O psi) Foam (g watertg foam) Fl 35 Cl 23 : , -Table III
Water Retention Foam Pressureg water/g foam Fl 0.2 34 F2 0.2 40-43 F2 1.0 22-29 F3 0.2 30-31 '', ., .
:,~
.~
:`
"~
Claims (31)
1. A water absorbent polyurethane foam derived from a prepolymer prepared from (a) a polyoxyethylene-containing diol having a molecular weight of about 2500 or less, and (b) a crosslinking agent comprising a low molecular weight polyol having 3 or 4 hydroxyl equivalents per mole, and (c) methylene bis(cyclohexyl isocyanate), wherein said foam possesses a high water capacity and retains substantial amounts of water under pressure.
2. A foam according to Claim 1 wherein the polyol contains at least 50% by weight polyoxyethylene.
3. A foam according to Claim 1 wherein the polyol contains at least 80% by weight polyoxyethylene.
4. A foam according to Claim 1 wherein the polyol contains substantially 100% by weight polyoxyethylene.
5. A foam according to Claim 1 wherein the crosslinking agent is trimethyolproprane.
6. A foam according to Claim 4 wherein the polyoxyethylene-containing diol is polyethylene glycol.
7. A foam according to Claim 1 wherein the foam has a density in the range of about 0.020g/cc to 0.040g/cc.
8. A foam according to Claim 1 wherein the foam has a water capacity of about 30-50g of water per gram of foam.
9. A foam according to Claim 1 wherein the foam absorbs water to a vertical wicking height of about 1.2cm in one minute and about 2.4cm in twenty minutes.
10. A foam according to Claim 1 wherein the foam absorbs water to a vertical wicking height in the range of about 2.0-2.7 cm in one minute, in the range of about 4.7-5.2 cm in twenty minutes and about 8cm in three hours.
11. A foam according to Claim 1 wherein the foam retains in the range of about 30-50 grams of water per gram of foam under 0.2 psi.
12. A foam according to Claim 1 wherein the foam retains about 20-30g of water per gram of foam under 1.0 psi.
13. A process for making water absorbent foams comprising:
(a) reacting (i) a polyol component comprising a polyoxyethylene-containing diol having a molecular weight of about 2500 or less and a crosslinking agent comprising a low molecular weight polyol having 3 or 4 hydroxyl equivalents per mole with (ii) an isocyanate component comprising methylene bis(cyclohexyl isocyanate) to form a prepolymer and (b) then reacting the prepolymer prepared in (a) with water to form said foam.
(a) reacting (i) a polyol component comprising a polyoxyethylene-containing diol having a molecular weight of about 2500 or less and a crosslinking agent comprising a low molecular weight polyol having 3 or 4 hydroxyl equivalents per mole with (ii) an isocyanate component comprising methylene bis(cyclohexyl isocyanate) to form a prepolymer and (b) then reacting the prepolymer prepared in (a) with water to form said foam.
14. A process according to Claim 13 wherein the polyol component (i) and the isocyanate component (ii) are reacted at a ratio of about 1:1.
15. A process according to Claim 13 wherein the crosslinking agent is added at a diol:crosslinking agent ratio of about 1:1 to 1:4.
16. A process according to Claim 15 wherein the ratio is about 2:1 to 3:1.
17. A process according to Claim 13 wherein the crosslinking agent is trimethylolpropane.
18. A process according to Claim 13 wherein the polyoxyethylene containing polyol is polyethylene glycol.
19. A process according to Claim 13 wherein a foaming catalyst is used in step (b).
20. A process according to Claim 19 wherein the foaming catalyst is sodium bicarbonate.
21. A process according to Claim 13 wherein in addition a surfactant is added in the foam forming step (b).
22. A process according to Claim 13 wherein in addition a catalyst is added to make said prepolymer in step (a).
23. A process according to Claim 22 wherein the catalyst is an organo-tin catalyst.
24. A process according to Claim 22 wherein the catalyst is stannous octoate.
25. An article of manufacture containing a water absorbent polyurethane foam derived from a prepolymer prepared from (a) a polyoxyethylene containing diol having a molecular weight of about 2500 or less;
(b) a crosslinking agent comprising a low molecular weight polyol having 3 or 4 hydroxyl equivalents per mole; and (c) methylene bis(cyclohexyl isocyanate);
wherein said foam possesses high water capacity and retains substantial amounts of water under pressure.
(b) a crosslinking agent comprising a low molecular weight polyol having 3 or 4 hydroxyl equivalents per mole; and (c) methylene bis(cyclohexyl isocyanate);
wherein said foam possesses high water capacity and retains substantial amounts of water under pressure.
26. An article according to Claim 25 wherein said foam has a density in the range of 0.020g/cc to 0.040g/cc.
27. An article according to Claim 25 wherein said foam possesses water capacity properties such that said foam holds up to 50g of water per gram of foam.
28. An article according to Claim 25 wherein said foam absorbs water to a vertical wicking height of about 1.2cm in one minute and 2.4cm in about twenty minutes.
29. An article according to Claim 25 wherein said foam absorbs water to a vertical wicking height of about 2.0 to 2.7cm in one minute, about 4.7 to 5.2cm in twenty minutes and about 8.0cm in about three hours.
30. An article according to Claim 25 wherein said foam retains in the range of about 30-50 grams of water per gram of foam under 0.2 psi.
31. An article according to Claim 25 wherein said foam retains in the range of about 20-30 grams of water per gram of foam under 1.0 psi.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US410,458 | 1989-09-21 | ||
US07/410,458 US5104909A (en) | 1989-09-21 | 1989-09-21 | Water-absorbent, high capacity polyurethane foams |
Publications (1)
Publication Number | Publication Date |
---|---|
CA2024508A1 true CA2024508A1 (en) | 1991-03-22 |
Family
ID=23624817
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA002024508A Abandoned CA2024508A1 (en) | 1989-09-21 | 1990-09-10 | Water-absorbent, high capacity polyurethane foams |
Country Status (6)
Country | Link |
---|---|
US (1) | US5104909A (en) |
EP (1) | EP0420515B1 (en) |
JP (1) | JP3012300B2 (en) |
CA (1) | CA2024508A1 (en) |
DE (1) | DE69023599T2 (en) |
NZ (1) | NZ235395A (en) |
Families Citing this family (35)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE4111098A1 (en) * | 1991-04-05 | 1992-10-08 | Beiersdorf Ag | HYDROPHILIC SHEARS AND METHOD FOR THE PRODUCTION THEREOF |
DE4116428C2 (en) * | 1991-05-18 | 1995-04-13 | Stockhausen Chem Fab Gmbh | Powdered absorbent for aqueous liquids based on a water-swellable polymer |
US5239040A (en) * | 1991-12-31 | 1993-08-24 | E.R.T. Environmental Research Technology K.S.P.W. Inc. | Liquid sorbent |
US5591779A (en) * | 1994-11-22 | 1997-01-07 | Imperial Chemical Industries Plc | Process for making flexible foams |
US5650450A (en) * | 1996-01-25 | 1997-07-22 | Foamex L.P. | Hydrophilic urethane foam |
US6011110A (en) * | 1996-09-13 | 2000-01-04 | Nisshinbo Industries, Inc. | Carrier for bioreactor and method of producing the same |
US7009034B2 (en) | 1996-09-23 | 2006-03-07 | Incept, Llc | Biocompatible crosslinked polymers |
US8003705B2 (en) * | 1996-09-23 | 2011-08-23 | Incept Llc | Biocompatible hydrogels made with small molecule precursors |
US20090324721A1 (en) * | 1996-09-23 | 2009-12-31 | Jack Kennedy | Hydrogels Suitable For Use In Polyp Removal |
AU4648697A (en) * | 1996-09-23 | 1998-04-14 | Chandrashekar Pathak | Methods and devices for preparing protein concentrates |
AUPO946297A0 (en) * | 1997-09-25 | 1997-10-16 | Holbray Pty Ltd | Ion exchange |
US6605294B2 (en) * | 1998-08-14 | 2003-08-12 | Incept Llc | Methods of using in situ hydration of hydrogel articles for sealing or augmentation of tissue or vessels |
JP2002531217A (en) * | 1998-12-04 | 2002-09-24 | チャンドラシェカー ピー. パサック, | Biocompatible crosslinked polymer |
US6902712B2 (en) * | 1999-10-12 | 2005-06-07 | General Hospital Supply Corporation | Absorbent liner for sterilization process and method of sterilizing surgical instruments |
DE60117134T2 (en) * | 2000-04-26 | 2006-08-03 | Dow Global Technologies, Inc., Midland | PERMANENT ABSORBENT LATEX FOAM WITH IMPROVED VERTICAL WELDING CHARACTERISTICS |
WO2003071986A2 (en) * | 2002-02-22 | 2003-09-04 | Control Delivery Systems, Inc. | Method for treating otic disorders |
WO2006086510A2 (en) * | 2005-02-09 | 2006-08-17 | Tyco Healthcare Group Lp | Synthetic sealants |
US7459488B2 (en) * | 2005-03-03 | 2008-12-02 | Polyfoam Products, Inc. | Composition and process for recovery of spilled hydrocarbons from aqueous environments |
US20070023309A1 (en) * | 2005-07-27 | 2007-02-01 | General Hospital Supply Corporation | Sterilization pouch for medical instruments and methods of use |
JP2009518522A (en) * | 2005-12-08 | 2009-05-07 | タイコ ヘルスケア グループ リミテッド パートナーシップ | Sprayable composition with reduced viscosity |
WO2007067806A2 (en) | 2005-12-08 | 2007-06-14 | Tyco Healthcare Group Lp | Biocompatible surgical compositons |
US20090227689A1 (en) * | 2007-03-05 | 2009-09-10 | Bennett Steven L | Low-Swelling Biocompatible Hydrogels |
US20090227981A1 (en) * | 2007-03-05 | 2009-09-10 | Bennett Steven L | Low-Swelling Biocompatible Hydrogels |
US8067028B2 (en) | 2007-08-13 | 2011-11-29 | Confluent Surgical Inc. | Drug delivery device |
US20090088723A1 (en) * | 2007-09-28 | 2009-04-02 | Accessclosure, Inc. | Apparatus and methods for treating pseudoaneurysms |
JP5890182B2 (en) | 2009-02-12 | 2016-03-22 | インセプト エルエルシー | Drug delivery with hydrogel plugs |
FR2974004B1 (en) | 2011-04-15 | 2014-05-02 | Urgo Lab | HYDROCELLULAR ABSORBENT DRESSING, ITS USES FOR THE TREATMENT OF CHRONIC AND ACUTE WOUNDS |
FR2974005B1 (en) | 2011-04-15 | 2014-05-02 | Urgo Lab | THIN ABSORBENT THIN ADHESIVE DRESSING, ITS USES FOR THE TREATMENT OF CHRONIC WOUNDS |
US20120278956A1 (en) | 2011-04-26 | 2012-11-01 | Hartman Gary R | Soil free planting composition |
FR3003463B1 (en) | 2013-03-20 | 2015-04-10 | Urgo Lab | DRESSING HAVING AN ADHESIVE PERIPHERAL EDGE WITH AN INUTED ROUND |
FR3056100B1 (en) | 2016-09-20 | 2019-07-05 | Urgo Recherche Innovation Et Developpement | ABSORBENT DRESSING COMPRISING A HYDRODELITABLE SUPERABSORBENT NON-WOVEN |
WO2019137879A1 (en) | 2018-01-12 | 2019-07-18 | Covestro Deutschland Ag | Method for producing low-swelling polyurethane foams, and uses thereof |
WO2019137882A1 (en) | 2018-01-12 | 2019-07-18 | Covestro Deutschland Ag | Method for producing elastic and tear-resistant polyurethane foams, and uses thereof |
CN113461904B (en) * | 2021-08-10 | 2022-10-11 | 中山成长鞋材有限公司 | Soft, high-elasticity, water-absorbing and non-swelling polyether foam and preparation method thereof |
FR3133122B1 (en) | 2022-03-03 | 2024-03-01 | Urgo Rech Innovation Et Developpement | Modular dressing |
Family Cites Families (33)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3790508A (en) * | 1972-03-20 | 1974-02-05 | Scott Paper Co | Light-stable polyurethane foam formed by reaction of a polyol and a mixture or aromatic and aliphatic polyisocyanates |
US3812619A (en) * | 1972-05-03 | 1974-05-28 | Grace W R & Co | Horticultural foam structures and method |
US3812618A (en) * | 1972-05-03 | 1974-05-28 | Grace W R & Co | Seed-foam-fabric composite |
US3833386A (en) * | 1972-07-07 | 1974-09-03 | Grace W R & Co | Method of prepairing porous ceramic structures by firing a polyurethane foam that is impregnated with inorganic material |
US3959191A (en) * | 1973-01-11 | 1976-05-25 | W. R. Grace & Co. | Novel hydrophobic polyurethane foams |
US3903232A (en) * | 1973-10-09 | 1975-09-02 | Grace W R & Co | Dental and biomedical foams and method |
US4137200A (en) * | 1973-10-09 | 1979-01-30 | W. R. Grace & Co. | Crosslinked hydrophilic foams and method |
GB1503732A (en) * | 1974-02-19 | 1978-03-15 | Grace W R & Co | Method for preparing dental and medical foam structures and products |
US3939123A (en) * | 1974-06-18 | 1976-02-17 | Union Carbide Corporation | Lightly cross-linked polyurethane hydrogels based on poly(alkylene ether) polyols |
JPS51139900A (en) * | 1975-05-15 | 1976-12-02 | Grace W R & Co | Hydrophilic polyurethane foam like natural sponge |
US4017428A (en) * | 1975-06-10 | 1977-04-12 | The United States Of America As Represented By The Secretary Of The Army | Abrasion resistant, non-discoloring polyurethane foams and method of making |
US4049592A (en) * | 1975-07-18 | 1977-09-20 | W. R. Grace & Co. | Biodegradable hydrophilic foams and method |
US4110508A (en) * | 1976-02-09 | 1978-08-29 | W. R. Grace & Co. | Foam sheet and method |
US4067832A (en) * | 1976-03-01 | 1978-01-10 | The Procter & Gamble Company | Flexible polyurethane foam |
US4132839A (en) * | 1976-10-12 | 1979-01-02 | W. R. Grace & Co. | Biodegradable hydrophilic foams and method |
US4127516A (en) * | 1977-02-28 | 1978-11-28 | W. R. Grace & Co. | Hydrophilic polyurethane foams with good wet strength |
US4201846A (en) * | 1977-11-25 | 1980-05-06 | W. R. Grace & Co. | Dimensionally stable polyurethane foam |
US4314034A (en) * | 1980-12-29 | 1982-02-02 | W. R. Grace & Co. | Polyurea polyurethane foamed sponge with high wet strength |
US4377645A (en) * | 1980-12-29 | 1983-03-22 | W. R. Grace & Co. | Dimensionally-stable polyurethane sponge and sponge-forming prepolymer |
US4357430A (en) * | 1981-10-02 | 1982-11-02 | Union Carbide Corporation | Polymer/polyols, methods for making same and polyurethanes based thereon |
CA1194642A (en) * | 1981-10-26 | 1985-10-01 | James L. Guthrie | Flexible polyurethane foam based on mdi |
US4384051A (en) * | 1981-10-26 | 1983-05-17 | W. R. Grace & Co. | Flexible polyurethane foam based on MDI |
US4384050A (en) * | 1981-10-26 | 1983-05-17 | W. R. Grace & Co. | Flexible polyurethane foam based on MDI |
US4595001A (en) * | 1982-04-08 | 1986-06-17 | Smith And Nephew Associated Companies P.L.C. | Surgical adhesive dressing |
US4385133A (en) * | 1982-06-07 | 1983-05-24 | The Upjohn Company | Novel compositions and process |
AU562370B2 (en) * | 1982-10-02 | 1987-06-11 | Smith & Nephew Associated Companies Plc | Moisture vapour permeable adhesive surgical dressing |
DE3587677D1 (en) * | 1984-06-16 | 1994-01-20 | Smith & Nephew | Absorbent hygiene template. |
US4798876A (en) * | 1985-11-12 | 1989-01-17 | Tyndale Plains-Hunter Ltd. | Hydrophilic polyurethane composition |
US4738992A (en) * | 1985-12-09 | 1988-04-19 | Minnesota Mining And Manufacturing Company | Hydrophilic polyurethane/polyurea sponge |
US4638017A (en) * | 1985-12-09 | 1987-01-20 | Minnesota Mining And Manufacturing Company | Hydrophilic polyurethane/polyurea sponge |
US4725629A (en) * | 1986-07-18 | 1988-02-16 | Kimberly-Clark Corporation | Process of making an interpenetrating superabsorbent polyurethane foam |
US4725628A (en) * | 1986-07-18 | 1988-02-16 | Kimberly-Clark Corporation | Process of making a crosslinked superabsorbent polyurethane foam |
US4725627A (en) * | 1987-03-16 | 1988-02-16 | Signastone Incorporated | Squeezable toy with dimensional memory |
-
1989
- 1989-09-21 US US07/410,458 patent/US5104909A/en not_active Expired - Lifetime
-
1990
- 1990-09-10 CA CA002024508A patent/CA2024508A1/en not_active Abandoned
- 1990-09-18 JP JP2246373A patent/JP3012300B2/en not_active Expired - Lifetime
- 1990-09-20 NZ NZ235395A patent/NZ235395A/en unknown
- 1990-09-21 DE DE69023599T patent/DE69023599T2/en not_active Expired - Lifetime
- 1990-09-21 EP EP90310339A patent/EP0420515B1/en not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
JP3012300B2 (en) | 2000-02-21 |
NZ235395A (en) | 1992-04-28 |
US5104909A (en) | 1992-04-14 |
DE69023599D1 (en) | 1995-12-21 |
JPH03119021A (en) | 1991-05-21 |
EP0420515A1 (en) | 1991-04-03 |
DE69023599T2 (en) | 1996-04-11 |
EP0420515B1 (en) | 1995-11-15 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US5104909A (en) | Water-absorbent, high capacity polyurethane foams | |
CA1179100A (en) | Dimensionally-stable polyurethane sponge and sponge- forming prepolymer | |
US3903232A (en) | Dental and biomedical foams and method | |
US5650450A (en) | Hydrophilic urethane foam | |
US4384051A (en) | Flexible polyurethane foam based on MDI | |
US6803495B2 (en) | Polyurethane foam composition and method of manufacture thereof | |
EP0225800B1 (en) | Hydrophilic polyurethane/polyurea sponge | |
US3778390A (en) | Hydrolytically unstable polyurethane foams | |
US4384050A (en) | Flexible polyurethane foam based on MDI | |
JPH0240244B2 (en) | ||
JP2702772B2 (en) | Method for producing molded article of water-absorbing polyurethane foam | |
US4314034A (en) | Polyurea polyurethane foamed sponge with high wet strength | |
US5686502A (en) | Water blown, hydrophilic, open cell polyurethane foams, method of making such foams and articles made therefrom | |
US4201846A (en) | Dimensionally stable polyurethane foam | |
US4456685A (en) | Microorganisms immobilized with hydrolysis resistant polyurethane foam | |
CA1194642A (en) | Flexible polyurethane foam based on mdi | |
WO2004013215A1 (en) | Water absorbent flexible polyurethane foam | |
US4439553A (en) | High molecular weight aromatic amine scavengers and method of use | |
US3573234A (en) | Flexible and hydrophilic polyurethane foam and method of making same | |
CA1087800A (en) | Biodegradable hydrophilic polyurethane foams and method | |
AU749640B2 (en) | Sponge | |
SU859388A1 (en) | Method of producing porous polyurethan | |
JP2669548B2 (en) | Method for producing water-absorbent polyurethane foam | |
JP2613834B2 (en) | Method for producing biodegradable polyurethane composite | |
JPH037690B2 (en) |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
EEER | Examination request | ||
FZDE | Dead |