Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
  • C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
• • D—TEXTILES; PAPER
  • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
  • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
  • D01D5/00—Formation of filaments, threads, or the like
  • D01D5/06—Wet spinning methods
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
  • C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
  • C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
  • C08B37/0009—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid alpha-D-Glucans, e.g. polydextrose, alternan, glycogen; (alpha-1,4)(alpha-1,6)-D-Glucans; (alpha-1,3)(alpha-1,4)-D-Glucans, e.g. isolichenan or nigeran; (alpha-1,4)-D-Glucans; (alpha-1,3)-D-Glucans, e.g. pseudonigeran; Derivatives thereof
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
  • C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
  • C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
  • C08B37/0009—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid alpha-D-Glucans, e.g. polydextrose, alternan, glycogen; (alpha-1,4)(alpha-1,6)-D-Glucans; (alpha-1,3)(alpha-1,4)-D-Glucans, e.g. isolichenan or nigeran; (alpha-1,4)-D-Glucans; (alpha-1,3)-D-Glucans, e.g. pseudonigeran; Derivatives thereof
  • C08B37/0021—Dextran, i.e. (alpha-1,4)-D-glucan; Derivatives thereof, e.g. Sephadex, i.e. crosslinked dextran
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L5/00—Compositions of polysaccharides or of their derivatives not provided for in groups C08L1/00 or C08L3/00
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L5/00—Compositions of polysaccharides or of their derivatives not provided for in groups C08L1/00 or C08L3/00
  • C08L5/02—Dextran; Derivatives thereof
• • D—TEXTILES; PAPER
  • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
  • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
  • D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
• • D—TEXTILES; PAPER
  • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
  • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
  • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S424/00—Drug, bio-affecting and body treating compositions
  • Y10S424/13—Burn treatment

Definitions

• the present invention is directed to a process for forming fibers of poly(a(1 ⁇ 3) glucan) by solution spinning a solution of xanthated poly(a(1 ⁇ 3) glucan) in an aqueous alkali metal hydroxide and to the solution itself.
• the poly(a(1 ⁇ 3) glucan) employed was synthesized by fermentation.
• polysaccharide polymers are also disclosed therein.
• glucan polymer characterized by a(1 ⁇ 3) glycoside linkages, has been isolated by contacting an aqueous solution of sucrose with GtfJ
• polysaccharides to such a hot aqueous environment results in chain cleavage and loss of molecular weight, with concomitant degradation of mechanical properties.
• Polysaccharides based on glucose and glucose itself are particularly important because of their prominent role in photosynthesis and metabolic processes.
• Cellulose and starch, both based on molecular chains of polyanhydroglucose are the most abundant polymers on earth and are of great commercial importance.
• Such polymers offer materials that are environmentally benign throughout their entire life cycle and are constructed from renewable energy and raw materials sources.
• glucan is a term of art that refers to a polysaccharide comprising beta-D-glucose monomer units that are linked in eight possible ways.
• Cellulose is a glucan.
• the repeating monomeric units can be linked in a variety of configurations following an enchainment pattern.
• the nature of the enchainment pattern depends, in part, on how the ring closes when an aldohexose ring closes to form a hemiacetal.
• the open chain form of glucose an aldohexose
• has four asymmetric centers see below.
• D and L glucose are two.
• a new asymmetric center is created at C1 thus making 5 asymmetric carbons.
• ⁇ (1 ⁇ 4)- ⁇ inked polymer e.g.
• starch or ⁇ (1 ⁇ 4)- linked polymer, e.g. cellulose, can be formed upon further condensation to polymer.
• the configuration at C1 in the polymer determines whether it is an alpha or beta linked polymer, and the numbers in parenthesis following alpha or beta refer to the carbon atoms through which enchainment takes place. 1 1
• the properties exhibited by a glucan polymer are determined by the enchainment pattern.
• the very different properties of cellulose and starch are determined by the respective nature of their enchainment patterns.
• Starch or amylose consists of a(1 ⁇ 4) linked glucose and does not form fibers among other things because it is swollen or dissolved by water.
• cellulose consists of ⁇ (1 ⁇ 4) linked glucose, and makes an excellent structural material being both crystalline and hydrophobic, and is commonly used for textile applications as cotton fiber, as well as for structures in the form of wood.
• cotton has evolved under constraints wherein the polysaccharide structure and physical properties have not been optimized for textile uses.
• cotton fiber is of short fiber length, limited variation in cross section and fiber fineness and is produced in a highly labor and land intensive process.
• U.S. Patent No. 7,000,000 discloses a process for preparing fiber from liquid crystalline solutions of acetylated poly(a(1 ⁇ 3) glucan). The thus prepared fiber was then de-acetylated resulting in a fiber of poly(a(1 ⁇ 3) glucan). Summary Of The Invention
• the present invention is directed to a solution comprising 0.75 to 2 molar aqueous alkali metal hydroxide and a solids content of 5 to 20 % by weight of xanthated poly(a(1 ⁇ 3) glucan); wherein the number average molecular weight of the xanthated poly(a(1 ⁇ 3) glucan) is at least 10,000 Daltons; and, wherein the degree of xanthation of the xanthated poly(a(1 ⁇ 3) glucan) lies in the range of 0.1 to 1 .
• the present invention is directed to a process comprising forming a solution by dissolving in a 0.75 to 2 molar aqueous alkali metal hydroxide, CS2, and 5 to 20 percent by weight of the total weight of the resulting solution of poly(a(1 - 3) glucan) characterized by a number average molecular weight of at least 10,000 Da, causing said solution to flow through a spinneret, forming a fiber thereby; and contacting said fiber with an acidic liquid coagulant; wherein said process the weight ratio of CS2 to poly(a(1 - 3) glucan) lies in the range of 0.1 to 1 .0.
• FIG. 1 is a schematic diagram of an apparatus suitable for air gap or wet spinning of the aqueous alkali metal hydroxide solutions of PAGX hereof. Detailed Description
• solids content is a term of art. It is used herein to refer to the percentage by weight of xanthated poly(a(1 - 3) glucan) (PAGX) in the aqueous alkali metal hydroxide solution hereof (MOH (aq). It is calculated from the formula:
• Wt(PAGX) + Wt(MOH(aq)) where SC represents "solids content,” and Wt(PAGX), Wt(MOH(aq)) are respectively weights of the poly(a(1 ⁇ 3) glucan) xanthate (PAGX), and of the aqueous alkali metal hydroxide.
• solids content is synonymous with the concentration by weight of xanthated poly(a(1 ⁇ 3) glucan) with respect to the total weight of solution.
• Percent by weight is represented by the term "wt-%.”
• MOH alkali metal hydroxide suitable for the practice of the invention.
• MOH(aq) aqueous alkali metal hydroxide solution suitable for the practice of the invention. It shall be understood that the expression “concentration of the MOH(aq)” shall refer to the molarity of the aqueous alkali metal hydroxide solution hereof.
• a polymer including glucan, and poly(a(1 ⁇ 3) glucan) (PAG) in particular, is made up of a plurality of so-called repeat units covalently linked to one another.
• the repeat units in a polymer chain are diradicals, the radical form providing the chemical bonding between repeat units.
• the term "glucose repeat units” shall refer to the diradical form of glucose that is linked to other diradicals in the polymer chain, thereby forming said polymer chain.
• glucan refers to polymers, including oligomers and low molecular weight polymers that are unsuitable for fiber formation.
• the glucan polymer suitable for the practice of the invention is a poly(a(1 ⁇ 3) glucan) or xanthated poly(a(1 ⁇ 3) glucan), characterized by a number average molecular weight of at least 10,000 Daltons, preferably of at least 40,000 - 100,000 Daltons.
• Suitable PAGX is characterized by a degree of xanthation in the range of 0.1 to 1 .
• xanthation is a term of art referring to the reaction of a hydroxyl group with CS 2 in alkali metal hydroxide, according to the following reaction:
• each cyclic hexose repeat unit offers three hydroxyls for potential reaction to form the xanthate according to the above reaction scheme.
• degree of xanthation refers to the average percentage of available hydroxyl sites in each repeat unit that have actually undergone reaction to the xanthate.
• the theoretical maximum degree of xanthation a suitable PAG polymer molecule can undergo is 3 - that is, every single hydroxyl site in the polymer would have undergone reaction.
• suitable PAGX polymers have undergone xanthation to the degree of 0.1 to 1 . This means that on the average between one hydroxyl site per ten repeat units, and 10 hydroxyl sites per ten repeat units have undergone the xanthation reaction, while the theoretical maximum would be 30 hydroxyl sites per ten repeat units.
• the present invention is directed to a solution comprising 0.75 to 2 molar aqueous alkali metal hydroxide and a solids content of 5 to 20 % by weight of PAGX; wherein the number average molecular weight of the PAGX is at least 10,000 Daltons; and, wherein the degress of xanthation of the PAGX lies in the range of 0.1 to 1 .
• the alkali metal hydroxide (MOH) is sodium hydroxide.
• concentration of the NaOH is in the range of 1 .0 to 1 .7 M.
• the solids concentration is in the range of 7.5 to 15 %.
• the PAG suitable for use in the process of the present invention is a glucan characterized by a number average molecular weight (M n ) of at least 10,000 Da wherein at least 90 mol-% of the repeat units in the polymer are glucose repeat units and at least 50% of the linkages between glucose repeat units are a(1 - 3) glycoside linkages.
• M n number average molecular weight
• at least 95 mol-%, most preferably 100 mol-%, of the repeat units are glucose repeat units.
• at least 90 %, most preferably 100 %, of the linkages between glucose units are ⁇ (1 - 3) glycoside linkages.
• polysaccharides The isolation and purification of various polysaccharides is described in, for example, The Polysaccharides, G. O. Aspinall, Vol. 1 , Chap. 2, Academic Press, New York, 1983. Any means for producing the a(1 ⁇ 3) polysaccharide suitable for the invention in satisfactory yield and 90 % purity is suitable.
• poly(a(1 ⁇ 3)-D-glucose) is formed by contacting an aqueous solution of sucrose with gtfJ glucosyltransferase isolated from
• the gtfJ is generated by genetically modified E. Coli, as described in detail, infra.
• the PAG suitable for use in the present invention can further comprise repeat units linked by a glycoside linkage other than a(1 ⁇ 3), including a(1 ⁇ 4), a(1 ⁇ 6), ⁇ (1 ⁇ 2), ⁇ (1 ⁇ 3), ⁇ (1 ⁇ 4) or ⁇ (1 ⁇ 6) or any combination thereof.
• at least 50% of the glycoside linkages in the polymer are a(1 ⁇ 3) glycoside linkages.
• Preferably at least 90 %, most preferably 100 %, of the linkages between glucose units are ⁇ (1 - 3) glycoside linkages.
• the solution hereof is prepared by adding a suitable PAG to MOH(aq), containing carbon disulfide and agitating to obtain thorough mixing. PAGX is formed in situ under these conditions.
• the solids content of PAGX in the solution ranges from 5 to 20 % by weight with respect to the total weight of the solution. When solids content of PAGX is below 5 %, the fiber-forming capability of the solution is greatly degraded. Solutions with solids content above 15 % are increasingly problematical to form, requiring increasingly refined solution forming techniques.
• the solubility limit of PAGX is a function of the molecular weight of the PAGX, the concentration of the MOH(aq), the degree of xanthation, the duration of mixing, the viscosity of the solution as it is being formed, the shear forces to which the solution is subject, and the temperature at which mixing takes place. Generally, higher shear mixing and higher temperature will be
• the maximum temperature for mixing is limited 46 °C, the boiling point of the CS2. From the standpoint of solubility and spinnability, the optimum concentrations of the MOH(aq) and CS2 may change depending upon the other parameters in the mixing process.
• CS2 with the PAG to form the xanthate occurs quantitatively within about one to three hours at room temperature.
• the xanthate so formed has also been observed to be chemically unstable, degrading completely into a variety of by-products after approximately 36 hours of solution time. It is therefore incumbent upon the
• solution hereof for fiber spinning after the time required for formation of the xanthate but before significant degradation can occur.
• spinning is thus performed preferably between 1 to 3 hours of solution time, depending upon the reaction time for xanthate formation.
• solution time refers to the time elapsed from when the ingredients of the solution are first combined.
• the ingredients are combined, allowed to stand for 1 to 3 hours, and then spun into fiber as described in detail, infra.
• a solution time on the order of 1 -5 hours is also suitable.
• the present invention is further directed to a process comprising forming a solution by dissolving in a 0.75 to 2 molar aqueous alkali metal hydroxide, CS 2 , and 5 to 15 percent by weight of the total weight of the resulting solution of PAG
• the alkali metal (M) is sodium.
• a suitable PAG is one wherein 100 % of the repeat units are glucose, and 100 % of the linkages between glucose repeat units are a(1 ⁇ 3) glycoside linkages.
• the minimum solids content of PAGX required in the solution in order to achieve stable fiber formation varies according to the molecular weight of the PAGX, as well as the degree of xanthation. It is found in the practice of the invention that a 5% solids content is an approximate lower limit to the
• a solution having a solids content of at least 7.5 % is preferred.
• a solids content ranging from about 7.5 % to about 15 % in a 1 .0 to 1 .7 M NaOH solution is more preferred.
• Preferred is a PAGX characterized by a number average molecular weight in the range of 40,000 - 100,000 Daltons and degree of xanthation in the range of 0.1 - 1 .
• Spinning from the solution hereof can be accomplished by means known in the art, and as described in O'Brien, op. cit.
• the viscous spinning solution can be forced by means such as the push of a piston or the action of a pump through a single or multi-holed spinneret or other form of die.
• the spinneret holes can be of any cross- sectional shape, including round, flat, multi-lobal, and the like, as are known in the art.
• the extruded strand can then be passed by ordinary means into a coagulation bath wherein is contained a liquid coagulant which converts the PAGX back to PAG, causing the polymer to coagulate into a fiber according to the present invention.
• Suitable liquid coagulants include but are not limited to glacial acetic acid, aqueous acetic acid, sulfuric acid, combinations of sulfuric acid, sodium sulfate, and zinc sulfate.
• the liquid coagulant is maintained at a temperature in the range of 0 - 100 °C, and preferably in the range of 15 - 70 °C.
• the coagulation bath comprises glacial acetic acid. It is found in the practice of the invention that satisfactory results are achieved by employing as the coagulant liquid an excess of glacial acetic acid. During the course of spinning, the glacial acetic acid neutralizes aqueous NaOH and regenerates PAG from PAGX as the spun fiber passes through the coagulant bath.
• extrusion is effected directly into the coagulation bath.
• the spinneret is partially or fully immersed in the coagulation bath.
• the spinnerets and associated fittings should be constructed of corrosion resistant alloys such as stainless steel or platinum/gold.
• the thus coagulated fiber is then passed into a second bath provided to neutralize and dilute residual acid from the coagulation bath.
• the secondary bath preferably contains H 2 O, methanol, or 5 % aqueous NaHCO3, or a mixture thereof.
• Aqueous NaHCO3 is preferred.
• the wound fiber package is soaked in one or more neutralizing wash baths for a period of time up to four hours in each bath. A sequence of baths comprising respectively 5 % aqueous NaHCO3, methanol, and H 2 O, has been found satisfactory.
• Dialysis tubing (Spectrapor 25225-226, 12000 molecular weight cut-off) was obained from VWR (Radnor, PA).
• Suppressor 7153 antifoam was obtained from Cognis Corporation (Cincinnati,
• the seed medium used to grow the starter cultures for the fermenters, contained: yeast extract (Amberx 695, 5.0 grams per liter (g/L)), K 2 HPO 4 (10.0 g/L), KH 2 PO 4 (7.0 g/L), sodium citrate dihydrate (1 .0 g/L), (NH 4 ) 2 SO 4 (4.0 g/L), MgSO 4 heptahydrate (1 .0 g/L) and ferric ammonium citrate (0.10 g/L).
• the pH of the medium was adjusted to 6.8 using either 5N NaOH or H 2 SO 4 and the medium was sterilized in the flask. Post sterilization additions included glucose (20 mL/L of a 50% w/w solution) and ampicillin (4 mL/L of a 25 mg/mL stock solution).
• the growth medium used in the fermenter contained: KH 2 PO 4 (3.50 g/L), FeSO 4 heptahydrate (0.05 g/L), MgSO 4 heptahydrate (2.0 g/L), sodium citrate dihydrate (1 .90 g/L), yeast extract (Ambrex 695, 5.0 g/L), Suppressor 7153 antifoam (0.25 milliliters per liter, mL/L), NaCI (1 .0 g/L), CaCI 2 dihydrate (10 g/L), and NIT trace elements solution (10 mL/L).
• the NIT trace elements solution contained citric acid monohydrate (10 g/L), MnSO 4 hydrate (2 g/L), NaCI (2 g/L), FeSO 4 heptahydrate (0.5 g/L), ZnSO 4 heptahydrate (0.2 g/L), CuSO 4 pentahydrate (0.02 g/L) and NaMoO 4 dihydrate (0.02 g/L).
• Post sterilization additions included glucose (12.5 g/L of a 50% w/w solution) and ampicillin (4 mL/L of a 25 mg/mL stock solution).
• Production of the recombinant gtfJ enzyme in a fermenter was initiated by expressing the gtfJ enzyme, constructed as described supra. A 10 ml_ aliquot of the seed medium was added into a 125 mL disposable baffled flask and was inoculated with a 1 .0 mL culture of the E. coli MG1655/pMP52 prepared supra, in 20% glycerol. This culture was allowed to grow at 37 °C while shaking at 300 revolutions per minute (rpm) for 3 hours.
• the cell paste obtained above was suspended at 150 g/L in 50 mM potassium phosphate buffer pH 7.2 to prepare a slurry.
• the slurry was homogenized at 12,000 psi (Rannie-type machine, APV-1000 or APV 16.56) and the homogenate chilled to 4 °C.
• 50 g of a floe solution Aldrich no. 409138, 5% in 50 mM sodium phosphate buffer pH 7.0
• Agitation was reduced to light stirring for 15 minutes.
• the cell homogenate was then clarified by centrifugation at 4500 rpm for 3 hours at 5-10 °C.
• FIG. 1 is a schematic diagram of an apparatus suitable for use in the fiber spinning process hereof.
• the worm gear drive, 1 drives a ram, 2, at a controlled rate onto a piston fitted into a spinning cell, 3.
• the spinning cell may contain filter assemblies.
• a suitable filter assembly includes 100 and 325 mesh stainless steel screens.
• a spin pack, 4, contains the spinneret, 5, and optionally stainless steel screens as prefilters for the spinneret.
• the extruded filament, 6, produced therefrom is directed into a liquid coagulation bath, 7. In all the examples listed in Table 1 , the filament was extruded from the spinneret directly into the liquid coagulation bath - the bottom of the spinneret was immersed in the bath.
• the extrudate can be, but need not be, directed back and forth through the bath between guides, 8, which are normally fabricated of Teflon® PTFE. Only one pass through the bath is shown in Figure 1 .
• the thus quenched filament, 9, can optionally be directed through a drawing zone using an independently driven roll, 10, around which the thus quenched filament is wrapped.
• the quenched filament may optionally be directed through a draw bath, 11 , that allows further treatment such as additional solvent extraction, washing or drawing of the extruded filaments.
• the thus prepared filament is then directed through a traversing mechanism, 12, to evenly distribute the fiber on the bobbin, and collected on plastic bobbins using a wind up, 13.
• the process comprises a plurality of independently driven rolls.
• the driven roll, 10, is removed from the fiber pathway, but the fiber is nevertheless immersed in the draw bath.
• the two are independent of each other. In all of the examples, infra, the driven roll, 10, was removed from the fiber pathway.
• a plurality of filaments is extruded through a multi-hole spinneret, and the filaments so produced are converged to form a yarn.
• the process further comprises a plurality of multi-hole spinnerets so that a plurality of yarns can be prepared simultaneously.
• the wound bobbin of fiber produced was soaked overnight in a bucket of the liquid indicated in Table 1 .
• the thus soaked bobbin of fiber was then air dried for at least 24 hours.
• the fiber tensile properties were then determined according to ASTM D2101 -82.
• the spin cell, the piston, the connecting tubing and the spinneret were all constructed of stainless steel. Fiber Physical Property Measurement.
• the physical properties were determined for every fiber prepared. The results are shown in Table 1 . Included are the denier of the fiber produced, and the physical properties such as tenacity (T) in grams per denier (gpd), elongation to break (E, %), and initial modulus (M) in gpd.
• Molecular weights were determined by size exclusion chromatography (SEC) with a GPCV/LS 2000TM (Waters Corporation, Milford, MA) chromatograph equipped with two Zorbax PSM Bimodal-s silica columns (Agilent, Wilmington, DE), using DMAc from J.T Baker, Phillipsburg, NJ with 3.0% LiCI (Aldrich, Milwaukee, Wl) as the mobile phase. Samples were dissolved in DMAc with 5.0% LiCI. Number and weight average molecular weights (Mn and Mw) were found to be 139,000 and 279,000 Daltons respectively.
• a 250 ml_ wide mouth glass bottle was charged with 25 g of polymer P1 and 225 g of 5 wt % sodium hydroxide.
• CS2 (7.5 g) was then added via a syringe.
• the container was fitted with a cap and a septum through which a polypropylene stirring rod had been fitted.
• the contents were manually mixed with the stirring rod and then allowed to stand at room temperature overnight.
• the partially dissolved solution (clear but containing a small amount of visible particulate) was transferred into a spin cell and piston containing screen packs including 100 and 325 mesh stainless steel screens.
• a piston was fitted over the viscous mixture.
• Example 1 Approximately 20 hours after the preparation of the solution of Example 1 , the solution thus prepared was fed to the spinning apparatus, as described, supra, referring to Figure 1 .
• the solution was fed to a 20 hole spinneret wherein each hole was characterized by a circular cross-section, a diameter of 0.003 in and a length of 0.006 in.
• Table 1 provides the spinning conditions that were used for the fibers prepared in Examples 2 - 4.
• the apparatus depicted in Figure 1 was modified by removal of the driven roll, 10, from the filament pathway in Examples 1 -3.
• the indicated spin stretch was attained by running the windup faster than the jet velocity.
• Example 1 The solution of Example 1 was metered at the rates shown in Table 1 through a spin pack having a filter assembly consisting of 100 and 325 mesh screens to the spinneret.
• the spinneret was immersed into a water coagulation bath containing, by weight, 8% H 2 SO 4 , 23% Na 2 SO 4 , and 0.5% ZnSO 4
• the filament was extruded directly into the quench bath vertically at the temperature indicated in Table 1 .
• Additional residence time in the 6 foot long coagulation bath was increased by directing the fiber over additional guide pins (8) for a total immersion distance of 4.1 or 1 1 ft. as indicated.
• Example 2 upon removal from the coagulation bath the thus coagulated filaments was directed to a speed controlled wind-up with a traversing guide, at wind-up speeds shown in Table 1 .
• Example 4 the coagulated filaments were directed to a second bath of methanol for the length and at the temperature indicated in Table 1 .
• several hundred feel of fiber were wound onto a bobbin.
• the fiber bobbins of Examples 2 - 4 were soaked sequentially respectively in 5% NaHCO3, MeOH, and H2O baths for a period of about 4 hours in each. The fiber was allowed to air dry before being subject to physical measurements Physical properties were determined; results are shown in Table 1 .
• Poly(a(1 - 3) glucan) polymer was synthesized, washed, and isolated using the materials and procedures employed for the preparation of Polymer P1 in
• Example 1 except that 200 ml of the enzyme extract was added to the pH-adjusted sucrose/dextran/boric acid solution instead of 180 ml. Yield: 246.08 grams of white flaky solids.
• Mn and Mw were determined as for polymer P1 to be 129,000 and 270,000 respectively.
• a 250 ml_ wide mouth glass bottle was charged with 18 g of polymer P2 and 225 g of 4.5 wt % sodium hydroxide.
• CS 2 (2.7 g)
• the container was fitted with a cap and a septum through which a polypropylene stirring rod had been fitted.
• the contents were manually mixed with the stirring rod and then allowed to stand at room temperature overnight.
• the partially dissolved solution was transferred into a spin cell and piston containing screen packs including 325 mesh stainless steel screens.
• a piston was fitted over the viscous mixture.
• the mixture was then pumped back and forth through 13 cycles using a motorized worm gear driven ram into an identically equipped spinning cell coupled head to head with the first cell via a coupler fabricated from 1 ⁇ 4 inch stainless steel tubing.
• Example 5 in the manner of the fibers of Examples 2 - 4, supra, under the conditions shown in Table 1 .
• the filament was extruded directly into a coagulation bath containing 5 % H 2 SO 4 (aq.).
• Example 10 the fiber was extruded directly into a coagulation bath containing glacial acetic acid.
• Example 1 into 50/50 acetic acid/ water (v/v) Additional length in the coagulation bath was provided by directing the fiber over additional guide pins (8) for a total immersion distance of 3, 4.3, or 4.5 ft.
• Example 7 upon removal from the coagulation bath the thus coagulated filament was directed through a second bath (11) of methanol at lengths and temperatures indicated in Table 1 .
• the fiber of Example 6 was guided directly to the wind-up. From the second bath, the coagulated fibers of Examples 7 - 1 1 were directed to the wind-up, at the wind-up speeds shown in Table 1 .
• the fiber bobbins were soaked as in Examples 2 - 4.
• a 250 ml_ wide mouth glass bottle was charged with 20 g of Polymer P2 and 180 g of 4.5 wt% sodium hydroxide.
• CS2 (3.0 g)
• the container was fitted with a cap and septum through which a polypropylene stirring rod had been fitted.
• the contents were manually mixed with the plastic stirrer and then allowed to stand 2 days.
• the partially dissolved solution was transferred into a 300 ml_ stainless steel cylinder fitted with 2x 100 mesh, 1x 325 mesh and 2x 20 mesh stainless steel screens.
• a piston was fitted over the viscous mixture.
• the mixture was then pumped back and forth through 13 cycles using a motorized worm gear driven ram into an identically equipped spinning cell coupled head to head with the first cell via a coupler fabricated from 1 ⁇ 4 inch stainless steel tubing.
• the fibers of Examples 13 - 15 were spun from the spinning solution of Example 12 in the manner of the fibers of Examples 2 - 4, supra, under the conditions shown in Table 1 .
• the fibers were extruded directly into 5% H 2 SO 4 (aq.) at the temperature indicated in Table 1 .
• the thus coagulated fibers upon removal from the coagulation bath were directed to the wind-up at wind-up speeds shown in Table 1 .
• the coagulated fibers of Examples 14 and 15 were first passed through the second bath, as indicated in Table 1 .
• the fiber bobbins were soaked and dried as in Examples 2 - 4.
• Poly(a(1 - 3) glucan) polymer was synthesized, washed, and isolated using the materials and procedures employed for the preparation of Polymer P1 in
• Example 1 except that 200 ml of the enzyme extract was added to the pH-adjusted sucrose/dextran/boric acid solution instead of 180 ml. Yield: 228.52 grams of white flaky solids. M n was 132,000 Daltons; M w was 301 ,000 Daltons. Example 16 Spinning Solution
• a 250 ml_ wide mouth glass bottle was charged with 18 g of polymer P3 and 225 g of 4.5 wt % sodium hydroxide.
• the container was fitted with a cap and a septum through which a polypropylene stirring rod had been fitted.
• the contents were manually mixed with the stirring rod and then allowed to stand at room temperature overnight.
• CS2 (5.4 g), was then added via syringe the following morning.
• the partially dissolved solution was immediately transferred into a spin cell and piston containing screen packs including 325 mesh stainless steel screens.
• a piston was fitted over the viscous mixture.
• the mixture was then pumped back and forth through 13 cycles using a motorized worm gear driven ram into an identically equipped spinning cell coupled head to head with the first cell via a coupler fabricated from 1 ⁇ 4 inch stainless steel tubing.
• Table 1 gives the spinning conditions that were used for the fibers prepared in Examples 17-23.
• the apparatus depicted in Figure 1 was modified by removal of the driven roll, 10, from the filament pathway. Spin stretch was attained by running the windup faster than the jet velocity.
• the spinning solution thus prepared was metered at the rates shown in Table 1 through a spin pack having a filter assembly consisting of 100 and 325 mesh stainless steel screens to a 20-hole spinneret having .003 inch diameter and .006 inch length holes.
• the filament was extruded directly into 5 % H 2 SO 4 for Examples 17-19 and 10% H 2 SO for Examples 20-23 at the coagulation bath temperature shown in Table 1 .
• the thus coagulated filament was directed through a second bath (11) of methanol at lengths and temperatures shown in Table 1 , and thence to the wind-up.
• the filaments of Examples 17, 20, and 21 were guided directly to the wind-up.
• the second bath in the case of Example 23 was filled with water. Fiber spinning was completed within 8 hours from the addition of carbon disulfide.
• the fiber bobbins were soaked in 5% NaHCO3 for 15 minutes, then soaked in water overnight. The bobbins were then removed and allowed to air dry before being subjected to physical measurements.
• a 250 ml_ wide mouth glass bottle was charged with 32.9 g of polymer P3 and 220 g of 5 wt % sodium hydroxide.
• the container was fitted with a cap and a septum through which a polypropylene stirring rod had been fitted.
• the contents were manually mixed with the stirring rod and then allowed to stand at room temperature overnight.
• CS2 (9.9 g) was then added via syringe the following morning.
• the partially dissolved solution was immediately transferred into a spin cell and piston containing screen packs including 325 mesh stainless steel screens.
• a piston was fitted over the viscous mixture.
• the mixture was then pumped back and forth through 1 1 cycles using a motorized worm gear driven ram into an identically equipped spinning cell coupled head to head with the first cell via a coupler fabricated from 1 ⁇ 4 inch stainless steel tubing.
• Table 1 gives the spinning conditions that were used for the fibers prepared in Examples 25-31 .
• the apparatus depicted in Figure 1 was modified by removal of the driven roll, 10, from the filament pathway for Examples 25-27. Spin stretch was attained by running the windup faster than the jet velocity.
• the spinning solution thus prepared was metered at the rates shown in Table 1 through a spin pack having a filter assembly consisting of 100 and 325 mesh stainless steel screens to a 20-hole spinneret having .003 inch diameter and .006 inch length holes.
• the filament was extruded directly into 10% H 2 SO 4 for Examples 25-30 and glacial acetic acid for Example 31 at the coagulation bath temperature shown in Table 1 .
• the fiber bobbins were soaked in 5% NaHCO3 overnight, and then soaked in water for an additional day. The bobbins were then removed and allowed to air dry before being subjected to physical measurements.
• Example 45 Determination of glucan xanthate formation and decomposition using
• the NMR tubes were removed from the centrifuge and placed in the magnet of a Bruker 500 MHz Avance II Spectrometer equipped with a 5mm CPDUL cryoprobe having z gradients. The probe was tuned and the magnet was shimmed before starting a series of consecutive experiments to investigate the formation and degradation of poly(a(1 - 3) glucan) .
• Each experiment was acquired using the Bruker zgig pulse sequence with a spectral width of 33333.3 Hz (265.0 ppm), a transmitter offset of 160 ppm, and 32768 time domain points for an acquisition time of 0.4916 sec. A 3 sec. delay was used between pulses and 3000 scans were acquired for each experiment, giving a total time of 2 hours and 56 minutes for each experiment.

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