Processes for making shaped articles such as filaments or films from solutions of polyglycolic acid
United States Patent 1 Schmitt et al.  
 [ 1 Apr. 15, 1975 1 PROCESSES FOR MAKING SHAPED ARTICLES SUCH AS FILAMENTS OR FILMS FROM SOLUTIONS OF POLYGLYCOLIC ACID [75] Inventors: Edward E. Schmitt, Norwalk,  
 &#39; Conn.; William J. Bailey,  
 Hyattsville, Md.  
 [73] Assignee: American Cyanamid Compan Stamford, Conn.  
  22 Filed:&#39; Feb. 13, 1973 211 Appl. No.: 332,462  
 Related U.S. Application Data- [60] Division of Ser. No. 171,320, Aug. 12, 1971, Pat. No. I 3,737,440, which is a continuation-in-part of Ser. No.  
 34,593, May 4, 1970, abandoned.  
 [52] U.S. Cl 264/184; 260/328 R; 260/33.4 R; 260/783 R; 264/205; 264/233; 264/331; 264/299 [51] Int. Cl C08g 17/017; C08g 17/02 [58] Field of Search 264/210 R, 331, 212, 216, 264/203-205, 184, 233; 260/783 R, 33.4 R, 32.8 R; 128/3355 Primary Examiner Jeffery R. Thurlow Attorney, Agent, or Firm.lames T. Dunn [57] ABSTRACT This invention relates to a process for making shaped articles from certain solutions of polyglycolic acid using hexafluoroisopropyl alcohol or hexafluoroacetone sesquihydrate as solvents. The solutions are used as spinning dopes for wet or dry spinning of polyglycolic acid into shaped articles such as filaments. The solutions can also be used to cast films of polyglycolic acid.  
 4 Claims, N0 Drawings PROCESSES FOR MAKING SHAPED ARTICLES SUCH AS FILAMENTS OR FILMS FROM SOLUTIONS OF POLYGLYCOLIC ACID CROSS REFERENCE TO RELATED APPLICATION This application is a division of our application Ser. No. 171,320 filed Aug. 12, 1971, now U.S. Pat. No. 3,737,440, which application is in turn a continuationin-part of our earlier application, Ser. No. 34,593. filed May 4, 1970 entitled Solutions of Polyglycolic Acid&#34; now abandoned.  
 BACKGROUND OF THE INVENTION Polyglycolic acid is a known polymer and has been prepared in the past by a variety of processes known to those skilled in the art. At least two varieties of this polymer have been described in detail in the prior art. The Higgins, U.S. Pat. No. 2,676,945, shows the high molecular weight polymers melting at about 232-233C and capable of being fashioned into useful articles and fibers. In the U.S. Pat. No. 3,468,853 polyglycolic acid is shown to be truly polymeric when it has a crystalline melting point falling between 230 and 232C although others have measured this physical property and reported it to fall between about 222 and 235C.  
  Bowman, U.S. Pat. No. 3,047,524, on the other hand, describes a class of oligomeric polymers melting between 90 and 130C which are useful in the field of oxidizer binders for solid propellants.  
  Oligomers are usually defined as the low members of the polymeric-homologous series, with molecular Weights up to about 1000-2000. Homologous oligomers due to their low molecular weight differ sufficiently in their physical properties so that they are, in general, far more soluble than their high molecular weight counter-parts. Indeed, we have found this to be true in the case of polyglycolic acid. High molecular weight polyglycolic acid is insoluble in all the common solvents but linear and cyclic oligomers that melt in the range of82 to 200C, are soluble in a variety of common solvents.  
  These same solvents are also useful in dissolving the oligomers and high molecular weight heterologs of polyglycolic acid but not the high molecular weight polyglycolic acid itself. It seems apparent therefore that the solubility of high molecular weight polyglycolic acid is a singularly unique phenomenon in the field of polymer science. For example, high molecular weight hydroxyacid polymer such as polylactic acid, poly a hydroxy isobutyric acid, polydimethyl ketene, poly a, a-diethyl B-propiolactone, poly -hydroxy caproic acid, and poly -hydroxy decanoic acid are soluble in one or a number of such common solvents such as chloroform, benzene, chlorobenzene, toluene, tetralin, anisole, cyclohexane, trifluoro acetic acid and a variety of aromatic and halogenated hydrocarbons. The oligomers and the polymers are also soluble in a variety of secondary and tertiary polyhalo alcohols as described by Middleton in U.S. Pat. No. 3,245,944.  
  Interest has recently been revived in polyglycolic acid because of the disclosure of U.S. Pat. No. 3,297,033 that the high molecular weight, common solvent insoluble, polyglycolic acid&#39;has been successfully employed to prepare absorbable surgical sutures. These synthetic sutures provide a viable alternative to the so called catgut sutures which have been historically used by the medical profession when absorbability in living tissue was required. Several collateral patents relating to polyglycolic acid absorbable sutures have recently appeared, such as, for example, U.S. Pat. Nos. 3,457,280, 3,435,008, 3,442,871, 3,442,181, 3,468,853, 3,414,939 and 3,463,158 and each of the aforesaid patents are incorporated herein by reference.  
  Heretofore, the principal way that polyglycolic acid polymer was fabricated into useable forms such as filamerits, films, and various other shapes was by the use of melt spinning techniques. Solution techniques could not be used because they require an acceptable solvent for polyglycolic acid, and such solvents were not heretofore available. A wide variety of known polymer solvents had been employed in an attempt to solubilize polyglycolic acid but generally to no avail. The lack of an available acceptable solvent for polyglycolic acid had the effect of preventing the use of wet and dry spinning techniques in the fabrication of shaped polyglycolic acid articles. Of the solvents investigated in the past, several problems have been found to exist. For example, none of the solvents would dissolve the polyglycolic acid. Moreover, certain other solvents investigated had the effect of chemically degrading the polymer or otherwise reacting with the polymer in such a way as to break down the polymer structure. To briefly summarize, all the common solvents heretofore employed had one or more drawbacks which detracted from their use as a solvent for polyglycolic acid.  
  It is therefore an object of this invention to provide solutions of polyglycolic acid which are eminently .suitable for the preparation of various shaped forms of polyglycolic acid by various solution techniques such as for example, wet and dry spinning of filaments or casting of films from said solutions.  
 SUMMARY OF THE INVENTION This invention relates to the use of solutions comprising polyglycolic acid dissolved in hexafluoroisopropyl alcohol or in hexafluoroacetone sesquihydrate to form shaped articles of polyglycolic acid. The nature of the polyglycolic acid employed in preparing these solutions, except as indicated hereinbelow with respectto the degree of crystallinity, is not critical and it has been found, for example, that polyglycolic acid of widely varying molecular weight above a minimum of several thousand is quite suitable as is polyglycolic acid prepared from a variety of different process routes provided that the melting point in the crystalline state falls within the range of 222C and 235C.  
  Hexafluoroisopropyl alcohol and hexafluoroacetone sesquihydrate are both known chemicals which are I commercially available or can be readily prepared in accordance with known procedures. For example, see the article by Middleton and Lindsey entitled Hydrogen Bonding in Fluoro Alcohols in the Journal of the American Chemical Society, Vol. 85, pages 4948-4952 inclusive. We have found that when either of these two unique solvents is employed to dissolve polyglycolic acid, a solution of polyglycolic acid is readily prepared which retains solubility of the polyglycolic acid therein over a wide range of temperatures, and wherein substantially no degradation of the polyglycolic acid occurs.  
  These solutuions of polyglycolic acid in either hexafluoroisopropyl alcohol or hexafluoroacetone sesquihydrate are useful as spinning dopes for wetand dry spinning of polyglycolic acid. as a vehicle for preparing cast films of various thicknesses of polyglycolic acid, and when dilute solutions are employed, as a very convenient means for performing a variety of analytical procedures upon polyglycolic acid which require that the polyglycolic acid be in solution.  
 DESCRIPTION OF THE PREFERRED EMBODIMENTS THE SOLUTIONS AND PREPARATION THEREOF As discussed heretofore the nature of the polyglycolic acid used to prepare the solutions is generally of no consequence except for its degree of crystallinity and its melting point in the crystalline state. However.  
 the nature of the polyglycolic acid employed does be come important in one respect. If the polyglycolic acid is in a substantially amorphous form, i.e.-, less than about 10 percent crystallinity, the polyglycolic acid will dissolve quickly and completely in both hexafluoroisopropyl alcohol and in hexafluoroacetone sesquihydrate. Moreover. it has been generally found that if the polyglycolic acid employed possesses a degree of crystallinity which is less than about 30 percent, solutions of polyglycolic acid in both solvents of this invention can still be readily and conveniently prepared; however, if the degree of crystallinity of the polymer exceeds about 30 percent. the polyglycolic acid is soluble only in hexafluoroacetone sesquihydrate. If the degree of crystallinity exceeds 75 percent, the polymer is soluble in neither. As the degree or percentage of crystallinity increases, the solubility of the polyglycolic acid diminishes and reciprocally as the degree of crystallinity diminishes, the solubility of the polyglycolic acid increases. As a consequence, the polyglycolic acid, having a degree of crystallinity between about and 30 percent, can be dissolved in the hexafluoroisopropyl alcohol in an amount varying between 0.01 and about 30 percent by weight of polyglycolic acid based on the total weight of solution. On the other hand, if the polyglycolic acid has a degree of crystallinity varying between about 0 percent and not more than 75 percent, the polyglycolic acid can be dissolved in the hexafluoroacetone sesquihydrate in amounts varying between about 0.01 and about 40 percent by weight of polyglycolic acid based on the total weight of the solution. The insolubility of crystalline polyglycolic acid in the cited solvents. however, can be readily overcome by insuring that the polyglycolic acid employed to prepare the solutions is in the substantially amorphous form. It is a relatively simple procedure to convert highly crystalline polyglycolic acid into the more desirable amorphous form by simply melting highly crystalline polyglycolic acid and thereupon quenching it quickly to assure formation of the amorphous form of the solid polymer. A typical procedure for converting crystalline polyglycolic acid into amorphous polyglycolic acid is shown hereinbelow in Example 5.  
  The concentration of dissolved polyglycolic acid which exists in the solutions of this invention can vary over wide ranges. However, the rate of solution of polyglycolic acid in the solvent will increase as the temperature of the solvent increases. Generally, higher temperatures and longer contact times can be employed to prepare solutions having higher contents of dissolved polyglycolic acid.  
  In the case of hexafluoroisopropyl alcohol solutions of polyglycolic acid, it has been found that solutions at lower temperatures. A 5 to percent solution for example, can be prepared in about 1 to 2 hours at 40C to 50C.  
  In the case of hexafluoroacetone sesquihydrate solutions of polyglycolic acid, it has been found that solutions containing from about 0.01 to about 40 percent polyglycolic acid can be readily prepared. For example, a 40 percent solution can be prepared at about 65C in about 36 hours. Again, more dilute solutions can be prepared in shorter times and at lower temperatures. A 5 to 10 percent solution, for example, can be prepared in about 1 to 2 hours at 40C to 50C.  
 ANALYTICAL UTILITY OF SOLUTIONS Very dilute solutions of polyglycolic acid, i.e., in the range of .01 to 1 percent by weight, find particular utility as a vehicle for analytically measuring various properties of the polymer in accordance with techniques well known to those skilled in the polymer art; for example, viscosity measurements, and the determination of molecular shape and size from light scattering equipment are but a few of these analytical applications. Generally, for most analytical work a concentration of dissolved polymer of from about 0.1 to 0.5 percent suf- &#39;fices.  
 CASTING OF FILMS The solutions of this invention are also useful as a vehicle for preparing cast films of polyglycolic acid. Such films can be conveniently prepared from solutions containing from about 0.5 to 25 percent by weight polyglycolic acid. These films are prepared by spreading the solution onto an appropriate surface which will not stick to the formed film and thereupon providing for removal of the solvent to deposit the film of polyglycolic acid upon the surface. If very thin films such as, for example, membranes or films having thicknesses of less than 0.5 mil are desired, the solutions of this invention can also be carefully deposited upon any suitable liquid which is a&#39;solvent for the hexafluoroisopropyl alcohol or hexafluoroacetone sesquihydrate wherein the liquid serves as the surface upon which the solution is deposited and whereupon the liquid will extract the hexafluoroisopropyl alcohol or hexafluoroacetone sesquihydrate leaving deposited upon the liquid surface a very thin film of polyglycolic acid. Suitable solvents for this purpose include ethyl acetate tertiary amyl alcohol. t-butanol and water.  
  The concentration of solution employed in preparing cast films will, of course, depend upon the desired thickness of the dried film. Generally, film thicknesses of anywhere from 0.5 mil to about 50 mils, and preferably 0.5 to 20 mils, can be readily prepared from the solutions of this invention. Solutions containing from about 0.5 to 5 percent polyglycolic acid are preferred for preparing cast films in accordance with the process of this invention. The films thus produced are tough, self-supporting films which when thin are quite clear but which upon standing tend to crystallize and become opaque.  
  Appropriate non-stick surfaces for preparing polyglycolic acid films include such items as glass, stainless steel, TEFLON and various fluorinated polymers such as, for example, fluorinated ethylene-propylene copolymers.  
  Best results are obtained when the casting solution is maintained at a temperature between about room temperature and about 60C and preferably between room temperature and about 50C.  
 WET AND DRY SPINNING The solutions of this invention are eminently suitable for spinning into filaments or thin films using the standard techniques of wet or dry spinning. The term shaped article of polyglycolic acid as used herein,-  
 means a filament or filaments of polyglycolic acid and thin films of polyglycolic acid, i.e., films having a thickness of mils or less.  
  In a typical wet spinning operation, a solution or spinning dope of polyglycolic acid dissolved in either hexafluoroisopropyl alcohol or hexafluoroacetone sesquihydrate is prepared and thereupon extruded through an appropriate extrusion orifice at a solution temperature of 40 to 80C, and preferably 60 to 80C, into a suitable liquid coagulating medium such as, for example, ethyl acetate, tertiary amyl alcohol, t-butanol, or water. The coagulating liquid is maintained at a temperature below that of the extrudate, such as, for example. room temperature or below, and as low as about C. The coagulant may be any solvent or system of solvents which coagulates polyglycolic acid and removes the solvent associated therewith in the spinning solution.  
  It should be noted that although the boiling point of hexafluoroisopropyl alcohol is about 58C at atmospheric pressure. the boiling point of solutions of polyglycolic acid in hexafluoroisopropyl alcohol will exceed 58C depending upon how much polymer is dissolved in the solvent, and the pressure exerted on the system. Thus solution temperatures and ranges of temperatures such as 40 to 80C and similar ranges which appear throughout this specification contemplate the temperatures of solutions containing varying amounts of polyglycolic acid under varying pressures which can elevate the boiling point of the solution into the upper limits of such temperature ranges.  
  A spinning solution will preferably contain as much polyglycolic acid as can be dissolved in the solution. It has been found in the case of hexafluoroisopropyl alcohol that a solution containing from about 10 percent to about 30 percent by weight polyglycolic acid provides an acceptable spinning solution whereas, when hexafluoroacetone sesquihydrate is the solvent, a polyglycolic acid concentration of from about 10 percent to about 40 percent can be employed. In general, it is preferred to use as high a concentration of dissolved polyglycolic acid as possible in the spinning dopes. In the case of a hexafluoroisopropyl alcohol spinning dope a polyglycolic acid concentration of 25-30% is preferred whereas a polyglycolic acid concentration of 35-40 70&#39; is preferred when hexafluoroacetone sesquihydrate spinning dopes are used. The spinning dopes may contain undissolved polyglycolic acid provided the undissolved particles are of sufficiently small size so as to not interfere with the extrusion of the solutions.  
  ,As the extrudate contacts the coagulant bath, it coagulates to form a shaped article of polyglycolic acid which is then washed with a solvent such as water, ethyl acetate, or tertiary amyl alcohol to remove residual hexafluoroacetone seaquihydrate or hexafluoroisopropyl alcohol. The shaped article is then stretched in accordance with standard fiber or film making precedures to orient the polyglycolic acid. In the case of a filament of polyglycolic acid, the strand will typically be stretched anywhere from three to seven times its original length. In the case where the shaped article is a thin film of polyglycolic acid, it may be similarly stretched or it may be subjected to a biaxial stretch of from about three to seven times its original length in the longitudinal direction and from about two to five times its original length in the lateral direction. The shaped article can be stretched before or after removal of residual solvent or concurrently with the removal of the solvent.  
  The solutions of this invention are also eminently suitable for the preparation of shaped articles of polyglycolic acid using dry spinning techniques. The solution concentrations which have been found suitable are the same as those discussed hereinabove for wet spinning. The temperatures at which the solutions are extruded are also the same as those discussed hereinabove for wet spinning. The extrudate emerges into a suitable gaseous inert medium which is usually a hot stream of a stripping gas such as, for example, air, nitrogen, or argon, which is maintained at a sufficiently high temperature to evaporate from the spinning solution, the solvent associated therein with the polyglycolic acid. The temperature of the stripping gas is typically maintained at about 40 to 130C, and preferably at 40 to 80C. As the solvent is removed from the polymer, the polyglycolic acid forms a shaped article of polyglycolic acid which is thereupon stretched in accordance with the procedures described above for the wet spinning operation. Residual solvent can be removed from the polyglycolic acid by a variety of known techniques such as, for example, drying under under vacuum.  
  The following examples are provided to further illustrate the invention.  
 EXAMPLE I PREPARATION OF POLYGLYCOLIC ACID SOLUTIONS Time required to By Weight Dissolved achieve complete Solvent Polyglycolic Acid Temp. (C.) solution (Hours) hexafluoroisopropyl alcohol 19 55 &#39;i hexafluoroacetone sesquihydrate I9 55 2 hexafluoroisopropyl alcohol 26 55 I6 hexafluoroacetone sesquihydrate 26 55 2 hexafluoroisopropyl alcohol 30 24 hexafluoroacetone sesquihydrate 35 65 3 hexafluormicetone sesquihydrate 40 65 36 EXAMPLE 2 DRY SPINNING OF POLYGLYCOLIC ACID A spinning solution was prepared by dissolving 30 parts by weight of polyglycolic acid having an intrinsic viscosity of 1.2 in 70 parts by 6 of hexafluoroisopropyl alcohol at 55C. The solution was heated to 70C and pumped at the rate of 30 cc. per minute through a spinnerette having 16 capillaries 100 microns in diameter into a vertical column 20 cms. in diameter and 6 meters long. The upper portion of the column was maintained at l 10C for a length of 4 /2 meters. The lower 150 cms. of the column was flushed with nitrogen at ambient temperature. A finish consisting of 10 percent mineral oil in xylene was applied and the yarn taken up at 300 meters/min. The yarn was found to contain 32.6 percent solvent which was removed in a vacuum oven at 35C overnight. The solvent-free yarn had a denier of 270.  
  This yarn was stretched in turbulent hot air at 80C to 3.5 to 5.5 times its original length, and heat-set at 135C for two hours to improve strength retention in living tissue when the yarn is used in the form of a braided surgical suture.  
  Similar results were obtained when the hexafluoroisopropyl alcohol was replaced with hexafluoroacetone sesquihydrate.  
 EXAMPLE 3 WET-SPINNING OF POLYGLYCOLIC ACID 30 Parts by weight of polyglycolic acid were dis solved in 70 parts by weight of hexafluoroisopropyl alcohol at 50C. The resulting spin dope was pumped at a rate of 27 cc./min. through a heater which warmed it to a temperature of 60C, and then through a 20-hole spinnerette with 100 micron capillary diameters which was submerged in an ambient temperature water bath 2 meters in length. The coagulated wet gel was pulled away at a speed of 30 meters per minute and subjected to a countercurrent wash with tap water using 30 wraps on a pair of advancing rolls, the ends of which were elevated 20 above horizontal.  
  The washed gel was then led through a 60C waterbath and stretched to about 7 times its original length.  
  Free water was removed by sponges and aspirators as the stretched gel left the water bath. The gel was further dried, and stretched 3-fold, by drawing in 150C air to achieve a final denier of 195.  
  Similar results were obtained when the hexafluoroisopropyl alcohol was replaced with hexafluoroacetone sesquihydrate.  
 EXAMPLE 4 CASTING OF POLYGLYCOLIC ACID FILM A solution of 25 percent polyglycolic acid (by weight) in hexafluoroacetone sesquihydrate was prepared by heating the mixture to 50C with stirring. The solution was poured onto a clean, smooth glass plate using a draw down blade to distribute the solution over the glass to a depth of about 5 microns. The solvent was allowed to evaporate and the resulting polyglycolic acid film was removed by peeling it off the glass.  
 The film produced was a tough, self-supporting clear EXAMPLE 5 CONVERSION OF CRYSTALLINE POLYGLYCOLIC ACID TO AMORPHOUS POLYBLYCOLIC ACID Five grams of polyglycolic acid which had been annealed at 175C for 24 hours was found to be insoluble in hesafluoroispropyl alcohol even when heated to 1 60C. This sample of polyglycolic possessed a degree of crystallinity greater than 40 percent. It was placed in a melt index unit, heated to 245C and extruded through a 30 mil orifice into liquid nitrogen by applying 20,000 psi to the piston of the unit. The substantially amorphous noodle was removed from the liquid nitrogen and allowed to warm up to room temperature in a vacuum dessicator. This treated polyglycolic acid was now readily soluble in ml. of hexafluoroisopropyl alcohol at room temperature.  
 We claim:  
  1. A process for preparing a shaped article of polyglycolic acid which comprises extruding a solution comprising polyglycolic acid, having a crystalline melting point between about 222 and 235C and having a degree of crystallinity not greater than about 30 percent, dissolved in hexafluoroisopropyl alcohol, in an amount varying between 0.01 and 30 percent by weight of polyglycolic acid based on the total weight of the solution, through an extrusion orifice and into a medium selected from the group consisting of a liquid coagulating bath and an inert stripping gas to form a shaped article of polyglycolic acid, treating said article to remove residual solvent, and stretching said article to orient the polyglycolic acid.  
  2. A process for preparing a shaped article of polyglycolic acid which comprises extruding a solution comprising polyglycolic acid, having a crystalline melting point between about 222 and 235C and having a degree of crystallinity not exceeding about 75 percent, dissolved in hexafluoroacetone sesquihydrate, in an amount varying between about 0.01 and 40 percent by weight of said polyglycolic acid based on the total weight of the solution, through an extrusion orifice and into a medium selected from the group consisting of a liquid coagulating bath and an inert stripping gas to form a shaped article of polyglycolic acid, treating said article to remove residual solvent, and stretching said article to orient the polyglycolic acid.  
  3. A process for preparing a cast film of polyglycolic acid which comprises depositing a solution comprising polyglycolic acid, having a crystalline melting point between about 222C and 235C and having a degree of I crystallinity not greater than about 30 percent, dissolved in hexafluoroisopropyl alcohol, in an amount varying between 0.01 and 30 percent by weight of polyglycolic acid based on the total weight of the solution, on to a surface and thereupon removing said solvent to deposit a film of polyglycolic acid upon said surface.  
  4. A process for preparing a cast film of polyglycolic acid, having a crystalline melting point between about 222 and 235C and having a degree of crystallinity not exceeding about percent, dissolved in hexafluoroacetone sesquihydrate, in an amount varying between about 0.01 and 40 percent by weight of said polyglycolic acid based on the total weight of the solution, on to a surface and thereupon removing said solvent to deposit a film of polyglycolic acid upon said surface.  
 Patent No. 3 878, 284  
  UNETED STATES PATENT OFFICE QETEFICATE GE CORRECTION Dated April 15, 1975 Inventor(s) EDWARD E, SCHMITT and WILLIAM J. BAILEY It is certified that error appears in the above-identified patent and that said&#39;Letters Patent are hereby corrected as shown below:  
 Column 1, line 52, insert before &#34;hydroxy&#34;;  
 Column 1, line 53, insert J before &#34;hydroxy&#34;;  
 Column 7, line 6, delete &#34;6&#34; and insert therefor weight [SEAL] fiigned and Sealed this ninth Day of September 1975 A ttest:  
 RUTH C. MASON Arresting Officer C. MARSHALL DANN (mmnissimwr oflatenrs and Trademarks