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    • 专利摘要:
    SOLUTION AND PROCESS. Solutions formed by combining poly (Alpha (1-3) glucan) with CS2 in aqueous alkali metal hydroxide solution have been shown to produce the xanthate form of poly (Alpha (1-3) glucan). Solutions thus formed have proven to be useful for solution spinning in the poly (Alpha (1-3) glucan) fiber when the spun fiber is coagulated in an acidic coagulation bath. The fibers thus produced exhibited desired physical properties. The poly (Alpha (1-3) glucan) used was synthesized by fermentation
    公开号:BR112014028870B1
    申请号:R112014028870-4
    申请日:2013-05-23
    公开日:2020-12-29
    发明作者:John P. O'brien
    申请人:Dupont Industrial Biosciences Usa, Llc；
    IPC主号:
    专利说明:

    FIELD OF THE INVENTION
    [001] The present invention is directed to a process for forming poly (α (1 ^ 3) glucan) fibers by spinning a solution of a solution of poly (α (1 ^ 3) glucan) in a metal hydroxide aqueous alkali and the solution itself. The poly (α (1 ^ 3) glucan) used was synthesized by fermentation. BACKGROUND OF THE INVENTION
    [002] Polysaccharides have been known since the dawn of civilization mainly in the form of cellulose, a polymer formed from glucose through natural processes via β (1 ^ 4) glycoside bonds; see, for example, Applied Fiber Science, F. Happey, Ed., Chapter 8, E. Atkins, Academic Press, New York, 1979. Numerous other polysaccharide polymers are also described herein.
    [003] Only cellulose among the well-known polysaccharides achieved commercial prominence as a fiber. In particular, cotton, a highly pure form of naturally occurring cellulose, is well known for its beneficial attributes in textile applications.
    [004] It is also known that cellulose exhibits sufficient chain length and main chain stiffness in solution to form liquid crystalline solutions; see, for example O'Brien, U.S. Pat. No. 4,501,886. State-of-the-art teachings suggest that sufficient polysaccharide chain length can be obtained only in linked β (1 ^ 4) polysaccharides and that any major deviation from that main chain geometry would reduce the molecular aspect ratio to below that required for the formation of an ordered phase.
    [005] More recently, glucan polymer, characterized by α (1 ^ 3) glycoside bonds, was isolated by contact with an aqueous solution of sucrose with GtfJ glucosyltransferase isolated from Streptococcus salivarius, Simpson et al., Microbiology, vol 141, pp . 1451-1460 (1995). Highly oriented, highly crystalline, low molecular weight films of α (1 ^ 3) -D-glucan were manufactured for the purpose of X-ray diffraction analysis, Ogawa et al., Fiber Diffraction Methods, 47, pp. 353-362 (1980). In Ogawa, the insoluble glucan polymer is acetylated, the acetylated glucan dissolved to form a 5% chloroform solution and the solution melted into a film. The film is then subjected to stretching in glycerin at 150 ° C, which guides the film and stretches it to a length 6.5 times the original length of the film melted in solution. After stretching, the film is deacetylated and crystallized by tempering in water superheated to 140 ° C. in a pressure vessel. It is well known in the art that exposure of polysaccharides in such a warm aqueous environment results in chain cleavage and loss of molecular weight with concomitant degradation of mechanical properties.
    [006] Polysaccharides based on glucose and glucose itself are particularly important due to their prominent role in photosynthesis and metabolic processes. Cellulose and starch, both based on molecular chains of polyanhydroglycosis, are the most abundant polymers on earth and are of great commercial importance. Such polymers offer materials that are compatible with the environment throughout their life cycle and are built from renewable energy and raw material sources.
    [007] The term "glucan" is a prior art term that refers to a polysaccharide comprising beta-D-glucose monomer units that are linked in eight possible ways. Cellulose is a glucan.
    [008] Within a glucan polymer the monomeric repeating units can be linked in a variety of configurations following a chaining pattern. The nature of the chaining 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). So there are 24 or 16 possible open chain forms of which D and L glucose are two. When the ring is closed a new asymmetric center is created in C1, thus producing 5 asymmetric carbons. Depending on how the ring closes, for glucose, α (1 ^ 4) -linked polymer, for example starch, or β (1 ^ 4) -linked polymer, for example cellulose, can be formed after further condensation to form polymer. The C1 configuration in the polymer determines whether it is an alpha- or beta-linked polymer and the numbers in parentheses following alpha or beta refer to the carbon atoms through which the chain occurs.
    [009] The properties exhibited by a glucan polymer are determined by the chaining pattern. For example, the very different properties of cellulose and starch are determined by the respective nature of their thread configurations. Starch or amylose consists of glucose α (1 ^ 4) bound and does not form fibers among other things as it is swollen or dissolved by water. On the other hand, cellulose consists of bound β (1 ^ 4) glucose and produces an excellent structural material, being both crystalline and hydrophobic and is commonly used for textile applications such as cotton fiber, as well as for structures in the form of wood.
    [010] Like other natural fibers, cotton has been developed under limitations and the polysaccharide structure and physical properties have not been optimized for textile applications. In particular, cotton fiber is of short fiber length, limited variation in cross section and fineness of fiber and is produced in a process of intensive labor and intensive use of the soil.
    [011] O'Brien, US patent document No. 7,000,000 describes a process for preparing fiber from liquid crystalline solutions of acetylated poly (α (1 ^ 3) glucan). The fiber thus prepared was then de-acetylated into a poly (α (1 ^ 3) glucan) fiber. BRIEF DESCRIPTION OF THE INVENTION
    [012] Considerable benefit increases the process by improving a highly oriented and crystalline poly (α (1 ^ 3) glucan) fiber without sacrificing molecular weight by spinning the fiber solution of the new solution.
    [013] In one aspect 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 poly (α (1 ^ 3) glucan) xanthanized; the numerical molecular weight of the poly (α (1 ^ 3) glucan) xanthate being at least 10,000 Daltons; and, since the degree of xanthogenation of the poly (α (1 ^ 3) glucan) xanthate is in the range of 0.1 to 1.
    [014] In another aspect, the present invention is directed to a process comprising the formation of a solution by dissolving in 0.75 to 2 molar aqueous alkali metal hydroxide, CS2, and 5 to 20% by weight of the total weight of the resulting solution poly (α (1 ^ 3) glucan) characterized by a numerical molecular weight of at least 10,000 Da, making the said solution flow through a die, thus forming a die; and placing said fiber in contact with an acidic liquid coagulant; being that in this process the weight ratio of CS2 to poly (α (1 ^ 3) glucan) is in the range of 0.1 to 1.0. BRIEF DESCRIPTION OF THE DRAWING
    [015] Figure 1 is a schematic diagram of equipment suitable for opening air or wet wiring of PAGX aqueous alkali metal hydroxide solutions. DETAILED DESCRIPTION
    [016] When a range of values is provided here, it is intended to include the end points of the range as long as there is no expressly different indication. Numerical values used here show the precision of the number of important figures provided, following the standard protocol in chemistry for important figures as highlighted in ASTM E29-08 section 6. For example, the number 40 encompasses a range of 35.0 to 44.9, while the number 40.0 encompasses a range from 39.50 to 40.49.
    [017] The term "solids content" is a term in the prior art. It is used here to refer to the percentage by weight of poly (α (1 ^ 3) glucan) xanthate (PAGX) in its aqueous alkali metal hydroxide solution (MOH (aq). It is calculated from the formula:
    where SC stands for “solids content” and Wt (PAGX), Wt (MOH (aq)) are respectively weights of poly (α (1 ^ 3) glucan) xanthate (PAGX), and aqueous alkali metal hydroxide. The term "solids content" is synonymous with the weight concentration of poly (α (1 ^ 3) glucan) xanthaned with respect to the total weight of the solution.
    [018] Percent by weight is represented by the term "% by weight."
    [019] The formula "MOH" should be used to refer to the alkali metal hydroxide suitable for the practice of the invention. The formula "MOH (aq)" should be used to refer to the aqueous alkali metal hydroxide solution suitable for the practice of the invention. It is understood that the expression “MOH concentration (aq)” refers to the molarity of the aqueous alkali metal hydroxide solution.
    [020] A polymer, including glucan, and poly (α (1 ^ 3) glucan) (PAG) in particular, consists of a plurality of so-called covalently linked repeating units. The repetition units in a polymeric chain are diradical, with the radical form providing the chemical bond between repetition units. For the purposes of the present invention, the term "glucose repeating units" refers to the diradical form of glucose that is linked to other diradicals in the polymer chain, thus forming said polymer chain.
    [021] The term "glucan" refers to polymers, including oligomers and low molecular weight polymers that are unsuitable for fiber formation. For the purposes of the present invention, the glucan polymer suitable for the practice of the invention is a poly (α (1 ^ 3) glucan) or poly (α (1 ^ 3) glucan) xanthanated, characterized by a numerical molecular weight of at least 10,000 Daltons, preferably at least 40,000 - 100,000 Daltons.
    [022] Suitable PAGX is characterized by a degree of xanthogenation in the range of 0.1 to 1. The term “xanthogenation” is a state of the art term that refers to the reaction of a hydroxyl group with CS2 in alkali metal hydroxide, according to with the following reaction:

    [023] In the case of PAG suitable for use in the process of the invention, each cyclic hexose repeat unit offers three hydroxyls for potential reaction to form the xanthate according to the above reaction scheme. The term "degree of xanthogenation" refers to the average percentage of hydroxyl sites available in each repetition unit that currently underwent reaction to form the xanthate. The theoretical maximum degree of xanthogenation of a suitable PAG polymer molecule that can undergo is 3 - that is, every single hydroxyl site in the polymer has undergone a reaction.
    [024] In accordance with the present invention, suitable PAGX polymers underwent xanthogenation in the degree of 0.1 to 1. This means that on average between one hydroxyl site per ten repeat units, and 10 hydroxyl sites per ten repeat units underwent the reaction of xanthogenation while the theoretical maximum should be 30 hydroxyl sites per ten repetition units.
    [025] In one aspect, 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; the numerical molecular weight of the PAGX being at least 10,000 Daltons; and the degree of xanthogenation of PAGX is in the range of 0.1 to 1.
    [026] In one embodiment, the alkali metal hydroxide (MOH) is sodium hydroxide. In another embodiment, the concentration of NaOH is in the range of 1.0 to 1.7 M.
    [027] In one embodiment, the concentration of solids is in the range of 7.5 to 15%.
    [028] The PAG suitable for use in the process of the present invention is a glucan characterized by a numerical weight molecular weight (Mn) of at least 10,000 Da with at least 90 mole percent of the repeating units in the polymer being glucose repeating units and at least 50% of the bonds between glucose repeat units are α (1 ^ 3) glycoside. Preferably at least 95 mole percent, most preferably 100 mole percent of the repeat units are glucose repeat units. Preferably at least 90%, most preferably 100% of the bonds between glucose units are α (1 ^ 3) glycoside.
    [029] The isolation and purification of various polysaccharides are described for example, The Polysaccharides, GO Aspinall, Vol. 1, chapter 2, Academic Press, New York, 1983. Any means of producing the α (1 ^ 3) polysaccharide suitable for the invention in satisfactory yield and 90% purity are suitable. In such a method, described in patent document 7,000,000, poly (α (1 ^ 3) -D-glucose) is formed by contacting an aqueous solution of sucrose with gtfJ glucosyltransferase isolated from Streptococcus salivarius according to the methods taught in the state of technical. In such an alternative method gtfJ is generated by genetically modified E. coli as described in detail below.
    [030] The PAG suitable for use in the present invention may also comprise repeating units linked by a glycoside bond other than that α (1 ^ 3), including α (1 ^ 4), α (1 ^ 6), β ( 1 ^ 2), β (1 ^ 3), β (1 ^ 4) or β (1 ^ 6) or any combination thereof. According to the present invention, at least 50% of the glycoside in the polymer is α (1 ^ 3) glycoside. Preferably at least 90%, most preferably 100%, of the bonds between glucose units are α (1 ^ 3) glycoside.
    [031] The solution of this is prepared by adding a PAG suitable for MOH (aq), containing carbon disulfite and by stirring to obtain complete 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. If the PAGX solids content is below 5%, the fiber forming capacity of the solution will be greatly affected. Solutions with solids contents above 15% become increasingly problematic to be formed, requiring more and more refined solution formation techniques.
    [032] In any given embodiment, the solubility limit of PAGX is a function of the molecular weight of PAGX, the concentration of MOH (aq), the degree of xanthogenation, the duration of mixing, the viscosity of the solution when it is being formed, the shear forces to which the solution is subjected and the temperature at which mixing takes place. In general, mixtures of higher shear and higher temperature are associated with greater solubility. The maximum temperature for mixing is limited to 46 ° C, the boiling point of CS2. From the point of view of solubility and spinning capacity, the ideal concentrations of MOH (aq) and CS2 can change depending on other parameters in the mixing process.
    [033] In the practice of the invention, it was found that the reaction of CS2 with PAG to form the xanthate occurs quantitatively in approximately one to three hours at room temperature. The xanthate thus formed has also been found to be chemically unstable, which degrades completely into a variety of by-products after approximately 36 hours of solution time. Therefore, it is up to the person skilled in the art to employ its solution for fiber spinning after the time required to form the xanthate but before significant degradation can occur. For the solution of this prepared at room temperature, the spinning is therefore carried out preferably between 1 to 3 hours of solution time, depending on the reaction time for formation of xanthate. The term "solution time" refers to the time that has elapsed since the ingredients of the solution were first combined. Therefore, in a preferred embodiment of the respective process, the ingredients are combined, left to stand for 1 to 3 hours and then spun to form fiber as described in detail above. In an embodiment that is somewhat less chemically preferred, but more preferred from a practical point of view, a solution time in the order of 1-5 hours is also suitable.
    [034] The present invention is also directed to a process comprising the formation of a solution by dissolving in 0.75 to 2 molar aqueous alkali metal hydroxide, CS2, and 5 to 15% by weight of the total weight of the solution resulting from PAG characterized by a numerical weight molecular weight of at least 10,000 Da; causing this solution to flow through a die, thus forming a fiber; and placing said fiber in contact with an acidic liquid coagulant; being that in this process a weight ratio of CS2 to PAG is in the range of 0.1 to 1.0.
    [035] In one embodiment, the alkali metal (M) is sodium.
    [036] In another embodiment of your process, a suitable PAG is one in which 100% of the repeat units are glucose, and 100% of the bonds between glucose repeat units are α (1 ^ 3) glycoside.
    [037] In the process, the minimum solids content of PAGX required in the solution in order to obtain stable fiber formation varies according to the molecular weight of the PAGX, as well as the degree of xanthogenation. It has been found in the practice of the invention that 5% solids content is an approximate lower limit in relation to the concentration required for the formation of stable fiber. In> 15%, especially in more than 20% solids, excessive amounts of undissolved PAGX are present, causing a degradation in fiber spinning performance. A solution with a solids content of at least 7.5% is preferred. A solids content ranging from approximately 7.5% to approximately 15% in a 1.0 to 1.7 M NaOH solution is preferred. A PAGX characterized by a numerical molecular weight in the range of 40,000 - 100,000 Daltons and degree of xanthogenation in the range of 0.1 - 1 is preferred.
    [038] Wiring of the solution thereof can be done 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 introduction of a piston or the action of a pump through a mutilated die or other form of matrix. The die holes can be of any cross-sectional shape including the Round, multi-lobal and similar shape as they are known in the art are known in the art. The extruded filament can then be passed through conventional means in a coagulation bath with a liquid coagulant being present which converts the PAGX back to PAG, causing the polymer to coagulate into a fiber according to the present invention.
    [039] 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. In one embodiment, the liquid coagulant is maintained at a temperature in the range of 0 - 100 ° C, and preferably in the range of 15 - 70 ° C.
    [040] In one embodiment, the coagulation bath comprises glacial acetic acid. It has been found in the practice of the invention that satisfactory results are obtained by employing an excess of liquid glacial acetic acid coagulant. During the spinning course, glacial acetic acid neutralizes aqueous NaOH and regenerates PAG from PAGX as the fiber spun through the coagulation bath.
    [041] In a preferred embodiment, extrusion is performed directly in the coagulation bath. In such a circumstance, known in the prior art as "wet spinning" the spinneret is partially or totally immersed in the coagulation bath. Spinners and associated equipment must be constructed of corrosion resistant alloys such as stainless steel or platinum / gold.
    [042] In one embodiment, the fiber thus coagulated is then passed in a second bath to neutralize and dilute residual acid in relation to the coagulation bath. The secondary bath preferably contains H2O, methanol, or 5% aqueous NaHCO3 or a mixture thereof. Aqueous NaHCO3 is preferred. In one embodiment, a bundle of rolled fiber is impregnated in one or more neutralizing wash baths for a period of time of up to four hours in each bath. A sequence of baths comprising NaHCO3, 5% methanol, and H2O, respectively, was found to be satisfactory.
    [043] The present invention is also described in but not limited to the following specific embodiments. EXAMPLES ENZYME PREPARATION GLUCOSYLTRANSFERASE (GTFJ) MATERIALS
    [044] Dialysis tubes (Spectrapor 25225-226, cutting molecular weight 12000) were obtained by VWR (Radnor, PA).
    [045] Dextran and ethanol were obtained by Sigma Aldrich. Sucrose was obtained from VWR.
    [046] Defoamer Suppressor 7153 was obtained by Cognis Corporation (Cincinnati, OH).
    [047] All other chemicals were obtained from the commonly used. SEED MIDDLE
    [048] The seed medium, used to grow lactic ferment for the fermenters present in: yeast extract (Amberx 695, 5.0 grams per liter (g / L)), K2HPO4 (10.0 g / L), KH2PO4 (7.0 g / L), sodium citrate dihydrate (1.0 g / L), (NH4) 2SO4 (4.0 g / L), MgSO4 heptahydrate (1.0 g / L) and ferric ammonium citrate (0.10 g / L). The pH of the medium was adjusted to 6.8 using 5N NaOH or H2SO4 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 concentrated solution). FERMENTING MEANS
    [049] The growth medium used in the fermenter contained: KH2PO4 (3.50 g / L), FeSO4 heptahydrate (0.05 g / L), MgSO4 heptahydrate (2.0 g / L), sodium citrate dihydrate (1.90 g / L), extract yeast (Ambrex 695, 5.0 g / L), defoamer Suppressor 7153 (0.25 milliliters per liter, mL / L), NaCl (1.0 g / L), CaCl2 dihydrate (10 g / L), and trace element solution NIT (10 mL / L). The NIT trace elements contained citric acid monohydrate (10 g / L), MnSO4 hydrate (2 g / L), NaCl (2 g / L), FeSO4 heptahydrate (0.5 g / L), ZnSO4 heptahydrate (0.2 g / L) ), CuSO4 pentahydrate (0.02 g / L) and NaMoO4 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 concentrated solution). CONSTRUCTION OF GLUCOSYLTRANSFERASE ENZYME EXPRESSION CEPA (GTFJ)
    [050] A gene encoding the mature glucosyltransferase enzyme (GtfJ; EC 2.4.1.5; GENBANK® AAA26896.1, SEQ ID NO: 3) from Streptococcus salivarius (ATCC 25975) was synthesized using codons optimized for expression in E. coli (DNA 2.0, Menlo Park CA). The nucleic acid product (SEQ ID NO: 1) was subcloned into pJexpress404® (DNA 2.0, Menlo Park CA) to generate the plasmid identified as pMP52 (SEQ ID NO: 2). Plasmid pMP52 was used to transform E. coli MG1655 (ATCC 47076) to generate the strain identified as MG1655 / pMP52.
    [051] Standard recombinant DNA and molecular cloning techniques used here are well known in the art and are described by Sambrook, J. and Russell, D., Molecular Cloning: A Laboratory Manual, Third Edition, Cold Spring Harbor Laboratory Press, Cold Spring Harbor, NY (2001); and by Silhavy, T. J., Bennan, M. L. and Enquist, L. W., Experiments with Gene Fusions, Cold Spring Harbor Laboratory Press, Cold Spring Harbor, NY (1984); and by Ausubel, F. M. et. al., Short Protocols in Molecular Biology, 5th Ed. Current Protocols, John Wiley and Sons, Inc., N.Y., 2002.
    [052] Suitable materials and methods for the maintenance and growth of microbial cultures are well known in the state of the art. Techniques suitable for use in the following examples can be considered as set out in Manual of Methods for General Bacteriology (Phillipp Gerhardt, RGE Murray, Ralph N. Costilow, Eugene W. Nester, Willis A. Wood, Noel R. Krieg and G. Briggs Phillips , Eds.), American Society for Microbiology: Washington, DC (1994)); or in the Manual of Industrial Microbiology and Biotechnology, 3rd Edition (Richard H. Baltz, Julian E. Davies, and Arnold L. Demain Eds.), ASM Press, Washington, DC, 2010. PRODUCTION OF RECOMBINANT GTFJ IN FERMENTATION
    [053] Production of the recombinant gtfJ enzyme in a fermenter was initiated by the expression of the gtfJ enzyme constructed as described above. A 10 ml aliquot of the seed medium was added to an Erlenmeyer flask with recesses in the 125 ml disposable bottom and inoculated with a 1.0 ml culture of E. coli MG1655 / pMP52 prepared above, in 20% glycerol. This culture was allowed to grow at 37 ° C while stirring at 300 revolutions per minute (rpm) for 3 hours.
    [054] A seed culture to start the fermenter was prepared by introducing it into a 2 L shaker bottle with 0.5 L of the seed medium. 1.0 mL of the pre-seed culture was aseptically transferred to 0.5 L of seed medium in the flask and grown at 37 ° C and 300 rpm for 5 hours. The seed culture was transferred at an ideal density 550 nm (OD550)> 2 to a 14 L fermenter (Braun, Perth Amboy, NJ) containing 8 L of the fermentor medium described above under 37 ° C.
    [055] E. coli MG1655 / pMP52 cells were allowed to grow in the fermenter and the introduction of glucose (50% w / w glucose solution containing 1% w / w MgSO47H2O) started when the glucose concentration in the medium decreased to 0.5 g / L. The introduction started at 0.36 grams of feed per minute (g feed / min) and progressively increased every hour to 0.42, 0.49, 0.57, 0.66, 0.77, 0.90, 1.04, 1.21, 1.41 1.63, 1.92, 2.2 g of feed / min respectively. The rate was subsequently kept constant by reducing or temporarily stopping the glucose supply when the glucose concentration exceeded 0.1 g / L. The glucose concentration in the medium was monitored using a YSI glucose analyzer (YSI, Yellow Springs, Ohio).
    [056] Induction of glucosyltransferase enzyme activity was initiated when cells reached an OD550 of 70, with the addition of 9 mL of 0.5 M IPTG (isopropyl β-D-1-thiogalactopyranoside). The concentration of dissolved oxygen (DO) was controlled at 25% air saturation. The DO was controlled first by the impeller agitation rate (400 to 1200 rpm) and later by the aeration rate (2 to 10 standard liters per minute, slpm). The pH was controlled to 6.8. NH4OH (14.5% w / v, w / v) and H2SO4 (20% w / v) were used to control pH 1. The back pressure was maintained at 0.5 bars. At various intervals (20, 25 and 30 hours), 5 mL of Defoamer Suppressor 7153 was added to the fermenter to prevent defoaming. The cells were harvested by centrifugation 8 hours after adding IPTG and were stored at -80 oC as a cell paste. PREPARATION OF GROSS GTFJ ENZYME EXTRACT FROM CELL PULP
    [057] The cell paste obtained above was suspended at 150 g / L in 50 mM potassium phosphate buffer pH 7.2 to prepare a paste. The paste was homogenized at 12,000 psi (machine type Rannie, APV-1000 or APV 16.56) and the homogenate cooled to 4 oC. Under moderately vigorous stirring, 50 g of a flocculant solution (Aldrich no. 409138, 5% in 50 mM sodium phosphate buffer pH 7.0) was added per liter of cell homogenate. The agitation was reduced to mild agitation for 15 minutes. The cell homogenate was then clarified by centrifugation at 4500 rpm for 3 hours at 5-10 oC. The supernatant containing crude gtfJ enzyme extract was concentrated (approximately 5X) with a 30 kilo Dalton (kDa) cut molecular weight membrane. The protein concentration in the gftJ enzyme solution was determined by the bincicroninic acid (BCA) protein test (Sigma Aldrich) to be 4-8 g / L. POLYMER PREPARATION, WIRING AND FIBER SOLUTIONS WIRING AND PROCEDURE EQUIPMENT
    [058] Figure 1 is a schematic diagram of an apparatus suitable for use in its fiber spinning process. The gear unit, 1, drives a plunger, 2, at a controlled rate on a piston fitted to a spinning cell 3. The spinning cell can contain filter assemblies. A suitable filter set includes stainless steel screens 100 and 325 mesh. One spinning block, 4 contains spinneret 5, and optionally stainless steel screens as pre-filters for the spinneret. The extruded filament 6 produced from there is directed to a liquid coagulation bath 7. In all the examples listed in table 1 the filament was extruded from the die directly into the liquid coagulation bath - the bottom of the die was immersed in the bath.
    [059] The extrudate can be, but need not be, directed back and forth through the path between guides 8, which are normally manufactured by Teflon® PTFE. Only one passes through the bath shown in figure 1. At the exit of the coagulation bath, 7, the tempered filament 9, can optionally be directed through a drawing zone using an independently driven roller 10, around which the filament so temper is packed. The tempered filament can optionally be directed through an extraction bath 11, which allows further treatment such as extraction of additional solvent, washing or drawing of the extruded filaments. The filament thus prepared is then directed through a through mechanism 12, to distribute the fiber evenly over the coil and collected in plastic coils using a winding 13. In one embodiment, the process comprises a plurality of independently driven rolls.
    [060] In one embodiment, the driven roller, 10, is removed from the fiber path but the fiber is nevertheless immersed in the extraction bath. The two are independent of each other. In all of the above examples, the driven roller 10 has been removed from the fiber path.
    [061] In one embodiment, a plurality of filaments are extruded through a multi-hole die and the filaments thus produced are converged to form a yarn. In another embodiment, the process comprises a plurality of multi-hole dies so that a plurality of yarns can be prepared at the same time.
    [062] In each example, the coiled fiber coil produced was impregnated overnight in a mug of the liquid shown in table 1. The fiber impregnated coil was then air-dried for at least 24 hours. The fiber tensile properties were then determined according to ASTM D2101-82.
    [063] The spinning cell, the piston, the connecting tubes and the die were all made of stainless steel. FIBER PHYSICAL PROPERTY MEASUREMENT
    [064] Physical properties such as toughness, elongation and initial module were measured using methods and instruments according to ASTM standard D 2101-82, except that the length of the test body was 10 inches. Results shown are averages for 3 to 5 individual yarn tests.
    [065] The physical properties were determined for each fiber prepared. The results are shown in table 1. The denier of the fiber produced is included, and physical properties such as toughness (T) in grams per denier (gpd), elongation at break (E,%), and initial modulus (M) in gpd. GLOSSARY OF TERMS
    MATERIALS
    EXAMPLE 1 PREPARATION OF POLYMER P1
    [066] Twenty liters of aqueous solution were prepared by combining 1000 g of sucrose (VWR # BDH8029), 20 g of Dextran T-10 (Sigma # D9260), and 370.98 g of boric acid (Sigma # B6768) were combined in approximately 18 l of water. 4N NaOH solution (EMD # SX0590-1) was used to adjust the pH to 7.5. Additional water was then added to bring the total volume up to 20 liters. The solution thus prepared was then introduced with 180 ml of enzyme extract prepared above and left to stand at room temperature for 48 hours. The resulting poly (α (1 ^ 3) glucan) solids were collected in a Büchner funnel using a 325 mesh screen over 40 micrometer filter paper. The filter cake was washed with deionized water and filtered as above. The wash with deionized water was repeated three more times. Finally, two washes with methanol were performed; the filter cake was pressed into the funnel and vacuum dried at room temperature. Yield: 237.68 grams of solid white scaly fracture.
    [067] Molecular weights were determined by size exclusion chromatography (SEC) with a GPCV / LS 2000TM chromatograph (Waters Corporation, Milford, MA) equipped with two Zorbax PSM Bimodal-s silica columns (Agilent, Wilmington, DE) using - DMAc from JT Baker, Phillipsburg, NJ with 3.0% LiCl (Aldrich, Milwaukee, WI) as a mobile phase. Samples were dissolved in DMAc with 5.0% LiCl. Average weighted and numerical molecular weights (Mn and Mw) were 139,000 and 279,000 Daltons respectively. EXAMPLE 1 WIRING SOLUTION
    [068] A 250 ml large neck glass bottle was loaded with 25 g of P1 polymer and 225 g of 5 wt% sodium hydroxide. CS2, (7.5 g), was then added via syringe. The container was attached to a lid and a septum through which a polypropylene stirring rod had been attached. The contents were manually mixed with the stirring rod and then allowed to rest at room temperature overnight. The following day the partially dissolved solution (clear but containing a small amount of visible particulates) was transferred to a spinning cell and piston containing mesh packages including 100 and 325 mesh stainless steel screens. A piston was fitted over the viscous mixture . The mixture was then pumped back and forth for 13 cycles using a motorized gear unit in a similarly matched spinning cell coupled contiguously with the first cell via a coupler made of% inch stainless steel tubes. EXAMPLES 2 - 4: FIBER WIRING Approximately 20 hours after the preparation of the solution of example 1, the solution thus prepared was introduced into the spinning equipment as described above, with respect to figure 1. The solution was introduced into a 20-hole die being that each hole was characterized by a circular cross-section with a diameter of 0.003 in. and in length 0.006 in. Table 1 shows the spinning conditions that were used for the fibers prepared in examples 2 - 4. The equipment described in figure 1, as described above, was modified by removing the driven roller, 10, from the filament path in examples 1- 3. The spinning stretch indicated was obtained by operating the winding faster than the jet speed. Example 1 solution was dosed at the rates shown in table 1 through a spinning package with a set of filters consisting of 100 and 325 mesh screens in the die. The die was immersed in a coagulation bath with water containing, by weight 8% H2SO4, 23% Na2SO4, and 0.5% ZnSO4. The filament was extruded directly into the rapid cooling 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 the additional guide pins (8) for a distance of total immersion of 4.1 or 11 feet as indicated. In examples 2 and 3, after removing the coagulation bath, the filaments thus coagulated were directed to a controlled speed winding with a crossing guide at winding speeds shown in table 1. In example 4 the coagulated filaments were directed to a second bath of methanol to the lengths and temperature indicated in table 1. In each example, many hundreds of fiber strands were wound in a coil. After winding, the fiber coils of examples 2 - 4, were sequentially impregnated in baths of 5% NaHCO3, MeOH, and H2O respectively for a period of approximately 4 hours respectively. The fiber was allowed to air dry before being subjected to physical measurements. Physical properties were determined: results are shown in table 1.TABELA 1



    EMPLOYS 5-11 P2YY POLYMER PREPARATION
    [069] Poly (α (1 ^ 3) glucan) polymer was synthesized, washed and isolated using the materials and procedures used for the preparation of Polymer P1 in example 1 except that 200 ml of the enzyme extract was added to the solution of sucrose / dextran / boric acid adjusted pH instead of 180 ml. Yield: 246.08 grams of white scaly solids.
    [070] Mn and Mw were determined to conform to polymer P1 to be 129,000 and 270,000 respectively. EXAMPLE 5: WIRING SOLUTION
    [071] A 250 ml wide-necked glass flask was loaded with 18 g of P2 polymer and 225 g of 4.5 wt% sodium hydroxide. CS2, (2.7 g), was then added by syringe. The container was equipped with a lid and a septum through which a polypropylene stirring rod was fitted. The contents were manually mixed with the stirring rod and then left at room temperature overnight. After 72 hours the partially dissolved solution was transferred to a spinning cell and piston containing mesh blocks including 325 mesh stainless steel screens. A piston was fitted over the viscous mixture. The mixture was then pumped back and forth for 13 cycles using a motorized gear unit in a similarly equipped spinning cell contiguously coupled to the first cell via a coupler made of% inch stainless steel tubes. EXAMPLES 6 - 11: FIBER WIRING
    [072] The fibers of examples 6 - 11 were spun from the spinning solution of example 5, as were the fibers of examples 2 - 4, above, under the conditions shown in table 1. In examples 6 - 9, the filament it was extruded directly into a coagulation bath containing 5% H2SO4 (aq.). In example 10, the fiber was extruded directly into a coagulation bath containing glacial acetic acid. In example 11, at 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 foot. In examples 7 - 11, but not in example 6, after removing the coagulation bath, the filament thus coagulated 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 winding. From the second bath, the coagulated fibers of examples 7 - 11 were directed to the winding at the winding speeds shown in table 1. The fiber spools were impregnated as in examples 2 - 4.
    [073] Physical properties have been determined; results are shown in table 1. EXAMPLES 12 - 15 EXAMPLE 12 WIRING SOLUTION
    [074] A 250 ml wide neck glass bottle was loaded with 20 g of P2 Polymer and 180 g of 4.5 wt% sodium hydroxide. CS2, (3.0 g), was then added by syringe. The vessel was equipped with a lid and a septum through which a stirring rod was fitted. The contents were manually mixed with the plastic stirring rod and then left to rest for 2 days. The partially dissolved solution was transferred to a 300 mL stainless steel cylinder equipped with 2x 100 mesh, 1x 325 and 2x 20 stainless steel screens. A piston was fitted over the viscous mixture. The mixture was then pumped back and forth for 13 cycles using a motorized gear unit in a similarly equipped spinning cell contiguously coupled to the first cell via a coupler made of 1/4 stainless steel tubes. EXAMPLES 13 - 15: FIBER WIRING
    [075] The fibers of examples 13 - 15 were spun from the spinning solution of example 12 like the fibers of examples 2 - 4, above, under the conditions shown in table 1. The fibers were directly extruded at 5% H2SO4 (aq.) At the temperature indicated in table 1. The fibers thus coagulated after removing the coagulation bath were directed to the winding at the winding 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 spools were impregnated and dried according to examples 2 - 4.
    [076] Physical properties have been determined; results are shown in table 1. EXAMPLE 16 PREPARATION OF POLYMER P3
    [077] Poly (α (1 ^ 3) glucan) polymer was synthesized, washed, and isolated using the materials and procedures used for the preparation of Polymer P1 in example 1 except that 200 ml of the enzyme extract was added to the solution of sucrose / dextran / boric acid adjusted pH instead of 180 ml. Yield: 228.52 grams of white scaly solids. Mn was 132,000 Daltons; Mw was 301,000 Daltons. EXAMPLE 16 WIRING SOLUTION
    [078] A 250 ml wide neck glass bottle was loaded with 18 g of P3 polymer and 225 g of 4.5 wt% sodium hydroxide. The container was equipped with a lid and a septum through which a polypropylene stirring rod was fitted. The contents were manually mixed with the stirring rod and then left at room temperature overnight. CS2, (5.4 g), was then added by syringe the next morning. After the addition of CS2 the partially dissolved solution was immediately transferred to a spinning cell and piston containing mesh blocks including 325 mesh stainless steel screens. A piston was fitted over the viscous mixture. The mixture was then pumped back and forth for 13 cycles using a motorized gear unit in a similarly equipped spinning cell contiguously coupled to the first cell via a coupler made of 1/4 stainless steel tubes. EXAMPLES 17-23 FIBER WIRING
    [079] Table 1 provides the spinning conditions that were used for the fibers prepared in examples 17-23. The equipment described in figure 1, as described above, was modified by removing the driven roller, 10, from the filament path. The spinning stretch was obtained by operating the winding faster than the jet speed. The spinning solution thus prepared was dosed at the rates shown in table 1 through a spinning block with a set of filters consisting of 100 and 325 mesh stainless steel screens to a spinneret with 20 holes with a diameter of 003 inches and holes length of .006 inches. The filament was directly extruded in 5% H2SO4 eg 17-19 and 10% H2SO4 eg 20-23 at the coagulation bath temperature shown in table 1. After removing the coagulation bath the coagulated filament was directed through a Second methanol bath (11) in lengths and temperatures shown in table 1, and hence the winding. The filaments of examples 17, 20, and 21 were guided directly to the winding. The second bath in the case of example 23 was filled with water. Fiber spinning was completed in 8 hours from the addition of carbon disulfite.
    [080] The fiber spools were soaked in 5% NaHCO3 for 15 minutes, then soaked in water overnight. The coils were then removed and left to air dry before being subjected to physical measurements. EXAMPLE 24 WIRING SOLUTION
    [081] A 250 ml wide neck glass bottle was loaded with 32.9 g of P3 polymer and 220 g of 5 wt% sodium hydroxide. The container was equipped with a lid and a septum through which a polypropylene stirring rod was fitted. The contents were manually mixed with the stirring rod and then left at room temperature overnight. CS2, (9.9 g), was then added by syringe the next morning. After the addition of CS2 the partially dissolved solution was immediately transferred to a spinning cell and piston containing mesh blocks including 325 mesh stainless steel screens. A piston was fitted over the viscous mixture. The mixture was then pumped back and forth for 11 cycles using a motorized gear unit in a similarly equipped spinning cell coupled contiguously with the first cell via a coupler made of% inch stainless steel tubes. EXAMPLES
    25- 31 FIBER WIRING
    [082] Table 1 provides the spinning conditions that were used for the fibers prepared in examples 25-31. The equipment described in figure 1, as described above, was modified by removing the driven roller, 10, from the filament path in examples 25-27. Spinning stretch was obtained by winding operation faster than the jet speed. The spinning solution thus prepared was dosed at the rates shown in table 1 through a spinning block with a filter set consisting of stainless steel screens of mesh q00 and 325 for a die with 20 holes with a diameter of .003 inch and holes in length of .006 inches. The filament was directly extruded in 10% H2SO4 in examples 25-30 and glacial acetic acid in example 31 at the coagulation bath temperature shown in table 1. After removing the coagulation bath the filaments thus coagulated from examples 26, 27, and 30 were directed through a second bath (11) of water in lengths and temperatures shown in table 1, and from there to the winding. The filaments of examples 25, 28, 29, and 31 were guided directly to the winding and were not passed through the second bath. The fiber spinning was completed in 8 hours from the addition of carbon disulfide to the spinning solution.
    [083] The fiber spools were soaked in 5% NaHCO3 overnight, and then soaked in water for another day. The coils were removed and allowed to air dry before being subjected to physical measurements. EXAMPLES 32 - 44, AND COMPARATIVE EXAMPLES A - W
    [084] 36 solutions were prepared to define the solution parameters that resulted in suitable solutions for fiber spinning. For each of examples 32-44 and comparative examples A - W, 40 ml glass vials were loaded with the aqueous alkali metal hydroxide shown in table 2. The concentration of the alkali metal hydroxide solution in% by weight and the The amount of that alkali metal hydroxide solution is also shown in Table 2. 2 g of Polymer P1 was then added to each vial. Carbon disulfide (CS2) was added in the amount shown in table 2 and the flask was equipped with a septum through which a polypropylene stir rod was fitted. The contents were manually mixed with the plastic shaker and allowed to rest at room temperature for at least 12 hours with intermittent mixing. The solubility designations in table 2 were determined by visual inspection. A clear solution was considered to be completely dissolved; a clear solution with some small particles that float around was also considered to be dissolved; it was considered that a partially dissolved solution could be brought to complete dissolution under more intense mixing. A cloudy solution with a lot of undissolved particles was considered undissolved. TABLE 2

    EXAMPLE 45: DETERMINATION OF GLUCAN XANTATE FORMATION AND DECOMPOSITION WITH THE USE OF NMR SPECTROSCOPY
    [085] 2 g of poly (α (1 ^ 3) glucan) were dissolved in 25 ml of aqueous sodium hydroxide (4.5% by weight). After completing the dissolution, 0.6 g of carbon disulfide was added and the mixture thus formed was then mechanically stirred and immediately transferred using a syringe and needle into a special 4.1 mm OD sample tube sold by New Era Enterprises, Inc The tube was capped and reduced to a 5 mm NMR tube. 7-inch standard containing 60μL of D2O as NMR blocking solvent. These concentric tubes were placed in a small, bench top centrifuge and spun for several minutes to take the sample to the bottom of the inner tube and to eliminate all air bubbles from the sample. The NMR tubes were removed from the centrifuge and placed on the magnet of a Bruker 500 MHz Avance II spectrometer equipped with a 5mm CPDUL cryoprobe with z gradients. The probe was tuned and the magnet was put on before starting the series of consecutive tests to investigate the formation and degradation of poly (α (1 ^ 3) glucan). Each test was acquired using a zgig Bruker pulse sequence with a spectral width of 33333.3 Hz (265.0 ppm), transmitter offset of 160 ppm, and 32768 time domain points for an acquisition time of 0.4916 seconds. A 3 second delay was used between pulses and 3000 scans were acquired for each test providing a total time of 2 hours and 56 minutes for each test.
    [086] To suppress a baseline roll and obtain better integrals and peaks, the digital data for each test was converted into analog data so that a retroactive linear prediction could be made. The first 12 points of each data set were replaced using Bruker's linear prediction data processing based on the first 1024 data points. The free induction decay was also multiplied by a 2.0 Hz exponential function before being transformed. To determine the degree of xanthate substitution, the integral area for the xanthate carbon centered at 232.5 ppm, was compared to the integral area (adjusted to 1.00) for the anomeric glucan C1 and 95.6 - 100.9 ppm, used as internal calibration. At no point in this series of tests was there a signal for 13 C of free CS2 (193.7ppm) although signs of sodium trithiocarbonate (269.4ppm) and sodium carbonate (168.4ppm) were present as by-products of glucan xantate degradation over time. Results are shown in Table 3. TABLE3

    权利要求:
    Claims (14)
    [0001]
    1. SOLUTION, characterized by comprising 0.75 to 2 molar aqueous alkali metal hydroxide and a solids content of 5 to 20 wt% poly (α (1–3) glucan); the numerical molecular weight of the poly (α (1–3) glucan) xanthate being at least 10,000 Da; wherein at least 90 mol% of the repeat units in the poly (α (1–3) glucan) xanthaned are glucose repeat units and at least 50% of the bonds between the glucose repeat units are α ( 1—3), and the degree of xanthogenation of the poly (α (1—3) glucan) is in the range of 0.1 to 1.
    [0002]
    2. SOLUTION according to claim 1, characterized by the solids content of poly (α (1—3) glucan) xantha being in the range of 7.5 to 15%.
    [0003]
    3. SOLUTION according to claim 1, characterized in that the alkali metal hydroxide is NaOH.
    [0004]
    4. SOLUTION according to claim 3, characterized in that the NaOH concentration is 1.0 to 1.7 molar.
    [0005]
    5. SOLUTION according to claim 1, characterized in that in the poly (α (1–3) glucan) xanthaned 100% of the bonds between glucose repeating units are α (1–3) glycoside bonds.
    [0006]
    6. SOLUTION according to claim 1, characterized by the numerical molecular weight of the poly (α (1–3) glucan) xanthated to be in the range of 40,000 - 100,000 Da.
    [0007]
    7. PROCESS, characterized by comprising the formation of a solution by dissolving in 0.75 to 2 molar aqueous alkali metal hydroxide, CS2, and 5 to 15% by weight of the total weight of the resulting solution of poly (α (1 - > 3) glucan, having a numerical molecular weight of at least 10,000 Da, in which at least 90 mol% of the repeat units in the poly (α (1—3) glucan) are glucose repeat units and at least 50 % of the connections between the glucose repeating units are glucose connections α (1–3), causing this solution to flow through a die, thus forming a fiber, and placing said fiber in contact with an acidic liquid coagulant; being that in this process the weight ratio of CS2 to poly (α (1 -> 3) glucan) is in the range of 0.1 to 1.0.
    [0008]
    PROCESS, according to claim 7, characterized in that from 7.5 to 15% by weight of poly (α (1 - 3) glucan) is dissolved in said solution.
    [0009]
    9. PROCESS according to claim 7, characterized in that the alkali metal hydroxide is NaOH.
    [0010]
    PROCESS according to claim 7, characterized in that the NaOH concentration is 1.0 to 1.7 molar.
    [0011]
    11. PROCESS, according to claim 7, characterized in that in poly (α (1—3) glucan) 100% of the repeating units are glucose, and 100% of the bonds between repeating units are α (1—3) bonds glycoside.
    [0012]
    PROCESS, according to claim 7, characterized in that it also comprises allowing the solution to rest for a period of 1 to 8 hours before spinning.
    [0013]
    13. PROCESS, according to claim 7, characterized in that the poly (α (1—3) glucan) has a numerical molecular weight in the range of 40,000 - 100,000 Da.
    [0014]
    14. PROCESS, according to claim 7, characterized in that CS2 is added last.
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    同族专利:
    公开号 | 公开日
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    JP2015518926A|2015-07-06|
    KR20150021053A|2015-02-27|
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    SG11201407488SA|2014-12-30|
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    IN2014DN08909A|2015-05-22|
    AU2013266331B2|2016-10-27|
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    EP2855536B1|2016-12-21|
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    CN104379607A|2015-02-25|
    US9540747B2|2017-01-10|
    US9034092B2|2015-05-19|
    AU2013266331A1|2014-11-13|
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    PH12014502607B1|2015-01-21|
    US20130313737A1|2013-11-28|
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    法律状态:
    2018-03-06| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|
    2018-03-13| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|
    2018-03-20| B06I| Technical and formal requirements: publication cancelled|Free format text: ANULADA A PUBLICACAO CODIGO 6.6.1 NA RPI NO 2462 DE 13/03/2018 POR TER SIDO INDEVIDA. |
    2019-11-12| B06U| Preliminary requirement: requests with searches performed by other patent offices: suspension of the patent application procedure|
    2020-02-11| B25A| Requested transfer of rights approved|Owner name: DUPONT INDUSTRIAL BIOSCIENCES USA, LLC (US) |
    2020-11-10| B09A| Decision: intention to grant|
    2020-12-29| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 23/05/2013, OBSERVADAS AS CONDICOES LEGAIS. |
    2021-02-09| B25A| Requested transfer of rights approved|Owner name: NUTRITION AND BIOSCIENCES USA 4, INC. (US) |
    优先权:
    申请号 | 申请日 | 专利标题
    US13/479,990|2012-05-24|
    US13/479,990|US9034092B2|2012-05-24|2012-05-24|Composition for preparing polysaccharide fibers|
    PCT/US2013/042329|WO2013177348A1|2012-05-24|2013-05-23|Novel composition for preparing polysaccharide fibers|
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