Composite materials

Abstract

A composite material is formed by combining an expandable polymer having a charge with another polymer having an opposite charge to produce. In particular, the composite material can be prepared by combining the polymers with a medium such as and water, and expanding the mixture using a treatment that expands the mixture to produce, for example, insoluble porous foam-like composites.

Claims

1. A process of preparing a composite material, the process comprising, in a single step: (a) mixing (i) at least one non-gelatinized starch having a charge, (ii) at least one polysaccharide of opposite charge, and (iii) at least one polar solvent to form a mixture, wherein at least one of said at least one non-gelatinized starch and said at least one polysaccharide is capable of expanding; and (b) expanding the mixture while removing said at least one polar solvent while gelatinizing said at least one non-gelatinized starch to form a composite material including gelatinized starch and said at least one polysaccharide, wherein said composite material is insoluble in water.

2. The process of claim 1, wherein said non-gelatinized starch comprises amylopectin.

3. The process of claim 1, wherein said polysaccharide is chitosan.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 provides three graphs showing the determination of swelling ratio (water uptake in % w/w of water to dry composite) of starch-chitosan composites swollen in solutions with different pH values according to embodiments of the present disclosure. FIG. 1(a) shows the swelling ratio with a pH 2, FIG. 1(b) shows the swelling ratio with a pH 7 and FIG. 1(c) shows the swelling ratio with a pH 12.

DETAILED DESCRIPTION OF THE DISCLOSURE

(2) The present disclosure relates to composite materials that are insoluble in liquid environments but can absorb a large amount of liquid. The composite materials of the present disclosure can advantageously absorb a liquid in an amount that is many times its own weight, e.g., as much as about 11 times its weight, and over a wide pH range, e.g., a range of about 2-12. Other advantages of the composites of the present disclosure include a very simple production process. In addition some of the composites can be fabricated to yield completely compostable materials when produced using natural biologically derived polymers. The composites can also be formed or molded into a wide variety of shapes, including a process where the hydrated material is dehydrated within a mold where it can expand during dehydration to fill the mold and take the shape of the mold. In an aspect of the present disclosure, the mold would have some pores to allow water vapor to escape. Composites of the present disclosure include, for example, insoluble low density composites such as highly porous foams containing at least one polymer having a charge, e.g., an anionic starch, and at least one polymer of opposite charge, e.g., cationic polysaccharide such as chitosan.

(3) The composites can be prepared by mixing at least one soluble polymer having a charge, at least one soluble polymer of opposite charge, and at least one polar solvent, wherein at least one of the soluble polymers is capable of expanding. The mixture is then expanded.

(4) Soluble polymers useful for the present disclosure include, for example, polymers that are soluble in the polar solvent and carrying either a negative or positive charge. Such polymers having a charge include anionic polymers, such as, for example, at least one anionic starch, alginic acid, pectin, xanthan gum, hyaluronic acid, chondroitin sulfate, keratin sulfate, gum arabic, gum karaya, gum tragacanth, heparin, chondroitin, polyacrylic acid and it's derivatives, many proteins such as the caseins.

(5) Soluble polymers of opposite charge, e.g., cationic polymers, that are soluble in the polar solvent include, for example, at least one cationic polysaccharide such as chitosan, cationic guar gum, cationic hydroxyethylcellulose, cationic starch, cationic cellulose, pectin, and cationic polyethylene glycol.

(6) Polar solvents useful for solubilizing the polymers include, for example, water, aqueous solvents including ethylene or propylene glycol, alkyl lactate, and optionally alcohol or organic carbonates, lower alcohols such as methanol, ethanol, n-propanol and isopropanol.

(7) It is believed that the polymers while soluble in the polar solvent when forming the mixture become insoluble upon expansion because the cationic polymer electrostatically crosslinks with the anionic polymer during the expansion process where the polymers can interact.

(8) In one aspect of the present disclosure, the process of preparing the composite material includes preparing a mixture containing (i) at least one anionic starch as the at least one soluble polymer having a charge, (ii) at least one cationic polysaccharide as the at least one soluble polymer of opposite charge, and (iii) at least one polar solvent, e.g. water. The mixture is then expanded by one or more techniques that are known to expand the at least one expandable polymers. Such techniques include, for example, thermal treatment, e.g., such as where the temperature of the treatment exceeds about 100 degrees Celsius, thermal extrusion, a microwave treatment, etc. Starch, for example, especially amylopectin, is well known to exhibit extensive expansion capacity under thermal processing, including microwave heating and thermal extrusion. Expanded starch, however, is readily soluble in aqueous solutions.

(9) An expandable soluble polymer such as an anionic starch can be combined with a cationic polymer such as chitosan and water to expand the mixture through microwave processing or other thermal treatments such as thermal extrusion. The anionic starch can be an anionic amylopectin or a starch which contains phosphate such as many starches derived from potato (where the starch contains one phosphate ester group per approximately 40 to 400 anhydroglucose units). The cationic polymer can also be a cationic guar or cationic starch.

(10) It is preferable to use a starch which has not been gelatinized to improve the characteristics of the expanded composite including the degree of expansion during thermal treatment which would result in a lower density insoluble composite.

(11) For example, an expanded insoluble composite can be produced using the following process. Chitosan solution was prepared by mixing chitosan (Sigma-Aldrich, Saint Louis, Mo.) in 1% (v/v) formic acid and magnetically stirred at 600 rpm for 24 hours under room temperature. The pH of the chitosan solutions ranged from 4 to 5; the preferred pH is 4.5. The contents of chitosan in the above solutions ranged from 1.67% to 5% (w/v), preferably at about 5% (w/v). After the chitosan was dissolved and the solution became clear, the solution was poured into a container for further mixing with potato starch (MP Biomedicals, Solon, Ohio).

(12) Starch-based chitosan composite foams were prepared as follows. 2.7 ml chitosan solutions with different concentrations ranged from 1.67% to 5% (w/v) were added to 1.8 gram non-gelatinized potato starch powder (containing at least 50-75% amylopectin). The final weight ratios of chitosan to potato starch were from 2.5% to 7.5% (w/w), where ratio of 7.5% was most desired. The starch-chitosan mixtures were then stirred at 250 rpm for about 2 minutes. After blending, the mixtures were heated by microwave at 100% power of 900 W at 2450 MHz for 35-50 seconds.

(13) FIG. 1 shows the swelling ratio (water uptake in % w/w of water to dry composite) of varied starch-chitosan composites prepared by microwave treatment. Swelling behavior was examined at three different pH values: 2, 7 and 12. It is shown in FIG. 1 that all composites can be immersed in acidic (pH2), neutral (pH7) and basic (pH12) environment and remain insoluble for as long as 120 hours. The swelling equilibriums for different starch composites are different depending on specific pH environment. Specifically, composites immersed in pH 2 and pH 12 reached equilibrium faster than that at pH 7. At pH 2 and pH 12, the equilibrium was achieved after immersion for 8 hours, whereas at pH 7 it took 24 hours to achieve equilibrium. Generally speaking, the higher the chitosan content in the composite, the better the swelling ratio will be in solution, except the case at pH12. At pH 2, the maximum values of swelling ratio for 2.5%, 5% and 7.5% starch-chitosan composite were 746%, 896% and 1137%, respectively. Likewise, at pH7 the maximum swelling ratios for 2.5%, 5% and 7.5% starch-chitosan composite were 698%, 896% and 1035%, respectively, However, such a behavior did not exist at pH12 where swelling ratios for all composites showed no significant difference, and the maximum swelling ratio reached around 613% for all composites after equilibrium. Furthermore, composites immersed in lower pH behave better than those immersed in higher pH in terms of swelling ratio. Take 7.5% starch-chitosan composite, for example, the maximum swelling ratios at pH2, pH7 and pH12 were 1137%, 1035% and 613%, respectively. Such a performance can be seen in 2.5% and 5% starch-chitosan composites as well.

(14) Other additives can also be included in the composite. For example, cellulose or other insoluble polymer fiber can be added to modify the mechanical properties of the composites. Specifically, starch:chitosan:cellulose composites can be created with modified properties where the component ratios can range from approximately 50-80% starch, 2-10% chitosan, and 10-48% cellulose. To reduce brittleness, approximately 1% to 25% of glycerol can be added w/w relative to the total dry weight of all composite components. Glycerol can be added and mixed into the solution before microwave, thermal extrusion, or other thermal processing. Other additives are also possible including but not limited to polyethylene glycol, poly lactic acid, or poly lactic glycolic acid. Final hydration levels before thermal processing can range from approximately 40% to 80% where 60% is preferred. Other component additives may be more suitable for specific applications. For example, collagen may provide a benefit for biomedical applications. In addition, various additives such as antimicrobial and therapeutic agents can be added before or after microwave processing. Therapeutic agents include compounds such as polyhexamethylene biguanide (PHMB), sodium benzoate, or any contained in U.S. Patent Application 20110150972, 2011. If added as a solution after microwave processing by soaking the composite in solution or spraying a solution onto the composite, the composite can be subsequently dehydrated by freeze drying to permit long term storage. The use of chitosan in the composite may provide some measure of natural antimicrobial properties.

(15) Insoluble expanded or non-expanded starch composites as described above using other production techniques can also be employed to prepare the composite. These production techniques include various extrusion, molding and electrospinning techniques, both of which are well known to those skilled in the art. Electrospinning of starch based materials is well known and often involves solvents other than water such as, for example, ethanol. The use of other polar solvents other than water is acceptable in the formation of any of the composites described herein.

(16) As disclosed herein, improvements to extruded and electrospun material can be achieved by adding cellulose and glycerol. In the case of materials with dimensions less than 1 mm, nanocellulose, cellulose nanofibers, cellulose nanocrystals or cellulose nanowhiskers can be used as the cellulose material. These forms of cellulose are cellulose materials which exhibit at least one dimension less than about 100 nm.

EXAMPLES

(17) The following examples are intended to further illustrate certain preferred embodiments of the invention and are not limiting in nature. Those skilled in the art will recognize, or be able to ascertain, using no more than routine experimentation, numerous equivalents to the specific substances and procedures described herein.

(18) Starch-chitosan composite foams were prepared as follows. Chitosan solutions were prepared with different concentrations ranging from 1.67% to 5% (w/v) by mixing chitosan (available from Sigma Aldrich, Saint Louis, Mo.) having a molecular weight between approximately 2 kDa and 100 kDa, where higher molecular weights may be preferred, including those in excess of 100 kDa, in an acidic solution where formic acid was added to DI water to a pH between 4 and 5, preferably 4.5 where the final concentration of chitosan ranged from approximately 1.67% to 5% (w/v), preferably at about 5% (w/v). Then 2.7 ml of the chitosan solution was added to 1.8 grams of non-gelatinized potato starch powder (containing at least 50-75% amylopectin) (available from MP Biomedicals, Solon, Ohio). The final weight ratios of chitosan to potato starch were from 2.5% to 7.5% (w/w). A final weight ratio of chitosan to potato starch of 7.5% was most desired to produce a composite which exhibited the most water absorption capacity and which was the most stable when submerged for prolonged periods (approximately 5 days) in highly acidic (pH 2) or highly basic (pH solutions. The starch-chitosan mixtures were then stirred at 250 rpm for about 2 minutes. After blending, the mixtures were heated by microwave at 100% power of 900 W at 2450 MHz for 35-50 seconds. During the microwave treatment water is converted to water vapor and the starch gelatinizes in the presence of the chitosan. The generation of water vapor causes the viscous starch-chitosan mixture to expand until dehydrated. During this process, the cationic chitosan binds with the anionic starch creating an insoluble composite.

(19) While the claimed invention has been described in detail and with reference specific embodiments thereof, it will be apparent to one of ordinary skill in the art that various changes and modifications can be made to the claimed invention without departing from the spirit and scope thereof. Thus, for example, those skilled in the art will recognize, or be able to ascertain, using no more than routine experimentation, numerous equivalents to the specific substances and procedures described herein. Such equivalents are considered to be within the scope of this invention, and are covered by the following claims.