|Publication number||US2664367 A|
|Publication date||Dec 29, 1953|
|Filing date||Sep 19, 1949|
|Priority date||Sep 19, 1949|
|Publication number||US 2664367 A, US 2664367A, US-A-2664367, US2664367 A, US2664367A|
|Inventors||Wilson Christopher Lumley|
|Original Assignee||Wilson Christopher Lumley|
|Export Citation||BiBTeX, EndNote, RefMan|
|Patent Citations (6), Referenced by (60), Classifications (10)|
|External Links: USPTO, USPTO Assignment, Espacenet|
Patented Dec. 29, 11953 P-LA STICIZED SPO METHOD OF NGE MATERIAL AND MAKING SAME Christopher Lumley Wilson, Columbus, Ohio No Drawing. A plication September 19,1949, Serial No. 116.643 '2. Claims. (Cl. 117-138.8)
"This invention relates to a sponge material comprising partially formalized polyvinyl alcohol, and relates particularly to such a sponge material having incorporated therein a plasticizer' to maintain the sponge in a soft and resilient condition.
Sponge and expanded materials comprising partially formalized polyvinyl alcohol and their preparation are described in my copending application Serial No. 29,657, filed Mayz l, 194$,and now Patent No. 2,609,347, which is a continuation-impart of my prior copend'ing application Serial No. 769,537, filed August 19, 1947, now abandoned. These sponge materials are prepared by reacting the formaldehyde with polyvinyl alcohol so that only a portion of the hydroxyl groups of the alcohol enters into the reaction. Preferably the solution of the materials is expanded as by beating air into the solution and the reaction is then permitted to proceedso that a solid is formed containing openings formerly occupied by the bubbles of air or other gas. is employed in order to speed up the reaction.
As further set forth in the above mentioned Patent 2,609,347, the sponge materials described therein are made by a process comprising providing an aqueous solution of formaldehyde, polyvinyl alcohol containing less than residual hydrolyzable material in the moleculean acid catalyst in which the acid functional group is inorganic and having a dissociation constant of at least 10- and a froth-stabilizing wetting agent soluble in and substantially stable to said solution; forming a substantially stable and homogeneous froth withsaid solution stabilized with the wetting agent; reacting the polyvinyl alcohol and the formaldehyde in the solution thereby causing gellation and solidification of the froth with the production of interconnected pores simultaneously with the progression of the" reaction, the froth being formed prior to appreciable reaction between the polyvinyl alcohol and the formaldehyde; and stopping the reaction when approximately 35-80% of the hydroxyl groups of the polyvinyl alcohol have beenreacted with the formaldehyde. I
Sponge materials prepared in the above mannor are soft and resilient when" they contain appreciable amounts of water. When the sponge materials become dry, however, they shrink to a certain extent and become hard and rigid. They are immediately softened as soon as water is re introduced into the sponge material. Although this re-wetting of the sponge material immediately changes it from a rigid solid to a resilient In the preferred procedure, an acid catalyst elastic material and the drying out of the material causes no deleterious eifects, the dry sponge material does not have as pleasing an appearance to the prospective purchaser.
I have discovered that the sponge material may be maintained soft and resilient if a plasticizer is incorporated therewith. These plasticizers are polyethylene glycols and polyalkanolamines and may be introduced by soaking the sponge material in either the heated plasticizer or in an aqueous solution of the plasticizer. After soak ing in the liquid, the excess liquid. is removed. These plasticizers, which are preferably liquid at ordinary room temperatures, maintain the sponge material in a soft, resilient condition.
One of the features of this invention is to provide a method of making a soft, resilient sponge material comprisingproviding a partially formalized polyvinyl alcohol sponge and soaking the sponge in a liquid including a member of the class consisting of polyethylene glycols and polyalkanolamines; another feature of this invention is the provision of a partially formalized polyvinyl alcohol sponge material containing as a plasticizer a member of the class consisting of polyethylene glycols and polyalkanolamines. Other features and advantages of the invention will become apparent from the following description and the accompanying claims.
The plasticizers of this inventionmay be intro du'c'e'd into the sponge material either in the form of a solution or as substantially anhydrous liquids. When a solution is used an aqueoussolution is preferred in which the sponge is soaked so as to absorb the maximum amount of solution and then. the excess solution is removed. When the plasticizers are added in substantially anhydrous form, the liquid plasticizer is heated and the sponge is immersed in the heated plasticizer for from a few seconds to several hours depending upon the temperature employed. The sponge is thenreinoved from the plasticizer and the excess plasticizer is removed.
Among the suitable plasticizers that have been discovered are diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol have ing a molecular weight of about 209, other polyethylene glycols having molecular weights of more than 200, triethanolamine and methyl diethanolamine. The plasticizers may be used alone or in combinations of two or more. When the substantially anhydrous plasticizer is employed, the liquid plasticizer is preferably heated at a temperature between about 37 to C. At the higher temperatures care must be used that the sponge is not immersed for too long a time, as ordinarily only a few seconds is required at the high temperatures. A temperature of about 50 C. is preferred.
Any amount of plasticizer desired may be used so long as a plasticizing effect is achieved. In general, the sponge should contain approximately 50% of the anhydrous plasticizer by weight of the dry sponge material. In actual practice, it has been found that excellent results have been achieved when at least 30% of the plasticizer is employed by weight of the dry sponge material. Ordinarily not more than about 100% is required, but in some instances it may be advisable to use more. Under conditions of high humidity, the minimum amount may be reduced below 30%. For example, 20% is satisfactory if the relative humidity of the atmosphere surrounding the sponge is at least 85-90%.
The following examples illustrate methods of practicing this invention:
Example 1 liquid. The sponge material retained about 6 grains of the solution and remained flexible in the atmosphere.
Example 2 A. partially formalized polyvinyl alcohol sponge made according to the above application was soaked overnight in triethylene glycol at 50 C. At the end of this time, the excess plasticizer was removed by squeezing the sponge. This sponge remained soft and flexible when exposed to air at room temperature.
Example 3 A portion of the sponge material Was soaked in a 30% by weight aqueous solution of triethanolamine. After the excess solution had been removed by squeezing, the sponge remained soft when exposed to air at room temperature. The sponge was found to contain 60% triethanolamine, calculated as anhydrous amine and based on the weight of the dry sponge.
Example 4 A portion of the sponge material was soaked in a 30% by weight aqueous solution of methyl diethanolamine. After the excess solution had been removed by squeezing, the sponge remained soft when exposed to air at room temperature. The sponge was found to contain 60% methyl diethanolarnine, calculated as anhydrous amine and based on the weight of the dry sponge.
Of the plasticizers described herein, the polyethylene glycols are preferred, and especially triethylene glycol. Diethylene glycol, triethylene glycol, tetraethylene glycol and other polyethylene glycols having a molecular weight of at least 200 may be employed. It is preferred, however, that the polyethylene glycol contain not more than 8 ethylene groups in the molecule.
Polyhydric alcohol plasticizers for partially formalized polyvinyl alcohol sponges are disclosed and claimed generally in my copending 4 application serial No. 116,642, filed September 19, 1949.
Having described my invention as related to various embodiments of the same, it is my intention that the invention be not limited by any of the details of description unless otherwise specified, but rather be construed broadly within its spirit and scope as set out in the accompanying claims.
1. The method of making a soft, resilient sponge material having interconnected pores by reacting polyvinyl alcohol and formaldehyde, which comprises: providing an aqueous solution of formaldehyde, polyvinyl alcohol containing less than 10% residual hydrolyzable material in the molecule, an acid catalyst in which the acid functional group is inorganic and having a dissociation constant of at least 10 and a frothstabilizing wetting agent soluble in and substantially stable to said solution; forming a substantially stable and homogeneous froth with said solution stabilized with the wetting agent; reacting the polyvinyl alcohol and formaldehyde in the solution thereby causing gellation and solidification of the froth with the production of interconnected pores simultaneously with the progression of the reaction, the froth being formed prior to appreciable reaction between the polyvinyl alcohol and the formaldehyde; stopping said reaction when approximately 35-80% of the hydroxyl groups of the polyvinyl alcohol have been reacted with the formaldehyde; whereby a sponge material is formed impregnating said sponge with a liquid including a mem ber of the class consisting of substantially anhydrous polyethylene glycols and polyalkanol' amines heated to a temperature of up to about 100 C. and aqueous solutions of said amines, and removing excess of said liquid until there remains deposited on said sponge about 20-100% of said liquid based on the dry weight of the p e.
2. A method according to claim 1 in which said liquid is triethylene glycol.
3. A method according to claim 1 in which said liquid is a polyethylene glycol having a molecular weight of approximately 200.
4. A method according to claim 1 in which said liquid is triethanolamine.
5. A method according to claim 1 in which said liquid is diethylene glycol.
6. A method according to claim 1 in which said liquid is methyl diethanolamine.
7. A sponge material prepared by the method of claim 1 and in which said liquid is a polyalkanolamine.
CHRISTOPHER LUMLEY WILSON.
References Cited in the file of this patent UNITED STATES PATENTS
|Cited Patent||Filing date||Publication date||Applicant||Title|
|US1779011 *||Jun 7, 1928||Oct 21, 1930||Railway Service And Supply Cor||Method of conditioning waste|
|US2037049 *||Oct 4, 1933||Apr 14, 1936||Theron P Sager||Gas retaining fabrics and method of preparing the same|
|US2056796 *||Apr 26, 1934||Oct 6, 1936||Du Pont||Polyvinyl resin compositions and process of preparing same|
|US2370126 *||Mar 6, 1942||Feb 27, 1945||Prophylactic Brush Co||Process of making polyvinyl acetals|
|US2478879 *||Feb 23, 1946||Aug 9, 1949||Wingfoot Corp||Porous compositions|
|GB573966A *||Title not available|
|Citing Patent||Filing date||Publication date||Applicant||Title|
|US2711969 *||Feb 25, 1954||Jun 28, 1955||Us Rubber Co||Method of treating sheet sponge rubber|
|US2993801 *||Aug 1, 1958||Jul 25, 1961||Hoehne Walter E||Method for conditioning extensible balloons|
|US3190843 *||Mar 13, 1961||Jun 22, 1965||Kalle Ag||Process of making a modified polyvinyl alcohol foam|
|US3491115 *||Oct 28, 1966||Jan 20, 1970||Standard Oil Co||Composition for degelling resins|
|US3661633 *||Jan 26, 1970||May 9, 1972||Rolf Erhard Moren||Process and composition for impregnating wood and wood products|
|US4098728 *||Jan 2, 1976||Jul 4, 1978||Solomon Rosenblatt||Medical surgical sponge and method of making same|
|US5284468 *||Aug 19, 1991||Feb 8, 1994||M-Pact Worldwide Management Corporation||Orthopedic splinting article|
|US5554658 *||Dec 14, 1993||Sep 10, 1996||Rosenblatt; Solomon||Injection molded PVA Sponge|
|US5554659 *||Jun 2, 1995||Sep 10, 1996||Rosenblatt; Solomon||Injection molded PVA sponge|
|US5567612 *||Jul 27, 1993||Oct 22, 1996||Massachusetts Institute Of Technology||Genitourinary cell-matrix structure for implantation into a human and a method of making|
|US5709854 *||Apr 30, 1993||Jan 20, 1998||Massachusetts Institute Of Technology||Tissue formation by injecting a cell-polymeric solution that gels in vivo|
|US5741685 *||Jun 7, 1995||Apr 21, 1998||Children's Medical Center Corporation||Parenchymal cells packaged in immunoprotective tissue for implantation|
|US5770417 *||Feb 28, 1994||Jun 23, 1998||Massachusetts Institute Of Technology Children's Medical Center Corporation||Three-dimensional fibrous scaffold containing attached cells for producing vascularized tissue in vivo|
|US5804178 *||Feb 28, 1994||Sep 8, 1998||Massachusetts Institute Of Technology||Implantation of cell-matrix structure adjacent mesentery, omentum or peritoneum tissue|
|US5843060 *||Jan 2, 1997||Dec 1, 1998||Xomed Surgical Products, Inc.||Non-adherent nasal, sinus and otic packing and method for processing sponge materials in fabrication of packings|
|US5851833 *||Aug 7, 1996||Dec 22, 1998||Children's Medical Center Corp.||Neomorphogenesis of urological structures in vivo from cell culture|
|US6129761 *||Jun 7, 1995||Oct 10, 2000||Reprogenesis, Inc.||Injectable hydrogel compositions|
|US6169123||Jul 23, 1998||Jan 2, 2001||Xomed Surgical Products, Inc.||Non-adherent nasal, sinus and otic packing and method for processing sponge materials in fabrication of packings|
|US6214895||Sep 14, 2000||Apr 10, 2001||Xomed Surgical Products, Inc.||Method for making a polyvinyl acetal sponge packing for use in the nasal, sinus and otic cavities|
|US6224630||May 29, 1998||May 1, 2001||Advanced Bio Surfaces, Inc.||Implantable tissue repair device|
|US6281015||Dec 16, 1994||Aug 28, 2001||Children's Medical Center Corp.||Localized delivery of factors enhancing survival of transplanted cells|
|US6309635||Nov 28, 1994||Oct 30, 2001||Children's Medical Center Corp.||Seeding parenchymal cells into compression resistant porous scaffold after vascularizing in vivo|
|US7044957||Feb 2, 2001||May 16, 2006||Ethicon Endo-Surgery, Inc.||Devices for defining and marking tissue|
|US7189235||Mar 19, 2003||Mar 13, 2007||Anulex Technologies, Inc.||Spinal disc annulus reconstruction method and spinal disc annulus stent|
|US7229417||Oct 15, 2004||Jun 12, 2007||Ethicon Endo-Surgery, Inc.||Methods for marking a biopsy site|
|US7615076||Nov 10, 2009||Anulex Technologies, Inc.||Method and apparatus for the treatment of the intervertebral disc annulus|
|US7625397||Dec 1, 2009||Ethicon Endo-Surgery, Inc.||Methods for defining and marking tissue|
|US7668582||Feb 23, 2010||Ethicon Endo-Surgery, Inc.||Biopsy site marker|
|US7670379||Feb 16, 2006||Mar 2, 2010||Anulex Technologies, Inc.||Spinal disc annulus reconstruction method|
|US7749273||Jul 6, 2010||Anulex Technologies, Inc.||Method and apparatus for the treatment of the intervertebral disc annulus|
|US7807150||Mar 8, 2004||Oct 5, 2010||Massachusetts Institute Of Technology||Injectable composition containing crosslinkable material and cells for forming animal tissue|
|US7828850||Feb 10, 2006||Nov 9, 2010||Anulex Technologies, Inc.||Methods and devices for spinal disc annulus reconstruction and repair|
|US7909879||Nov 9, 2006||Mar 22, 2011||Anulex Technologies, Inc.||Intervertebral disc annulus stent|
|US7922768||Nov 14, 2006||Apr 12, 2011||Anulex Technologies, Inc.||Spinal disc annulus reconstruction method and deformable spinal disc annulus stent|
|US7935147||Sep 26, 2005||May 3, 2011||Anulex Technologies, Inc.||Method and apparatus for enhanced delivery of treatment device to the intervertebral disc annulus|
|US7951201||Jan 12, 2007||May 31, 2011||Anulex Technologies, Inc.||Method and apparatus for the treatment of the intervertebral disc annulus|
|US7963992||Jun 21, 2011||Anulex Technologies, Inc.||Method and apparatus for the treatment of the intervertebral disc annulus|
|US7985257||Nov 6, 2006||Jul 26, 2011||Anulex Technologies, Inc.||Methods and devices for spinal disc annulus reconstruction and repair|
|US7993405||Dec 8, 2006||Aug 9, 2011||Anulex Technologies, Inc.||Spinal disc annulus repair system and methods|
|US8034112||Oct 11, 2011||Anulex Technologies, Inc.||Spinal disc annulus reconstruction method and spinal disc annulus stent|
|US8048160||Dec 22, 2005||Nov 1, 2011||Anulex Technologies, Inc.||Intervertebral disc annulus stent|
|US8088165||Mar 23, 2006||Jan 3, 2012||Anulex Technologies, Inc.||Spinal disc annulus reconstruction method and deformable spinal disc annulus stent|
|US8128698||Oct 14, 2008||Mar 6, 2012||Anulex Technologies, Inc.||Method and apparatus for the treatment of the intervertebral disc annulus|
|US8277391||Aug 7, 2002||Oct 2, 2012||Devicor Medical Products, Inc.||Methods and devices for defining and marking tissue|
|US8306602||Sep 30, 2005||Nov 6, 2012||Devicor Medical Products, Inc.||Biopsy cavity marking device|
|US8320993||Nov 27, 2012||Devicor Medical Products, Inc.||Subcutaneous cavity marking device|
|US8320994||Oct 6, 2004||Nov 27, 2012||Devicor Medical Products, Inc.||Biopsy cavity marking device and method|
|US8454697||Apr 5, 2012||Jun 4, 2013||Anulex Technologies, Inc.||Method and apparatus for the treatment of tissue|
|US8556977||Nov 12, 2010||Oct 15, 2013||Anulex Technologies, Inc.||Tissue anchoring system and method|
|US8600481||Sep 5, 2012||Dec 3, 2013||Devicor Medical Products, Inc.||Subcutaneous cavity marking device|
|US8632590||Sep 26, 2006||Jan 21, 2014||Anulex Technologies, Inc.||Apparatus and methods for the treatment of the intervertebral disc|
|US9095442||Jan 23, 2012||Aug 4, 2015||Krt Investors, Inc.||Method and apparatus for the treatment of the intervertebral disc annulus|
|US9114025||Jun 29, 2011||Aug 25, 2015||Krt Investors, Inc.||Methods and devices for spinal disc annulus reconstruction and repair|
|US9192372||Jun 3, 2013||Nov 24, 2015||Krt Investors, Inc.||Method for the treatment of tissue|
|US9380998||Feb 20, 2014||Jul 5, 2016||Devicor Medical Products, Inc.||Subcutaneous cavity marking device and method|
|US20040170612 *||Mar 8, 2004||Sep 2, 2004||Griffith Linda G.||Injectable polysaccharide-cell compositions|
|US20070197457 *||Mar 29, 2004||Aug 23, 2007||Dan Gazit||Tak1-mediated inhibition of osteogenesis|
|US20100209400 *||Nov 30, 2009||Aug 19, 2010||Dan Gazit||TAK1-Mediated Regulation of Osteogenesis|
|EP2075015A1||Jul 2, 1998||Jul 1, 2009||Massachusetts Institute of Technology||Tissue-engineered constructs|
|WO2004087862A2||Mar 29, 2004||Oct 14, 2004||Yissum Research Development Company Of The Hebrew University Of Jerusalem||Tak1-mediated inhibition of osteogenesis|
|U.S. Classification||15/244.4, 521/55, 427/244, 524/245, 521/141, 524/377|
|Cooperative Classification||C08J2329/14, C08J9/40|